Synthesis of methanol and isobutanol from syngas over ZrO2-based catalysts

doi:10.1016/S0378-3820(96)01060-0

Fuel Processing Technology

Volume 50, Issues 2–3, February 1997, Pages 163-170

https://doi.org/10.1016/S0378-3820(96)01060-0 Get rights and content

Abstract

The effects of reaction conditions on the synthesis of isobutanol and methanol from syngas over ZrK and ZrMnK catalysts have been investigated, with the reactions carried out at pressures between 8 and 16 MPa, temperatures between 380 and 440 °C, and gas hourly space velocity (GHSV) between 3 000 and 8 000 h⁻¹. It was found that the ZrK catalyst exhibited the highest activity and selectivity at 420 °C, 10.0 MPa, and 5 000 h⁻¹, and that the Mn-promoted catalyst increased the yield of isobutanol with the corresponding optimum temperature being 400 °C. Moreover, the higher pressure and GHSV favored isobutanol synthesis. At 16. 0 MPa, 400 °C, 5 000 h⁻¹, the space time yield of isobutanol was about 21.5 ml per ml cat. h⁻¹, and selectivity reached 98% over the ZrMnK catalyst.

References (9)

A. Sofianos
Catal. Today
(1992)
W. Otto Ken
Oil and Gas J.
(1993)
O.C. Feeley et al.
Am. Chem. Soc. Div. Fuel Chem. prepr.
(1992)
M. Ichikawa
J. Chem. Soc. Chem. Commun.
(1978)

There are more references available in the full text version of this article.

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Synthesis of methanol and isobutanol from syngas over ZrO2-based catalysts

Abstract

Catal. Today

Oil and Gas J.

Am. Chem. Soc. Div. Fuel Chem. prepr.

J. Chem. Soc. Chem. Commun.

Synthesis of methanol and isobutanol from syngas over ZrO₂-based catalysts