ZSM-5分子筛上甲醇与丁烯耦合反应研究  

Methanol-butene coupling reaction on ZSM-5 catalyst

作　　者：李冰寒 杨闯 彭明伟 李金哲[1] 刘中民[1,3] LI Binghan;YANG Chuang;PENG Mingwei;LI Jinzhe;LIU Zhongmin(Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China;Shenyang University of Chemical Technology,Shenyang 110142,Liaoning,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院大连化学物理研究所 [2]中国科学院大学 [3]沈阳化工大学

出　　处：《工业催化》2025年第1期14-20,共7页Industrial Catalysis

基　　金：国家自然科学基金重大项目(21991093,21991090)。

摘　　要：研究了ZSM-5分子筛上甲醇和丁烯耦合转化反应,发现不同温度下耦合反应呈现出不同的耦合特征,大于350℃的高温有利于生成乙烯、丙烯等低碳烯烃,而较低的温度下更有利于生成大量长链烃类。在250℃及更低的温度下,单独甲醇进料几乎没有烃类产物生成,表现出显著的反应诱导期特征;加入不同浓度丁烯均能大幅提高甲醇转化率,缩短反应诱导期;但随着丁烯加入量的增加,甲醇转化率随反应时间呈现先上升后下降的趋势,丁烯浓度越高,变化速率越快;反应后催化剂上存留的有机物种主要是多甲基苯,催化剂积碳量的变化规律与丁烯的加入量密切相关,表明积碳物种的生成主要与烯烃/甲醇耦合产物的进一步转化相关,这些积碳物种的生成极大地影响了耦合反应的产物分布,反映了甲醇转化反应机理的复杂性,并为进一步调控烯烃产物分布提供了可能的途径。In this paper,the coupling reaction of methanol and butene on ZSM-5 molecular sieve was studied,and it was found that the coupling reaction showed different characteristics at different temperatures.The high temperature above 350℃was conducive to the formation of light olefins such as ethylene and propylene,while the low temperature was more conducive to the formation of long chain hydrocarbons.At 250℃and lower temperatures,almost no hydrocarbon products were generated from methanol feed alone,showing a significant reaction induction period.Adding different concentrations of butene can greatly increase the methanol conversion and shorten the reaction induction period.However,with the increase of butylene concentration,the methanol conversion increased first and then decreased with the reaction time.The higher the butylene concentration,the faster the change rate.The organic species retained in the catalyst after reaction are mainly polymethylbenzenes,and the coke deposition is closely related to the amount of butene added,indicating that the formation of coke species is mainly related to the further transformation of the olefin/methanol coupling products,and the formation of these species greatly affects the product distribution of the coupling reaction,reflecting the complexity of the methanol conversion reaction mechanism.It also provides a possible way to further regulate the distribution of olefin products.

关 键 词：催化化学 甲醇 丁烯 耦合转化 诱导期 ZSM-5 

分 类 号：O643.36[理学—物理化学] TQ221.21[理学—化学]