Ethers from Ethanol. 4. Kinetics of Liquid-Phase Synthesis of Two tert-Hexyl Ethyl Ethers

Abstract

Tertiary ethers produced from reactive C{sub 5} and C{sub 6} olefins and ethanol or methanol are being investigated as oxygenate gasoline additives in addition to isobutylene-derived methyl tert-butyl ether and ethyl tert-butyl ether. The kinetics of liquid-phase etherification and accompanying isomerization of four reactive C{sub 6} olefin isomers with ethanol catalyzed by the ion-exchange resin catalyst Amberlyst 15 were determined at temperatures from 313 to 353 K and a pressure of 0.69 MPa in a differential packed-bed reactor. Rate expressions in terms of species activities, with the activity coefficients determined by the UNIFAC method, were developed to correlate the experimental data over a wide range of compositions. The rate expressions are based on the Langmuir-Hinshelwood-Hougen-Watson formalism involving a dual-site surface etherification reaction and a single-site surface isomerization reaction as the rate-limiting steps, along with the assumption of ethanol as the most abundant surface species. The negligibility of olefins and ether adsorption terms, but the nonnegligibility of vacant sites, was confirmed by independent liquid-phase adsorption experiments. The developed rate expressions were finally tested in an integral reactor and found to be accurate.