Fuels and Chemicals From Biomass

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
UnderstandingFeedstockOptions Lipidrichbiomass Lignocellulosicbiomass Wastebiomass(alloftheaboveplusmore)
LipidFeedstocks:Almosthydrocarbons
Triglycerides: threefattyacids attachedtoglycerol backbone;foundin oilseedsand microalgae Waxyesters: fattyacidandfatty alcoholcombination; foundinjojobaseeds Isoprene: buildingblockofterpenes; naturalhydrocarbonsusually producedinsmallquantitiesin plantsandmicroorganisms
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
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.
GeneralizedThermochemicalProcess
Feedstock
Depolymerization/Decomposition
Thermolytic Substrate Upgrading Biofuel
Gasification
Thermaldecompositionoforganicmatterintoflammablegases
Low Temperature Gasification (Bubbling Fluidized Bed) High Temperature Gasification (Entrained Flow Gasifier)
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
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
GasificationChallenges Technical
Gascleaningtechnologiesstill underdevelopment Gasificationandfuelsynthesis operationsmustbecloselycoupled Fuelsynthesisoccursathigh pressuresandexacting stoichiometries
Commercial
Demandslargescaleoperations Highcapitalcosts Mustcompletewithsteam reformingofnaturalgas
Pressurized, oxygen-blown entrained flow gasifier at ISUs Biorenewables Laboratory
FastPyrolysis
Thermaldecompositionoforganicmatterintheabsence ofoxygentoproduce:
Gas noncondensablegaseslikecarbondioxide,carbon monoxide,hydrogen Solid mixtureofinorganiccompounds(ash)andcarbonaceous material(char) Liquid mixtureofwater andorganiccompounds knownasbiooilrecovered frompyrolysisvaporsand aerosols(smoke)
Bio-oil
Biochar
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)
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%
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
FastPyrolysisStrengths
Technical
Rapid(afewseconds) Atmosphericoperation Pathwaytodropinfuels Multipleproducts Newtechnologiesemerging (catalyticpyrolysis)
tonperdayfastpyrolysispilotplantat ISUBioCenturyResearchFarm
Commercial
Lowestcostoptionfordropinbiofuelsatpresent Pyrolyzersassmallas200tpd Opportunitiesfordistributedprocessing
FastPyrolysisChallenges
Technical
Biooilhashighoxygenand watercontent Biooilunstableandcorrosivein storageandupgrading Fundamentalsofpyrolysis poorlyunderstood
Commercial
Freefallpyrolyzerforfundamental studiesunderconstructionatISUs BiorenewablesResearchLaboratory
Nodemonstrationsofbiooilproductionandupgrading Pathwaytofinishedfuelsstilluncertain
CatalyticPyrolysis
Definition:Catalystsemployedinthepyrolysisreactor orimmediatelydownstreambeforebiooilrecovery Twomajorapproaches:
Catalyticcracking(doesnotrequirehydrogen) Hydropyrolysis(carbonefficient)
Advantage:Produceshighlyreducedmolecules Challenge:Yieldsarerelativelylowduetocoking Commercialization:Largenumberofcompaniesare exploringthisapproachalthoughfundamental chemistryisnotwellunderstood
Solvolysis
Definition:Pyrolysisinasolvent Twomajormanifestations:
Directliquefaction(DL)toproducepartiallydeoxygenated biocrude Hydrothermalprocessing(HTP)tosugarsandlignin
Advantagesandchallengesaresimilartofast pyrolysiswithaddedchallengeofoperatingathigh pressures Commercializationexamples:

DL:Catchlight(ChevronWeyerhauserjointventure) HTP:Renmatix(KleinerPerkinsbackedstartup)
UpgradingThermolyticSubstrates
Syngas:Mixtureofcarbonmonoxide(CO)andhydrogen (H2)derivedfromgasificationoforganicmaterials BioOil:Highlyoxygenatedorganiccompoundsderived fromfromfastpyrolysis BioCrude:Partiallydeoxygenatedorganiccompounds derivedfromdirectliquefactionorcatalyticpyrolysisof biomass. Solubilizedcarbohydrate: Aqueoussolutionof monosaccharides,anhydrosugars,andotherwatersoluble compoundsderivedfromplantcarbohydratesusinga varietyofprocessesincludingacidorenzymatichydrolysis, fastpyrolysis,andhydrothermalprocessing
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
SyngasUpgradingtoFuels
Catalytic performedatmoderate temperaturesandhighpressures usingmetalcatalysts
FischerTropschsynthesisto hydrocarbonssuitableforfuels Methanolsynthesisfollowedby upgradingtogasoline Ethanolsynthesis
Syngasfermentation performed atambienttemperatureand pressureusingbiocatalysts
UpgradingBioOil:WhatsinIt?
CarbohydrateDerivedCompounds
Lightoxygenates(ringbreaking):carboxylicacids,aldehydes, ketones,alcohols.
Furans(productsofcarbohydratedehydration)
HOH2C O CHO 5-hydroxymethyl furfural
Sugars(depolymerization):Monosaccharides,anhydrosugars, oligosaccharides.
Levoglucosan
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
UpgradingBioOilViaPetroleumRefiningTechnology Hydrotreating (removalofheteroatoms)

Deoxygenation,desulfurization,denitrification,and demetalization
Cracking
Reductioninsizeoflargemoleculestofuelrange
Condensation
Reactionoftwomoleculestoproducealarger(fuelrange) moleculeandasmallmolecule
Oligomerization
Reactionofmonomerwithanothermonomer,dimer,etc. toproducelargermolecules(oligomers)
RenewableCrude:SolubilizedCarbohydrate
Sugarscanbecatalyticallyconvertedto hydrocarbonsviaaqueousphase processingifcheapfeedstockavailable Commerciallyavailablefeedstocks:Sugar caneandcornstarch
Constrainedbycostandfoodvs.fuel concerns
Pyrolytic dextrin (>20wt%sugars)
Promisingfeedstock:Lignocellulose
Requiresdeconstructiontosugarmonomers Canbeaccomplishedviaacidhydrolysis, enzymatichydrolysis,orthermal depolymerization
ThermalDepolymerizationtoMonomers
Secureasource ofcleanstraw (orotherlignocellulose)
Infusebiomasswitha diluteacidsolution
Bakeitinahotoven (setthetimerfor2seconds)
Sugar Gasolineorethanol Phenolics Bioasphalt,chemicals,fuels Washoutthesugars
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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