KINETICS OF METHYL TERTIARY BUTYL ETHER LIQUID-PHASE SYNTHESIS CATALYZED BY ION-EXCHANGE RESIN .1. INTRINSIC RATE EXPRESSION IN LIQUID-PHASE ACTIVITIES

被引:224
作者
REHFINGER, A
HOFFMANN, U
机构
[1] TECH UNIV BRAUNSCHWEIG,INST TECH CHEM,HANS SOMMER STR 10,W-3300 BRAUNSCHWEIG,GERMANY
[2] TECH UNIV CLAUSTHAL,CHEM VERFAHRENSTECH ABT,W-3392 CLAUSTHAL ZELLERFE,GERMANY
关键词
D O I
10.1016/0009-2509(90)80013-5
中图分类号
TQ [化学工业];
学科分类号
0817 ;
摘要
The microkinetics for the liquid phase synthesis of methyl tertiary butyl ether (MTBE) from methanol and isobutene using a macroporous sulfonic acid ion exchange resin as catalyst (Amberlyst 15, CVT resin) were determined experimentally in a continuous stirred tank reactor in the temperature range 323-363 K at 2.1 MPa. The reaction proceeds within the gel phase of the microspheres as the rate-controlling step overlapped by a multiple sorption equilibrium between components in the macropore liquid and the gel phase, where methanol is highly selectively sorbed. The experimental results can be described by a three-parameter model based on a Langmuir-Hinshelwood rate expression in liquid phase activities from the UNIQUAC method. The forward reaction is proportional to the activity ratio of isobutene to methanol (quasi-autocatalytic in methanol). The reverse reaction is first-order in MTBE and negative second-order in methanol (product inhibition). The activation energy was determined to 92.4 kJ/mol. No pressure dependence could be observed. The developed microkinetic model is independent of the degree of cross-linking of the resin in the investigated range 7.5-20% DVB by weight. The formation of isobutene dimers, the main by-product, was only observed if internal mass transfer influenced the rate of reaction. © 1990.
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页码:1605 / 1617
页数:13
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