·912·
石油化工
PETROCHEMICAL TECHNOLOGY
2019 年第48 卷第 9 期
DOI：10.3969/j.issn.1000-8144.2019.09.006
近临界条件下苯与直链烯烃烷基化
反应动力学研究
任?杰，邓?优，周子健，慎?炼
（浙江工业大学 化学工程学院，浙江 杭州 310014）
［摘要］采用固定床反应装置进行近临界条件下的AlPO4-5分子筛催化剂上苯与直链烯烃烷基化反应。利用反应实验数据进
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行反应动力学模拟研究，确定了表观反应速率常数（kV）和外扩散传质模型参数。实验结果表明，kV在较低温度下随着反
应压力增大先减小后增大，而在较高温度下呈现减小趋势。通过分子团簇分析，这种压力影响是压力对总反应活化能和内扩散系数影响的综合结果。基于总反应活化能与反应压力的线性关系，确定了表观活化能和活化体积。建立了表观反应速率常数频率因子、外扩散传质模型参数与反应条件的数学关系式。模型预测结果显示，烯烃转化率随着空塔流速增大；在消除外扩散影响情况下，在温度578～588 K、压力3.0～4.0 MPa、WHSV=0.5 h-1的条件下，烯烃转化率接近100%。［关键词］苯；直链烯烃；烷基化；反应动力学；近临界流体
［文章编号］1000-8144（2019）09-0912-09 ［中图分类号］TQ 203.2 ［文献标志码］A
Kinetics of benzene alkylation with linear olefins under near critical conditions
Ren Jie，Deng You，Zhou Zijian，Shen Lian
（College of Chemical Engineering，Zhejiang University of Technology，Hangzhou Zhejiang 310014，China）
［Abstract］The benzene alkylation with linear ole?ns over AlPO4-5 zeolite catalyst in the ?xed bed
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reactor was carried out under near critical conditions. The apparent reaction rate constant(kV) and external diffusion mass transfer model parameters were determined by using the experimental data of the reaction to simulate the reaction kinetics. The results showed that with the increase of pressure，
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the kV ?rstly decreased then increased at lower temperature，and decreased at higher temperature. The molecular cluster analysis showed that this pressure effect was the comprehensive result of the in?uence of pressure on the total reaction activation energy and internal diffusion coefficient. The apparent activation energy and the activation volume were determined based on the linear relationship between the overall activation energy and reaction pressure. The mathematical relations of the apparent reaction rate constant frequency factor，the external diffusion mass transfer model parameters with the reaction conditions were established. The prediction results of the model showed that the olefin conversion increased with the ?ow rate of the empty tower. Under the condition of eliminating the in?uence of external diffusion，the ole?n conversion was close to 100% under the conditions of temperature range of 578-588 K，pressure range of 3.0-4.0 MPa and WHSV of 0.5 h-1.
［Keywords］benzene；linear ole?n；alkylation；reaction kinetics；near critical ?uid
目前主要采用氢氟酸（HF）催化工艺生产直链烷基苯，主要用于生产合成洗涤剂。由于HF腐蚀设备、污染环境，人们致力于开发环境友好的固
［收稿日期］2019-03-15；［修改稿日期］2019-05-20。
体酸烷基化催化工艺［1-2］。研究的固体酸催化剂包
［3］［4-6］［7-10］［11］
、Hβ、丝光沸石、AlMCM-41、括USY
AlMCM-41/Beta［12］、负载杂多酸［13-16］、MCM-41
［作者简介］任杰（1961—），男，辽宁省抚顺市人，博士，教授，电话 0571-88320208，电邮 Renjie.R@263.net。
近临界条件下苯与直链烯烃烷基化反应动力学研究
