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Stability and performance of supported Fe-V-oxide catalysts in methanol oxidation

Häggblad, Robert LU ; Massa, Mariano LU and Andersson, Arne LU (2009) In Journal of Catalysis 266(2). p.218-227
Abstract
As the commercial Fe-Mo-oxide catalyst for methanol oxidation to formaldehyde suffers from deactivation by Mo volatilization, alternative catalysts are of interest. Therefore, TiO2-, alpha-Al2O3- and SiO2-supported (Fe)-V-O catalysts were prepared with loading up to 30 μmol of each metal per msq. surface area of the support. The samples were activity tested using a high inlet concentration of methanol (10 vol.%) and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XANES). The activity measurements show that the preparations with the highest loads of V give the best performance. With regard to the support, the activity of the supported catalysts decreases in the order... (More)
As the commercial Fe-Mo-oxide catalyst for methanol oxidation to formaldehyde suffers from deactivation by Mo volatilization, alternative catalysts are of interest. Therefore, TiO2-, alpha-Al2O3- and SiO2-supported (Fe)-V-O catalysts were prepared with loading up to 30 μmol of each metal per msq. surface area of the support. The samples were activity tested using a high inlet concentration of methanol (10 vol.%) and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XANES). The activity measurements show that the preparations with the highest loads of V give the best performance. With regard to the support, the activity of the supported catalysts decreases in the order TiO2 > Al2O3 > SiO2. According to XPS the surface concentration of V decreases in the same order, confirming that vanadium is an active element. At high methanol conversion, the selectivity to formaldehyde decreases from 90% to 80% in the sequence unsupported FeVO4 > (Fe)VOx/TiO2 = (Fe)VOx/Al2O3 > FeVOx/SiO2 > VOx/SiO2. Iron has only a small effect on the catalytic performance, whereas it has a stabilizing effect on vanadium decreasing its volatility. However, compared with bulk FeVO4, volatilization experiments reveal that the volatilization of V from the supported (Fe)-V-oxide is much severer due to the dispersion and the comparatively low amount of active metal. Our data demonstrate that neither supported V-oxide nor supported Fe-V-oxide is suitable as catalyst in the industrial scale production of formaldehyde by methanol oxidation. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
TiO2, SiO2, alpha-Al2O3, Supported Fe-V-oxide, Formaldehyde, Selective oxidation, Methanol, XRD, XPS, XANES, Volatility
in
Journal of Catalysis
volume
266
issue
2
pages
218 - 227
publisher
Elsevier
external identifiers
  • wos:000270116300007
  • scopus:68749085768
ISSN
1090-2694
DOI
10.1016/j.jcat.2009.06.010
language
English
LU publication?
yes
id
5b61379e-84b7-434c-94b2-b0e18ed3f4c9 (old id 1465095)
date added to LUP
2009-08-25 17:38:37
date last changed
2017-01-01 05:06:32
@article{5b61379e-84b7-434c-94b2-b0e18ed3f4c9,
  abstract     = {As the commercial Fe-Mo-oxide catalyst for methanol oxidation to formaldehyde suffers from deactivation by Mo volatilization, alternative catalysts are of interest. Therefore, TiO2-, alpha-Al2O3- and SiO2-supported (Fe)-V-O catalysts were prepared with loading up to 30 μmol of each metal per msq. surface area of the support. The samples were activity tested using a high inlet concentration of methanol (10 vol.%) and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XANES). The activity measurements show that the preparations with the highest loads of V give the best performance. With regard to the support, the activity of the supported catalysts decreases in the order TiO2 > Al2O3 > SiO2. According to XPS the surface concentration of V decreases in the same order, confirming that vanadium is an active element. At high methanol conversion, the selectivity to formaldehyde decreases from 90% to 80% in the sequence unsupported FeVO4 > (Fe)VOx/TiO2 = (Fe)VOx/Al2O3 > FeVOx/SiO2 > VOx/SiO2. Iron has only a small effect on the catalytic performance, whereas it has a stabilizing effect on vanadium decreasing its volatility. However, compared with bulk FeVO4, volatilization experiments reveal that the volatilization of V from the supported (Fe)-V-oxide is much severer due to the dispersion and the comparatively low amount of active metal. Our data demonstrate that neither supported V-oxide nor supported Fe-V-oxide is suitable as catalyst in the industrial scale production of formaldehyde by methanol oxidation.},
  author       = {Häggblad, Robert and Massa, Mariano and Andersson, Arne},
  issn         = {1090-2694},
  keyword      = {TiO2,SiO2,alpha-Al2O3,Supported Fe-V-oxide,Formaldehyde,Selective oxidation,Methanol,XRD,XPS,XANES,Volatility},
  language     = {eng},
  number       = {2},
  pages        = {218--227},
  publisher    = {Elsevier},
  series       = {Journal of Catalysis},
  title        = {Stability and performance of supported Fe-V-oxide catalysts in methanol oxidation},
  url          = {http://dx.doi.org/10.1016/j.jcat.2009.06.010},
  volume       = {266},
  year         = {2009},
}