Effect of Metal Dispersion on the Catalytic Performance of Monometallic Ni/SBA-15 and Cu/SBA-15 Catalysts in the Hydroconversion of HMF PDF Download

Author: Shuo Chen
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Languages : en
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Book Description
The production of fuel additives, having high octane numbers, from biosourced molecules such as 5-hydroxymethylfurfural (HMF), is the subject of many studies. The Pt, Pd and Ru-based catalysts are described as particularly active in the conversion reaction of HMF to 2,5-dimethylfuran (DMF) and to 2,5-dimethyltetrahydrofuran (DMTHF). However, their substitutions in the catalytic formulations are desirable in view of their high cost and low availability. The substitution elements can be transition metals (for example Cu or Ni), which are more abundant, but generally less active. My research has focused on the preparation of catalysts, based on transition metals, active and selective for the hydrogenation of HMF into molecules that can be incorporated into fuels. The active phases studied during my Ph. D. are based on Ni and Cu transition metals. These active phases were supported on mesoporous silica of SBA-15 type. The study is divided into two distinct parts, depending on the metal studied. The first part of the Ph. D. presents the results obtained with Ni supported monometallic catalysts. In a first step, the optimization of the reaction parameters for the selective hydroconversion of HMF to DMF and DMTHF was carried out using a catalyst prepared by the incipient wetness impregnation (IWI) of the nitrate precursor solution (Chapter 3). Optimized reaction parameters include reaction temperature, dihydrogen pressure, HMF/Ni molar ratio, and reaction time. A preliminary kinetic study was also performed. The effect of the dispersion and size of Ni metal particles on the catalytic performance of Ni/SBA-15 catalysts was studied on materials prepared by the melt infiltration (MI) method of nitrate precursors (Chapter 4). The level of dispersion of the nickel was modified using SBA-15 supports containing different interconnection porosities, obtained at different synthesis temperatures. The results show that the Ni/SBA-15 catalyst, prepared by the simple IWI method, achieves high yields of DMF and DMTHF under optimal reaction conditions. The level of Ni dispersion, as observed from the materials obtained by infiltration of molten salts, has a significant effect on the catalytic activity of the catalyst. The second part of my research focuses on the catalytic properties of Cu/SBA-15 monometallic catalysts prepared by different methods, and having different Cu phase division degree (Chapter 5). The methods of preparation applied include the IWI method, the in situ autocombustion method (ISAC) and the deposition-precipitation method (DP). The first part of the study therefore focused on the optimization of the reaction conditions for the selective hydroconversion of HMF to DMF (over the Cu/SBA-15 catalyst prepared by the ISAC method). Optimized reaction parameters, as for Ni/SBA-15, were reaction temperature, hydrogen pressure, HMF/Cu molar ratio, and reaction time. The reuse of the catalyst was also studied, and a kinetic study of the transformation of HMF on Cu/SBA-15 conducted. This part demonstrates that the activity of Cu for the selective conversion of HMF to DMF depends mainly on the state of dispersion of Cu. The use of the DP method led to a highly divided Cu/SBA-15 catalyst, which made it possible to achieve high yields of DMF.