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

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