1. Production of Second-Generation Biofuels from Palm Wastes Shinichi Yano Biomass Technology Research Center, National Institute for Advanced Industrial Science and Technology, Japan

2. Biofuels Any fuels produced from biomass can be called biofuels, but recently, most of interests are focused on liquid biofuels for automobiles. According to the differences of engines, totally different properties are required for biofuels. ●Biodiesel fuel (BDF) for diesel engines → High cetane number is required. ●Ethanol for Otto cycle engines. (engines for gasoline) → High octane number is required.

3. What should be feedstock for liquid biofuels? The present feedstock : Starch, or sugars for ethanol Vegetable oil, or animal fats for BDF First-generation biofuels (Converted by conventional technologies) Problems 1. Competition with food usage (supplies and costs) 2. Bumper crops or poor harvest → instability 3. Can be real energy production? → LCA analysis is necessary.

4. Resources not for food or feed use. Lignocellulosic biomass (Wood wastes, Agricultural residues, Energy crops) Second-generation biofuels ● Cellulosic ethanol ● BTL （ Biomass to Liquid) diesel fuels However, several technological barriers exist for the production of Second-generation biofuels Further R & D’s are required. Feedstock for the future

5. CHO H OH OH H H OH CH ２ OH Hydrolyzed products → mainly D - xylose Pentose sugars cannot be metabolized by Saccharomyces cerevisiae. Technologies to overcome this problem are required. CHO H OH OH H H OH CH ２ OH Cellulose ・ Crystalline ・ Difficult to hydrolyze Efficient and low-cost technologies are required. Cellulose ・ Crystalline ・ Difficult to hydrolyze Efficient and low-cost technologies are required. Lignin Hydrolyzed product → D - glucose Easily fermented to ethanol with conventional systems Hemicellulose ・ Amorphous ・ Relatively easy to hydrolyze Hemicellulose ・ Amorphous ・ Relatively easy to hydrolyze Two major technological barriers for the ethanol production from lignocellulosic biomass

6. Pretreatments Enzymatic saccharification Acid hydrolysis Fermentation Distillation/Purification Ethanol ETBE Lignocellulosic biomass Scheme for ethanol production from lignocellulose

7. Mechanical Milling Treatment Hot-Compressed-Water Treatment Technologies of AIST for pretreatments of lignocellulosic biomass ・ Separation of lignocellulosic components ・ Saccharification of hemicellulose ・ Separation of lignocellulosic components ・ Saccharification of hemicellulose ・ Pulverize to fine particles ・ Change strurcture of cellulose → Increasing reactivity of enzymes ・ Pulverize to fine particles ・ Change strurcture of cellulose → Increasing reactivity of enzymes

8. Glucose yields from pretreated eucalyptus powder after enzymatic saccharification

9. OOOOO O O OOO OOOOOOOOOO O OO OO OOOOOOOO OO Endoglucanase （ for amorphous region ） Exoglucanase （ for crystalline region ） β-glucosidase (produce glucose ） Cellulase: consists of three kinds of enzymes Synergetic effects of three enzymes are observed. O O OO O O ････････ ･･････ ････････ ･･････ OOOOOOOO OOO For the cost reduction of cellulase ● Appropriate pretreatments ● Selection of enzymes and combination of enzymes ● On-site production of enzymes Enzymatic saccharification

10. AIST original cellulase: Acremonium cellulase Acremonium cellulolyticus : A fungi isolated from soil in Japan by Takashi Yamanobe, AIST, in 1982 Industrially produced by Meiji Seika Co. LTD., mainly for silage preparation Acremonium cellulase has higher β-glucosidase activity than Trichoderma cellulase. suitable for ethanol production The research for elevating enzyme productivity is underway.

11. Improvement of enzyme productivitiy by mutation FPU CMCase  -glucosidase Avicelase Parental strainMutant 100% 200% Enzyme activities /ml of cultures

12. Sugar yields from BM-treated wood powder after enzymatic saccharification

13. 4FPU/g40FPU/g4FPU/g40FPU/gComposition Sugar yield (g/g dry materials) Sugar yields from BM-treated palm-trunk and EFB fiber after enzymatic saccharification (4 or 40FPU/g) Saccharification rate: Glucose 57%, Xylose 72% Glucose 42%, Xylose 42%

14. RCOO-CH 2 RCOO-CH RCOO-CH 2 ３ R-CH 3 H2OH2O CH 3 -CH 2 -CH 3 ３ R-H 3CO 2 or 3CH 4 CH 3 -CH 2 -CH 3 + ３ H 2 ~+15H 2 +12H 2 Dehydration Decarboxylation Triglycerides +3CH 3 OH Hydro-treated biodiesel New biodiesel fuels (1) Hydro-treated biodiesel 3RCOOCH 3 (BDF) + Glycerol

15. Palm hydro- treated diesel Palm FAME Diesel fuel (Japanese Standard-2) Density g/cm 3 0.78520.87420.8283 Flash point ℃ 13218075 Iodine value0.1590.0 Pour point ℃ 2015-22.5 Viscosity mm 2 /s@30 ℃ 4.1405.5104.063 Distilla -tion T10 ℃ 284.5333.0221.0 T90 ℃ 301.0359.0337.5 Cetane number1016260 Oxygen mass%<0.112<0.1 Higher cetane number, higher stability, better quality, than FAME data from Nippon Oil Co. Ltd Property of hydro-treated biodiesel

16. CO, H 2 tar ， S Purification CO, H 2 (100 ～ 400 ℃） gasificatio n ～ 900 ℃ FT synthesis ● Diesel fuels from lignocellulosic biomass ● High quality, high cetane number Biomass New biodiesel fuels (2) Biomass to Liquid (BTL)

17. AIST’s bench-scale BTL production plant AIST Chugoku (Kure, Hiroshima) Biomass Technology Research Cente r AIST has constructed bench-scale BTL production plant and started its operation this spring. The BTL production capacity is 1.9L/d.

18. Possible Second-generation Biofuel Production from Palm Wastes Wasted Trunk Empty Fruit Bunch Oil Palm Fresh Fruit Bunch Fruit Fiber, Shell Saccharification Fermentation Purification Pretreatment ETHANOL Crude Palm Oil Palm Kernel Gasification Lignocellulosic Biomass Purification FT synthesis Upgrading BTL

19. Conclusions The first-generation biofuels (BDF and ethanol from sugars or starch ) are used as alternatives of petroleum fuels for automobiles at the present time. There will be problems, however, because their feedstock is also utilized as foods or feeds. To solve those problems, the use of second-generation biofuels produced from lignocellolosic biomass is anticipated. But there are some technical barriers to be overcome to produce them in large quantity with low costs. Further R&D’s are necessary.