Czernik, S.

Evans, R. J.

French, R.

Marda, J.

UNT Digital Library

Distributed Bio-Oil Reforming2006 DOE Hydrogen, Fuel Cells & Infrastructure Technologies Program ReviewR. J. Evans, S. Czernik, R. French, J. Marda National Renewable Energy LaboratoryMay 16, 2006Project ID#PD5This presentation does not contain any proprietary or confidential informationNREL/PR-560-49948Disclaimer and Government LicenseThis work has been authored by Midwest Research Institute (MRI) under Contract No. DE-AC36-99GO10337 with the U.S. Department of Energy (the “DOE”).  The United States Government (the “Government”) retains and the publisher, by accepting the work for publication, acknowledges that the Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for Government purposes.Neither MRI, the DOE, the Government, nor any other agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe any privately owned rights.  Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not constitute or imply its endorsement, recommendation, or favoring by the Government or any agency thereof.  The views and opinions of the authors and/or presenters expressed herein do not necessarily state or reflect those of MRI, the DOE, the Government, or any agency thereof. OverviewTimeline• Project start 2005• Project end 2010• 15% completedBudget• FY05 $100K• FY06 $300KProduction BarriersA. Fuel Processor Capital B. Fuel Processor ManufacturingC. Operation & MaintenanceD. Feedstock Issues F.  Control & SafetyTarget   $3.60/ggePartners• Colorado School of Mines (FY06) - Oxidative cracking• Chevron  (FY06) - Feedstock Project planned for FY06  ApproachPYROLYSIS Bio-oilREFORMINGH2Biomass Methanol Show that bio-oil and blends with methanol can be fed without excessive cokingand develop a process to meet HFC&IT cost and performance objectives.VOLATILIZATIONO2 Low TemperatureOxidative CrackingSHIFTCO2SEPARATIONH2 O Objectives• Overall: – Develop the necessary understanding of the process chemistry, compositional effects, catalyst chemistry, deactivation, and regeneration strategy as a basis for process definition for automated distributed reforming• FY06– Demonstrate partial oxidation and show that it can reduce the required catalyst loading in the reforming step by 50%Distributed Bio-Oil Reforming ApproachVolatilization Oxidative CrackingBio-Oil (+MEOH) O2Catalytic Auto-Thermal H2Enabling Research:   Process Integration: H2 OOxidative Cracking Kinetics and MechanismsProcess OptimizationCatalyst ScreeningLow Temperature Catalytic Oxidation MechanismsEngineering TestingAirIndirect HeatHeat and Mass Balance H2O, CO, CH4,CO2SeparationH2O + CO2~400oC ~650oCQTechnical Accomplishments• FY05: Whole oil successfully run– With 10% MeOH addition, bio-oil processing was trouble free over short run durations (up to 16 hrs)• FY06: Accomplishments to date– Bio-oil volatilization method developed– Oxidative cracking promising results – Progress toward July milestone on targetPrimary Secondary TertiaryBiomass H2 OCOCO2Char“Carbon”Thermal SeverityBio-Oil H2OH2CH4COCO2PAHH2 , CO, CO2 , H2 O, C2 H4 ,+Furans, Phenols, BTX, Ketenes, Olefins…HCOCH2HOOHOHO0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0C0.00.10.20.30.40.50.60.70.80.91.0H0.00.10.20.30.40.50.60.70.80.91.0650 oC550 oCP = 1 atm   CarbonDepositionNo CarbonDeposition12 34 5 6 7891011121314151617181920212223Equilibrium Modeling Results1 = Bio-Oil composition, which liesin the region where carbon will form at 650 C 2-8 = O2 addition points9-13 = H2 O addition14-23 = both O2 and H2 OGoal is to identify the thermodynamic and kinetic domains for deposit free operationSpray Injector Reactor SystemSpray Injector ResultsSpray injection resulted in low carbon conversionto CO and formation of aromatics and carbonRun Liq. Feed g/minAir coeff. % Temp, C Time, s N2 O2 H2 CO CO2 CH4 C Bal, %1 0.5 163 600 2.4 79 15.96 0.00 1.19 4.19 0.00 76%2 0.5 162 599 1.1 78 17.18 0.00 0.59 4.16 0.00 68%3 1.0 99 602 1.4 79 11.61 0.00 2.78 6.26 0.00 69%4 1.0 65 601 1.5 79 5.27 0.00 4.06 11.64 0.00 65%5 1.0 66 636 1.4 80 2.28 0.00 5.96 11.74 0.08 74%6 1.0 59 650 1.4 78 0.95 0.82 6.92 13.36 0.23 71%7 1.0 53 649 1.4 75 0.48 1.45 11.05 11.27 0.40 65%8 1.0 47 650 1.4 72 0.24 3.24 14.75 9.33 0.72 56%9 1.0 34 647 1.4 29 0.19 22.11 32.11 15.38 1.63 32%10 0.9 54 698 1.3 73 0.13 2.56 12.52 10.94 0.63 70%11 1.0 52 748 2.9 68 0.00 6.55 13.20 11.21 1.26 76%12 1.0 54 750 2.7 75 0.03 3.92 9.05 11.23 0.74 72%Gas Composition, vol. %Schematic of   Pyrolysis Reactor & NREL’s MBMS Sampling SystemMolecularDragPumpCollisionsQ1 Q2 Q3ArgonCollisionGasTurbomolecularPumpTurbomolecularPumpTurbomolecularPumpProductsandTransients Three Stage Free-JetMolecular Beam SourceTriple QuadrupoleMass Analyzer{P+} {D+}Detectore-EISourceHeHeTpyT1 T3 T4 T5HeT2Bio-Oil Film Volatilization – 400 oC00.511.522.533.544.550 0.25 0.5 0.75 1Time, Min.Diferential Signal, % of total0255075100Integrated Signal,% of total46 mg51 mg54 mgAverage Residue  = 6%Bio-Oil Film Volatilization MBMS Bio-Oil SpectrumToil = 300 oC Tvc = 300 oC  no O2312721641376043180123450 25 50 75 100 125 150 175 200 225 250 275 300m/z% of Total Ion SignalHCOCH2HOCH3OHOMeOOHOBio-Oil Film Volatilization Cracking 0.5 s @ 650 CToil = 400 oC Tvc = 650 oC  no O21241361102831604318012345670 25 50 75 100 125 150 175 200 225 250 275 300m/z% of Total Ion SignalOHOHOHCHOCH3Bio-Oil Film Volatilization Oxidative Cracking 0.5 s @ 650 C44110601805101520250 25 50 75 100 125 150 175 200 225 250 275 300m/z% of Total Ion SignalToil = 400 oC Tvc = 650 oC  with O22562402262121981621441221100.000.100.200.300.400.500.60100 125 150 175 200 225 250 275 300H2 OCOCO2Ultrasonic Nozzle• Generating a fine mist at 0.3g/min• Enables steady liquid feed at low rates      Dual Syringe PumpBio-OilWaterPower SupplyGas MFM  MBMSUltrasonic NozzleFurnace Catalyst Bed Temperature Read-Out Gas MFM Ultrasonic Nebulizer Oxidative Cracking 0.5 s @ 650 C0.0E+005.0E+071.0E+081.5E+082.0E+082.5E+083.0E+083.5E+080 2 4 6 8 10 12 14Time, minAbundance183244280.0E+001.0E+082.0E+083.0E+084.0E+0810 10.5 11 11.5 120.0E+001.0E+072.0E+073.0E+074.0E+072844187832% Residual Carbon:   7.7%Ultrasonic Nebulizer Thermal Cracking 0.5 s @ 650 C150136771109460431801234560 20 40 60 80 100 120 140 160 180 200m/z% of Total Signal31 = 13.4%32 = 8.8%OHCHOCH3OHOHOHCH3 COHHCOCH2HOUltrasonic Nebulizer Oxidative Cracking 0.5 s @ 650 C311828447894 128 17805101520253035400 20 40 60 80 100 120 140 160 180 200m/z% of Total SignalOHCO2COH2O7894 12817800.511.522.533.5475 125 175MeOHCarbon Conversion Oxidative Cracking 0.5 s @ 650 CEquil. COEquil. CO20204060800.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3O/C Mole RatioCarbon Conversion, %CO-Bio-Oil/MeOHCO-MeOHCO2-Bio-Oil/MeOHCO2-MeOHCO-Bio-Oil/MeOH/H2OCO2-Bio-Oil/MeOH/H2OCO-Bio-Oil/MeOH/(H2O)**H2O not included in O/CProject TimelineTask 2: Distributed Reforming of Renewable Liquid FeedstocksDistributed ReformingFY 2003 FY 2004 FY 2007FY 2005 FY 2006 FY 2008 FY 2009 FY 2010 FY 2011 FY 2012P2 P5F2 C125P6Sf3 C5 A1 A2 Sf5V9C3P3 4Milestones4 Verify feasibility of achieving $3.60/gge for renewable liquids distributed reforming.5 Down-select research for distributed production from bio-derived renewable liquids.Outputs P2 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.P3 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P5 Output to Systems Analysis and Systems Integration: Impact of hydrogen purity on cost and performance.P6 Output to Delivery, Storage and Fuel Cells: Assessment of fuel contaminant composition.InputsC3 Input from Codes and Standards:  Preliminary Assessment of Safety, Codes and Standards requirements for the hydrogen delivery infrastructure.Sf3 Input from Safety:  Safety requirements and protocols for refueling.C5 Input from Codes and Standards:  Completed hydrogen fuel quality standard as ISO Technical Specification.A1 Input from Systems Analysis: Complete technoeconomic analysis on production and delivery technologies currently being researched to meet overall Program hydrogen fuel objective.F2 Input from Fuel Cells:  Research results of advanced reformer development.V9 Input from Technology Validation:  Final report on safety and O&M of three refueling stations.A2 Input from Systems Analysis: Initial recommended hydrogen quality at each point in the system.C12 Input from Codes and Standards:  Final hydrogen fuel quality standard as ISO Standard.Sf5 Input from Safety: Safety requirements and protocols for refueling.Project TimelineTask NameBio-Oil VolatilizationProcessing OptionsModification and CharacterizationInjector DevelopmentCoking StudiesGo / No Go on Bio-Oil performanceOxidative CrackingProof of ConceptReduce Catalyst Loading by 50%Partial Oxidation DatabaseModeling and OptimizationJon Marda ThesisCatalytic Auto-Thermal ReformingCatalyst DevelopmentIntegrated SeparationConcept EvaluationMembrane SupportIntegrated Laboratory System ExperimentGo / No Go on Conceptual DesignSystems Engineering Oxygen, Steam and Heat IntegrationEngineering Design and ConstructionPrototype System DevelopedHeat and Mass BalancesProcess UpsetsLong Duration RunsDemonstrate Distributed Hydrogen Production fromBio-Oil for $3.6/ggeSafety AnalysisReview  and Analysis of Pressure, O2, H2Systems Integration5/316/305/306/16/3012/32005 2006 2007 2008 2009 2010 2011Future Work• FY06– July milestone:  Oxidative cracking proof of concept• FY07– Catalyst testing and collaborative development for this new approach with emphasis on deactivation and poisoning – “Go/no go” on bio-oil performance– Kinetic modeling and process optimization– Reaction engineering• FY08– Bench scale bio-oil reforming tests for long-term testing– Prototype design– “Go/no go” on conceptual design• FY09– Scale up system development• FY10– Long duration runsSummaryRelevance Near Term Renewable Feedstock for Distributed ReformingApproach Bio-Oil Processed at Low Temp Homogeneous and Catalytic Auto- Thermal Reforming Accomplishments Progress in Volatilization and Oxidative CrackingCollaborations •Colorado School of Mines•ChevronFuture Work •Low Temperature Oxidative         Cracking Proof of Concept in FY06•Catalysis in FY07Response to Reviewers Comments• Project would benefit from commercial and university collaborations  – Work to date has been proof of concept  – Collaboration began in FY06 with School of Mines on modeling and Chevron on feedstock effects– Discussions with UMN on catalysis and GE on prototype development in progress• More detailed collaborative research plan needed– Elements are in the plan, pending budget• Bio-feed variation effects• Oxidative cracking kinetics• Catalytic oxidation mechanisms • Factor interactions• Catalyst developmentPublications and PresentationsCzernik, S. and French, R., Production of Hydrogen from Plastics by Pyrolysis and Catalytic Steam Reforming, Energy & Fuels, 2006, 20, 754-758Czernik, S., Evans, R., and French, R., Hydrogen from Biomass; Distributed Production by Steam Reforming of Biomass Pyrolysis Oil,  1st International Symposium on Hydrogen from Renewable Resources, 231 ACS National Meeting, Atlanta, GA, March 26-30, 2006Critical Assumptions and Issues• Bio-Oil Volatilization• Oxidative Homogeneous Cracking  Performance & Benefits• Catalyst Design and Performance• Carbon Deposit Removal and Catalyst Regeneration Management• Process Energy• Hydrogen Separation

Distributed Bio-Oil Reforming

https://digital.library.unt.edu/ark:/67531/metadc891058/m2/1/high_res_d/908181.pdf

Distributed Bio-Oil Reforming

Abstract

Similar works

Full text

Available Versions

UNT Digital Library