Production fuel from cellulosic biomass Presentation.pdf · Pyrolysis O Methanol Ethanol (BC)...
Transcript of Production fuel from cellulosic biomass Presentation.pdf · Pyrolysis O Methanol Ethanol (BC)...
Production fuel from cellulosic biomass
Ri k G t fRick GustafsonSchool of Forest Resources 22 October 2009
Motivation for biofuelsMotivation for biofuelsClimate Change
Biomass is renewable and can be carbon neutral
Cellulosic ethanolCorn ethanol
Source: National Geographic
Motivation for biofuelsMotivation for biofuels
Economic utilizationEconomic utilization of waste biomass
Motivation for biofuelsMotivation for biofuels
Energy Independence
http://www.nationmaster.com/red/graph/ene_oil_exp_net-energy-oil-exports-net&b_map=1#
Motivation for biofuelsMotivation for biofuelsExpensive oil? Running out of oil?
‘Peak Oil’ Is a Waste of Energy – NY Times 24 August 2009
BP Finds Giant Oil Field Deep in G lf f M iGulf of MexicoNY Times 2 Sept. 2009
Washington State ‐ Climate change mitigation
Fires 33.5 M mt/2006
Figure 4 4 2 Washington historic CO2e emissions by sector with fire emissions superimposed (adapted from Waterman-Hoey andFigure 4.4.2. Washington historic CO2e emissions by sector with fire emissions superimposed (adapted from Waterman-Hoey and Nothstein 2007, Wiedinmyer and Neff 2007).
Climate change mitigation: CO2 emission goals relative to current emissions
WA GHG Reduction Goals
2020 to 1990
2050 to 50% 1990
2035 to 75% 1990
2050 to 50% 1990
Waterman‐Hoey and Nothstein. 2007. Washington’s Greenhouse Gas Emissions: Sources and Trends ‐ 2006. WA Dept. of Community, Trade and Economic Development. Olympia, WA. 18 pp. http://www.cted.wa.gov/site/853/default.aspx
Current Market Overview
Current ethanol capacity =10.6 billion gal/year
Current biodiesel capacity =700 million gal/year
Source: http://www.ethanolrfa.org/industry/statistics,
Ethanol futures, $/gal
Energy Independence and Security Act 2007(Now they are talking about 60 billion gals/year!!!!)(Now they are talking about 60 billion gals/year!!!!)
40
30
35
Year
)
2005 EPAct RFSCurrent Ethanol Production2007 RFS - Conventional2007 RFS - Cellulosic Biofuels2007 RFS - Biomass-based Diesel2007 RFS - Unaffiliated
20
25
Billio
n G
allo
ns p
er
Cellulosic
10
15
Ren
ewab
le F
uel (
B
mat
ed
0
5
R
Estim
Corn
02000 2005 2010 2015 2020
Total US oil consumption = 320 billion gals/year Total US oil imports = 220 billion gals/year
U.S. Biomass Resource AssessmentU d t d t A il 2005• Updated resource assessment - April 2005
• Jointly developed by U.S. DOE and USDA• Referred to as the “Billion Ton Study”
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• Current biomass production less than 500 million tons/year
The “Billion Ton” potential represents about 1/3 of our petroleum use whenThe Billion Ton potential represents about 1/3 of our petroleum use when converted to liquid fuels
Billion Barrel of Oil Equivalents
Based on ORNL & USDA Resource Assessment Study by Perlach et.al. (April 2005) http://www.eere.energy.gov/biomass/pdfs/final_billionton_vision_report2.pdf
Washington State situation is different
Source: WSU, WA DOE. http://www.ecy.wa.gov/pubs/0507047.pdf
Replace oil with biofuels in Washington State???
18 illi t f bi il bl ll18 million tons of biomass available annuallyAssume 90 gallons fuel/ton biomassTotal biofuel = 1,620,000,000 gallons/year
Total WA oil consumption = 6 500 000 000 gallons/year6,500,000,000 gallons/year
Range of Biorefinery ConceptsRange of Biorefinery Concepts
UUC iC iBiBi UsesUsesFuels
EthanolRenewable DieselMi d Al h l
Conversion ProcessesConversion Processes
Biomass FeedstockBiomass Feedstock
Mixed AlcoholsDimethyl Ether
PowerElectricityHeat
ChemicalsPlasticsSolventsChemical IntermediatesPhenolics
Enzymatic FermentationGas/liquid Fermentation
TreesGrasses
AdhesivesFurfuralFatty AcidsAcetic AcidCarbon BlackEt
Acid Hydrolysis/FermentationGasificationPyrolysis
Agricultural CropsResiduesAnimal WastesM i i l S lid W t
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Etc.Food and Feed
PyrolysisCombustionCo-firing
Municipal Solid Waste
Adapted from Holmgren etal (2008); Hydrocarbon Processing, Sep.
What is biomass made of?Representation of Cell Wall Components
Cellulose
Hemicelluloses
LigninLignin
Cellulose For Chemists• Very long straight chain polymer of glucose: approximately
10 000 in a row in wood Cotton is nearly pure cellulose10,000 in a row in wood. Cotton is nearly pure cellulose.
• Cellulose molecules link up in bundles and bundles of bundles and bundles of bundles of bundles to make fibers
• Cellulose forms tight bundles which are very resistant to chemical attack
Cellobiose Unit
O
O O
O
O
O
O
O
CH2OH
OHHO
OHHO
CH2OHOH
CH2OH
HO
OH
CH2OH
HO
O
β
ββ
β
2ββ
Cellulose
Hemicelluloses for ChemistsHemicelluloses for Chemists• Branched little uncolored sugar polymers (~ 50 to g p y (300 sugar units)– Composition varies between wood species
• 5 carbon sugars: xylose, arabinose5 ca bo suga s: y ose, a ab ose• 6 carbon sugars: mannose, galactose, glucose• Uronic Acids: galacturonic acid, glucuronic acid• Acetyl and methoxyl groups (acetic acid & methanol)
O OO
O
OOHHO HO OH
OO
OO
OHHO OO
HO OH
O
O
CO2HH3CO OHHOH2C
O
O
CO2HOH
Lignin for Chemists
OHOCH3 CH3
CHCH
H2COH
16
H2COHCH2
CH2
H C26
CH
28
27
O
CH2OHH
CH3
CH
O
O
H2COH
H3COOCH3
COHHHC
CH2OH
OH CH2OHCO
H3CO
CH
6
OCH3
OO
C
CHO
H3C
H
CH3
CH
OHOH3C
15
16
Carbohydrate
CH2OH
OH
OCH3
HC 14
O
C O
OCH3
24
25 H2COHHH3CO
CH
CHO
O
C O
CH
H
CH
CHOH2
HOOCH3
OH4
5 7
HHC CH
CH2O
C
CHO
H2C
8
HO
CH2OHH3C13
O
CH
O CH
O
H2COHHC
CHO
24
H2COH
OHCH
23
COH
OCHCHHOH
CH
C
OH2C
CHO
O CH2OHH3C
2
3O
O CHH3C
8
OHC CH CH2OH
CH2OH
OOH3C
9
10
H3C12 CHO
17
HOCHO
OH C
O
OCH
CH
O
COHH2CH
H2COH
OCH3
C
CHCHCHO
22
OCH3
C O
O
O CH
H3CCH2OH
1
C
OH10
OHC CH
COHH2
CH2O
CH
11
O
C O CH2
H3C18
HCHO
O
H
H3C
19COHHCOHH2
H O
HC O
C
OCH3
21
CH2 O
COHHHCOH
OOH
H3C
OHOCH3
20
Chemical compositionChemical composition
Feedstock Glucan (cellulose) (%) Xylan (hemicellulose) (%) Lignin (%)
Corn stover 37.5 22.4 17.6
Corn fiber 14 3 16 8 8 4Corn fiber 14.3 16.8 8.4
Pine wood 46.4 8.8 29.4
Poplar 49.9 17.4 18.1p
Wheat straw 38.2 21.2 23.4
Switchgrass 31.0 20.4 17.6g
Chemical composition of biomass (adapted from Mosier et al., 2005).
Approaches to cellulosic biofuels
EthanolEthanol
J.A. Dumesic / Catalysis Today 111 (2006) 119–132
Bioconversion of biomass to
Liquid Sugars Eth l
ethanol (hydrolysis)
Pretreatment
qphase Sugars Ethanol
Fermentation
BiomassLignin
RSolid phaseCellulose
Recovery
FermentationHydrolysis
EthanolSugars
PretreatmentPretreatment
Schematic of goals of pretreatment on lignocellulosic material (adapted from Hsu et al., 1980).
Various pretreatment methodsVarious pretreatment methodsIncreases accessible
surface area
Decrystalizes cellulose
Removes hemicellulose
Removes lignin
Alters lignin structure
surface area
Uncatalyzed steam explosion ■ ■
Liquid hot water ■ ND ■q
pH controlled hot water ■ ND ■ ND
Flow-through liquid ■ ND ■hot water ■ ND ■
Dilute acid ■ ■ ■
Flow-through acid ■ ■ ■
AFEX ■ ■ ■ ■
ARP ■ ■ ■ ■
Lime ■ ND ■ ■
Adapted from Mosier et al., 2005Minor effect Major effect
Bioconversion of biomass to
Liquid Sugars Eth l
ethanol (hydrolysis)
Pretreatment
qphase Sugars Ethanol
Fermentation
BiomassLignin
RSolid phaseCellulose
Recovery
FermentationHydrolysis
EthanolSugars
E y e Fu tioEnzyme FunctionThere are a large number of fungal enzymesThere are a large number of fungal enzymes responsible for the breakdown of each wood component. Each enzyme plays specific roles:E do beta 1 4 lu a a e a t ithi the hai b eaki it» Endo‐beta‐1,4‐glucanase acts within the chain, breaking it into smaller units and providing more ʺendsʺ for CBH.
» Cellobiohydrolase (CBH), acts on the end of the molecule successively cleaving off the disaccharide cellobiosesuccessively cleaving off the disaccharide cellobiose.
» Beta‐glucosidase (or cellobiase) which cleaves cellobiose to two glucose units.
CellulasesCellulases
Binding domain Catalytic domainBinding domain Catalytic domain
E d l (EG)Endoglucanases (EG)cutting the cellulose chains randomly
Cellobiohydrolyses (CBH) cutting cellobiose units of the ends of the cellulose chains
FermentationFermentationDefined as:Cellular metabolism under anaerobic conditions for the production of energy and metabolic intermediatesMany organisms can “ferment” (i e growMany organisms can ferment (i.e., grow anaerobically)Not all produce ethanol as an end‐product of p pfermentation» Butanol» Acetic acid» Acetic acid» Propionic acid» Lactic acid
Pyrolysis
Thermoconversion - Basic Definitionsy y
• Thermal conversion (destruction) of organics in the absence of oxygen • In the biomass community, this commonly refers to lower temperature thermal
processes producing liquids as the primary productp p g q p y p• Possibility of chemical and food byproducts
Gasification• Thermal conversion of organic materials at elevated temperature and
reducing conditions to produce primarily permanent gases, with char, water, and condensibles as minor products
• Primary categories are partial oxidation and indirect steam• Primary categories are partial oxidation and indirect steam
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Biomass Conversion to Fuels –Major Biochemical Conversion StepsMajor Biochemical Conversion Steps
Feed Processing
and Handling
• Size Reduction• Storage and Handling• De-watering• Drying
Gasification
Pyrolysis
Gas Cleanup
High T Separation
Gas Conditioning
Collection/Fractionation
Fuel Synthesis
Upgrading
Heat&
Powery y Separation pg g
• Partial Oxidation• Air blown
O bl
• Particulate removal• Tar reforming• Benzene removal
• Methane reforming• CO2 removal• H2/CO adjustment
• C1 chemistry– FT liquids– MTG• Oxygen blown
• Indirect
• Flash pyrolysis• Steam pyrolysis• Vacuum pyrolysis
Benzene removal• S, N, Cl mitigation
• High T Filtration• Alkali removal
H2/CO adjustment• Sulfur polishing
• Aerosol collection• Microfiltration• Chemical Stabilization
MTG– Mixed OH
• Upgrading• Production Separation
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• Hydrotreating• Dehydration
Th di t ib ti f d t d d t t d id ti
Liquid Char Gas
The distribution of products depends on temperature and residence time
FAST PYROLYSIS 75% 12% 13%moderate temperatureshort residence timeshort residence time
GASIFICATION 5% 10% 85%high temperaturelong residence time
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Source: Bridgewater and Czernik
Primary Energy Source Syngas Step Conversion Technology Products
Fischer Tropsch
(FT)Upgrading Naphtha
DieselSyngas to Liquids (GTL) ProcessNatural
Gas(FT)
Lubes
Syngas to Chemicals TechnologiesCoal
Syngas(CO + H2)
Syngas to Chemicals Technologies
M th l
Acetic Acid
MethanolBiomass
Hydrogen
Mixed Alcohols (e.g. ethanol, propanol)
Others (e.g. Triptane, DME, etc)
Extra Heavy
Oil
10/29/2009 35Source: BP
Pyrolysis is usually performed at lower temperature to produce a liquid biocrude.
• Thermal decomposition occurring in the absence of oxygenabsence of oxygen
• Is also the first step in combustion and gasification processes
• Known as a technology for producing• Known as a technology for producing charcoal and chemicals for thousands years
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Biocrude is water miscible and is comprised of many oxygenated organic chemicals.
• Dark brown mobile liquidCombustible• Combustible
• Not miscible with hydrocarbons• Heating value ~ 17 MJ/kg
D it 1 2 k /l• Density ~ 1.2 kg/l• Acid, pH ~ 2.5• Pungent odour
“ ”• “Ages” ‐ viscosity increases with time
10/29/2009 37Source: Bridgewater and Czernik
There are a number of applications for biocrudesThere are a number of applications for biocrudes
B io-o il
Extract
Bo ile r U pgrade
H eat Chemicals
10/29/2009 38E lectric ity T ransport fue l Source: Bridgewater and Czernik
Potential for mobile unit
Forest
Upgrade biooil at refineryForest Residuals
BioOilPyrolysis
Much cheaper to ship biooil than biomass beca se of higher energ
39FOREST
biomass because of higher energy density
Yields & Carbon UtilizationCellulosic
( C)Cellulosic
( C)Cellulosic
( C)Ethanol Corn Ethanol
SPyrolysis
OMethanol
Ethanol (BC) Ethanol (TC) Steam
Ethanol (TC) POX
Dry Mill SugarCane
Fuel OilIntermediate
Intermediate
Yield gal/ton biomass 90 80 77 102 12.3 137 149 gal Ethanol eq/ton biomass 90 80 77 102 12.3 135 115B P d tBy-Product type -- C3+OH C3+OH DDGS Sugar -- -- gal Ethanol eq/ton biomass -- 14 15 33 wt% 5.7 wt% -- -- Electricity, kWh/ton 196 -- -- -- -- 26 --External Fuel Nat Gas, MMBtu/dry ton 3.11Process Efficency, HHV Overall (Prod + Byprod) % 48 47 46 74 68 55 Product % 44 40 37 44 67 55Carbon Utilization (basis feed carbon)Carbon Utilization (basis - feed carbon) Product % 31 27 26 39 59 35 By-Product % -- 6 5 37 -- 0 Acid Gas/Fermentation CO2 % 16 15 24 19 -- 0.3 Combustion Flue Gas CO2 % 53 52 36 5 41 47 Other %
Type char NG Flue Gas % 8 10 18
Plant Gate Prices100 MMGPY EtOH Production, $2005$
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Geographic, Feedstock, and Technology DiversityMajor DOE Biofuels Project Locations
RSE Pulp & Chemical, LLCBi h i l
DOE Great LakesNewPage
Thermochemical
MascomaBiochemical
Various (Lebanon, NH)
Cargill IncBiochemical
Various(Minneapolis, MN)
Regents of the University of Minnesota
Various(Minneapolis, MN)
Cornell University(I h NY)
BiochemicalWoody Biomass-
Mill Residues(Old Town, ME)
MascomaBiochemicalHardwoods
(Upper Peninsula, MI)Flambeau RiverThermochemical
Forest Residues/Wood Waste(Park Falls, WI)
Pacific EthanolBiochemical
Wheat Straw, Stover, Poplar Residues(Boardman, OR) Montana State University
Bozeman, (MT)
University of Maine(Orono, ME)
University of M h A h
PoetBiochemical
Corn Cob/Corn Fiber(Emmetsburg, IA)
DOE Joint Bioenergy Institute(Berkeley, CA)
DOE Great Lakes Bioenergy Research Center
(Madison, WI)
ThermochemicalWoody Biomass – Mill Residues
(Wisconsin Rapids, WI)
DSM Innovation CenterBiochemical
Various(Parsippany, NJ)
NovozymesBiochemical
Various
Purdue University(West Lafayette, IN)
(Ithaca, NY)
GE Global Research(Niskayuna, NY)
Emery Energy
Gas Technology Institute (Des Plaines, IL)
UOP, LLCThermochemical(Des Plaines, IL)
Stevens Institute of Technology
(Hoboken NJ)Univeristy of
Toledo(Toldeo, OH)
Massachusetts – Amhers(Amherst, MA)
BlueFire EthanolBiochemical
Municipal Solid Waste(M CA)
Lignol Biochemical
Woody Biomass- Ag Residues
(Grand Junction, CO) ICMBiochemical
Switchgrass, Forage Sorghum, Stover(St. Joseph, MO)
AbengoaBiochemica
Agricultural Residue(Hugoton, KS)
DOE Bioenergy Science Center
(Oak Ridge, TN)
(Davis, CA)Genencor
BiochemicalVarious
(Palo Alto, CA)
Dupont Biochemical
Various(Wilmington, DE)
Purdue UniversityBiochemical
(West Lafayette, IN)
Ceres, IncVarious
(Thousand Oaks CA)
AlltechBiochemical
Corn Cobs/Corn Fiber(Washington County, KY)
Emery EnergyThermochemical
Corn Stover(Salt Lake City, UT)
Iowa State (3)University(Ames, IA)
Research Triangle Institute (2)ThermochemicalWoody Biomass
(Research Triangle Park, NC)University of Georgia(Ath GA)
( , )
Virginia Tech(Blacksburg, VA)
(Mecca, CA)
Range FuelsThermochemical
Woody Waste(Soperton, GA)
Verenium CorpBiochemical
Various (San Diego, CA)
Nine Small-Scale Biorefinery Projects
(Thousand Oaks, CA)Southern Research
InstituteThermochemical
Various(Birmingham, AL)
(Athens, GA)Georgia Tech(Atlanta, GA)
Regional Partnerships
Four Commercial-Scale Biorefinery Projects
Four Improved Enzyme Projects
Five Projects for Fermentation Organisms
Five Thermochemical Syngas Projects
Th Offi f S i Bi C t
Verenium Biofuels Corp.Biochemical Process
Energy Cane and Bagasse(Jennings, LA)
g pSouth Dakota State Univ., Brookings, SD
Cornell University, Ithaca, NYUniv. of Tennessee, Knoxville, TN
Oklahoma State Univ., Stillwater, OKOregon State Univ., Corvallis, OR
Three Office of Science Bioenergy Centers
DOE Joint Solicitation Biomass Projects
Five Thermochemical Bio-Oil Projects
Six University Projects Modified 10/1/2008