石油学报(石油加工) ›› 2020, Vol. 36 ›› Issue (1): 196-202.doi: 10.3969/j.issn.1001-8719.2020.01.024

• 研究报道 • 上一篇    下一篇

乙烯生成苯副反应网络和反应机理数值模拟

张红梅1,张锦涛1,李金莲1,马辽1,郝玉兰1,赵晶莹2,赵亮3   

  1. 1东北石油大学学院 石油与天然气化工省重点实验室,黑龙江 大庆 163318; 2中国石油 大庆化工研究中心,黑龙江 大庆 163714;3中国石油大学(北京) 重质油国家重点实验室,北京 102249
  • 收稿日期:2018-12-03 修回日期:2019-08-24 出版日期:2020-01-25 发布日期:2020-04-01
  • 通讯作者: 张红梅,女,教授,博士,从事化工过程及计算机数值模拟方面的研究,E-mail: cxhzhm@163.com E-mail:cxhzhm@163.com
  • 基金资助:
    中国石油和化学工业联合会科技指导计划项目(2016-13-03)、黑龙江省教育厅自然科学基金项目(12541074)和东北石油大学青年科学基金项目(2019QNL-35)资助

Numerical Simulation on the Side Reaction Network and Mechanism of Ethylene to Benzene

ZHANG Hongmei1, ZHANG Jintao1, LI Jinlian1, MA Liao1, HAO Yulan1, ZHAO Jingying2, ZHAO Liang3   

  1. 1Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, China; 2Daqing Chemical Research Center, CNPC, Daqing 163714, China; 3State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
  • Received:2018-12-03 Revised:2019-08-24 Online:2020-01-25 Published:2020-04-01

摘要: 结合Materials Studio软件与Aspen Plus软件计算结果,提出了乙烯生成苯副反应网络是经自由基+烯或自由基+炔发生加成反应生成大自由基,并由大自由基继续发生环化、脱氢直到生成苯的反应方式进行的观点。建立了乙烯生成苯的副反应网络,得到其自由基反应机理。乙烯生成苯的副反应网络共包括54个自由基反应,共6条生成苯的反应路径。将此6条路径进行产物标记,通过Aspen Plus软件进行过程模拟计算,根据产物分布对反应网络进行简化,得到由乙烯生成苯的2条主要路径:一是C2H3?与乙烯进行加成反应生成1-C4H7?4,再环化生成C6H11?,再经过脱氢、传递,最终生成苯;另一个途径是C2H3?与乙炔加成为1,3-C4H5?4以及C2H3?分解为乙炔,乙炔链传递为乙炔基,乙炔基与乙烯加成生成1-C4H5?4,1-C4H5?4再异构为1,3-C4H5?4,生成的1,3-C4H5?4再环化生成C6H9?,然后脱氢、传递,最终生成苯。将得到的模拟产物分布与文献中的实验数据进行对比,证明了模拟计算结果的准确性。

关键词: 乙烯, 苯, 副反应, 热裂解, 自由基, 反应机理, 模拟

Abstract: Combining the results of calculated by Materials Studio with Aspen Plus softwares, we propose that the side reaction network of ethylene to benzene is formed by “free radical + olefin or free radical + alkyne”. Based on this viewpoint, we have established the side reaction network of ethylene to benzene and obtained the free radical reaction mechanism, which consists of 54 radical reactions and 6 reaction paths. The reaction network is simplified via Aspen Plus according to the product distribution to obtain two main routes for ethylene to benzene. The first path is that C2H3?reacts with ethylene to form 1-C4H7?4, which further reacts with ethylene to form C6H11?.Subsequently, benzene is produced by dehydrogenation of C6H11?. The second path is that acetylene is produced by dehydrogenation of C2H3?, and reacts with C2H3? to form 1,3-C4H5?4 or 1-C4H5?4. C2H? from dehydrogenation of acetylene reacts with ethylene to form 1,3-C4H5?4 or 1-C4H5?4. 1,3-C4H5?4 or 1-C4H5?4 reacts with ethylene to form C6H9?. Subsequently, benzene is produced by dehydrogenation of C6H9?. Comparing simulation results with the experimental data, the accuracy of the simulation results is proved.

Key words: ethylene, benzene, side reaction, pyrolysis, free radical, reaction mechanism, simulation

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