【作者】 颜范勇；

【导师】 汪宝和；

【作者基本信息】 天津大学 ， 化学工程， 2004， 硕士

【摘要】 本文主要研究了甲苯气相SO3磺化的反应过程，确定了适宜的工艺条件，并对气相SO3磺化甲苯反应的宏观动力学进行了研究。在研究过程中，主要作了以下工作：1、实验重点考察了反应温度，SO3配气浓度和原料中水含量等因素对反应转化率、产物中甲苯磺酸异构体含量及产物中二甲苯砜含量的影响。同时，从理论上对工艺条件如何影响产物中三种异构体分配比例进行了分析和解释。2、通过对不同抑制剂醋酸、磷酸、硼酸、硫化钠、亚硫酸钠和二甲苯砜的实验对比，筛选出具有较好阻砜效果的抑制剂二甲苯砜，并对其抑制砜的机理进行了探讨。3、在不添加其它非反应体系物质的情况下，选择系统中副反应产物二甲苯砜作为抑制剂，确定了适宜于工业化生产的砜抑制剂加入量，二甲苯砜的添加量占反应物的3.3%左右，降低了砜的生成，提高了甲苯的选择性，为工业化生产提供了必要的理论及实验依据。4、重复稳定实验表明，当砜的加入量为反应物甲苯量的3.3%时，经过5批重复实验，副产物砜没有生成，也没有累积。在此条件下，甲苯转化率在35%左右，反应产物中三种磺酸异构体的组成为对位：89%，邻位：10%，间位：1%。5、通过实验测定了磺化反应的宏观动力学常数，确定出了各步反应的频率因子、活化能以及各步反应速率表达式。各步反应的指前因子和活化能为：k01=7.56×103，E1=6.63KJ/mol，k02=25.05×103，E2=18.276KJ/mol，k03=5.258×103，E3=11.027KJ/mol,k04=1.149×108,E4=111.491KJ/mol,k05=2.667×103,E5=17.366KJ/mol。更多还原

【Abstract】 In this thesis various, influences of reaction conditions on the sulfonation of toluene with gaseous SO3 are studied in order to establish the optimum reaction condition and kinetics of the procedure.It is shown that temperature, concentration of SO3 and water quantity in dilute gas are important factors to determine the conversion of toluene、 the acid concentration and sulphone content in products. By means of Gc and HPLC, the concentration distribution of the three isomers of toluenesulfonic acid under different reaction conditions have been determined.Through investigation of six inhibitors such as phosphoric acid, acietic acid, sodium sulphide, boracic acid and sulphone, an excellent inhibitor sulphone was identified. And also, mechanism about the action of this inhibitor was theoretically discussed.Without addition of other unreactional system material, sulphone was chosen as the inhibitor, and the amount of sulphone was decided. The emergence of sulphone was inhibited successfully. Selectivity of the reaction was enhanced, therefore, necessary theoretical and experimental data of the industrial product of toluene were figured out: 3.3%, The concentration of the three isomers of toluenesulfonic acid: p-89%，o-10%,m-1%.According to the tests, kinetic constants are measured. The consecutive reactions frequency factor and activation energy are determined, equations can represent the reaction rate expression: k01=7.56×103，E1=6.63KJ/mol，k02=25.05×103，E2=18.276KJ/mol,k03=5.258×103,E3=11.027KJ/mol,k04=1.149×108,E4=111.491KJ/mol,k05=2.667×103,E5=17.366KJ/mol。更多还原