Fast Pyrolysis and Bio-OilUpgradingRobert C. BrownIowa State UniversityandJennifer HolmgrenUOPFast Pyrolysis•Rapid thermal decomposition of organiccompounds in the absence of oxygen toproduce liquids, char, and gas–Dry feedstock: <10%–Small particles: <3 mm–Short residence times: 0.5 -2s–Moderate temperatures (400-500oC)–Rapid quenching at the end of the process–Typical yieldsOil: 60 -70%Char: 12 -15%Gas: 13 -25%Source: Piskorz, J., et al. In Pyrolysis Oilsfrom Biomass, Soltes, E. J., Milne,T. A.,Eds., ACS Symposium Series 376, 1988.WhiteSprucePoplarMoisture content, wt%7.03.3Particle size,μm (max)1000590Temperature500497Apparent residence time0.650.48Product Yields,wt %, m.f.Water11.612.2Gas7.810.8Bio-char12.27.7Bio-oil66.565.7Bio-oil composition, wt %, m.f.Saccharides3.32.4Anhydrosugars6.56.8Aldehydes10.114.0Furans0.35--Ketones1.241.4Alcohols2.01.2Carboxylic acids11.08.5Water-Soluble –Total Above34.534.3Pyrolytic Lignin20.616.2Unaccountedfraction11.415.2Bio-OilPyrolysis liquid (bio-oil)from flash pyrolysis is alow viscosity, dark-brownfluid with up to 15 to 20%waterMultiple reaction pathways forpyrolysis of celluloseCelluloseFastSlowAlkali-catalyzeddehydrationChar + waterLevoglucosanHydroxyacetaldehydeDepolymerizationFast Pyrolysis•Advantages–Operates at atmospheric pressure and modesttemperatures (450 C)–Yields of bio-oil can exceed 70 wt-%•Disadvantages–High oxygen and water content of pyrolysis liquidsmakes them inferior to conventional hydrocarbonfuels–Phase-separation and polymerization of the liquidsand corrosion of containers make storage of theseliquids difficultSeveral Kinds of Fast PyrolysisReactors•Bubbling fluidized bed•Circulating fluidized beds/transport reactor•Rotating cone pyrolyzer•Ablative pyrolyzer•Vacuum pyrolysis•Auger reactorBubbling Fluidized BedGas, Char, and OilVapors and AerosolFreeboardFluid bedFluidizing gasBiomassFeederDistributorplateHeat•Heat supplied externallyto bed•Good mass & heattransfer•Requires small biomassparticles (2-3 mm)Circulating Fluidized Bed/TransportReactorGas and Oil Vaporsand AerosolFluidizing gasBiomassFeederDistributorplateAirFlueGasPyrolyzerCombustorSand& charHotSand•Hot sand circulatedbetween combustorand pyrolyzer•Heat supplied fromburning char•High throughputsbut more charattritionRotating Cone PyrolyzerHot SandBiomassVapors andAerosolRotation•Sand and biomassbrought into contactwithin rotating cone•Compact design anddoes not need carriergas•Requires very smallbiomass particles andis hard to scale-upAblative Pyrolyzer•High pressure of particleon hot reactor wallachieved by centrifugalor mechanical motion•Can use large particlesand does not requirecarrier gas•Complex and does notscale wellSpinningDiskPressureAppliedto WoodBio-oilLiquidReleasedfrom WoodVacuum Pyrolysis•Biomass moved bygravity and rotatingscrappers throughmultiple hearthpyrolyzer withtemperature increasingfrom 200 C to 400 C•Can use largerparticles and employslittle carrier gas•Expensive vacuumpump and difficult toscale-upScrapperDriverBiomassCharVacuumpumpMultiple hearthvacuum pyrolysisreactorCondensersAuger ReactorBiomassAugerdriverChar &sandVapors &aerosol tocondenserHotsandAugerreactor•Hot sand andbiomass mixed byauger•Suitable for smallscale•Requires hot sandheating andcirculation systemRelative Merits of Various ReactorsPropertyStatusBiooilwt%ComplexityFeedsizeInertgasneedSpecificsizeScaleupFluid bedDemo75MediumSmallHighMediumEasyCFBPilot75HighMediumHighLargeEasyEntrained None65HighSmallHighLargeEasyRotatingconePilot65HighV smallLowSmallHardAblativeLab75HighLargeLowSmallHardAugerLab65LowSmallLowMediumEasyVacuumDemo60HighLargeLowLargeHardThe darker the cell color, the lessdesirable the process.Lab: 1 –20 kg h-1Pilot: 20–200 kg h-1Demo: 200 –2000 kg h-1Adapted from PYNE IEA Bioenergy http://www.pyne.co.ukWhich will dominate?TECHNOLOGY STRENGTHStrongAverageWeakAblativeCyclonicRotating coneEntrained flowFluid bedCirculating fluid bedand transport reactorAuger

MARKET ATTRACTIVENESSHighLowAdapted from PYNE IEA Bioenergy http://www.pyne.co.ukFast Pyrolysis SystemMillAirQuencherBio-oilBio-oilstorageHopperFluidizinggasFluegasVapor,gas, charproductsCycloneCombustorPyrolysisgasesLignocellulosicfeedstockPyrolysisreactorCharFeederMotorScale$0$1,000$2,000$3,000$4,000$5,000$6,000$7,000$8,0000.0 1.02.0 3.04.0 5.0Biomass Input(millionUStons/yr)

C a p i t a l Co st ( m illio n 2005 US d o llar s)050100150200250Diesel Output(millionUSgallons/yr)Smallgasification(multipleunits110,000USton/yr)+smallFTmultipleunitsSmallpyrolysis(multipleunits110,000USton/yr)+largeFTLarge gasification+largeFT$400,000 pbpd$100,000 pbpdAdapted from: Bridgwater, ACSMeeting, Washington, D.C., 2005Suitable Feedstocks•Wide variety of feedstocks can be used•Fibrous biomass usually employed•Wood higher yielding than herbaceousbiomassStorage & Transportation•Distributed preprocessing allows transportand storage as liquid•High acidity requires storage in stainlesssteel or plastic•Stability problems need to be solvedPost Processing to Motor Fuels•Direct application of bio-oil•Hydrocrackingof bio-oil•Gasification of bio-oil•Fermentation of Bio-oilBio-Oil Burned in Diesel Engines•Bio-oil used as directly as diesel fuel substitute•Only suitable for stationary power applications

PyrolyzerBio-OilRecoveryBio-OilStorageStationaryDiesel EngineFibrousbiomassBio-oil vaporCycloneBio-OilCharBio-Oil Hydrocracking•Directly converts biomass into liquid bio-oil (lignin,carbohydrate derivatives, and water) and char•Bio-oil catalytically converted into hydrocarbon fuel(green diesel)

PyrolyzerCarbohydrate derivedaqueous phaseBio-OilRecoveryPhaseSeparationSteamReformer HydrocrackerFibrousbiomassBio-oil vaporHydrogenGreendieselCycloneLigninCharBio-Oil Gasification•Bio-oil and char slurried together to recover 90% ofthe original biomass energy•Slurry transported to central processing site where it isgasified in an entrained flow gasifier to syngas•Syngas is catalytic processed into green diesel (F-Tliquids) PyrolyzerBio-OilRecoverySlurryPreparationPump Entrained Flow GasifierFibrousbiomassBio-oil vaporSlagCycloneBio-OilChar Fischer Tropsch ReactorGreenDieselBio-Oil FermentationFermenterFiber PyrolyzerAnhydrosugar&other carbohydrateBio-OilRecoveryPhaseSeparationDetoxificationLigninHot waterextractionPentose

Fiber byproductBio-oil vaporFermenterDistillationWaterEthanolCycloneCharEnergy Efficiency•Conversion to 75 wt-% bio-oil translates toenergy efficiency of 70%•If carbon used for energy source (processheat or slurriedwith liquid) then efficiencyapproaches 94%Source: http://www.ensyn.com/info/23102000.htmCo-Products•Gas (CO, H2, lighthydrocarbons)–Can be used to heatpyrolysis reactor•Char: Several potentialapplications–Process heat–Activated carbon–Soil amendmentPotential Co-Products from Bio-OilProducts of pyrolysis for several differentpretreatments of cornstover (Brownet al. 2001)NoPretreatmentAcidHydrolysisAcidWashAcidWashwithcatalystProducts (Wt%maf)Char15.813.213.215.9Water2.5710.610.47.96Organics59.167.268.567.7Gases22.69.027.888.44Organics (Wt %)Cellobiosantrace4.553.344.97Levoglucosan2.7517.6920.1223.10Hydroxy-acetaldehyde11.575.973.733.93Formic acid2.61TraceTrace0.73Acetic acid3.401.511.260.40Acetol4.53tracetracetraceFormaldehyde2.751.63trace0.70Pyrolytic lignin33.4016.8917.7420.08Quality Assurance•Bio-oil quality issues:–Moisture content–Particulate content–Sulfur and nitrogen content–StabilityEquipment Maintenance•Potential problems with pyrolysisequipment–Bed agglomeration–Clogging of condensers–ESP performance•Catalytic reactors–Poisoning by sulfur and chlorine– CokingWaste Streams•Main products (gas, char, bio-oil) accountfor all mass of biomass feedstockTechnical Barriers•Preparing dry, finely divided biomassparticles•Maintaining high bio-oil yields•Improving bio-oil stability•Determining optimal scale of facilityAlternative Fuels: TargetsAlternative Fuels: TargetsAlternative fuels may need to target:Alternative fuels may need to target:–< 100 gm CO< 100 gm CO2/km WTW/km WTW–GTL, DME from gasGTL, DME from gas–close, butclose, butere yetnot there yetSeveral other alternatives in sSeveral other alternatives in study(not shown for simplicity)(not shown for simplicity)Engine manufacturers developingEngine manufacturers developingmore efficient advancedmore efficient advancedICE’sinaddition to hybrids and FCaddition to hybrids and FC’s–Variable DI gasolineVariable DI gasoline–“Part HomogeneousPart Homogeneous”dieselcombustioncombustion–“Combined CombustionCombined Combustion”systemssystems–Improve fuel efficiencyImprove fuel efficiencySource: CONCAWE / EU CAR /Source: CONCAWE / EU CAR /EUComm’n,Dec2003WTW Energy /GHG Emissions ClustersWTW Energy /GHG Emissions Clusters05010015020025030035040002004006008001000Energy, MJ/km

GHG, CO 2 Equivalent, gm/kmHydrogenHydrogenfrom coal, FCfrom coal, FCDME from NGFAMEentionalConventionalEtOHHydrogen frombio, ICEbio, ICEGasoline & DieselGasoline & Dieselfrom NGGTLGreen DieselGreen DieselGasoline & Diesel in AdvancedGasoline & Diesel in AdvancedICE’sSet Tough Targets!Set Tough Targets!Biorenewables and PetroleumBiorenewables and PetroleumFeeds: Relative AvailabilityFeeds: Relative Availability01020304050CurrentCurrentPotentialPotentialLiquid Transport FuelsLiquid Transport FuelsDieselAvailable Oil/GreaseAvailable Oil/GreaseCellulosic WasteCellulosic Waste

MBPD MBPDGlobalUS0246810CurrentCurrentPotentialPotential

MBPDLiquid Transport FuelsLiquid Transport FuelsGasolineGasolineDieselAvailable Oil/GreaseAvailable Oil/GreaseCellulosic WasteCellulosic Waste1214Available Cellulosic Biomass Could Make aAvailable Cellulosic Biomass Could Make aSignificant Impact in Fuels PoolSignificant Impact in Fuels PoolUOP4434A-09PyOil PortfolioOil PortfolioSolidCellulosicBiomassPyrolysis Oil/LigninHydrogen/Power GenerationDieselGasolineLignin Molecular StructureTreating TechnologiesTreating TechnologiesHydrotreatingHydrotreating•Hydrotreating is the key processto meet quality specifications forrefinery fuel products•Removes sulfur, nitrogen, olefins,and metals using hydrogen•Hydrogen addition alsoimprovesthe quality of distillate fuels (polyaromatics, cetane, smoke point)•Treating feedstocks for otherprocessing unitsConversion TechnologiesConversion TechnologiesHydrocrackingHydrocracking•Hydrocracking upgrades heavyfeeds including gas oils andcycle oils into lighter, highervalue, low sulfur products•High pressure is used to addhydrogen and producepremium distillate products•Naphtha products normally arelow octane and are upgradedin a reformer•Product volume is 10-20%higher than the feedstockDistillates SelectivityActivityNew GenerationNew GenerationMaxDieselDistillatesDistillatesFlexibleFlexibleMaxNaphthaNaphthaHydrocracking Catalyst PortfolioHydrocracking Catalyst PortfolioHC-150HC-29HC-215HC-115DHC-32HC-33DHC-8HC-24HC-43Current GenerationCurrent GenerationDHC-39-41DHCHC-34HC-26Distillate Selectivity Decreases with Increasing ActivityDistillate Selectivity Decreases with Increasing ActivityHC-170HC-190YE forHydrocrackingHydrocrackingPyrolysis OilPyrolysis OilFeedWt%bpdPyrolysis OilPyrolysis Oil1004-51530851-522,250H2ProductsProductsLt endsLt endsGasolineGasoline1,010Diesel250Water, COWater, CO2Gasoline Production fromGasoline Production fromPyOil($40/bbl crude)($40/bbl crude)Feed$/DbpdPyrolysis OilPyrolysis Oil40,500H225,68021.4 T19,30352,52012,000UtilitiesUtilities-4,800Net12,8432,250ProductsProductsLt HydrocarbonsLt Hydrocarbons64T/DGasolineGasoline1,010Diesel250$ 4.2 million/yearHydroprocessing costs:Hydroprocessing costs:Effect of ScaleEffect of ScaleHDTCapitalCostvs Capacity$0.0$5.0$10.0$15.0$20.0$25.0$30.0$35.005000100001500020000250003000035000Capacity,BPD

C a p i tal C o st, $M M (2006)Unitsize(bpd)Cost,$MMCost/1000bpd$MM30000$28.90.96$27500$27.41.00$25000$25.91.04$22500$24.31.08$20000$22.71.13$17500$20.91.19$15000$19.11.27$12500$17.11.37$10000$14.91.49$7500$12.61.68$5000$9.91.97$2500$6.52.60$Size of Hydroprocessing UnitsSize of Hydroprocessing Units2000 bpd HC units2000 bpd HC units2500bbl/day38.3Mgal/yearpyrolysisoilprocessed174072tonnes/yrpyrolysisoilprocessed65%Conv.tobiooil267803tonnes/yrbiomass734tonne/dayplantDynamotiveDynamotive’sPlannedPlanned200tpdPlantDynamotive's200 tonne/dayfacility(planned production)200tonne/daybiomassprocessed200000kg/day65%% conversionbiomass to pyrolysisoil130000kg/daybiooil1.2kg/literdensityofpyrolysisoil108333liter/day28622gal/day681bbl/dayHydroprocessing unit30,000 bpd HC unit30,000 bpd HC unit(typical refinery size)(typical refinery size)30000bbl/day459.9Mgal/yearpyrolysisoilprocessed2088866tonnes/yrpyrolysisoilprocessed65%Conv.tobiooil3213640tonnes/yrbiomass8804tonne/dayplantExample:Example:Potential from logging residuesPotential from logging residues41Million drytonslogging residue available (Billion ton annual study)10%% waterofbiomassforpyrolysisunit46Million tonsoflogging residue feed65%% conversion to pyrolysisoil29.6milliontonsofpyrolysisoil6519M gallonsofpyrolysisoil fromlogging residue425271bbl/day~14 30,000 bpd hydroprocessing units~14 30,000 bpd hydroprocessing units–Estimated cost: $405 MMEstimated cost: $405 MM~170 2500 bpd hydroprocessing units~170 2500 bpd hydroprocessing units–Estimated cost: $1105 MMEstimated cost: $1105 MMDistributed Pyrolysis Plants; Centralized RefiningDistributed Pyrolysis Plants; Centralized RefiningIntegrated into traditionalIntegrated into traditionalnatural gas conversionnatural gas conversionprocess or refineryprocess or refinery

Gasif i erPPPPPPBiomassGasificationNatural GasDMEMethanolH2GTL, BTLSynthesis GasReformingKey Decision: What are we planning toKey Decision: What are we planning totransport?transport?Technical BarriersTechnical BarriersSecuring a consistentSecuring a consistentpyOil feedstockOil feedstockLogisticsLogisticsBalance of distributed vs. centralizedBalance of distributed vs. centralizedCatalyst and processCatalyst and processinvention/development/commercializationinvention/development/commercializationSummarySummaryVegetable oils, grease and pyrolysis oil could beVegetable oils, grease and pyrolysis oil could befeasible feedstocks for conventional petroleumfeasible feedstocks for conventional petroleumrefineriesrefineries–Other feedstocks and processing options also lookOther feedstocks and processing options also lookpromisingpromising–Increased volumes of biobased feedstocks requiredIncreased volumes of biobased feedstocks required•Consistent source of pyrolysis oil or otherConsistent source of pyrolysis oil or otherlignocellulosiclignocellulosicbiomassbiomassBiorenewable processing options identified areBiorenewable processing options identified arenot limited to refinery integrationnot limited to refinery integration–Stand alone units possibleStand alone units possible•BiorefiBiorefineries;BiofeedstockBiofeedstocksource•Portable HPortable H2UOP4434A-36AcknowledgementsAcknowledgementsDOE, Project DEDOE, Project DE-FG36-05GO1508505GO15085ContributorsContributorsMTU–DavidShonnardShonnardNREL–StefanCzernikCzernik–Richard BainRichard BainContributorsContributorsPNNL–Doug ElliottDoug Elliott–Don StevensDon StevensUOP–Tom KalnesTom Kalnes–Terry MarkerTerry Marker–Dave MackowiakDave Mackowiak–Mike McCallMike McCall–John PetriJohn PetriProject Manager: Rich MarinangeliProject Manager: Rich Marinangeli