Ni-based sol–gel catalysts as promising systems for crude bio-oil upgrading: Guaiacol hydrodeoxygenation study

Abstract Catalytic hydrotreatment or hydrodeoxygenation (HDO) has been researched extensively with the crude bio-oil and its model compounds over conventional sulfided Ni(Mo), Co(Mo) catalysts and supported noble metal catalysts. These types of catalysts showed themselves unsuitable for the target HDO process, which resulted in an urgent need to search for a new catalytic system meeting such requirements as low cost, stability against coke formation and leaching of active components due to adverse effect of the acidic medium (bio-oil). In the present work a series of Ni-based catalysts with different stabilizing components has been tested in the hydrodeoxygenation (HDO) of guaiacol (2-methoxyphenol), bio-oil model compound. The process has been carried out in an autoclave at 320 °C and 17 MPa H 2 . The main products were cyclohexane, 1-methylcyclohexane-1,2-diol, and cyclohexanone. The reaction scheme of guaiacol conversion explaining the formation of main products has been suggested. The catalyst activity was found to rise with an increase in the active component loading and depend on the catalyst preparation method. The most active catalysts in HDO of guaiacol were Ni-based catalysts prepared by a sol–gel method and stabilized with SiO 2 and ZrO 2 . According to TPR, XRD, XPS, and HRTEM, the high activity of these catalysts correlates with the high nickel loading and the high specific area of active component provided by the formation of nickel oxide–silicate species. The effect of temperature on the product distribution and catalyst activity in the target process (HDO) has been investigated as well. The catalysts were shown to be very promising systems for the production of hydrocarbon fuels by the catalytic upgrading of bio-oil.

[1]  Heterogeneous catalysts for the transformation of fatty acid triglycerides and their derivatives to fuel hydrocarbons , 2011 .

[2]  V. Parmon,et al.  Guaiacol hydrodeoxygenation in the presence of Ni-containing catalysts , 2011 .

[3]  I. Melián-Cabrera,et al.  Catalyst studies on the hydrotreatment of fast pyrolysis oil , 2010 .

[4]  F. P. Petrocelli,et al.  MODELING LIGNIN LIQUEFACTION 1. CATALYTIC HYDROPROCESSING OF LIGNIN-RELATED METHOXYPHENOLS AND INTERAROMATIC UNIT LINKAGES , 1987 .

[5]  M. A. Ermakova,et al.  High-loaded nickel–silica catalysts for hydrogenation, prepared by sol–gel: Route: structure and catalytic behavior , 2003 .

[6]  Yu Lin,et al.  Catalytic Hydrodeoxygenation of Guaiacol on Rh-Based and Sulfided CoMo and NiMo Catalysts , 2011 .

[7]  H. Knözinger,et al.  Characterization of mixed copper-manganese oxides supported on titania catalysts for selective oxidation of ammonia , 1993 .

[8]  Anja Oasmaa,et al.  Solvent fractionation method with Brix for rapid characterization of wood fast pyrolysis liquids , 2008 .

[9]  A. Frennet,et al.  Hydrogen Spillover from Ni to CuNi Alloys , 1983 .

[10]  V. Nefedov,et al.  Esca investigations of some NiO/SiO2 and NiO—Al2 O3 /SiO2 catalysts , 1979 .

[11]  T. Choudhary,et al.  Renewable fuels via catalytic hydrodeoxygenation , 2011 .

[12]  Anja Oasmaa,et al.  Stabilization of biomass‐derived pyrolysis oils , 2010 .

[13]  Albert Frederick Carley,et al.  The formation and characterisation of Ni3+ — an X-ray photoelectron spectroscopic investigation of potassium-doped Ni(110)–O , 1999 .

[14]  He'an Luo,et al.  Amorphous Co–Mo–B catalyst with high activity for the hydrodeoxygenation of bio-oil , 2011 .

[15]  A. Proctor,et al.  Curve Fitting Analysis of ESCA Ni 2p Spectra of Nickel-Oxygen Compounds and Ni/Al2O3 Catalysts , 1984 .

[16]  D. Stirling,et al.  The location of nickel oxide and nickel in silica-supported catalysts: Two forms of “NiO” and the assignment of temperature-programmed reduction profiles , 1988 .

[17]  S. Ted Oyama,et al.  Transition metal phosphide hydroprocessing catalysts: A review , 2009 .

[18]  Bernard Delmon,et al.  Influence of the Support of CoMo Sulfide Catalysts and of the Addition of Potassium and Platinum on the Catalytic Performances for the Hydrodeoxygenation of Carbonyl, Carboxyl, and Guaiacol-Type Molecules , 1995 .

[19]  N. Bakhshi,et al.  Catalytic upgrading of pyrolysis oil , 1993 .

[20]  S. Oyama,et al.  Hydrodeoxygenation of guaiacol as model compound for pyrolysis oil on transition metal phosphide hydroprocessing catalysts , 2011 .

[21]  A. Krause,et al.  Hydrotreatment of wood-based pyrolysis oil using zirconia-supported mono- and bimetallic (Pt, Pd, Rh) catalysts , 2011 .

[22]  Peter Arendt Jensen,et al.  A review of catalytic upgrading of bio-oil to engine fuels , 2011 .

[23]  M. G. Cook,et al.  X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper , 1975 .

[24]  C. Xu,et al.  Hydrodeoxygenation of bio-crude in supercritical hexane with sulfided CoMo and CoMoP catalysts supported on MgO: A model compound study using phenol , 2009 .

[25]  D. Hercules,et al.  Surface spectroscopic characterization of Cu/Al2O3 catalysts , 1985 .

[26]  A. Andersson,et al.  Ammoxidation of Toluene by YBa2Cu3O6 + x and Copper Oxides. Activity and XPS Studies , 1990 .

[27]  J. Fierro,et al.  Hydrodeoxygenation of 2-methoxyphenol over Mo2N catalysts supported on activated carbons , 2011 .

[28]  N. Bakhshi,et al.  Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part II: Comparative catalyst performance and reaction pathways , 1995 .

[29]  Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/γ-Al2O3 catalysts , 2010 .

[30]  Qiang Li,et al.  Qualitative and quantitative analysis of pyrolysis oil by gas chromatography with flame ionization detection and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry. , 2011, Journal of chromatography. A.

[31]  G. Moretti.  Auger parameter and wagner plot in the characterization of chemical states: initial and final state effects , 1995 .

[32]  A. Burggraaf,et al.  Zirconia as a support for catalysts: influence of additives on the thermal stability of the porous texture of monoclinic zirconia , 1991 .

[33]  D. A. Shirley,et al.  High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold , 1972 .

[34]  P. Fornasiero,et al.  Methane partial oxidation on NiCu-based catalysts , 2009 .

[35]  V. Kaichev,et al.  X-ray photoelectron spectroscopy as a tool for in-situ study of the mechanisms of heterogeneous catalytic reactions , 2005 .

[36]  D. Block,et al.  Catalytic Reactions of Guaiacol: Reaction Network and Evidence of Oxygen Removal in Reactions with Hydrogen , 2011 .

[37]  M. Jenko,et al.  XPS and TPR examinations of γ-alumina-supported Pd-Cu catalysts , 2001 .

[38]  Anja Oasmaa,et al.  Characterization of Hydrotreated Fast Pyrolysis Liquids , 2010 .

[39]  G. Davies,et al.  Electrodeposition of Metal Alloy and Mixed Oxide Films Using a Single‐Precursor Tetranuclear Copper‐Nickel Complex , 1995 .

[40]  S. Suib,et al.  Metal contaminant effects on the properties of a silica-rich fluid cracking catalyst , 1986 .

[41]  A. Krause,et al.  Hydrodeoxygenation of guaiacol on noble metal catalysts , 2009 .

[42]  George W. Huber,et al.  Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO2―Al2O3: Identification of reaction intermediates , 2010 .

[43]  D. Laurenti,et al.  Hydrodeoxygenation of guaiacol with CoMo catalysts. Part I: Promoting effect of cobalt on HDO selectivity and activity , 2011 .

[44]  Chen Zhao,et al.  Highly selective catalytic conversion of phenolic bio-oil to alkanes. , 2009, Angewandte Chemie.

[45]  He'an Luo,et al.  Preparation and hydrodeoxygenation properties of Co–Mo–O–B amorphous catalyst , 2011 .

[46]  N. Kosova,et al.  Mixed layered Ni–Mn–Co hydroxides: Crystal structure, electronic state of ions, and thermal decomposition , 2007 .

[47]  O. Joo,et al.  Stabilization of Ni/Al2O3 catalyst by Cu addition for CO2 reforming of methane , 2004 .

[48]  Stephen Poulston,et al.  Surface Oxidation and Reduction of CuO and Cu2O Studied Using XPS and XAES , 1996 .

[49]  M. P. Demeshkina,et al.  Characterization of the nickel-amesite-chlorite-vermiculite system. , 2003 .

[50]  P. J. Reucroft,et al.  Characterization of coprecipitated nickel on silica methanation catalysts by x-ray photoelectron spectroscopy , 1979 .

[51]  J. Vakros,et al.  Benzene hydrogenation over Ni/Al2O3 catalysts prepared by conventional and sol-gel techniques , 2008 .

[52]  Weiyan Wang,et al.  Influence of ultrasonic on the preparation of Ni–Mo–B amorphous catalyst and its performance in phenol hydrodeoxygenation , 2009 .

[53]  A. Lemonidou,et al.  Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes , 2011 .

[54]  R. Nava,et al.  Upgrading of bio-liquids on different mesoporous silica-supported CoMo catalysts , 2009 .

[55]  J. Radnik,et al.  Gas-phase carbonylation of methanol to dimethyl carbonate on chloride-free Cu-precipitated zeolite Y at normal pressure , 2007 .

[56]  J. H. Scofield,et al.  Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV , 1976 .

[57]  Deborah J. Jones,et al.  Surface characterisation of zirconium-doped mesoporoussilica , 1997 .

[58]  V. Parmon,et al.  Development of new catalytic systems for upgraded bio-fuels production from bio-crude-oil and biodiesel , 2009 .

[59]  Qiang Lu,et al.  Overview of fuel properties of biomass fast pyrolysis oils , 2009 .

[60]  Nickel catalysts for the hydrodeoxygenation of biodiesel , 2010 .

[61]  Christophe Geantet,et al.  Co-processing of pyrolisis bio oils and gas oil for new generation of bio-fuels: Hydrodeoxygenation of guaïacol and SRGO mixed feed , 2009 .