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

Wickman, A; Wallenberg, Reine LU and Andersson, Arne LU (2000) In Journal of Catalysis 194(1). p.153-166
Abstract
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,... (More)
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. (Less)
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organization
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type
Contribution to journal
publication status
published
subject
keywords
propane, ammoxidation, acrylonitrile formation, Sb-V-Ti oxide catalysts, catalyst characterization, XRD, FT-Raman, DRIFT, transmission electron, microscopy, electron diffraction, X-ray microanalysis
in
Journal of Catalysis
volume
194
issue
1
pages
153 - 166
publisher
Elsevier
external identifiers
  • wos:000088947800018
  • scopus:0034662920
ISSN
1090-2694
DOI
10.1006/jcat.2000.2918
language
English
LU publication?
yes
id
0ee63a97-30ca-464a-90f3-477119731a86 (old id 3915455)
date added to LUP
2013-07-02 08:35:30
date last changed
2017-04-30 09:56:23
@article{0ee63a97-30ca-464a-90f3-477119731a86,
  abstract     = {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.},
  author       = {Wickman, A and Wallenberg, Reine and Andersson, Arne},
  issn         = {1090-2694},
  keyword      = {propane,ammoxidation,acrylonitrile formation,Sb-V-Ti oxide catalysts,catalyst characterization,XRD,FT-Raman,DRIFT,transmission electron,microscopy,electron diffraction,X-ray microanalysis},
  language     = {eng},
  number       = {1},
  pages        = {153--166},
  publisher    = {Elsevier},
  series       = {Journal of Catalysis},
  title        = {Effect of titanium substitution in approximate to SbVO4 used for propane ammoxidation},
  url          = {http://dx.doi.org/10.1006/jcat.2000.2918},
  volume       = {194},
  year         = {2000},
}