【作者】 李正； 袁裕霞； 杨朝合； 山红红； 张建芳；

【Author】 LI Zheng, YUAN Yuxia, YANG Chaohe, SHAN Honghong, ZHANG Jianfang (State Key Laboratory of Heavy Oil Processing, University of Petroleum, Dongying, Shandong 257061, P R China)

【机构】 石油大学重质油国家重点实验室；

【摘要】 以USY和HZSM - 5分子筛为模型催化剂,在脉冲式反应器上考察了40 0～50 0℃时1-庚烯的反应情况。通过对产物分布中大量异构一次产物的分析,表明传统正碳离子机理对烯烃固体酸催化反应描述存在片面性;认为烯烃所形成的初始正碳离子在进行裂化反应和氢转移反应之前已经发生了骨架异构,并在此基础之上将环状过渡态引入到烯烃的反应之中,提出了描述烯烃固体酸反应的CTS (Cyclo-TransitionState)机理。该机理的预测结果能够较好地与实验数据吻合。更多还原

【Abstract】 A pulsating reaction system was employed to investigate the fast reactions of 1-heptene over USY and HZSM-5 zeolites under reaction temperature of 400 to 500 centigrade It was proven that the existing reaction mechanisms of alkenes were not accurate enough via the structural correlation between products and substrates According to the feature of excess extent of products branching, skeletal isomerization of carbenium ions may precede cracking and hydrogen transfer, and CTS (Cyclo-Transition State) mechanism were proposed in which protonated dialkylcyclopropane and dialkylcyclobutane were introduced as transition states The predictions of the CTS mechanism were consistent with the experimental results更多还原