Solid state chemistry of bulk mixed metal oxide catalysts for the selective oxidation of propane to acrylic acid

Abstract Syntheses of Mo–V–Sb–Nb–O bulk materials, which are candidate catalyst systems for the selective oxidation of propane to acrolein and acrylic acid, were made using soluble precursor materials. The products were characterized by X-ray powder diffraction and Raman spectroscopic studies. The objectives of this work were to explore the utility of liquid phase automated synthesis for the preparation of bulk mixed metal oxides, and the identification of the oxide phases present in the system. This is the first published study of the phase composition for these materials. After calcination of these bulk oxides under flowing nitrogen at 600°C, and using stoichiometric ratios of Mo–V–Sb–Nb (1:1:0.4:0.4) and Mo–V–Sb–Nb (3.3:1:0.4:0.4) it was demonstrated that a mixture of phases were obtained for the syntheses. X-ray powder diffraction studies distinguished SbVO 4 , Mo 6 V 9 O 40 , MoO 3 , and a niobium-stabilized defect phase of a vanadium-rich molybdate, Mo 0.61–0.77 V 0.31–0.19 Nb 0.08–0.04 O x , as the major phases present. Complementary data were provided by the Raman spectroscopic studies, which illustrated the heterogeneity of the phases present in the mixture. Raman also indicated bands attributable to the presence of phases containing terminal MO bonds as well as M–O–M polycrystalline phases. Previous studies on this system have identified SbVO 4 and niobium-stabilized vanadium molybdate species as the active phases necessary for the selective oxidation of alkanes.

[1]  S. Hansen,et al.  An Investigation of the Al–Sb–V–W–Oxide System for Propane Ammoxidation , 1999 .

[2]  G. Centi,et al.  VSb-oxide catalysts for the ammoxidation of propane , 1997 .

[3]  G. Centi,et al.  Functionalization of alkanes by heterogeneous vapour-phase oxidation.: II. Propane ammoxidation , 1987 .

[4]  Gabriele Centi,et al.  Structure-activity relationship in Sb-V-oxide catalysts for the direct synthesis of acrylonitrile from propane , 1996 .

[5]  G. Centi,et al.  Kinetics and reaction network in propane ammoxidation to acrylonitrile on vanadium-antimony-aluminum based mixed oxides , 1992 .

[6]  G. Centi,et al.  Dependence of the catalytic behavior of V—Sb-oxides in propane ammoxidation to acrylonitrile from the method of preparation , 1997 .

[7]  Hans-Werner Schmidt,et al.  Combinatorial Material Libraries on the Microgram Scale with an Example of Hydrothermal Synthesis. , 1998, Angewandte Chemie.

[8]  R. Burch,et al.  Mo–V–Nb Oxide Catalysts for the Partial Oxidation of Ethane: II. Chemical and Catalytic Properties and Structure Function Relationships , 1998 .

[9]  P. H. Kasai,et al.  The oxidative dehydrogenation of ethane over catalysts containing mixed oxides of molybdenum and vanadium , 1978 .

[10]  J. Stencel Raman spectroscopy for catalysis , 1990 .

[11]  Narayanan C. Ramani,et al.  Selective Oxidation of 1-Butene over Silica-Supported Cr(VI), Mo(VI), and W(VI) Oxides , 1998 .

[12]  E. Pierron,et al.  Compound oxides present in vanadium-molybdenum oxide maleic catalysts☆ , 1964 .

[13]  H. Stenger,et al.  Molecular structure–reactivity relationships for the oxidation of sulfur dioxide over supported metal oxide catalysts , 1999 .

[14]  R. Grasselli Advances and future trends in selective oxidation and ammoxidation catalysis , 1999 .