Wang Wenke, Zhao Jie, Jia Dandan, Fu Zhaolin, Xing Enhui, Zhu Zhongpeng, Yan Rui, Tao Zhiping, Luo Yibin, Shu Xingtian
Research Institute of Petroleum Processing, Sinopec, 18 Xueyuan Road, Haidian District, Beijing 100083, China.
ACS Omega. 2021 Jun 30;6(27):17173-17182. doi: 10.1021/acsomega.1c00212. eCollection 2021 Jul 13.
The fast deactivation caused by serious formation of coke is a major challenge in catalytic isomerization of -tetrahydrodicyclopentadiene (-THDCPD) into -tetrahydrodicyclopentadiene (-THDCPD) over the HY zeolite. In order to suppress the coke formation for the isomerization process, the conventional HY zeolite was modified with Pt at 0.3 wt %. Then, the hydroisomerization of -THDCPD into -THDCPD was evaluated over a fixed-bed reactor. The catalytic stability of Pt/HY was greatly enhanced in comparison to that of the HY zeolite. The Pt/HY catalyst provided 97% -THDCPD conversion and 96% selectivity for -THDCPD without deactivation after 100 h. Moreover, the formation mechanism of coke on the HY zeolite during the isomerization process was proposed based on the results of the coke analysis. It was indicated that the coke was generated from the oligomerization and condensation of olefin species, which originated from the β-scission reaction or hydride transfer reaction of intermediates. The lower coke formation over Pt/HY was attributed to the lower amount of coke precursors, which could be hydrogenated by activated H over Pt sites. Therefore, Pt on Pt/HY and H were two crucial factors in efficiently enhancing the catalytic stability of the HY zeolite for this isomerization reaction.
在HY沸石上,由严重积炭导致的快速失活是将α-四氢二环戊二烯(α-THDCPD)催化异构化为β-四氢二环戊二烯(β-THDCPD)过程中的一个主要挑战。为了抑制异构化过程中的积炭,用0.3 wt%的Pt对传统的HY沸石进行了改性。然后,在固定床反应器中对α-THDCPD加氢异构化为β-THDCPD的反应进行了评估。与HY沸石相比,Pt/HY的催化稳定性大大提高。Pt/HY催化剂在100 h后提供了97%的α-THDCPD转化率和96%的β-THDCPD选择性,且没有失活。此外,基于积炭分析结果,提出了异构化过程中HY沸石上积炭的形成机理。结果表明,积炭是由烯烃物种的齐聚和缩合产生的,这些烯烃物种源于中间体的β-断裂反应或氢转移反应。Pt/HY上较低的积炭归因于较少的积炭前体数量,这些积炭前体可以在Pt位点上被活化的H氢化。因此,Pt/HY上的Pt和H是有效提高HY沸石对该异构化反应催化稳定性的两个关键因素。