Thermodynamic and kinetic study of tert-amyl methyl ether (TAME) synthesis

The etherification of methanol (MeOH) with 2-methyl-1-butene(2MIB) and 2-methyl-2-butene (2M2B) catalyzed by the macroporous cation ion-exchange resin (D005II) was studied in a batch reactor. The thermodynamic properties and kinetic data were obtained under different initial molar ratio of methanol and isoamylenes (0.5-2) in the temperature range between 323 and 353 K with pressure (1 MPa) constant. Because of the nonideal property of the reaction, activities were adopted to calculate equilibrium constants and the activity coefficients were estimated by Wilson method. There were three mechanisms adopted for simulating reaction rate equations, containing homogeneous reaction mechanism, Langmuir-Hinshelwood (LH) type mechanism and Eley-Rideal (ER) type mechanism and the equations based on the LH type mechanism was found to get better fit with the experimental data. The results showed that the experimental data for thermodynamics agreed with the theoretical predications well, and the activation energy was 88.1 and 102.1 kJ mol(-1) for the etherification of 2MIB and 2M2B, respectively, by kinetic calculation. (c) 2007 Elsevier B.V. All rights reserved.