Conversion of Waste Biomass to Animal Feed, … · Diisopropyl Ether. Calcium Propionate. Propionic...
Transcript of Conversion of Waste Biomass to Animal Feed, … · Diisopropyl Ether. Calcium Propionate. Propionic...
MixAlco Process Waste Biomass to Fuels and ChemicalsMixAlco Process Waste Biomass to Fuels and Chemicals
Technology DevelopmentMark Holtzapple and Richard DavisonDepartment of Chemical EngineeringTexas AampM University
LicenseeDavid Carrabba PresidentTerrabon LLC
MarketingWilliam Settles Jim GloverStandard-Gen Inc Harvest Chemicals Ltd
Looking for treasures in the TRASH
Waste Generation
integral part of a developed society
Municipal Solid Waste Generation in the US
0
40
80
120
160
200
240
1960 1970 1980 1990 1995 1997 1998 2000 2005
Milli
on T
ons
year
Total generation
Net genetration (afterrecycling)
2395
1628
MSW Management in the US
5050Land DisposalLand Disposal3030RecoveryRecovery
1616CombustionCombustion
Total Generation 217 million tons EPA
Municipal Solid Waste
Disposal costs
$10-$110wet ton
gt 45 lb MSW(personbullday)
OtherOtherGlassGlass
Food WasteFood WasteWoodWood
MetalsMetalsPlasticsPlastics
Yard WastesYard WastesPaper wastesPaper wastes
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Looking for treasures in the TRASH
Waste Generation
integral part of a developed society
Municipal Solid Waste Generation in the US
0
40
80
120
160
200
240
1960 1970 1980 1990 1995 1997 1998 2000 2005
Milli
on T
ons
year
Total generation
Net genetration (afterrecycling)
2395
1628
MSW Management in the US
5050Land DisposalLand Disposal3030RecoveryRecovery
1616CombustionCombustion
Total Generation 217 million tons EPA
Municipal Solid Waste
Disposal costs
$10-$110wet ton
gt 45 lb MSW(personbullday)
OtherOtherGlassGlass
Food WasteFood WasteWoodWood
MetalsMetalsPlasticsPlastics
Yard WastesYard WastesPaper wastesPaper wastes
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Waste Generation
integral part of a developed society
Municipal Solid Waste Generation in the US
0
40
80
120
160
200
240
1960 1970 1980 1990 1995 1997 1998 2000 2005
Milli
on T
ons
year
Total generation
Net genetration (afterrecycling)
2395
1628
MSW Management in the US
5050Land DisposalLand Disposal3030RecoveryRecovery
1616CombustionCombustion
Total Generation 217 million tons EPA
Municipal Solid Waste
Disposal costs
$10-$110wet ton
gt 45 lb MSW(personbullday)
OtherOtherGlassGlass
Food WasteFood WasteWoodWood
MetalsMetalsPlasticsPlastics
Yard WastesYard WastesPaper wastesPaper wastes
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Municipal Solid Waste Generation in the US
0
40
80
120
160
200
240
1960 1970 1980 1990 1995 1997 1998 2000 2005
Milli
on T
ons
year
Total generation
Net genetration (afterrecycling)
2395
1628
MSW Management in the US
5050Land DisposalLand Disposal3030RecoveryRecovery
1616CombustionCombustion
Total Generation 217 million tons EPA
Municipal Solid Waste
Disposal costs
$10-$110wet ton
gt 45 lb MSW(personbullday)
OtherOtherGlassGlass
Food WasteFood WasteWoodWood
MetalsMetalsPlasticsPlastics
Yard WastesYard WastesPaper wastesPaper wastes
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
MSW Management in the US
5050Land DisposalLand Disposal3030RecoveryRecovery
1616CombustionCombustion
Total Generation 217 million tons EPA
Municipal Solid Waste
Disposal costs
$10-$110wet ton
gt 45 lb MSW(personbullday)
OtherOtherGlassGlass
Food WasteFood WasteWoodWood
MetalsMetalsPlasticsPlastics
Yard WastesYard WastesPaper wastesPaper wastes
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Municipal Solid Waste
Disposal costs
$10-$110wet ton
gt 45 lb MSW(personbullday)
OtherOtherGlassGlass
Food WasteFood WasteWoodWood
MetalsMetalsPlasticsPlastics
Yard WastesYard WastesPaper wastesPaper wastes
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Paper Wastes
Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper
gt 100 millions tonsyear
30 MSW
50 recovery in the year 2000
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Sewage Sludge
69 million dry tons generated in 1998
Municipal wastewater treatment
Disposal costs $80-$440dry ton
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Combine Wastes
Carbohydrate Rich
MSW
(40ndash80)
Nutrient Rich
Sewage Sludge
(20ndash60)
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
MixAlco ProcessMixAlco Process
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversion
CarboxylicCarboxylicAcid Acid SaltsSalts
DewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
PatentsPatents
598613359691896262313
59623075874263
58658985693296
60433926395926
HydrogenHydrogen
BiomassBiomass
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
HydrogenateHydrogenate
MixedMixedKetonesKetonesThermalThermal
ConversionConversionDewaterDewaterFermentFermentPretreatPretreat
Calcium CarbonateCalcium CarbonateLimeLime
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
PretreatmentPretreatment
FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Lime TreatmentLime Treatment
TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
In situ DigestionIn situ Digestion
bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
In-Situ DigestionIn-Situ Digestion4848
-- h D
iges
tion
h D
iges
tion
(g d
iges
ted
g fe
d)(g
dig
este
dg
fed)
0606040402020000
10100808
UntreatedUntreated
SugarSugar--canecanebagassebagasse
AfricanAfricanmilletmilletstrawstraw
SorghumSorghumstrawstraw
TobaccoTobaccostalksstalks
LimeLime--treatedtreated
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
FermentationFermentation
Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Environments where organic acids naturally formEnvironments where organic acids naturally form
bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants
bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Why are organic acids favoredWhy are organic acids favored
The actualThe actual stoichiometrystoichiometry is more complexis more complex
CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol
CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol
5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)
glucose ethanolglucose ethanol
glucose acetic acidglucose acetic acid
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures
40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt
100 wt 100 wt
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Countercurrent FermentationCountercurrent Fermentation
FreshFreshBiomassBiomass
LiquidLiquidHarvestHarvest
SpentSpentSolidsSolids
Fresh Fresh LiquidLiquid
Product Concentration
Biomass Digestion
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Suppress MethaneSuppress Methane
bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Fermentation GoalsFermentation Goals
bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Affordable FermentorsAffordable Fermentors
AboveAbove--ground stainless steelground stainless steel
AboveAbove--ground carbon steelground carbon steel
AboveAbove--ground concreteground concrete
InIn--ground plastic
$380m$380m33
$125m$125m33
$ 69m$ 69m33
$ 12m$ 12m3ground plastic 3
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
CPDM ModelingCPDM ModelingPr
oduc
tPr
oduc
t Con
cC
onc
Initi
al S
ubst
rate
Initi
al S
ubst
rate
Con
cC
onc
rrrr
xPP
TimeTime
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Rate EquationRate Equation
r a xb P
= minus+( )
( )
1
1
6 0
4 38
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)
0
5
10
15
20
25
30
35
40
025 035 045 055 065 075Digestion (fraction of VS)
LRT (days)
75
1125
15
1875225
34
567375
89
Solids loading rate(g(Lmiddotd))
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
DewateringDewatering
FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Heat RequirementsHeat Requirements
BtuBtulb water removedlb water removed
SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Thermal ConversionThermal Conversion
FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Thermal ConversionStoichiometryThermal ConversionStoichiometry
HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33
OO
Calcium Acetate AcetoneCalcium Acetate Acetone
OO OO
HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33
Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone
OO OO OO
HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33
Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone
OO OO OO
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Thermal Conversion KineticsThermal Conversion Kinetics
001001
0101
11
1010
100100
10001000
1000010000
Hal
f Life
(min
)H
alf L
ife (m
in)
AcetateAcetate
PropionatePropionate
ButyrateButyrate
380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
HydrogenationHydrogenation
FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate
Lime KilnLime Kiln
MixedMixedAlcoholAlcoholFuelsFuels
MixedMixedKetonesKetones
CarboxylicCarboxylicAcid Acid SaltsSalts
BiomassBiomass
HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry
OHOH3CCCH3 + H2 rarr H3CCCH3
HAcetone Isopropanol
H3CCCH2CH3 + H2 rarr H3CCCH2CH3H
O OH
Methyl Ethyl Ketone 2-Butanol
H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3
O
H
OH
Diethyl Ketone 3-Pentanol
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Ketone HydrogenationKetone Hydrogenation
Liquid Liquid KetonesKetones
Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )
HH22
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Advantages of MixAlcoApproachAdvantages of MixAlcoApproach
bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Potential ProductsPotential Products
bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Carboxylic Acid ProductionCarboxylic Acid Production
BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo
CarboxylateCarboxylateSaltSalt
COCO22
Carboxylic AcidCarboxylic Acid
Lime KilnLime Kiln
CaOCaO
COCO22
CaCOCaCO33
acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo
Ca(Ac)2
CO2 CaCO3
R3N
H2O
R3NHAc
HAc
R3NHAc
R = - CH2CH3
R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Chemical FlowchartChemical Flowchart
BBIIOOMMAASSSS
CalciumCalciumAcetateAcetate
AceticAceticAcidAcid
EthanolEthanol
EthylEthylAcetateAcetate
CalciumCalciumMagnesiumMagnesiumAcetateAcetate
AcetoneAcetone
HH22
IsopropanolIsopropanol
IsopropylIsopropylTertiaryTertiaryButylButylEtherEther
IsobutyleneIsobutylene
HH22
DiisopropylDiisopropylEtherEther
CalciumCalciumPropionatePropionate
PropionicPropionicAcidAcid
nn--PropanolPropanolPropylPropylPropionatePropionate
DiethylDiethyl KetoneKetone 33--PentanolPentanol
HH22
HH22
CalciumCalciumButyrateButyrate
ButyricButyricAcidAcid
nn--ButanolButanolButylButylButyrateButyrate
DipropylDipropylKetoneKetone
HH2244--HeptanolHeptanol
HH22
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Alcohol Production from Municipal Solid Waste
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Plant CapacityPlant Capacity
((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity
City Population
2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000
160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000
Base Base CaseCase
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Optimization (40 tonneh)Optimization (40 tonneh)
0
5
10
15
20
25
30
10 15 20 25 30 35Product Concentration (gL)
Cos
t ($
tonn
e)
TotalTotal
DewateringDewateringFermentationFermentation
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)
Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv
147147
23235050
3030 39391010
Total = $30 millTotal = $30 mill
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
12021202
AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv
184184
862862 910910686686 600600 524524
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Effect of Scale on Capital CostEffect of Scale on Capital Cost
1
10
100
1000
1 10 100 1000Plant Capacity (tonneh)
Cap
ital C
ost (
mill
$)
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)
$054L$054L$205gal$205gal
$028L$028L$105gal$105gal $019L$019L
$071gal
2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)
$071gal $016L$016L$059gal$059gal
$013L$013L$048gal$048gal
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Mixed Alcohol Selling Price(40 tonneh)
Mixed Alcohol Selling Price(40 tonneh)
-02-01
0010203040506
-100 -80 -60 -40 -20 0 20 40
Biomass Cost ($tonne)
Alc
ohol
Sel
ling
Pric
e ($
L) 6060
454530301515
ROI ()ROI ()
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Average MSW Tipping FeesAverage MSW Tipping Fees
State Tipping FeeState Tipping Fee($dry($dry tonnetonne))
New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Net Tipping Fee (New York)Net Tipping Fee (New York)
060060
024024
016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20
$53
RecyclableRecyclable
$53
$53 $53 $ 88 $ 88
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Net Tipping Fee (Average US)Net Tipping Fee (Average US)
Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW
060060
024024
016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63
-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10
$ 1
RecyclableRecyclable
$ 1
$ 1 $ 1 $ 153 $ 153
0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Scenarios(40 tonneh)Scenarios(40 tonneh)
New York New York Average US Average US Bagasse Bagasse
--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069
+26 15 029 109 +26 15 029 109
Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost
($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Energy Content
Energy(MJL) (Btugal)
GasolineGasoline
Mixed AlcoholsMixed Alcohols
Ethanol
349 125000
290 104000
234 84300Ethanol
Energy Content
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Properties of Fuel OxygenatesProperties of Fuel Oxygenates
Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))
EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88
Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols
MethanolMethanol 108 31108 31++
Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Acid Production from Los Angeles Yard Waste
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
FeedstockFeedstock
Yard ClippingsYard Clippings
hdry tonne16
h 8000yr
yrd 280
ton11tonne
wet tondry ton50
dwet ton1000
=timestimestimestimes
Sewage Sludge
hdry tonne8
h 8000yr
yrd 365
ton11tonne
wet tondry ton30
dwet ton650
=timestimestimestimes
htonne 24 Total =
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Estimated Capital CostEstimated Capital Cost
$30 million$20 million for mixed acid production$10 million for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Key AssumptionsKey Assumptions
fedtonnedigestedtonne075 Conversion =
fedtonneacidstonne065 y Selectivit =
fed tonneacidstonne490
digested tonneacidstonne065
fed tonnedigestedtonne075 Yield =times=
Solid residue will be burned for process heat sold as compost or landfilled
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill85
acid totallbC2lb410
yracid totallb mill207 C2 =times=
yrlbmill3700 (23)
yrlbmill31
acid totallbC3lb150
yracid totallb mill207 C3 =times=
yrlbmill250 (124)
yrlb mill91
acid totallbC4 lb 440
yracid totallb mill207 C4 =times=
++
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)
yrlbmill 207
tonnelb2200
biomass tonneacidtonne490
yrh8000
hbiomasstonne24 Acid Total =timestimestimes=
US ProductionPlant Production
yrlbmill166
acid totallbC2lb800
yracid totallb mill207 C2 =times=
yrlbmill3700 (45)
yrlbmill38
acid totallbC3lb040
yracid totallb mill207 C3 =times=
yrlbmill250 (33)
yrlb mill33
acid totallbC4 lb 160
yracid totallb mill207 C4 =times=
++
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Tipping Fee IncomeTipping Fee Income
Both sewage sludge and clippings have a tipping fee of $22wet ton
yrmill 15$
dry tonne80$
yrh8000
hsludgesewage dry tonne8 =timestimes
yrmill 16$
dry tonne48$
yrh8000
hclippingsdry tonne16 =timestimes
yrmill$112 Total =
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)
Price Basis
yrmill315$
lb180$
yrlb mill852C =times=
yrmill09$
lb290$
yrlb mill313C =times=
yrmill34$
lb0470$
yrlb mill914C =times=+
yrmill$286 Total =
69 of spot price
69 of spot price
Fuel value $44mill Btu
Chemical Market Reporter
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)
Price Basis
yrmill30$
lb180$
yrlb mill1662C =times= 69 of spot price
yrmill42$
lb290$
yrlb mill383C =times= 69 of spot price
yrmill61$
lb0470$
yrlb mill334C =times=+ Fuel value $44mill Btu
yrmill$34 Total = Chemical Market Reporter
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
ExpensesExpenses
yrmill 219$
biomass tonne100$
yrh8000
hbiomasstonne24 Expense =timestimes=
$70tonne for mixed acid production$30tonne for product purification
Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
ProfitabilityProfitability
Mesophilic Thermophilic($ millyr) ($ millyr)
Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260
87mill 30$millyr$260 ROI ==69
mill 30$millyr$206 ROI ==
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Recent Improvements
Recent Improvements
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Steam-Sorted Real MSW
0
5
10
15
20
25
30
35
0 02 04 06 08 1
Conversion
LRT(days)
12 8
35
6 5 4 3 10
3025
15
VSLRg VS(Ld)
12 10
46
53
8
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
Steam-Sorted Real MSW
ldquoSynthetic MSWrdquo
Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton
Terrestrial inocula200 g VSL
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Synthetic MSWSynthetic MSW
Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117
Component Amount() a
MoistureContent ()
Fats and oils b 27 -
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Marine Inocula
0
10
20
30
40
50
60
70
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L)
456812
1510
2530
35LRT (days)
VSLR g(Lmiddotd) 456812
Marine
Terrestrial
300 g VSL liquid
ldquoSynthetic MSWrdquo
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Advanced Lime Treatment
0
10
20
30
40
50
60
0 02 04 06 08 1
Conversion
Tota
l car
boxy
lic a
cid
conc
entr
atio
n (g
L) 35
128 6 5
3025
15
104 3
LRT (days)
VSLRg(Ld) 12 8 6 5 4 3
Advanced Lime
Conventional Lime
200 g VSLMarine Inocula
ldquoSynthetic MSWrdquo
bull Handles high-lignin biomassbull Less equipment
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Jet Ejector DewateringJet Ejector Dewatering
SaltSolution(FermentorBroth)
Jet Ejector
High-PressureSteam
Distilled Water
Filter
Salt Crystals
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Advantages of Jet EjectorAdvantages of Jet Ejector
bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Advanced BioreactorAdvanced Bioreactor
bullLess solids handlingbullEasier solids handlingbullLower cost
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Next StepsNext Steps
bull Complete pilot plant bull 6 mo $200000
bull Operate pilot plant bull1 yr $100000
bull Preliminary process economics bullNofsinger $30000
bull Market assessment bullChemical Market Resources Inc $20000
Note All costs are estimates
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
ConclusionsConclusionsbull Well-developed technology
bull Pilot plant under constructionbull 12 years of research
bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested
bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-
Thank you for yourtime and attention
- MixAlco Process Waste Biomass to Fuels and Chemicals
- Potential Products
- MixAlco Process
- Patents
- Lime Treatment
- In situ Digestion
- In-Situ Digestion
- Environments where organic acids naturally form
- Why are organic acids favored
- Typical Product Spectrumat Different Culture Temperatures
- Fermentation Goals
- Countercurrent Fermentation
- Fermentation Goals
- Suppress Methane
- Fermentation Goals
- Affordable Fermentors
- CPDM Modeling
- Rate Equation
- 4-Stage Countercurrent Fermentors (MSWSS)
- Heat Requirements
- Thermal Conversion Stoichiometry
- Thermal Conversion Kinetics
- Ketone Hydrogenation Stoichiometry
- Ketone Hydrogenation
- Advantages of MixAlco Approach
- Potential Products
- Carboxylic Acid Production
- Acid ldquoSpringingrdquo
- Chemical Flowchart
- Economics
- Plant Capacity
- Optimization (40 tonneh)
- Capital Cost of Each Section (mill $)(40 tonneh)
- Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
- Effect of Scale on Capital Cost
- Effect of Scale on Alcohol Price(15 ROI free biomass)
- Mixed Alcohol Selling Price(40 tonneh)
- Average MSW Tipping Fees
- Net Tipping Fee (New York)
- Scenarios (40 tonneh)
- Energy Content
- Properties of Fuel Oxygenates
- Economics
- Feedstock
- Estimated Capital Cost
- Key Assumptions
- Expected Product Yields (mesophilic 40oC)
- Expected Product Yields (thermophilic 55oC)
- Tipping Fee Income
- Income from Acid Sales(mesophilic 40oC)
- Income from Acid Sales(thermophilic 55oC)
- Expenses
- Profitability
- Recent Improvements
- Synthetic MSW
- Advantages of Jet Ejector
- Advanced Bioreactor
- Next Steps
- Conclusions
-