In the name of God Master of science seminar Biorefinery Supervisor : Prof . H . S . Ghaziaskar By : Somayeh Azizi

2. In the name of GodMaster of science seminarBiorefinery Supervisor : Prof . H . S . Ghaziaskar By : Somayeh Azizi

3. Contents Biorefinery Green chemistry Categories of biomass Biomass conversion Thermo chemical Biochemical Mechanical Chemical Fischer Tropsch process Applications Conclusion References 1

4. What is the biorefinery? The processes of biomass into a spectrum of chemical products, fuels, and energy. • Reduction of fossil CO2 emissions • Secure and revitalization energy supply (Green process) • Producing wide ranges of bioproducts NREL = National Renewable Energy Laboratory (U.S.A.-1990)Green chemistry(Supercritical carbon dioxide, Microwaves and ultrasounds, Modification of natural polymers) 2

5. Biochemical plat form 1.Pretreatment , Hydrolysis & Fermentation2.Lignin products Sugar & lignin Intermediates Biomass 1.Agricultural residues2.Energy crops Biorefinery Products Ethanol Methanol Middle distillates Biopolymer Chemicals Heat & power Thermo chemical platform 1.Gasification 2.Pyrolysis Gas & liquid intermediates 3

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7. Biomass: Synthesized via photosynthetic process by plants • Solid biomass : Wood, Waste of plants, municipal waste, and charcoal • Liquid biomass : Bioethanol, Biodiesel, Biooil • Gas biomass : Land fill gas, Biogas, Gas of sewage sludge LFG (CO2 , CH4 , N2, O2 ,Organic materials) Depolymerization and DeoxidationRenewable carbon-based raw materials : • Agricultural • Forestry • Industries and households • Aquaculture 5

8. Biomass as renewable feedstock for biorefinery 6

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10. Difference in composition of some lignocellulosic feedstocks 8

11. Types of biorefinery • Green biorefinery • Forest and Lignocellulosic based biorefinery • Aquatic algae-based biorefinery • Integrated biorefinery 9

12. Categories of biomass : Carbohydrates and Lignin Triglycerides Mixed organic residues • Carbohydrates and Lignin • Starch :(C6H10O5)n Be hydrolyzed by enzymes or acid attack to the single sugar monomers • Cellulose :(C6H10O6)n - Crystalline polymer of Glucose more easy to hydrolyze than starch and convert to glucose monomers -(30-50%) of dry biomass • Hemicellulose : (C5H8O5)n - Amorphous polymer of Xylose and Arabinose That is easier to break down with chemicals or heat than cellulose -(20-40% )of dry biomass • Lignin : (C9H10O2(OCH3)n) - poly aromatic polymer The largest noncarbohydrate fraction of lignocelluloses -(15-25%) of dry biomass 10

13. Triglycerides • Oils and fats (C8-C20) Glycerin , Saturated and unsaturated fatty acids Vegetable and animal raw materials (Soy bean , Palm and sunflower oil) • Mixed organic residues • Manure , municipal solid waste , proteins and residues from fresh fruit , Sewage sludge and vegetable industries Moisture contents of it , is over 70% (anaerobic digestion process to generate biogas) High potential for energy recovery 11

14. Technological processes in biorefinery • Thermo chemical processes • Gasification • Pyrolysis • Direct combustion • Biochemical processes • Fermentation • Anaerobic digestion • Mechanical processes • Chemical processes • Hydrolysis • Transesterification • Supercritical water conversion 12

15. Thermo chemical processes • Gasification At high temperature ( >700 ˚C ) whit low oxygen levels to produce syngas Syngas can produce fuels ( Dimethyl ether , ethanol , Isobutene ,…) or chemicals ( Alcohols , organic acids , ammonia , methanol and so on ) • Pyrolysis At intermediate temperatures ( 300-600 ˚C ) in the absence of oxygen to convert the feedstock in to liquid pyrolytic oil (or bio-oil ) , solid charcoal and syngas • Direct combustion 13

16. Biochemical processesMicrobial and enzymatic process At lower temperature and reaction rate than Thermo. Process • Fermentation To convert a fermentable substrate into recoverable products ( Alcohols or organic acids) whit microorganisms or enzymes (Ethanol , hydrogen , methanol , succinic acid , …) 14

17. Anaerobic digestion Bacterial breakdown of biodegradable organic material in the absence of oxygen ( 30-65 ˚C ) Bio gas is the main product (A gas mixture made of methane , CO2 and other impurities ) 15

18. Mechanical processeschanging the particle size , shape and bulk density of biomass (feedstock , handling and further conversion processes ) Split of lignocellulosic biomass methods for pretreatment Hot water Sulfur dioxide Diluted acid Ammonia explosion Organic solvent Steam/Peroxide explosion Alkaline pretreatment Dilute acid & elevated temperature 16

19. Chemical processes Hydrolysis To depolymerise polysaccharides and proteins in to sugars(e.g. glucose from cellulose) or chemicals(e.g. levulinic acid from glucose) Acid hydrolysis Hydrothermal (by use of hot water or supercritical methods) Enzymatic hydrolysis Attack to chains more efficiently High yields of fermentable sugars Operation under mild pH & temperature conditions Do not create the harsh environment 17

20. Solid acid catalyzed simultaneous esterification and Transesterification • Transesterification conversion of vegetable oils to methyl or ethyl esters of fatty acids ( Biodiesel ) 18

21. Supercritical water conversion Conversion of cellulose to sugars or biomass to mixed of oils , organic acids , alcohols and methane. (Without catalyzer)2 C6H12O6 + 7 H2O CO2 + 2 CH4 +CO + 15 H2 19

22. Researchers use this continues Ion exchange / chro.g.system for product recovery & purification This evaporation system concentrate sugar-rich steams or removes volatile compounds 20

23. Automated basket centrifuge & pump separate sugar rich liquors from pretreated Biomass slurries Whit this pressurized filter press system researchers can separate liquid hydrolyzed from the remaining solids at the high temperature using NREL,s patented hot wash process. 21

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25. Fischer–Tropsch Synthesis(By Franz Fischer and Hans Tropsch) Gas to liquid technology (2n+1) H2 + n CO 150-300˚C CnH(2n+2) + n H2O ( n>1 ) By product : Alkenes , Alcohols , other oxygenated Hydrocarbons catalysts : Co, Fe, Ru and Ni LTFT Co-based catalysts (vehicle grade diesel) On low grade coal (In South Africa) HTFT Fe-based catalyst (Building block for high value chemicals)(In Malaysia) Bio fuels : Combination of biomass gasification(BG) and Fischer- Tropsch(FT) synthesis 23

26. Conversion of lignocellulosic biomass to ethanol 24

27. Biomass chips/plant fiber Enzymes Enzyme production Fermentation & Recovery Biomass pre-treatment Ethanol fermentation Ethanol purification Enzymatic Hydrolysis lignin Steam Steam Power generation Electricity 25

28. Biorefinery crops 26

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31. Conclusion • conversion of Biomass to solid , liquid , and gaseous fuels. • The advantages of Biorefinery • Reduction of CO2 emission • Reduction fossil fuel use • Improve energy security • Displacement of bioproducts whit fossil fuel 29

32. References [1] EC. Towards a European knowledge-based bioeconomy – workshop conclusions on the use of plant biotechnology for the production of industrial biobased products. EUR 21459. European Commission, Directorate-General for Research. Brussels, Belgium. <http://ec.europa.eu/ research/agriculture/library_en.htm>; 2004. [2] Kamm B, Kamm M, Gruber PR, Kromus S. Biorefinery systems – an overview. In: Kamm B, Gruber PR, Kamm M, editors. Biorefineries – industrial processes and products (status quo and future directions), vol. 1. Wiley-VCH; 2006. [3] IEA. IEA bioenergy Task 42 on biorefineries: co-production of fuels, chemicals, power and materials from biomass. In: Minutes of the third Task meeting, Copenhagen, Denmark, 25–26 March 2007 <http://www.biorefinery.nl/ ieabioenergy-task42/>; 2008. [4] Rajagopal D, Zilberman D. Review of environmental, economic and policy aspects of biofuels. In: Policy research working paper of the World Bank development research group; September 2007. [5] Hoogwijk M, Faaij A, van den Broek R, Berndes G, Gielen D, Turkenburg W. Exploration of the ranges of the global potential of biomass for energy. Biomass Bioenergy 2003;25(2):119–33.

33. [6] Demirabas A. Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesterifications and other methods: a survey. Energy Convers Manage 2003;44(13):2093–109 [7] Achten WMJ, Mathijs E, Verchot L, Singh VP, Aerts R, Muys B. Jatropha biodiesel fueling sustainability? Biofuels Bioprod Bioref 2007;1:283–91. [8] Tsai WT, Lin CC, Yeh CW. An analysis of biodiesel fuel from waste edible oil in Taiwan. Renew Sustain Energy Rev 2007;11:838–57. [9] Cherubini F, Bargigli S, Ulgiati S. Life Cycle Assessment of urban waste management: energy performances and environmental impacts. The Case of Rome, Italy. J Waste Manage 2008;28:2552–64. [10] Demirbas T. Overview of bioethanol from biorenewable feedstocks: technology, economics, policy and impacts. Energy Edu Sc’ Technol Part A 2009;22:163–77. [11] Balat M. New biofuel production technologies. Energy Edu Sc’ Technol Part A 2009;22:147–61. [12] Deshmukh MK, Deshmukh SS. System sizing for implementation of sustainable energy plan. Energy Edu Sci Technol 2007;18:1–15. [13] Gujrathi AM, Babu BV. Environment friendly products from black wattle. Energy Edu Sci Technol 2007;19:37–44.

34. [14] Hashem A, Akasha A, Ghith A, Hussein DA. Adsorbent based on agricultural wastes for heavy metal and dye removal: a review. Energy Edu Sci Technol 2007;19:69–88 [15] Demirbas A. New liquid biofuels from vegetable oils via catalytic pyrolysis. Energy Edu Sci Technol 2008;21:1–59. [16] Demirbas A. Bio-fuels from agricultural residues. Energy Sources Part A [17] Balat M. An overview of biofuels and policies in the European Union. Energy Sources Part B 2007;2:167–81. [18] Bridgwater AV, Peacocke GVC. Fast pyrolysis processes for biomass. Sustain Renew Energy Rev 2000;4:1–73. [19] Guo Y, Wang Y, Wei F, et al. Research progress in biomass flash pyrolysis technology for liquids production. Chem Ind Eng Progr 2001;8:13–7 [20] Zhuang XL, Zhang HX, Thang JJ. Levoglucosan kinase involved in citric acid fermentation by Aspergillus niger CBX-209 using levoglucosan as sole carbon and energy source. Biomass Bioenergy 2001;21:53–60. [21] Helle S, Bennett NM, Lau K, Matsui JH, Duff SJB. A kinetic model for production of glucose by hydrolysis of levoglucosan and cellobiosan from pyrolysis oil Carbohyd Res 2007;342(16):2365–70. [22] Senneca O. Kinetics of pyrolysis, combustion and gasification of three biomass fuels. Fuel Process Technol 2007;88(1):87–97.