Waste management in the emerging Philippine biofuel industry
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Rex B. DemafelisChemical Engineering
DepartmentCEAT, UPLB
June 15 2010SEARCA Drilon Hall
College, Laguna
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•Biofuels Act of 2006
• Projected demand
• Incentives and support
•Wastewater Generation Potential
•Bioethanol wastewater management
•Biodiesel wastewater management
•Recommendations
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TRANSPORT SECTOR
Biodiesel
Bioethanol
INDUSTRIAL SECTOR
Biogas
Biomass
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BIOFUELS ACT OF 2006Republic Act 9367
Mandates blending of biofuels
Objectives:
To reduce the Philippine’sdependence on imported oil
To increase the economic activity in the country & boost employment
To mitigate Toxic and Green House Gas Emissions
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PROJECTED DEMAND BIOETHANOL -PEP 2007
Year Projected Gasoline Demand*
(In Million Liters)
PEP 2007
Mandated Blend
BioethanolRequirement(In Million
Liters)
ForexSavings**
(Php Million)
A B C D = B x C
2010 5,650 5% 283 20,339
2011 5,939 10% 594 21,380
2012 6,239 10% 624 22,460
2013 6,549 10% 655 23,578
2014 6,872 10% 687 24,738
2015 7,210 10% 721 25,955
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PROJECTED DEMAND BIODIESEL - PEP2007
Year Mandated Blend (%)
Diesel Demand*(In Million
Liters) PEP 2007
Biodiesel Requirement (In Million
Liters)
Forex Savings**
(Php Million)
2010 2 8,653 173 5,538
2011 2 9,030 181 5,779
2012 2 9,411 188 6,023
2013 2 9,794 196 6,268
2014 2 10,122 202 6,478
2015 2 10,461 209 6,695
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INCENTIVES & SUPPORT FOR BIOFUELS PROVIDED BY THE LAW
Provides various incentives
Income tax holiday
Tax and Duty-free Importation
Zero specific tax
Priority financing project classification\
Exemption from waste discharge fees and provision for reuse
Creation of the National Biofuels Board
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WASTEWATER REUSE OPTION
All water effluents, such as, but notlimited to distillery slops from theproduction of biofuels used as liquidfertilizer and for other agricultural purposesare considered “reuse”, and are therefore,exempt from wastewater charges under thesystem provided under Section 13 of R.A. No.9275, also known as the Philippine CleanWater Act.
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Safeguard to Reuse Option
Provided, however, That such application shall be in accordance with the guidelines issued
pursuant to R.A. No. 9275, subject to the monitoring and evaluation by DENR and
approved by DA.
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BIOETHANOL WASTEWATER
WHAT ARE THE TECHNOLOGIES CURRENTLY USED IN FOOD GRADE ETHANOL DISTILERY
WASTEWATER MANAGEMENT ?
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Dilute alkali pretreatment, steam
explosion
Enzymatic
hydrolysis
Fermentation
distillation and dehydration
Cellulase
Saccharomyces
cerevisiae/
Zymomonas
mobilis
Dilute NaOH, steam
Distillery slops
Saccharafication
Starch
Sugar
Sources of Wastewater
Rice Straw
ETHANOL
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WASTEWATER GENERATION
o Bioethanol
10 to 18 liters distillery slops is produced per liter ethanol
75,000 – 120,000 mg/li COD
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Estimated Generation, MLi
Graph volume ethanol requirement v.s. wastewater generation max and minimum curves
0
2000
4000
6000
8000
10000
12000
14000
2007 2008 2009 2010 2011 2012 2013 2014 2015
Bioethanol Requirement Waste Volume (LowerLimit) Waste Volume (Higher Limit)
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WASTEWATER CHARACTERISTICS
Characteristic/Composition
FreshSlops
pH 4.55
Absorbance (475 mm) 18.02
TOC (X 104 ppm) 3.18
F- (ppm) 710.00
Cl- (ppm) 3786.00
S042- (ppm) 2741.00
Na+ (ppm) 133.00
K+ (ppm) 7614.00
Ca2+ (ppm) 2746.00
Mg2+ (ppm) 384.00
Fe3+ (ppm) 74.00
Al3+ (ppm) 112.00
Total N (ppm) 1644.00
Total P (ppm) 131.00
Reducing sugars g/L 10.02
Total sugars (g/L) 16.00
Chemical Composition of Distillery Slops from Molasses
(Source: Migo et al., 1993 as cited by Sison et al, n.d.).
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WASTEWATER MANAGEMENT
To Solid
Storage
Bin
Effluent
Dried Solids
Primary
Settling
Pond
Blower
CO2
Scrubber
Slops
holding
Tank
Methane
Reactor
Degassing
Tank
H2S
Scrubber
Emergency
Flare
To Steam
Generating
Unit
Aeration/Secondary
Settling Pond
Ranola et al, 2008
1,139 m3 / day
Cooled slops
34,000 m3 / day Biogas
31,000 m3
Biogas / day
Sludge
Decanter
Primary
Settling Pond
CO2
Scrubber
Distilling
Column
Equalization
Pond
Recirculation
Pump
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Anaerobic DigestionFor 100,000 Liters/day Ethanol
1,139,000 Liters distillery slops per day
34, 000,ooo Liters3 Biogas generated per day
30 gas productivitity
up to 40 % boiler fuel substitution
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BIOETHANOL WASTEWATER
WHAT ARE NEW TECHNOLOGIES USED IN THE EMERGING FUEL
ETHANOL PRODUCTION?
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PHILIPPINES’ BEST OPTION?
ANAEROBIC DIGESTION FOR THE
PRODUCTION OF BIOGAS COUPLED WITH
DRYING or CONCENTRATION OF SLOPS for FUEL
COMPOSTING
LIQUID FERTILIZATION
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ROXOL Bioenergy Corp
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ROXOL Bioenergy Corp
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CHARACTERISTICS OF DISTILLERY STILLAGE FROM MOLASSES, CANE JUICE & MIXED (JUICE +MOLASSES)
Chemical Data *Molasses Juice Juice + Molasses
pH 4.2-5.0 3.7-4.6 4.4 -4.6
Temperature (oC) 75-95 75-95 75-95
BOD (mg O2/li) 45,000 6,500-16,500 19,800
COD (mg O2/li) 120,000 15,000-33,000 45,000
Total Solids (mg/li) 90,500 23,700 52,700
Volatile Solids (mg/li) 65,000 20,000 40,000
Fixed Solids (mg/li) 25,500 3,700 12,700
Nitrogen (mg N/li) 450-1,600 150-700 480-710
Phosphorous (mg
P2O5/li)
100-290 10-210 9-200
Potassium (mg K2O/li) 3,740-7,830 1,200-2,100 3,340-4,600
Calcium (mg CaO/li) 450-5,180 130-1,540 1,330-4,570
Magnesium (mg MgO/li) 420-1,520 200-490 580-700
Sulphate (mg SO4/li) 6,400 600-700 3,700-3,730
Carbon (mg/li) 11,200-22,900 5,700-13,400 8,700-12,100
C/N Rate 16.0-16.27 19.7-21.07 16.4-16.43
Organic Matter (mg/li) 63,400 19,500 38,000
Reducing Matter (mg/li) 9,500 7,900 8,300
*Continuous fermentation process
ROXOL Presentation-2009
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SLOPS TREATMENT PLANT (BIOMETHANATION)
SLOPS
FERTIGATION
TREATED SLOPS
EVAPORATION/ CONCENTTRATION
CONCENTRATED
SLOPS
UTILIZED
AS FUEL
CONDENSATES
RECYCLED
BIOGAS UTILIZED AS FUEL
METHANE CAPTURE & ZERO WASTE MANAGEMENT - ROXOL
MOLASSES
SPRAY/CONDUCTION DRYING
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Alternative Wastewater Management Option Worth Considering (Conduction Dryer)
ROXOL METHANE RECOVERY PROJECT
Forced-circulation Evaporators Scraped Evaporators and Dryers
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Alternative Wastewater Management Option Worth Considering (Spray Dryer)
ROXOL METHANE RECOVERY PROJECT
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Alternative Wastewater Management Option Worth Considering (Spray Dryer)
Final Product – Dry Vinasse Powder
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San Carlos Bioenergy Inc.
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San Carlos Bioenergy Inc.
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Material Balance
Distillation Column
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Distillery Slops Utilization
Anaerobic
Digestion
Reverse
Osmosis
Compost
Production
(160m3/day)
Fertigation
(40m3/day)Biogas
10, 000m3/day
BIOLER(Steam Prd’tn)
Permeate
200m3/day
As Process Water (cooling
& cleaning)
400m3/dayOther wastewater
1, 400m3/day
Fermentation
DISTILLERY SLOPS
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UPLB BIOTECH TECHNOLOGYDistillery slops application of 200 cu m per hectare-year ( Migo et. al .)
Basis:
65 Tons cane per hectare and
67 liters ethanol per ton cane
Slops generation volume ratio to ethanol is
12.5
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Distillery slops as Fertilizer
7,000 hectares is needed to produce 30M li per year ethanol
375,000 cu m slops generated
1,875 hectares will be needed for slops fertilization
60 hectares will be needed for slops fertigation
( San Carlos Bioenergy Incorporated)
Area is within a 5 km radius or 27% of the total land area requirement
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CAPITAL REDUCTION FROM BIOGAS PRODUCTION COUPLED WITH
FERTILIZATION
WASTEWATER TREATMENT PLANT
Capital Investment Requirement- P 70M
2.33-5% of the Total Capital Investment
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BIODIESEL WASTEWATER
WHAT BIODIESEL PRODUCTION TECHNOLOGIES CURRENTLY USED WITH BEST WASTEWATER
MANAGEMENT OPTION ?
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Process Characteristics
LURGI Technology Leading Global
Commercial Technology for Biodiesel Production
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Lurgi Process-Hold-up time: 2-3 hours
-NaOCH3 catalyst
-Packed coaslescing tank
-Efficiency > 99%
-No need for centrifuge
-Packed column
-Countercurrent
-Vacuum distillation
-Max MeOH in heavy key: 3% w/w
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CHEMREZ TECHNOLOGIES
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WASTEWATER PROBLEM ?
VILLAGE SCALE BIODIESEL PRODUCTION SYSTEM
SMALL BIODIESEL PRODUCTION SYSTEM
BATCH BIODIESEL PRODUCTION SYSTEM
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Sources of Wastewater
Oil
Biodiesel
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WASTEWATER GENERATION
o Village Scale Biodiesel Production
Up to 6 liters wastewater per liter biodiesel
60,000 mg/li COD
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Graph volume biodiesel requirement v.s. wastewater generation Max and minimum
0
200
400
600
800
1000
1200
1400
2007 2008 2009 2010 2011 2012 2013 2014 2015
Biodiesel Requirement Waste Volume (lower limit) Waste Volume (higher Limit)
Estimated Generation,MLi
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ANAEROBIC DIGESTION
No literature on biogas digestion of biodiesel wastewater
UPLB Preliminary work on Treatability
( Demafelis , R. B. et al)
Methane increases with OLR up to 2,500 mg/l-d
55.84 % methane
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Characterization and Treatment
Combined Wastewater from Acid Esterification and Transesterification (Upflow Filter Bed Reactor)
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Upflow Filter Bed Reactor
Source: Alonzo, Movillon, Demafelis et al, April 2009
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Combined Acid Esterification and Transesterification WastewaterInitial Characterization
Parameter Value
BOD, ppm 35563
COD, ppm 61465
BOD/COD 0.58
pH 4.23
Oil and Grease, ppm 485
Alonzo, Movillon, Demafelis et al April 2009
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Combine Acid Est. And Trans. Wastewater Treatment Results
Organic Loading Rate(mg COD/L-day)
AlkalinityMean Cumulative Gas
Volume
Control
1000 1685.5 – 1798.8 63.5 – 496.8
800 1356.4 – 1574.8 0 – 747.2
1200 (pH=7.0) 991.2 – 1121.4 102.5 – 880.5
1200 (pH=7.4) 751 – 1098.5 129 – 969.5
Filter Bed Reactor
1000 2267.5 – 2698.2 0 – 386.5
800 1236.1 – 1831.6 0 – 800.2
1200 (pH=7.0) 881.1 – 862.7 129 – 1135.5
1200 (pH=7.4) 660.8 – 734.2 265 – 1093.9
Source: Alonzo, Movillon, Demafelis et al April 2009
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Characterization and Treatment
Combined Wastewater from Acid Esterification and Transesterification (Upflow AnaerobicFixed-Film Bed Reactor)
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Upflow Anaerobic Fixed-Film Reactor
Source: Manalo, Movillon, Demafelis et al April 2009
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Combined Acid Esterification and Transesterification WastewaterInitial Characterization
Parameter Value
BOD, ppm 35563
COD, ppm 61465
BOD/COD 0.58
pH 4.23
Oil and Grease, ppm 485
Manalo,Movillon ,Demafelis et al April 2009
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Combine Acid Est. And Trans. Wastewater Treatment Results
Organic Loading
Rate(mg COD/L-day)
Alkalinity
Mean
Cumulative Gas
Volume
COD
Control
1000 986.4 – 1884.5 0 – 795.5 3469.7 – 4478.4
800 734.2 – 963.1 795.5 – 2536.5 2692.2 – 4512
1200 (pH=7.0) 587.4 – 835.2 2671.5 – 4405.5 2884.8 - 4126.5
1200 (pH=7.4) 477.2 – 541.5 4822.5 – 6414.5 2841.3 – 6137.1
Filter Bed Reactor
1000 1237.6 – 1970.1 0 – 571.5 2868.7 – 7200
800 1156.4 – 1340.5 747.5 – 2950.5 954 – 4960
1200 (pH=7.0) 853.5 – 1110.5 3178.5 – 5975.5 688.2 – 1296.9
1200 (pH=7.4) 587.4 – 761.7 6353.5 – 8208.5 802.9 – 2159.4
Source: Manalo, Movillon, Demafelis et al April 2009
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Biogas PotentialBASIS:
For a 1,000 li per day village scale production system
REQUIREMENT
75 ,000 liter biogas reactor ( min )
Php 2.4M TCI
INCOME
Php 0.8 M Total Annual Income
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DRY WASHING TECHNOLOGY
Purification of biodiesel using dry washing
UPLB Research works on Dry Washing
( Demafelis , R. B. et al)
Using Magnesol
Using Amberlite
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DRY WASHING
Methanol
Sodium Hydroxide
Crude Jatropha Biodiesel
Refined Jatropha Oil
Degummed Jatropha Oil
Crude Jatropha Oil
Centrifuge
Acid Esterification/ Caustic Refining Tank
Transesterification Vessel
Mixer
Dryer
Mechanical Presser
Degumming Tank
Glycerine Layer Separator
Rotary Filter 2
Rotary Filter 3
Rotary Filter 1
Jatropha Seeds
Purified Jatropha Biodiesel
Water Gums
FFA
Removal
Waste
Methanol,
Sodium
Hydroxide or
Sulfuric acid
Magnesol
or
Amberlite
Waste
Magnesol or
Amberlite
Methanol
Glycerine
Trace Magnesol
Residual Traces of
Production
Residues
Soaps and Moisture
Cake
Cake
Residue
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Dry WashingInitial Characterization of unwashed
Jatropha curcas L. biodiesel
Component %(wt)
Jatropha Methyl Ester 95.7194
SOURCE:Gelasin,,Demafelis et al April 2010
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Magnesol™ Properties
synthetic magnesium silicate
fine, white, powder
used in some industrial plants for biodiesel purification
high affinity to polar compounds
(e.g. excess methanol, free glycerin, glycerides, metal contaniminants, free fatty acids, and soap)
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Optimized Dry Washing Using Magnesol™
PARAMETER Goal Lower LimitUpper
LimitImportance Optimum
Temperature (°C) Minimize 42 66 1 42
Ratio (% wt) Minimize 1 2 1 1
Reaction
Duration (min)Minimize 20 40 1 20
Mixing Speed
(rpm)Minimize 200 400 1 200
Purity of
Biodiesel (%)Maximize 5 99.0563
SOURCE: Gelasin, Demafelis et al April 2010
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Amberlite™ Properties
a type of ion exchange resin
effective in removing both soap and glycerine
absorbs impurities
(e.g. excess water, glycerol, KOH-catalyst)
How ever it does not remove methanol, which is very essential to maximize its recovery
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Optimized Dry Washing Using Amberlite™
PARAMETER Goal Lower LimitUpper
LimitImportance Optimum
Residual
Methanol (mol)Minimize 1 3 1 1.01
Ratio (% wt) Minimize 1.75 2.25 1 1.84
Reaction
Duration (min)Minimize 30 60 1 59.4
Mixing Speed
(rpm)Minimize 200 400 1 201.63
Purity of
Biodiesel (%)Maximize 5 99.86%
SOURCE: Roma, Demafelis et al, April 2010
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RECOMMENDATIONS
FINANCIAL AND POLICY SUPPORT
R and D on energy recovery from biodiesel wastewater
R and D on reused options for biodiesel wastewater
R and D on waste minimization in the
pretreatment stage
R and D on production of high value products from wastewater
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END OF PRESENTATION
THANK YOU VERY MUCH !!