乙烯生成苯副反应网络和反应机理数值模拟

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。

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

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.