In the name of GodMaster of science seminar
BiorefinerySupervisor : Prof . H . S . Ghaziaskar
By : Somayeh Azizi
Contents Biorefinery Green chemistry Categories of biomass Biomass conversion
• Thermo chemical• Biochemical• Mechanical • Chemical
Fischer Tropsch process Applications Conclusion References
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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 (
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Biochemical plat form1.Pretreatment , Hydrolysis & Fermentation2.Lignin products
ProductsEthanolMethanolMiddle distillatesBiopolymer ChemicalsHeat & power
Sugar & lignin Intermediates
Thermo chemical platform1.Gasification2.Pyrolysis
Gas & liquid intermediates
Biomass1.Agricultural
residues2.Energy crops
Biorefinery
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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 Deoxidation
Renewable carbon-based raw materials : Agricultural Forestry Industries and households Aquaculture
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Biomass as renewable feedstock for biorefinery
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Difference in composition of some lignocellulosic feedstocks
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Types of biorefinery
Green biorefinery Forest and Lignocellulosic based biorefinery Aquatic algae-based biorefinery Integrated biorefinery
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Categories of biomass: Carbohydrates and LigninTriglyceridesMixed organic residues
Carbohydrates and LigninStarch : (C6H10O5)n
Be hydrolyzed by enzymes or acid attack to the single sugar monomers
Cellulose : (C6H10O6)n - Crystalline polymer of Glucosemore easy to hydrolyze than starch and convert to glucose monomers -(30-50%) of dry biomassHemicellulose : (C5H8O5)n - Amorphous polymer of Xylose and Arabinose
That is easier to break down with chemicals or heat than cellulose -(20-40% )of dry biomassLignin : (C9H10O2(OCH3)n) - poly aromatic polymer
The largest noncarbohydrate fraction of lignocelluloses
10 -(15-25%) of dry biomass
TriglyceridesOils and fats (C8-C20) Glycerin , Saturated and unsaturated fatty acidsVegetable and animal raw materials (Soy bean , Palm and sunflower oil)
Mixed organic residuesManure , municipal solid waste , proteins and residues from fresh fruit , Sewage sludge and vegetable industriesMoisture contents of it , is over 70% (anaerobic digestion process to generate biogas)High potential for energy recovery
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Technological processes in biorefinery Thermo chemical processes
GasificationPyrolysisDirect combustion
Biochemical processesFermentationAnaerobic digestion
Mechanical processes
Chemical processesHydrolysisTransesterificationSupercritical water conversion
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Thermo chemical processesGasificationAt high temperature ( >700 ˚C ) whit low oxygen levels to produce syngasSyngas can produce fuels ( Dimethyl ether , ethanol , Isobutene ,…) or chemicals ( Alcohols , organic acids , ammonia , methanol and so on )PyrolysisAt 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
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Biochemical processesMicrobial and enzymatic process
At lower temperature and reaction rate than Thermo. ProcessFermentation
To convert a fermentable substrate into recoverable products ( Alcohols or organic acids) whit microorganisms or enzymes(Ethanol , hydrogen , methanol , succinic acid , …)
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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 )
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Mechanical processes changing the particle size , shape and bulk density of biomass (feedstock , handling and further conversion processes ) Split of lignocellulosic biomass
methods for pretreatment
Hot water
Diluted acid Sulfur dioxide
Ammonia explosion Organic solvent
Steam/Peroxide explosion Alkaline pretreatment
Dilute acid & elevated temperature16
Chemical processesHydrolysis
To depolymerise polysaccharides and proteins in to sugars(e.g. glucose from cellulose) or chemicals(e.g. levulinic acid from glucose)
Acid hydrolysisHydrothermal (by use of hot water or supercritical methods)Enzymatic hydrolysis
Attack to chains more efficientlyHigh yields of fermentable sugarsOperation under mild pH & temperature conditionsDo not create the harsh environment
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Transesterification
conversion of vegetable oils to methyl or ethyl esters of fatty acids ( Biodiesel )
Solid acid catalyzed simultaneous esterification and Transesterification
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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
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Researchers use this continues Ion exchange / chro.g.system for product recovery & purification
This evaporation system concentrate sugar-rich steams or removes volatile compounds
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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.
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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 oxygenatedHydrocarbonscatalysts : Co, Fe, Ru and Ni
LTFT Co-based catalysts (vehicle grade diesel)On low grade coal (In South Africa) HTFTFe-based catalyst (Building block for high value chemicals)(In Malaysia)Bio fuels : Combination of biomass gasification(BG) and Fischer-Tropsch(FT) synthesis
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Conversion of lignocellulosic biomass to ethanol
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Fermentation & Recovery
Biomass chips/plant fiber
Ethanol fermentation
Ethanol purificationEnzymatic Hydrolysis
Power generation
Biomass pre-treatment
Electricity
Enzyme production
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Biorefinery crops
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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
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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/
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of biofuels. In: Policy research working paper of the World Bank development research group; September 2007.
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[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.
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