Abatzoglou, Nicolas

Aluha, James

Braidy, Nadi

Dalai, Ajay

Hu, Yongfeng

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBiorefinery I: Chemicals and Materials FromThermo-Chemical Biomass Conversion and RelatedProcessesProceedings2015Synthetic fuels from 3-φ Fischer-Tropsch synthesisusing bio-derived gas feed and novel nanometriccatalystsJames AluhaUniversite' de SherbrookeNadi BraidyUniversita' de SherbrookeYongfeng HuUniversity of SaskatchewanAjay DalaiUniversity of SaskatchewanNicolas AbatzoglouUniversite' de SherbrookeFollow this and additional works at: http://dc.engconfintl.org/biorefinery_IPart of the Chemical Engineering CommonsThis Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion inBiorefinery I: Chemicals and Materials From Thermo-Chemical Biomass Conversion and Related Processes by an authorized administrator of ECIDigital Archives. For more information, please contact franco@bepress.com.Recommended CitationJames Aluha, Nadi Braidy, Yongfeng Hu, Ajay Dalai, and Nicolas Abatzoglou, "Synthetic fuels from 3-φ Fischer-Tropsch synthesisusing bio-derived gas feed and novel nanometric catalysts" in "Biorefinery I: Chemicals and Materials From Thermo-ChemicalBiomass Conversion and Related Processes", Nicolas Abatzoglou, Université de Sherbrooke, Canada Sascha Kersten, University ofTwente, The Netherlands Dietrich Meier, Thünen Institute of Wood Research, Germany Eds, ECI Symposium Series, (2015).http://dc.engconfintl.org/biorefinery_I/2Synthetic fuels from 3-φ Fischer-Tropsch synthesis using bio-derived gas feed and novel nanometric catalystsJames  Aluha, Nadi Braidy, Yongfeng Hu, Ajay Dalai and Nicolas AbatzoglouBiorefinery I: Chemicals and Materials from Thermo-Chemical Biomass Conversion and Related ProcessesChania (Crete), Greece, Sept. 27 – Oct. 2, 20151. Introduction2. Experimental Methodsa) Catalyst synthesisb) Catalyst testing (set up and conditions)3. Results and Discussiona) Catalyst testingb) Catalyst characterisation4. ConclusionHighlightsINTRODUCTIONCurrent industrial fuel production competing with petroleum. Natural gasCoalBiomass GasificationSteam reformingFeedstock Syngas generation Fischer-Tropsch Synthesis (FTS)GasolineDieselWaxesOxygenatesLight gases(CO + H2)FTS polymerises syngas to gasoline (C4 – C12), diesel (C13 – C20) and waxes (C21+).INTRODUCTIONBiomass Atmosphere Crude oilFTSEnd-usersRefining+ Carbon Green process: Advantage of biomass applicationFischer-Tropsch Synthesis (FTS): a targeted technology for biofuel production from renewable resources. INTRODUCTIONIn this project, the target syngas source = BiomassProperties of a choice catalyst include:• High surface area; low porosity• Nanometric = No diffusion limitations• Inert support = carbon• Metallic Co or Fe-carbides speciesPlasma technology to provide the impetus towards process efficiency in catalyst synthesis because it is a single step process.INTRODUCTIONvs.• In previous work, plasma-synthesised Fe/C catalyst performed better than commercially available nano-hematite (Fe-Nanocat®): 24 h activation by CO reduction(a)Temperature = 220oCPressure = 31-bar (~ 450 psi)GHSV = 2, 575 ml.gcat-1.h-1INTRODUCTION(a)J. Blanchard, N. Abatzoglou, R. Eslahpazir-Esfandabadiand F. Gitzhofer, Ind. Eng. Chem. Res., 49 (2010) 6948.EXPERIMENTALCatalyst Synthesis by Plasma:Main reactorAuxiliary reactorSuspension of 60 g metal in mineral oil was introduced into plasma to produce various compositions• Co/C• Fe/C• 30%Co-70%Fe/C• 50%Co-50%Fe/C• 80%Co-20%Fe/C• 70%Co-20%Fe-10%Mo/C• 70%Co-25%Fe-5%Ni/C• Doped with 5%Au:70%Co-25%Fe-5%Ni/C.EXPERIMENTALCatalyst Testing: Fischer-Tropsch conditions  (i) Reducing conditions:o 5.0 g Catalyst o T = 400oCo P = 1-2 bar (abs)o Gas = pure H2o Flow rate = 250 ml.min-1o Time = 24 h(ii) Add solvent: 150 ml (C16)(iii) Reaction: Regimes to avoid:1. High CH4 and H2O selectivity2. Mass transfer limitationsEXPERIMENTALCatalyst Testing: Slurry CSTRReaction conditions:• Temperature = 220-260oC; • Pressure       = 20-bar• Stirring rate   = 2,000 rpm• Gas composition = 60%H2; 30%CO; 10%Ar• H2:CO ~ 2:1 ratio • Flow rate = 300 ml.min-1• GHSV = 3,600 ml.gcat-1.h-1• Test time: = 24 h on stream.(b) M.C. Bahome, L.L. Jewell, D. Hildebrandt, D. Glasser, N.J. Coville, Appl. Catal. A: Gen., 287 (2005) 60.(b)RESULTSSummary I: Unique Catalyst Properties1. Catalysts are non-porous2. There is uniform distribution of metal in the carbon matrix3. No sintering occurs during use in Fischer-Tropsch reactionRESULTSCatalyst Characterisation: BET surface area• Material = non-porous (no hysteresis)• Micro-porosity an effect of nano-particles packingSample  BET surface area  (m2/g) 100%Fe 72 30%Co-70%Fe 89 50%Co-50%Fe 89 80%Co-20%Fe 65 100%Co 56 Relative Pressure (P/Po)0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0Quantity Adsorbed (cm³/g STP)0100200300Co_C_Filter - Desorption√ xPore Diameter (nm)1 5 10 50 100dA/dD Pore Area (m²/g·nm)05101520BJH Adsorption dA/dD Pore Area: FiltersHalsey : Faas Correction30%Co-70%Fe/C50%Co-50%Fe/C80%Co-20%Fe/CFe/CCo/CRESULTSCatalyst Characterisation: BET surface area• Material = non-porous• Micro-porosity an effect of nano-particles packing√ xRESULTSCatalyst Characterisation: SEM imagingSecondary image Backscattered image30%Co-70%Fe/CEDXRESULTSCatalyst Characterisation: SEM• X-ray imaging: Uniform metal distribution750 particles measuredMean ≈ 11 nmNB: no sinteringRESULTSSummary II: Catalyst Performance1. Activity: Highly active for Fischer-Tropsch synthesis; - Co/C better than the commercial one2. Selectivity: Favourable towards gasoline and diesel fractions3. Low-Temperature Operation: Single metals catalysts High-Temperature Operation: Bimetallics are better203040506030%Co-70%Fe/C50%Co-50%Fe/C80%Co-20%Fe/CCO conversion (%)12 16 20 2401020304050Fe/C_plasmaFe_NanoCatCo/C_plasmaCO conversion (%)Time on stream (h)Bimetallic catalysts: No deactivation after 24 hSingle-metal catalysts: Activity problems at 24 hLow activitySinteringWaterAt 260oCAt 220oCRESULTSCatalyst Characterisation: TEM (used Fe-NanoCat)0 10 20 30 40 50 60020406080100120Frequency (no. of particles)Particle size (nm) Fe-NanoCat used; m = 21.11 nm Fe-NanoCat fresh; m = 4.00 nmSinteringRESULTSCatalyst Characterisation: XANESDeactivation in Fe/C: Oxidation in used sample.RESULTSCatalyst Selectivity: Single metals at 220oC0 5 10 15 20 25 30 350510 0 5 10 15 20 25 30 350510 0 5 10 15 20 25 30 35051015No. of carbon atomsFe/C_plasmaCH4CO2Selectivity (%)Co/C_plasmaFe-NanoCatGasolineC4 - C12DieselC13 - C20WaxesC21+GasesC1 – C3C0 = CO2C1 = CH4RESULTSCatalyst Activity: Single metals at 260oC1. Activity: High2. Selectivity: Poor3. Water tolerance: LowRaise TempoC to enrich diesel fraction:25 26 27 28020406080100Fe-NanoCatCo/CplasmaFe/CplasmaReduction: 400oC; 10hReaction: 260oC; 20-bar; GHSV = 3,600 ml.g-1.h-1; Time on stream (h)CO conversion (%)RESULTS• Problem: Excessive CH4 and CO2 formation by single metal catalysts at high temperatures• Solution: Co-Fe/C bimetallics0 4 8 12 16 20 24 28 3201020304050Reduced at 400oC for 24h;Tested at 260oC, 20-bar for 24hCO conversion: 100% Produced: 40 ml of H2OCo/C_plasma filtersC2CH4CO2Selectivity for FTS (%)No. of Carbon atoms0 4 8 12 16 20 24 28 32 360246810Reduced at 400oC for 24h;Tested at 260oC, 20-bar for 24hCO conversion: 55% Produced: 30 ml of H2OFe/C_plasma filtersC2CH4CO2Selectivity for FTS (%)No. of Carbon atomsCatalyst Selectivity: Single metals at 260oCRESULTSSummary III: The Bimetallic Effect1. Activity: Poor reaction (low conversion) at low temperatures2. Particle size: Increases at 50%Co-50%Fe composition due to alloys formation = most of them CoFe crystallites3. Water-gas shift: More Fe (%) means less H2O production; but more CO2RESULTSCatalyst Testing: Activity at 220o and 260oCt=24h0 20 40 60 80 100020406080100220oC260oC30%Co-70%Fe Fe/C50%Co-50%Fe80%Co-20%FeCo/CComposition of Fe in catalyst (%)CO conversion (%)• Single metal catalysts: more active RESULTSCatalyst Selectivity: Overall (at 260oC) CO conversion > 40%I II III0204060WaxesDieselGasoline 80Co-20Fe/C 50Co-50Fe/C 30Co-70Fe/CC21- C36C13- C20C4- C12Cumulative selectivity (%)Carbon fractionsMore Biodiesel: 80%Co-20%Fe/C30%Co-70%Fe/CMore Gasoline: 50%Co-50%Fe/C20 30 40 50 60 70 80 900... .**hcp;    fcc** *Co-metalFe-metalIntensity2O angle100%Fe/C30%Co-70%Fe/C50%Co-50%Fe/C80%Co-20%Fe/C100%Co/CRESULTSCatalyst Characterisation: XRDFe-carbides = good for FTSCoFe alloys= bad for FTSRESULTSXRD by Rietveld Quantitative Analysis (RQA) Cohenite = Fe3C (26%) Source  =   plasmaFe/C catalystRESULTSSummary IV: Promotion with Mo & Au1. Effect of Au: Lowers FTS activity; we expected Au-Ni-Fe to enhance water gas shift reaction(c) 2. Effect of Mo: Surface acidity (+Mo) improves selectivity towards diesel fraction,  low CO conversions (activity)(c) A. Venugopal, J. Aluha, M.S. Scurrell, Catal. Lett., 90 (Issue 1 – 2) (2003) 1.18 19 20 21 22 23 24020406080100CO conversion (%)Time on stream (h)Mo-Fe-Co/CAu-Ni-Fe-Co/CNi-Fe-Co/CRESULTS• Au depresses catalyst activity: less products formed.55 ml H2O30 ml H2O35 ml H2OReaction at 260oC0 5 10 15 20 25 30 350510152025 CH4CO2Selectivity (%)Hydrocarbon chain 5%Ni-25%Fe-70%Co;       90% CO conversion Au-5%Ni-25%Fe-70%Co; 60% CO conversion 10%Mo-20%Fe-70%Co;   30% CO conversionRESULTSSelectivity: Promotion with Mo & Au• Surface acidity (Mo) improves selectivity towards the diesel fraction• Au lowers catalyst activityDiesel GasolineRESULTSCharacterisation: TEM (used catalysts)20 nm 20 nmMo-Fe-Co/C Au-Ni-Fe-Co/CCONCLUSION1. All catalysts have capacity to produce both gasoline and diesel fractions depending on composition and reaction conditions.2. Catalysts have uniform distribution of metal in the carbon matrix.3. Non-porous catalysts are excellent in dealing with mass transfer limitations.4. No sintering occurs during use in Fischer-Tropsch reaction.5. Plasma synthesis produces significant amounts of Fe-carbides (Fe3C, Fe5C2) responsible for FTS catalysis.CONCLUSIONSustainableTechnologyBiomassFischer-TropschTechnologyPlasma Technology+ +This research is funded by BioFuelNet Canada, a network focusing on the development of advanced biofuels and associated bioproducts. BioFuelNet is a member of the Networks of Centres of Excellence of Canada program. Website: www.biofuelnet.caThank you!CCM Staff:(Centre for Characterisation of Materials)Prof. François GitzhoferDr. Kossi BereMr. Henri GauvinCatalysis Group GRATITUDEProf. Yongfeng Hu RESULTSCatalyst Selectivity: Only the 80%Co-20%Fe/C was active at both temperatures0 4 8 12 16 20 24 28 320246810C2CH4CO2Reduced at 400oC for 24h;Tested at 220oC, 20-bar for 24hSelectivity for FTS (%)No. of Carbon atoms220oC; CO conversion = 10% 0 4 8 12 16 20 24 28 320246810C2CH4CO2Reduced at 400oC for 24h;Tested at 260oC, 20-bar for 24hSelectivity for FTS (%)No. of Carbon atoms260oC; CO conversion = 42%0 5 10 15 20 25 30010203040 80%Co-20%Fe/C; mean = 8.9 nmFe/C; mean = 11.3 nm30%Co-70%Fe/C; mean = 9.1 nm50%Co-50%Fe/C;mean = 14.4 nmCo/C; mean = 11.0 nmFrequency (No. of particles)Particle size (nm)RESULTSMetal particle size distribution: Particle growth due to more alloy formationLess alloy formation

Synthetic fuels from 3-φ Fischer-Tropsch synthesis using bio-derived gas feed and novel nanometric catalysts

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Synthetic fuels from 3-φ Fischer-Tropsch synthesis using bio-derived gas feed and novel nanometric catalysts

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