Abstract
The gas-phase oxidative dehydrogenation of 4-vinylcyclohexene (VCH) to styrene in high selectivities was successfully carried out at moderate temperatures, 200-260°C, using a vanadium substituted polyoxometalate, PV2Mo10O5- 40, supported on carbon as catalyst. The major co-product was ethylbenzene and only a small amount of over-oxidation to COx was observed. Maximum conversions and selectivity were obtained at a O2/VCH ratio of ∼1.9. The identity of the counter cation also affected the results with activity and selectivity decreasing in the following order H5∼(NH4)4K>Cs3H 2≫(NH4)5. Ethylbenzene and styrene are not formed by the same reaction pathway. For ethylbenzene formation, oxydehydrogenation is preceded by isomerization of the exocylic double bond to an endocyclic position, whereas for styrene formation there is no such isomerization. A mechanism is proposed whereby the active catalyst is a polyoxometalate - carbon support complex, which yields in the presence of oxygen quinone/hydroquinone or aroxy/phenol redox couples responsible for the oxydehydrogenation.
| Original language | English |
|---|---|
| Pages (from-to) | 67-72 |
| Number of pages | 6 |
| Journal | Applied Catalysis A: General |
| Volume | 172 |
| Issue number | 1 |
| Publication status | Published - Aug 24 1998 |
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Keywords
- Heteropolyanions
- Oxidative dehydrogenation
- Polyoxometalate
- Styrene
- Vinylcyclohexene
ASJC Scopus subject areas
- Catalysis
- Process Chemistry and Technology
Cite this
Oxidative dehydrogenation of 4-vinylcyclohexene to styrene catalyzed by PV2Mo10O5- 40 heteropolyacids. / Neumann, Ronny; Dror, Ishai.
In: Applied Catalysis A: General, Vol. 172, No. 1, 24.08.1998, p. 67-72.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Oxidative dehydrogenation of 4-vinylcyclohexene to styrene catalyzed by PV2Mo10O5- 40 heteropolyacids
AU - Neumann, Ronny
AU - Dror, Ishai
PY - 1998/8/24
Y1 - 1998/8/24
N2 - The gas-phase oxidative dehydrogenation of 4-vinylcyclohexene (VCH) to styrene in high selectivities was successfully carried out at moderate temperatures, 200-260°C, using a vanadium substituted polyoxometalate, PV2Mo10O5- 40, supported on carbon as catalyst. The major co-product was ethylbenzene and only a small amount of over-oxidation to COx was observed. Maximum conversions and selectivity were obtained at a O2/VCH ratio of ∼1.9. The identity of the counter cation also affected the results with activity and selectivity decreasing in the following order H5∼(NH4)4K>Cs3H 2≫(NH4)5. Ethylbenzene and styrene are not formed by the same reaction pathway. For ethylbenzene formation, oxydehydrogenation is preceded by isomerization of the exocylic double bond to an endocyclic position, whereas for styrene formation there is no such isomerization. A mechanism is proposed whereby the active catalyst is a polyoxometalate - carbon support complex, which yields in the presence of oxygen quinone/hydroquinone or aroxy/phenol redox couples responsible for the oxydehydrogenation.
AB - The gas-phase oxidative dehydrogenation of 4-vinylcyclohexene (VCH) to styrene in high selectivities was successfully carried out at moderate temperatures, 200-260°C, using a vanadium substituted polyoxometalate, PV2Mo10O5- 40, supported on carbon as catalyst. The major co-product was ethylbenzene and only a small amount of over-oxidation to COx was observed. Maximum conversions and selectivity were obtained at a O2/VCH ratio of ∼1.9. The identity of the counter cation also affected the results with activity and selectivity decreasing in the following order H5∼(NH4)4K>Cs3H 2≫(NH4)5. Ethylbenzene and styrene are not formed by the same reaction pathway. For ethylbenzene formation, oxydehydrogenation is preceded by isomerization of the exocylic double bond to an endocyclic position, whereas for styrene formation there is no such isomerization. A mechanism is proposed whereby the active catalyst is a polyoxometalate - carbon support complex, which yields in the presence of oxygen quinone/hydroquinone or aroxy/phenol redox couples responsible for the oxydehydrogenation.
KW - Heteropolyanions
KW - Oxidative dehydrogenation
KW - Polyoxometalate
KW - Styrene
KW - Vinylcyclohexene
UR - http://www.scopus.com/inward/record.url?scp=0002379746&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0002379746&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0002379746
VL - 172
SP - 67
EP - 72
JO - Applied Catalysis A: General
JF - Applied Catalysis A: General
SN - 0926-860X
IS - 1
ER -