This presentation by Bob Evans at the 2007 DOE Hydrogen Program Annual Merit Review Meeting provides information about NREL's distributed bio-oil reforming efforts

Czernik, S.

Dean, A. M.

Evans, R. J.

French, R.

Marda, J.

Ratcliff, M.

UNT Digital Library

Distributed Bio-Oil Reforming2007 DOE Hydrogen, Fuel Cells & Infrastructure Technologies Program ReviewR. J. Evans1, S. Czernik1, R. French1, M. Ratcliff1, J. Marda2, A. M. Dean21National Renewable Energy Laboratory2Colorado School of MinesMay 15, 2007Project ID# PDP7This presentation does not contain any proprietary or confidential informationNREL/PR-560-41573Presented at the 2007 DOE Hydrogen Program Annual Merit Review and Peer Evaluation on May 15-18, 2007 in Arlington, Virginia.OverviewTimeline• Project start: 2005• Project end: 2012• 20% completedBudget• FY 2005: $100K• FY 2006: $300K• FY 2007: $300KProduction BarriersA. Fuel processor capital C.  Operation & maintenanceD.  Feedstock issues F.  Control & safety2012 Targets• $3.80/gallon gasoline equivalent• 72% energy efficiencyPartners• Colorado School of Mines (FY 2006) - Oxidative cracking• Chevron (FY 2006) – CRADA started in FY 2007  H2 Distributed Production via Biomass PyrolysisBiomass pyrolysis produces a liquid product, bio-oil, which contains a wide spectrum of components that can be efficiently produced, stored, and shipped to a site for renewable hydrogen production. NREL is investigating the low-temperature, partial oxidation, and catalytic autothermal reforming of bio-oil for this application.Pyrolysis:CH1.46O0.67→0.71CH1.98O0.76 + 0.21CH0.1O0.15 + 0.08CH0.44O1.23Biomass Bio-Oil (75%) Char (13%) Gas (12%)Catalytic Steam Reforming of Bio-Oil:CH1.98O0.76 + 1.24 H2O  ⎯→ CO2 + 2.23 H2  Practical Yield:10 wt%, 65% overall energy efficiencyObjectives• 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; demonstrate the process• FY 2007– Demonstrate integration of bio-oil atomization, partial oxidation, and catalytic conversion to obtain equilibrium syngas composition at 650oCDistributed Bio-Oil Reforming ApproachAtomization Oxidative CrackingBio-Oil (+MEOH) O2Catalytic Auto-Thermal H2Enabling Research:   Process Integration: H2OOxidative Cracking Kinetics and MechanismsProcess OptimizationCatalyst ScreeningLow-Temperature Catalytic Oxidation MechanismsEngineering TestingAirIndirect HeatHeat and Mass Balance H2O, CO, CH4,CO2SeparationH2O + CO2~400oC ~650oCQTechnical Accomplishments• FY 2006– Bio-oil volatilization method developed– Oxidative cracking conversion to CO with minimal CO2 • FY 2007 – Introduction of catalysts– Demonstrated equilibrium conversion to syngas at low temperature and low H2O/C– Improved bio-oil atomization– Methanol modeling studies– Parametric studies begun      Dual Syringe PumpBio-Oil Water Power Supply Gas MFM   MBMSUltrasonic Nozzle Furnace Catalyst Bed Temperature Read-Out Gas MFM Ultrasonic Nozzle• Generates a fine mist at 0.3g/min• Enables steady liquid feed at low ratesUltrasonic NebulizerOxidative Cracking 0.3 s @ 650 oCMeOH-Bio-Oil (50:50 mixture)0.0E+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%Thermal Cracking at 650 oC (0.3 s;O:C 0.81)Oxidative Cracking at 650 oC (0.3 s;O:C 1.6)4418312878 94 128051015202530350 20 40 60 80 100 120 140 160 180 200m/z% of total signalH2OMeOH1787894 12800.511.5260 80 100 120 140 160 180 200OHCO2CO4313694601811001234567890 20 40 60 80 100 120 140 160 180 200m/z% of total signal1361109400.10.20.30.40.50.60.70.80.9160 80 100 120 140 160 180 200H2O MeOHOHCHOCH3OHOHOHCH3 COHHCOCH2HO31 = 15.3%32 = 10.4%Under thermal cracking conditions, unconverted methanol and secondary products from the bio-oilpredominate. Under oxidative cracking conditions, H2 (not shown), water, CO, and CO2 predominate.  Hence the role of the catalyst to be added is to finish the conversion and catalyze the water-gas shift. Gas-phasepartial oxidationleads to high CO yields with low CO2.01020304050600.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7O:C (Molar Ratio)Yield (wt. %) jCOCO2BenzeneResidual CarbonO:C of 0.81 isBio oil/Methanol with no O2 added01020304050607080500 525 550 575 600 625 650Temperature (oC)Yield (wt. %) j COCO2BenzeneResidual Carbon650C0.3 sO:C = 1.60.3 s Byproduct yields surprisingly insensitive to O:C or temperature variations.Model Development• Use model compounds to understand the complex system that undergoes low-temperature partial oxidation– Begin with methanol and other small oxygenates• Next steps– Improved model for molecular weight growth• Recombination of resonantly stabilized radicals– Extend gas-phase models to account for partial oxidation of higher hydrocarbons– Improve catalytic mechanisms– Catalytic models to higher hydrocarbons– Apply to biomass kinetics for hydrogen production Modeling Methanol Pyrolysis and Partial OxidationModel Development• CSM model–Rule based model originally developed to predict hydrocarbon pyrolysis and oxidation•Extended to methanol–Three types of reaction used to describe system•Dissociation, hydrogen abstraction, and -scission–360 species and nearly 3550 reactions• Princeton model*–Based on methanol pyrolysis and oxidation experiments–22 species and 97 reactions*Held and Dryer, Int. J. Chem. Kin., 32, 805-830 (1998) 0.000.010.020.030.040.050.060.070.080.090.101.00 1.25 1.50 1.75 2.00 2.25 2.50O:C (Molar Ratio)Methanol (Mole Fraction)Day 1Day 2Day 3Day 4Day 5CSM ModelPrinceton Model0.000.010.020.030.040.050.060.070.081.00 1.25 1.50 1.75 2.00 2.25 2.50O:C (Molar Ratio)CO (Mole Fraction)0.000.010.020.030.040.050.060.070.080.091.00 1.25 1.50 1.75 2.00 2.25 2.50O:C (Molar Ratio)H2 (Mole Fraction)Issue:  Need to account for potential temperature change.Catalytic ConversionOxidative Cracking .3 s @ 650oC + .25% Rh on Al2O3Bio-Oil:Methanol (50:50)0501001502002503003504004500 20 40 60 80 100 120MillionsTime, minProduct Ion Intensity, Arbitraty UnitsH2H2OCOCO2Methanol Conversion020406080100120Equil. Gas Alumina Rh Pd Pt Ru% MeOH (in Bio-Oil Feed) ConvertedO/C=1.3O/C=1.7Hydrogen Yield0102030405060708090Equil. Gas Alumina Rh Pd Pt RuWt.% Hydrogen in Feed Converted to H2O/C=1.3O/C=1.7CO2 Yield051015202530354045Equil. Gas Alumina Rh Pd Pt RuWt% C in CO2O/C=1.3O/C=1.7CO Yield01020304050607080Equil. Gas Alumina Rh Pd Pt RuWt% C in COO/C=1.3O/C=1.7% C in Feed Converted to Carbon Deposits3.61.04.40.00.91.40.01.02.03.04.05.0Equil. Gas RhO/C=1.3O/C=1.7% C in Feed Converted to Methane 02468Equil. Gas RhO/C=1.3O/C=1.7% C in Feed Converted to Benzene 0.01.3 1.40.02.70.50.01.02.03.0Equil. Gas RhO/C=1.3O/C=1.7By-products are typically above equilibrium levels and thought to be generated from non-volatile species in aerosols and processes in the gas phase. Process ComparisonFluid Bed StagedBio-Oil Organics % 80 78MeOH % 0 10water,wt% 20 18C 45 44.2H 7.9 8.4O 47.1 47.4H/C 2.1 2.3O/C 0.8 0.8H2 production rate, kg/day 1500 1500H2 Yield, wt% 11.9 11.9Conversion efficiency,% 70 70Bio-Oil Feed Rate, kg/hr 525 525Feed C feed rate, kg/hr 236 232O2 feed rate, kg/hr 0 246Ratios with O2H/C(H2Ofree) 1.5 1.7O/C(H2Ofree) 0.5 1.3Starting H2O/C 0.30 0.27H2O/C after Oxcrack 0.30 0.75Water addition, Kg/hr 1668 407Catalyst load, kg 1734 430Temperature, C 800 600Reactor diameter, M 1.03 0.31Reactor height,  M 6 5Catalyst reactor volume, L 5029 372Cracking reactor volume, L 0 130Vaporizer, L 0 130Total reactor volume, L 5029 632Program TimelineProject TimelineID Task Name1 Bio-Oil Volatilization2 Processing Options3 Modification and Characterization4 Injector Development5 Coking Studies6 Go / No Go on Bio-Oil performance7 Oxidative Cracking8 Proof of Concept9 Reduce Catalyst Loading by 50%10 Partial Oxidation Database11 Modeling and Optimization12 Jon Marda Thesis13 Catalytic Auto-Thermal Reforming14 Catalyst Screening15 Catalyst Process optimization16 Demonstrate catalyst performance consistent with $3.80/gge h17 Catalyst Mechanistic Studies18 Integrated Separation19 Concept Evaluation20 Materials Evaluation21 Integrated Laboratory System Experiment22 Go / No Go on Conceptual Design23 Systems Engineering 24 Oxygen, Steam and Heat Integration25 Engineering Design and Construction26 Prototype System Developed27 Heat and Mass Balances28 Process Upsets29 Long Duration Runs30 Demonstrate Distributed Hydrogen Production fromBio-Oil for $3.8/gge31 Safety Analysis32 Review  and Analysis of Pressure, O2, H233 Systems Integration5/316/3012/315/308/315/319/2005 2006 2007 2008 2009 2010 2011 2012Future Work• FY 2007– Continued catalyst testing and collaborative development with emphasis on deactivation and poisoning – Modeling and process optimization (continues in 2008)• FY 2008– Reaction engineering– Bench-scale tests for long-term catalyst testing• FY 2009– Integrated laboratory experiment • FY 2010– “Go/no-go” on conceptual design• FY 2011– Prototype system • FY 2012– Long duration runsSummaryRelevance Near-Term Renewable Feedstock for Distributed ReformingApproach •Bio-Oil Processed at Low Temp• Homogeneous and Catalytic Auto-Thermal Reforming Accomplishments System for Bio-Oil Volatilization, Oxidative Cracking, and CatalysisCollaborations •Colorado School of Mines•ChevronFuture Work •Oxidative Cracking Mechanism and Catalysis in FY 2007•System Development in FY 2008

Distributed Bio-Oil Reforming

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Distributed Bio-Oil Reforming

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