Effect of titanium substitution in approximate to SbVO4 used for propane ammoxidation

TY - JOUR

T1 - Effect of titanium substitution in approximate to SbVO4 used for propane ammoxidation

AU - Wickman, A

AU - Wallenberg, Reine

AU - Andersson, Arne

PY - 2000

Y1 - 2000

N2 - Catalysts of the nominal composition Sb0.9V0.9-xTixOy, 0.0 less than or equal to x less than or equal to 0.9, were prepared and characterized with X-ray diffraction, Fourier transform-Raman spectra, diffuse reflectance infrared Fourier transform spectra, transmission electron microscopy, electron diffraction, and X-ray microanalysis. The catalysts were used for the ammoxidation of propane to give acrylonitrile. Compared with the pure approximate to SbVO4 (Sb0.92V0.92O4) it is observed that the activity decreases while the selectivity to acrylonitrile formation is improved when the Ti : V ratio of the preparation is increased. The characterization of the catalysts shows the formation of a rutile-type phase in all preparations with vanadium, Additionally, alpha-Sb2O4 is formed in an amount that increases with the amount of titanium in the sample. X-ray microanalysis data confirm that two substitution mechanisms occur in parallel, namely, one Ti4+ substitutes for one V4+ and two Ti4+ substitute for one V3+ and one Sb5+, forming the solid solution series Sb-(0.92-z/2)(5+) V-(0.28-z/2)(3+) V-(0.64-u)(4+) Ti-(z+u)(4+) square(0.16)O(4) (square is a cation vacancy). Quantitative model calculations considering data obtained by the characterization methods give the content of cations in the unit cell of the rutile phase. It is demonstrated that the activity can be correlated with the content of V3+ in the unit cell, indicating that the activation of propane occurs on a V3+ center. Moreover, the selectivity to acrylonitrile can be correlated to the Sb5+/V3+ ratio, which indicates that the ammonia is activated on a Sb5+ moiety. Considering both activity and selectivity, the best performance for propane ammoxidation is obtained for a sample with the nominal composition Sb0.9V0.3Ti0.6Oy. The selectivity to acrylonitrile is 53% at 25% propane conversion to be compared with 12% at 15% propane conversion for the nonsubstituted approximate to SbVO4, The improved selectivity can be explained by isolation of the vanadium centers in the active phase, which gives fewer bridging V-O-V moieties that are active for degradation and combustion of propane and the subsequently formed propylene. (C) 2000 Academic Press.

AB - Catalysts of the nominal composition Sb0.9V0.9-xTixOy, 0.0 less than or equal to x less than or equal to 0.9, were prepared and characterized with X-ray diffraction, Fourier transform-Raman spectra, diffuse reflectance infrared Fourier transform spectra, transmission electron microscopy, electron diffraction, and X-ray microanalysis. The catalysts were used for the ammoxidation of propane to give acrylonitrile. Compared with the pure approximate to SbVO4 (Sb0.92V0.92O4) it is observed that the activity decreases while the selectivity to acrylonitrile formation is improved when the Ti : V ratio of the preparation is increased. The characterization of the catalysts shows the formation of a rutile-type phase in all preparations with vanadium, Additionally, alpha-Sb2O4 is formed in an amount that increases with the amount of titanium in the sample. X-ray microanalysis data confirm that two substitution mechanisms occur in parallel, namely, one Ti4+ substitutes for one V4+ and two Ti4+ substitute for one V3+ and one Sb5+, forming the solid solution series Sb-(0.92-z/2)(5+) V-(0.28-z/2)(3+) V-(0.64-u)(4+) Ti-(z+u)(4+) square(0.16)O(4) (square is a cation vacancy). Quantitative model calculations considering data obtained by the characterization methods give the content of cations in the unit cell of the rutile phase. It is demonstrated that the activity can be correlated with the content of V3+ in the unit cell, indicating that the activation of propane occurs on a V3+ center. Moreover, the selectivity to acrylonitrile can be correlated to the Sb5+/V3+ ratio, which indicates that the ammonia is activated on a Sb5+ moiety. Considering both activity and selectivity, the best performance for propane ammoxidation is obtained for a sample with the nominal composition Sb0.9V0.3Ti0.6Oy. The selectivity to acrylonitrile is 53% at 25% propane conversion to be compared with 12% at 15% propane conversion for the nonsubstituted approximate to SbVO4, The improved selectivity can be explained by isolation of the vanadium centers in the active phase, which gives fewer bridging V-O-V moieties that are active for degradation and combustion of propane and the subsequently formed propylene. (C) 2000 Academic Press.

KW - propane

KW - ammoxidation

KW - acrylonitrile formation

KW - Sb-V-Ti oxide catalysts

KW - catalyst characterization

KW - XRD

KW - FT-Raman

KW - DRIFT

KW - transmission electron

KW - microscopy

KW - electron diffraction

KW - X-ray microanalysis

U2 - 10.1006/jcat.2000.2918

DO - 10.1006/jcat.2000.2918

M3 - Article

VL - 194

SP - 153

EP - 166

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 1090-2694

IS - 1

ER -