碱处理ZSM-5分子筛催化噻吩烷基化反应性能及其反应动力学  

Performance and Kinetics of Thiophene Alkylation Over the ZSM-5 Zeolite by Alkali Treatment

作　　者：毛艳红[1] 刘冬梅[1] 魏民[1] 王迪 

机构地区：[1]辽宁石油化工大学化学化工与环境学部,辽宁抚顺113001 [2]中国石油安徽销售分公司,安徽合肥230041

出　　处：《石油学报（石油加工）》2017年第4期746-756,共11页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：辽宁省自然基金资助项目(201202126)博士启动资金资助

摘　　要：分别采用Na2CO3和TPA+/CO_3^(2-)混合碱处理ZSM-5分子筛,用XRD、SEM、BET和Py-IR等手段对碱处理前后的ZSM-5分子筛催化剂进行表征,并考察其催化噻吩烷基化反应性能。结果表明,TPA+/CO_3^(2-)混合碱处理后的ZSM-5分子筛(HZ(CO_3^(2-)-TPA+))比表面积和孔径最大、B酸量最多且最适合催化噻吩烷基化反应。在反应温度120℃、反应压力1.0 MPa、反应空速1.0h-1、反应时间6.0h,HZ(CO_3^(2-)-TPA+)分子筛催化噻吩烷基化转化率最高,为99.1%。在最佳工艺条件下研究了碱处理前后ZSM-5分子筛催化噻吩烷基化反应动力学。结果表明,碱处理前后ZSM-5分子筛催化噻吩烷基化反应动力学均符合一级反应速率方程,HZ、HZ(CO_3^(2-))、HZ(CO_3^(2-)-TPA+)分子筛上噻吩类硫化物烷基化反应的活化能分别为57.15kJ/mol、49.14kJ/mol、43.71kJ/mol,反应指前因子分别为1.660×107 h-1、4.335×106 h-1、1.365×106 h-1。ZSM-5 zeolites were treated by Na2C03 solution and TPA^＋/CO3^2- mixed alkali respectively. The ZSM-5 zeolites before and after alkali treatment were characterized by a complementary combination of X-ray diffraction, SEM, BET and Py-IR, The performance of the thiophene alkylation over zeolite was investigated. The results showed that after the TPAOH/Na2CO3 mixed alkali treatment, the specific surface area and aperture are the biggest among observed cases, and the content of Bronsted acidity are also the biggest. The catalyst is most suitable for thiophene alkylation. With the reaction temperature of 120°C , reaction pressure of 1. 0 MPa, reaction velocity of 1. 0 h^-1,and reaction time of 6. 0 h,the conversion rate of thiophene alkylation was up to 99. 1 %. The kinetic of thiophene alkylation over ZSM-5 zeolite with mixed alkali treatment was studied under the optimum conditions. The results showed that with the reaction temperature of 120°C , reaction pressure of 1.0 MPa, and reaction velocity of 1.0 h^-1 , the conversion rate of thiophene alkylation was up to 99. 1 %. The thiophene alkylation is found to be a first order reaction. The value of the activation energy of the reaction over HZ, HZ（CO3^2-）、 HZ（CO3^2- - TPA^ ＋ ） is about 57. 15 kJ/mol、49. 14 kJ / mol、 43. 71 kJ/mol , and the reaction constant is 1. 660 × 10^7 h^-1、4. 335 × 10^6 h^-1、 365 × 10^6 h^-1.

关 键 词：分子筛 碱处理 噻吩烷基化 反应动力学 

分 类 号：TQ426.95[化学工程]