裂解C5与甲醇合成甲基叔戊基醚的本征动力学  

Intrinsic Kinetics of Synthesis of tert-Amyl Methyl Ether from Pyrolysis C_5 and Methanol

作　　者：刘立新[1] 余自明[1] 翁惠新[2] 

机构地区：[1]信阳师范学院化学化工学院,河南信阳464000 [2]华东理工大学石油加工研究所,上海200237

出　　处：《石油化工》2008年第5期480-485,共6页Petrochemical Technology

基　　金：中国石油天然气集团公司中青年创新基金项目(05E7002)

摘　　要：采用管式反应器，以QRE型磺酸离子交换树脂为催化剂，在消除内外扩散的基础上，研究了裂解C5与甲醇醚化反应的本征动力学。采用Wilson活度系数模型计算组分的活度，由实验数据以非线性最小二乘法对模型参数进行回归，得到了均相、Rideal-Eley和Langmuir-Hinshelwood（LH）3种动力学模型的反应速率常数。均相动力学模型对裂解C5与甲醇醚化反应不适合。LH模型中的2-甲基-1-丁烯异构化和2-甲基-1-丁烯、2-甲基-2-丁烯与甲醇合成甲基叔戊基醚反应的活化能分别为：92．17，100．19，102．48kJ／mol。计算结果表明，在反应温度为60～70℃、n（甲醇）：n（异戊烯）大于0．5时，LH模型对TAME活度的预测值与实验值的平均相对偏差均小于7％，LH模型可用于C5与甲醇醚化反应工艺的优化。Intrinsic kinetics for synthesis of tert-amyl methyl ether （TAME） from pyrolysis C5 and methanol on a sulfonic ion exchange resin catalyst （ QRE ） with free of both internal and external diffusions was studied in a continuous tubular reactor. Activities of components were calculated by Wilson model. Reaction rate constants of three kinetic models, namely homogeneous, Rideal-Eley and Langmuir-Hinshelwood （LH） were estimated by nonlinear least square method. Homogeneous model is not suitable for the etherification. Under conditions of reaction temperature 60 -70 ℃ and mole ratio of methanol to isoamylene more than 0.5, the average relative error of TAME activity predicted by LH model to experimental data is less than 7%. LH model can be used in optimizing of etherification process. The activation energies are determined to be 92.17 kJ/mol for isomerization of 2-methyl-1- butene to 2-methyl-2-butene, 100. 19 kJ/mol for etherification of 2-methyl-1butene to TAME, and 102.48 kJ/mol for etherification of 2-methyl-2-butene.

关 键 词：裂解碳五 甲醇 甲基叔戊基醚 2-甲基-1-丁烯 2-甲基-2-丁烯 本征动力学 

分 类 号：TQ013.2[化学工程]