Arias, P.L.

Barrio, V.L.

Cambra, J.F.

Echandia, S.

Fierro, J.L.G.

Guernez, M.B.

Pawelec, B.

Requies, J.

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBioEnergy IV: Innovations in Biomass Conversionfor Heat, Power, Fuels and Chemicals ProceedingsSpring 6-11-2013Hydrodeoxygenation of biofuel-precursors on Ni-promoted catalystsJ.F. CambraFaculty of Engineering (UPV/EHU), SpainS. EchandiaFaculty of Engineering (UPV/EHU), SpainV.L. BarrioFaculty of Engineering (UPV/EHU), SpainP.L. AriasFaculty of Engineering (UPV/EHU), SpainJ. RequiesFaculty of Engineering (UPV/EHU), SpainSee next page for additional authorsFollow this and additional works at: http://dc.engconfintl.org/bioenergy_ivPart 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 inBioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives. Formore information, please contact franco@bepress.com.Recommended CitationJ.F. Cambra, S. Echandia, V.L. Barrio, P.L. Arias, J. Requies, M.B. Guernez, B. Pawelec, and J.L.G. Fierro, "Hydrodeoxygenation ofbiofuel-precursors on Ni-promoted catalysts" in "BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels andChemicals", Manuel Garcia-Perez,Washington State University, USA Dietrich Meier, Thünen Institute of Wood Research, GermanyRaffaella Ocone, Heriot-Watt University, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, The Netherlands Eds,ECI Symposium Series, (2013). http://dc.engconfintl.org/bioenergy_iv/27AuthorsJ.F. Cambra, S. Echandia, V.L. Barrio, P.L. Arias, J. Requies, M.B. Guernez, B. Pawelec, and J.L.G. FierroThis conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/bioenergy_iv/27Hydrodeoxygenation of Biofuel-precursors on Ni-promoted catalystsS. Echeandía,  V.L. Barrio1, P.L.Arias1, J. Requies1, M.B. Güemez1, B. Pawelec2, J.L.G. Fierro2, J.F. Cambra1(1) Faculty of Engineering (UPV/EHU), Spain(2) Institute of Catalysis and Petrochemistry (CSIC), Spaine-mail: laura.barrio@ehu.esBioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels, and ChemicalsJune 9-14, 2013Otranto (Italy)Overview:1. Introduction1.1. New alternatives1.2. HDO1.3. Previous results2. Scope3. Experimental3.1. Catalyst preparation3.2. Activity tests4. Results & Discussion4.1. Phenol HDO4.2. HDO of model compounds mixture4.3 Used catalysts characterization5. ConclusionsSustainable development : Environmentally friendly clean fuelsBiomass:  Renewable Almost CO2 neutral Interesting economic potential1.1. Introduction. New alternativesBiofuels: Fuels obtained from biomasspyrolisis route η= 60-70%Problem:T ype of raw material  ProcessHigh content of oxygenated compounds: InmiscibilityHigh viscosityCorrosionThermal inestability1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions1.2. Introduction. HDOPhenolBenzeneCyclohexanolCyclohexeneCyclohexaneMethyl-cyclopentaneHydrogenolysis Reaction route (1)Hydrogenation+ Hydrogenolysis Reaction route (2)Most frecuently studied catalysts: NiMo/Al2O3 and CoMo/Al2O3Active carbon+ W+ NiModel compound mixtures1. Introduction2. Scope3. Experimental4. Results & Discussion5. ConclusionsThe objectives of this work are:► To detect any synergistic effect between Ni and W oxide speciessupported on activated carbon (AC) when used ashydrodeoxygenation (HDO) catalysts.► To study the effect of different W precursors -silicotungstic (HSiW)and phosphotungstic (HPW) acids- on the activity of Ni-W/ACcatalysts.► To study the HDO of phenol and of model compound mixturesrepresentative of bio-oil: ethanol, acetone, tetrahydrofuran, phenoland guaiacol .2. Scope Wet impregnation3.1. Catalysts preparationSUPPORT Active Carbon H3[P(W3O10)4]·xH2O H4[Si(W3O10)4]·xH2ONi(NO3)2·6H2O Wet impregnation W(P) W(Si)Ni-W(P) Ni-W(Si)Dried   8h.   in   air   at   383 K   &   Decomposed   2h.   in   He   at   673 KDried   8h.   in   air   at   383 K   &   Decomposed   2h.   in   He   at   673 K1. Introduction2. Scope3. Experimental4. Results & Discussion5. ConclusionsH2WO4WNi-W1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions3.2. Activity testsProduct Analysis:• GC-FID• GC-MSDCatalyst mass: 0.2 gCatalysts pre-treatment : in situ in a 1:3 H2:N2 mixture with a H2 flow of 2,5 L·h-1 (NTP) at 593 K 0,1 MPa of total pressureExperimental conditions : - Temperature in the range 423 – 523 K and total pressure 1,5 MPa- Feed:   * Phenol  1 wt.% * Model feed consisting of: ethanol, acetone, tetrahydrofuran, phenoland guaiacol (1 wt.% each) in n-dodecane as solvent - H2:oxygenate compound molar ratio of 100:11. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions3.3. Catalysts characterization Fresh samples:o ICP-AESo BETo TPRo TPD-NH3 Used samples:o XRDo XPSo HRTEMo TGA/DGTInfluence of temperature on thephenol conversion andselectivities in the HDO of phenol(WHSV = 0,5 h-1) over:(b) Ni-W(Si) catalyst(c) Ni-W(P) catalyst440 480 520 560020406080100440 480 520 560020406080100  Conversion and Selectivities (%)Temperature (K) Phenol conversion Cylohexane Cylohexanol OthersNi-W(Si)(b)  Conversion and Selectivities (%)Temperature (K) Phenol conversion Cylohexane Cylohexanol OthersNi-W(P)(c)Ni-W(P)Ni-W(Si) Ni-W W(P) W(Si) W Ni C020406080100  Phenol conversion at 423 K (%)Catalyst(a)4.1. Phenol HDO440 480 520 560020406080100440 480 520 560020406080100  Temperature (K) Phenol conversion Cylohexane Cylohexanol OthersNi-W(Si)(b)  Conversion and Selectivities (%)Temperature (K) Phenol conversion Cylohexane Cylohexanol OthersNi-W(P)(c)(a) Comparison of the steady-statephenol conversions of differentc talysts in HDO of phenol at T = 423K, P = 1,5 MPa and WHSV = 0,5 h-1.Ni-W(P) ≈ Ni-W(Si) >> Ni-W >> Ni >W(Si) > W(P) >> W > AC support1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions523 KA0,00,20,40,60,81,0Ethanol Acetone THF Phenol GuaiacolFeed componentsConversionNiW(P) 423 K NiW(P) 473 K NiW(P) 523 K NiW(Si) 423 K NiW(Si) 473 K NiW(Si) 523 K4.2. HDO of model compounds mixtureComparison of the conversion of AC-supported catalysts in HDO at different temperatures(T = 423-523 K, P = 1,5 MPa)  1. Introduction2. Scope3. Experimental4. Results & Discussion5. ConclusionsComparison of the product distribution  of AC-supported catalysts in HDO at different temperatures(T = 423-523 K, P = 1.5 MPa)  10containingOfreeO*Relative abundance18 124.2. HDO of model compounds mixture1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions0102030405060708090100NiW(P) NiW(Si)Yield of products (%)O-containingO-free1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions4.3. Used catalysts characterizationCatalyst W Ni 2p Si 2p, P 2p Ni/AC at W/AC at (Ni+W)/AC atNi -853.0 (47)856.5 (53)- 0.0038 - -W 35.6 - - - 0.0047 -W(Si) 35.7 - 103.1 - 0.0052 -W(P) 35.7 - 134.2 - 0.0048 -Ni-W 35.6853.0 (30)856.7 (70)- 0.0092 0.0065 0.0157Ni-W(Si) 35.7852.9 (20)856.7 (80)103.2 0.0183 0.0146 0.0329Ni-W(P) 35.6852.9 (28)856.7 (72)134.1 0.0127 0.0082 0.0209Binding energy (eV) of  core electrons and surface atomic ratios of  spent catalysts tested in HDO as determined by XPS.1. Introduction2. Scope3. Experimental4. Results & Discussion5. ConclusionsVariation of  surface atomic ratio (XPS) of  spent binary catalysts, (Ni +W)/C,against total (ICP) atomic ratio of  the oxide precursors, (Ni +W)/C.4.3. Used catalysts characterization1. Introduction2. Scope3. Experimental4. Results & Discussion5. ConclusionsHRTEM4.3. Used catalysts characterization1. Introduction2. Scope3. Experimental4. Results & Discussion5. Conclusions5. ConclusionsHydrodeoxygenation was carried out on oxide Ni-W catalysts supported on activated carbon. The main conclusions derived from this work are the following:The use of non-conventional W precursors (heteropolyacids) allowed the preparation of more active bimetallic hydrotreating catalysts.Ni-W/AC catalysts are not only good HDS catalysts but also promising candidates for HDO processes. The promoting effect of Ni on W/AC catalysts was measured in the HDO of phenol and of model compounds mixtures. Analyses of the products indicate that HDO reaction on these catalysts occurs via two separate pathways: one leading to aromatics and the other to cyclohexane, in good agreement with literature. Using phosphotungstic (HPW) heteropolyacid -as W precursor- more active and stable catalysts are obtained as compared to the silicotungstic (HSiW) heteropolyacid. Thank you very much for your attention !!Norit 1310 m2/g

Hydrodeoxygenation of biofuel-precursors on Ni-promoted catalysts

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Hydrodeoxygenation of biofuel-precursors on Ni-promoted catalysts

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