Development of Oil Palm Byproduct Utilization Technology (Ecofriendly Pretreatment) Hwa-Jee Chung

Transcription

1 1 Development of Oil Palm Byproduct Utilization Technology (Ecofriendly Pretreatment) Hwa-Jee Chung

2 Global trend of biofuel development 2 Amount of technically recoverable global resources (source: BP) Petroleum Coal Natural Gas Amount 16,526 M Barrels 8,609 M ton 208 trillion m 3 Years World biofuel development policy Biofuel production grows to 60 billion gallons by 2030 Liquid biofuels currently provide about 1% of total U.S. energy At least 10% of transportation fuel to biofuels by 2020 In Germany, increase mandatory blend ratio range from 5 to 10% E10 by 2020, production 1.8 million tons 2 million tons of biodiesel by 2020

3 Biomass Feedstock Cellulosic Biomass : for the 2 nd generation ethanol Total biofuel production by biomass type Palm byproduct Pa 드ㅡㅔ쇼 Source: World Biofuels Production Potential, DOE, 2008

4 Empty Fruit Bunch (EFB) as Biomass Feedstock 4 * 2012 CPO production in Malaysia Biomass Products/yr remarks Empty Fruit Bunch (EFB) 22.7 million tons Mulching Boiler fuel Palm tree trunk 13.5 million tons Not use Fronds 58.5 million tons Not use Palm oil mill effluent (POME) & Others Total 87.4 million tons biogas ~ 182 million tons Abundant supply and year-round availability Homogenous biomass High cellulose, low lignin No logistics cost Biomass Glucan(%) Xylan(%) Lignin(%) 기타 (%) Corn stover EFB Poplar

5 Bioenergy from Empty Fruit Bunch (EFB) 5 EFB pretreatment saccharification Fermentation Bioethanol press shred Oil recovery Fast pyrolysis Biodiesel Puri. Bio oil

6 Biomass Cluster 6 Daekyung Esco YS Univ. Fast pyrolysis KIER EFB Pretreatment Bio-oil pretreated EFB EFB Supply 0.1 ton/day Bioethanol Enzyme Sugar platform Enzyme Gendocs Integrated system KRIBB EFB glucose Saccharification/ Fermentation Dehydration/ Purification Bioethanol KRIBB Ethanol Changhae KIER: Korea Institute of Energy Research KRIBB: Korea Research Institute of Bioscience & Biotechnology

7 Development of Core Technologies 7 Fast pyrolysis Bio-oil production Environmentfriendly pretreatment Enzyme Sugar platform Ethanol fermentation/purification of anhydrous ethanol 1 st phase (3yr) Optimization of fast pyrolysis Particle control process High-efficiency system for oil recovery Exhaust control Demonstration scale production of bio-oil system (2t/day) Hydrothermal pretreatment process Ammonia/NaOH pretreatment process Two-step continuous pretreatment process Development and operation of the device High activity strains High activity enzymes Mass production of recombinant enzymes Biomass-specific enzyme cocktail Solid fermentation for enzyme production Ethanol fermentation process C5/C6 simultaneous fermentation strain Solid state of ethanol fermentation process Ethanol purification and dehydration process 2 nd phase (2yr) Bio oil fuel Development of application elements for bio-oil production Commercial plant design Large-scale of continuous pretreatment process(1t/day) Bench-Scale of Integration Process System Large-scale of enzyme sugar platform (250L/day) Large-scale of anhydrous ethanol production (100L/day) Pilot-Scale of Integration Process System for Anhydrous ethanol & Bio-oil production

8 Core Technology for Bio-oil Production 8 Heat recycle High heat transfer rate Catalyst Pressure Gas residence time Particle size Temp. control Cooling speed Solvent recovery Yield Emission standards Dry/Shred Fast pyrolysis Particle control Oil recovery Exhaust control Char recycle Purification Bio-oil Adsorption Fertilizer Heat Viscosity Ash Performance Test

9 Core Technology of Bioethanol Production Enzyme cost Low activity/stability Various biomass Dry/ Shred High energy cost Waste-water Toxic chemical use Enzyme Production SSF Ethanol Pretreatment Biomass recalcitrance Toxic chemical use Inhibitors of saccharification & fermentation Low C5 recovery Washing/ Neutralization Cellulose Hydrolysis Low saccharification Inhibitors C6 Fermentation C5 Fermentation Fermentation inhibitors C5/C6 simultaneous fermentation Refinery/ Dehydration High energy cost

10 Pretreatment : process to destroy the structure of cellulosic biomass plant cell walls and make cellulose more accessible to the subsequent process of hydrolysis Dilute acid Acidic conditions Concentrated acid Acid activated steam explosion Liquid hot water Hemicellulose solubilization Neutral conditions Uncatalyzed steam explosion Ozone autohydro lysis rate-limited energy-intensive expensive processing step in the production of cellulosic ethanol Alkali conditions AFEX Dilute NaOH Dilute CaCO3 Lignin solubilization

11 NaOH-Steam Pretreatment To get the maximum yield of sugar & to reduce the waste-water Condition Pretreatments Hot water Ammonia Sulfuric acid 0.1L reactor (6g EFB) Sodium Hydroxide Temp, o C Conc, % Solid/Liq. 1:20 1:8 1:8 1:5 Pretreatments Hot water Ammonia Sulfuric acid Sodium Hydroxide Sugar yield C C Digestibility, % 69.5 (60 FPU) 62.5 (60 FPU) 80.4 (60 FPU) 87.0 (30 FPU) Hot water-ammonia NaOH soaking steam pretreatment Data: Korea Institute of Energy Research

12 Drawbacks of NaOH pretreatment Expensive Generate toxic gas during manufacturing the catalyst Requires toxic chemicals for neutralization Requires excess water for washing the solid before saccharification High loss of glucan Electrolyzed reduced water as alternative catalyst

13 Electrolyzed reduced water (ERW) Reduced water OH - H + OH - Power supply H + OH - K 2+ CO H H K 2+ Drain H 2 CO 3 CO 3 2- Alkaline, > ph 12.8 Power specification Power consumption Minimum flow AC220V, 1 phase, 60Hz 0.7kwh 10L/min H + OH - OH - K 2+ H 2 O Cation selective membrane H 2 O K 2 CO 3

14 Comparison between NaOH and ERW Dry mass 30g, 1L reactor 180, 60 min, S/L 1: % NaOH ERW Glucose recovery (g) Biomass recovery Glucan yield Xylan yield delignification Digestibility % NaOH ERW Reduced glucan loss Increased glucose recovery in the condition of lower delignification

15 Hg Porosimeter Analysis before after Intrusion (cm 3 /g) Intrusion (cm 3 /g) Pore diameter (nm) Pore diameter (nm) Before After Total Pore Area m/g m/g Average Pore Diameter X 2.25 (4V/A) nm nm Porosity % %

16 FT-IR Analysis aromatic C=C vibration C-H stretching in cellulose CH 3 - and CH 2 -stretching in cellulose Guaiacyl ring C-O stretching Conjugated C=O stretching between lignin & hemicellulose O-H stretching in hydrogen bond of cellulose

17 Auto-Neutralization Process 2% NaOH (ph 12.9) ERW (ph 12.8) S/L 1: min 30min 60min 30min 60min ~ ~ ~ ~5.1 Composition of liquid after pretreatment (180 /60 min) Sample Liquid (g/l) Glucan XMG Cellobiose Formic acid Acetic acid Tap water n/a n/a n/a ERW a XMG ( xylan + mannan + galactan ) No requirement of neutralization No requirement of buffer solution for saccharification

18 Wash-Free Process *adjust ph to 4.8 with citric acid Cellulase: C-Tec2 30FPU/g glucan Conditions Original 1L Batch pretreatment of EFB Temp. 160 * 180 Time(min) ph Glucose(%) No wash Xylose(%) C6 digestibility (%) Glucose(%) wash Xylose(%) C6 digestibility (%) No washing process after pretreatment

19 Optimum S/L ratio Dry mass 30g; 180, 60 min; No washing Yield (g)/(%) Digestibility(%) Glucose ratio ph Glucan Xylan Glucose Xylose recovery(g) EFB (Original) (100.00) 6.82 (100.00) : (93.08) 3.27 (48.00) (8.89) 1: (93.41) 2.59 (41.07) : (88.08) 2.35 (34.52) (7.98)

20 Optimum enzyme concentration Pretreatment ph change S/L ratio Enzyme (FPU) C6 (%) before C6 (%) after (loss) C6 digestibility (%) Fermentation yield (%) : min ph > ph (-6.67) :

21 Mass balance for ERW pretreatment of EFB Pretreatment Enzymatic Hydrolysis Fermentation EFB :30g (dry weight) EFB : 21g (dry weight) Sugars : 9.84g Ethanol : 4.73g (Yield : 94.2%) - Glucan : 11.49g - Xylan : 7.32g - Lignin : 6.96g - Others : 4.23g - Glucan : 10.65g - Xylan : 4.50g - Lignin : 3.81g - Others : 2.04g - Glucose : 9.84g (Yield : 92.40%) - Xylose : 3.52g (Yield : 78.29%) Bioethanol Yield (based on dry EFB) : 15.8% Pretreatment: 180 /1h, S/L 1:9 Hydrolysis: C-Tec2 50FPU, 50 /72h Fermentation: S.cerevisiae 10% inoculation, 30 /24h

22 22 Conclusion ERW pretreatment does not require the washing and neutralization steps before saccharification, thereby reducing waste-water generation ph of the ERW pretreated solid was automatically adjusted to optimal ph range of enzyme hydrolysis during the pretreatment process; the use of citrate buffer for enzyme hydrolysis is not necessary ERW pretreatment resulted in 92.7% glucan yield, 92.4% of digestibility after 72 h of hydrolysis, and 15.8% ethanol yield. A mercury intrusion analysis showed that ERW increased the total pore volume and diameters of cellulose fibrils that may improve enzyme accessibility to cellulose ERW is an effective pretreatment catalyst of EFB, equivalent to NaOH, and has the potential to become more efficient than other chemical pretreatments in terms of cost effectiveness

23 Acknowledgement Daekyung Esco Mr. Oh Chang-Ho Bio-oil KIER Dr. Lee Jin Suk YS Univ. Prof. Seo Yong Chil EFB Supply pretreated EFB KRIBB Dr. Sohn Jung Hoon Enzyme Gendocs Inc. Drs. Lee Yong Woog Jang Sung Soo Mr. Won Kyung Yeon Kim Dong Woog EFB Supply Waris Selesa Sdn Bhd Datuk Miller Munang EFB glucose Changhae Dr. Choi Gi Woog Bioethanol KRIBB Dr. Kim Chul Ho Ethanol This work was supported from the New & Renewable Energy Technology Development Program of the Korea Institute of Energy Technology Evaluation and Planning grant funded by the Korea government Ministry of Trade, Industry and Energy

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