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The Effect of Supercritical Fluids on Solid Acid Catalyst Alkylation

Daniel M. Ginosar,*^† David N. Thompson,^† Kyle Coates,^† and David J. Zalewski^‡

Idaho National Engineering and Environmental Laboratory, P.O. Box 1625, Idaho Falls, Idaho 83415-2208, and Marathon-Ashland Petroleum LLC, P.O. Box 911, Catlettsburg, Kentucky 41129

Ind. Eng. Chem. Res., 2002, 41 (12), pp 2864–2873

DOI: 10.1021/ie0106938

Publication Date (Web): May 15, 2002

Corresponding author. Phone: (208) 526-9049. E-mail: dmg@inel.gov. Fax number: (208) 526−8541.

†

Idaho National Engineering and Environmental Laboratory.

‡

Marathon-Ashland Petroleum LLC.

Abstract

The alkylation of isobutane with trans-2-butene was explored over six solid acid catalysts in the liquid, near-critical liquid, and supercritical regions through the addition of an inert cosolvent to the reaction feed mixture. The addition of supercritical cosolvents did not result in sustained catalytic alkylation activity. A modest improvement in product yield was obtained with the addition of methane in the modified-liquid region; however, catalyst longevity and product selectivity were decreased compared to cosolvent-free liquid conditions. This paper describes the catalyst screening and selection process, an exploration of catalyst performance with varying concentrations of methane, and an examination of the effects of seven supercritical fluids on catalyst performance. The catalysts included two zeolites, two sulfated metal oxides, and two Nafion catalysts. Three hydrocarbons, two fluorocarbons, carbon dioxide, and sulfur hexafluoride were explored as inert cosolvents added to the reaction mixture.

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