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Abstract

A process for the simultaneous manufacture of pure methyl tertiary butyl ether (MTBE) and a substantially isotubene-free mixture of C.sub.4 -hydrocarbons, by reacting the isobutene contained in the mixture of C.sub.4 -hydrocarbons with excess methanol in the liquid phase at elevated temperatures on strongly acid, macroporous, organic ion exchange resins. The process has the following steps: (a) methanol and isobutene are reacted in a molar ratio of 2:1 to 5:1 at temperatures between 30.degree. and 100.degree. C.; (b) the unconverted hydrocarbons are then removed as the top product under a pressure of 2 to 10 bars from a first rectification column; (c) the bottom product from this first column is rectified in a second column under normal pressure or under a slight excess pressure of up to 2 bars at the top of the column, the bottom product of this rectification is recycled to reaction zone (a), if necessary, after separating off a portion of the tertiary butanol formed and the C.sub.8 -olefins; and (d) the distillate from this second column is rectified in a third rectification column under a pressure of 5 to 30 bars, the distillate thus obtained is recycled into the feed to the second column and pure methyl tertiary butyl ether is withdrawn from the bottom of the third column.

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