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Center for Sustainable Environmental Technologies

Fuels and Chemicals from Biomass via Thermochemical Routes


RobertC.Brown CenterforSustainableEnvironmentalTechnologies IowaStateUniversity
Presentedat OpportunitiesandObstaclesinLargeScaleBiomassUtilization TheRoleoftheChemicalSciences WorkshopSponsoredby BoardonChemicalSciencesandTechnology NationalAcademyofSciences Washington,DC May31,2012

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UnderstandingFeedstockOptions Lipidrichbiomass Lignocellulosicbiomass Wastebiomass(alloftheaboveplusmore)

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LipidFeedstocks:Almosthydrocarbons
Triglycerides: threefattyacids attachedtoglycerol backbone;foundin oilseedsand microalgae Waxyesters: fattyacidandfatty alcoholcombination; foundinjojobaseeds Isoprene: buildingblockofterpenes; naturalhydrocarbonsusually producedinsmallquantitiesin plantsandmicroorganisms

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Lignocellulose:NaturallyRecalcitrant
A three-dimensional polymeric composite that resists biological degradation Polymeric constituents:
Cellulose: main source of glucose (C6 sugar) Hemicellulose: source of xylose (C5 sugar) Lignin: polymer of monolignols
Glycosidic bonds

Lignocellulose

Monolignols of lignin p-coumaryl alcohol coniferyl alcohol sinapyl alcohol


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Cellulose

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LipidsvsLignocellulose
Which Kind of Plant Should be Used to Deoxygenate Carbohydrate?

Plant No. 2

Plant No. 1

CO2 H2O

Lipidbiosynthesis involvesbiological deoxygenationof carbohydrates,too!

Lipid

CO2

Cellulosetohydrocarbons involvesdeoxygenationof carbohydrate

CO2
Source:NatureMedicine 11,599 600,2005.

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GeneralizedThermochemicalProcess
Feedstock

Depolymerization/Decomposition

Thermolytic Substrate Upgrading Biofuel

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Gasification
Thermaldecompositionoforganicmatterintoflammablegases
Low Temperature Gasification (Bubbling Fluidized Bed) High Temperature Gasification (Entrained Flow Gasifier)

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Syngas
Gasificationcanbeapproximatedasanequilibriumreaction
Compositionofsyngas (volumepercent) Hydrogen Carbon Carbon Monoxide Dioxide 32 48 15 Methane 2 Nitrogen 3 HHV (MJ/m3) 10.4

Inpractice,equilibriumnotattainedandtarandchararepresent Syngasalsocontainssmallamountsofalkalimetals,sulfur, nitrogen,andchlorinethatmustberemovedbeforeupgradingto preventpoisoningofcatalysts.


RawSyngas Gasifier Particulat eRemoval Biofuel Tar Alkali Sulfur Nitrogen Catalytic Removal Removal Removal Removal Synthesis

Biomass Oxygen/Stea m

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GasificationStrengths
Technical
Consumesallofthefeedstock (carbohydrateandlignin) Producesuniformintermediate product(syngas) Multipleapplications:heat, power,fuels,chemicals

Commercial
Notfinickyaboutfeedstock Proventechnologyforcracking thelignocellulosicnut Allowsenergyintegrationin biorefineryoperations

tpd gasification plant at ISUs BioCentury Research Farm

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GasificationChallenges Technical
Gascleaningtechnologiesstill underdevelopment Gasificationandfuelsynthesis operationsmustbecloselycoupled Fuelsynthesisoccursathigh pressuresandexacting stoichiometries

Commercial
Demandslargescaleoperations Highcapitalcosts Mustcompletewithsteam reformingofnaturalgas

Pressurized, oxygen-blown entrained flow gasifier at ISUs Biorenewables Laboratory

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FastPyrolysis
Thermaldecompositionoforganicmatterintheabsence ofoxygentoproduce:
Gas noncondensablegaseslikecarbondioxide,carbon monoxide,hydrogen Solid mixtureofinorganiccompounds(ash)andcarbonaceous material(char) Liquid mixtureofwater andorganiccompounds knownasbiooilrecovered frompyrolysisvaporsand aerosols(smoke)
Bio-oil

Biochar

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Themanyfacesofpyrolysis
Technology carbonization conventional gasification fastpyrolysis flashliquid flashgas ultra vacuum hydropyrolysis methanopyrolysis Residence Time days 530min 0.55 min 0.55s <1s <1s <0.5s 230s <10s <10s HeatingRate verylow low moderate very high high high very high high high high Temperature (C) 400 600 >700 650 <650 <650 1000 <500 <500 <700 Predominate Products charcoal oil,gas,char gas oil oil chemicals,gas chemicals,gas oil oil chemicals

MohanD.,PittmanC.U.Jr.,andSteeleP.H.PyrolysisofWood/BiomassforBiooil:A CriticalReviewEnergy&Fuels,20,848889(2006)

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FastPyrolysis

Rapid thermal decomposition to produce predominately liquid


Dryfeedstock:<10% Smallparticles:<3mm Moderatetemperatures(400 500oC) Shortresidencetimes:0.5 2s Rapidquenchingattheendof theprocess Typicalyields Oil:60 70% Char:1215% Gas:13 25%

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PyrolysisChemistryisPoorlyUnderstood
Research at ISU indicates several stages of competitive processes during cellulose pyrolysis:*
Depolymerizationvs.alkalicatalyzeddecompositionofcellulose Vaporizationvs.repolymerizationoflevoglucosan (LG)tooligomers Dehydrationofoligomerstolightoxygenatesorchar
Alkali-catalyzed decomposition Cellulose Depolymerization Liquid LG evaporation LMW products LMW products LG oligomers LG polymer LG vapors LMW products + char

polymerization

Note: LMW (low molecular weight products) include H2O, CO2, 5-HMF, furfural, furan, carboxylic acid, etc.

*Hemicellulose and lignin similarly go through several stages of depolymerization or dehydration

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FastPyrolysisStrengths
Technical
Rapid(afewseconds) Atmosphericoperation Pathwaytodropinfuels Multipleproducts Newtechnologiesemerging (catalyticpyrolysis)

tonperdayfastpyrolysispilotplantat ISUBioCenturyResearchFarm

Commercial
Lowestcostoptionfordropinbiofuelsatpresent Pyrolyzersassmallas200tpd Opportunitiesfordistributedprocessing

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FastPyrolysisChallenges
Technical
Biooilhashighoxygenand watercontent Biooilunstableandcorrosivein storageandupgrading Fundamentalsofpyrolysis poorlyunderstood

Commercial

Freefallpyrolyzerforfundamental studiesunderconstructionatISUs BiorenewablesResearchLaboratory

Nodemonstrationsofbiooilproductionandupgrading Pathwaytofinishedfuelsstilluncertain

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CatalyticPyrolysis
Definition:Catalystsemployedinthepyrolysisreactor orimmediatelydownstreambeforebiooilrecovery Twomajorapproaches:
Catalyticcracking(doesnotrequirehydrogen) Hydropyrolysis(carbonefficient)

Advantage:Produceshighlyreducedmolecules Challenge:Yieldsarerelativelylowduetocoking Commercialization:Largenumberofcompaniesare exploringthisapproachalthoughfundamental chemistryisnotwellunderstood

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Solvolysis
Definition:Pyrolysisinasolvent Twomajormanifestations:
Directliquefaction(DL)toproducepartiallydeoxygenated biocrude Hydrothermalprocessing(HTP)tosugarsandlignin

Advantagesandchallengesaresimilartofast pyrolysiswithaddedchallengeofoperatingathigh pressures Commercializationexamples:


DL:Catchlight(ChevronWeyerhauserjointventure) HTP:Renmatix(KleinerPerkinsbackedstartup)

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UpgradingThermolyticSubstrates
Syngas:Mixtureofcarbonmonoxide(CO)andhydrogen (H2)derivedfromgasificationoforganicmaterials BioOil:Highlyoxygenatedorganiccompoundsderived fromfromfastpyrolysis BioCrude:Partiallydeoxygenatedorganiccompounds derivedfromdirectliquefactionorcatalyticpyrolysisof biomass. Solubilizedcarbohydrate: Aqueoussolutionof monosaccharides,anhydrosugars,andotherwatersoluble compoundsderivedfromplantcarbohydratesusinga varietyofprocessesincludingacidorenzymatichydrolysis, fastpyrolysis,andhydrothermalprocessing

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Deoxygenation Animportantpartofallbiomassupgrading
Idealization:C6H12O6 +H2 C6H14 +3O2 Inpractice,oxygenremovedasCO2 orH2O Examples:
Ethanolfermentation(biocatalyticupgrading) C6H12O62C2H5OH+2CO2 Gasification/FischerTropschSynthesis C6H12O6 +3H2O 6H2+3CO+3CO2 (2n+1)H2 +nCOCnH2n+2 +nH2O

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SyngasUpgradingtoFuels
Catalytic performedatmoderate temperaturesandhighpressures usingmetalcatalysts
FischerTropschsynthesisto hydrocarbonssuitableforfuels Methanolsynthesisfollowedby upgradingtogasoline Ethanolsynthesis

Syngasfermentation performed atambienttemperatureand pressureusingbiocatalysts

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UpgradingBioOil:WhatsinIt?
CarbohydrateDerivedCompounds
Lightoxygenates(ringbreaking):carboxylicacids,aldehydes, ketones,alcohols.

Furans(productsofcarbohydratedehydration)
HOH2C O CHO 5-hydroxymethyl furfural

Sugars(depolymerization):Monosaccharides,anhydrosugars, oligosaccharides.

Levoglucosan

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UpgradingBiooil:WhatsinIt?
LigninDerivedCompounds Depolymerizationoflignin: Substitutedphenolicmonomers Repolymerizedmonomers: Phenolicoligomers
2-methoxy phenol phenolic oligomers
1.2 1 0.8 Area 0.6 0.4 0.2 0 10 100 1000 MolecularWeight(Da) 10000

Consistingofasmanyas50to80 monomericunits

MolecularWeightDistributionof WaterInsolubleFraction

Toproducedieselfuel(C10C24), thephenolicoligomersshould occurasdimers(C14)ortrimers (C21)of2methoxyphenol

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UpgradingBioOilViaPetroleumRefiningTechnology Hydrotreating (removalofheteroatoms)


Deoxygenation,desulfurization,denitrification,and demetalization

Cracking
Reductioninsizeoflargemoleculestofuelrange

Condensation
Reactionoftwomoleculestoproducealarger(fuelrange) moleculeandasmallmolecule

Oligomerization
Reactionofmonomerwithanothermonomer,dimer,etc. toproducelargermolecules(oligomers)

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RenewableCrude:SolubilizedCarbohydrate
Sugarscanbecatalyticallyconvertedto hydrocarbonsviaaqueousphase processingifcheapfeedstockavailable Commerciallyavailablefeedstocks:Sugar caneandcornstarch
Constrainedbycostandfoodvs.fuel concerns
Pyrolytic dextrin (>20wt%sugars)

Promisingfeedstock:Lignocellulose
Requiresdeconstructiontosugarmonomers Canbeaccomplishedviaacidhydrolysis, enzymatichydrolysis,orthermal depolymerization

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ThermalDepolymerizationtoMonomers

Secureasource ofcleanstraw (orotherlignocellulose)

Infusebiomasswitha diluteacidsolution

Bakeitinahotoven (setthetimerfor2seconds)

Sugar Gasolineorethanol Phenolics Bioasphalt,chemicals,fuels Washoutthesugars

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FutureInnovations?
GasificationChallenge Innovation Transport,storage, andpressurized Preprocessingofbiomassintotorrefied biocoal, feedingofbiomass pelletizedfeedstock,orbiooil Demanding operatingconditions forcatalyticsynthesistofuel Highcapitalcosts Substitute biocatalyst(syngasfermentation) Operationatatmosphericpressureandwith fewerunitoperationsforgascleaning Innovation Recoverbiooilasfractionswithsimilarphysical andchemicalproperties Catalyticpyrolysisforinsitudeoxygenationof pyrolysis products Thermaldepolymerizationto monomers (monosaccharidesandphenolicmonomers)
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FastPyrolysisChallenge Complexchemicalcompositionof biooilmakes upgradingdifficult Biooilishighlyoxygenated Goldilocks dilema:Moleculesare eithertobigortoosmallforideal upgrading

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