甲醇与丁烯耦合反应制丙烯的热力学研究  

Thermodynamics of coupling conversion of methanol and butylene to propylene

作　　者：白婷 钞译娴[1] 曹彬 王进[1] 张昕[2] Bai Ting;Chao Yixian;Cao Bin;Wang Jin;Zhang Xin(College of Chemistry and Chemical Engineering,Xi’an Shiyou University,Xi’an Shannxi 710069,China;School of Chemical Engineering,Northwest University,Xi’an Shannxi 710065,China)

机构地区：[1]西安石油大学化学化工学院,陕西西安710069 [2]西北大学化工学院,陕西西安710065

出　　处：《石油化工》2018年第10期85-91,共7页Petrochemical Technology

基　　金：教育部新世纪优秀人才支持计划项目(NCET-10-878);陕西省重大科技专项(2011ZKC4-08;2009ZDKG-70);西安石油大学大学生创新创业训练计划项目

摘　　要：对甲醇与丁烯耦合反应体系进行了热力学计算,分析了反应温度、压力、甲醇与丁烯摩尔比、水加入量对反应平衡组成的影响。研究了催化剂的孔道、酸性和反应条件对甲醇与丁烯耦合反应中产物分布的影响。实验结果表明,温度对甲醇与丁烯耦合反应的影响最大。压力变化对乙烯含量的影响比对丙烯含量的影响大。适当提高甲醇与丁烯摩尔比有利于提高丙烯的平衡组成。水的加入对丙烯的生成不利,但加入适量的水可延长催化剂的寿命。对催化剂进行Ag改性,适度降低催化剂的酸性可以有效抑制氢转移、环化及芳构化等反应,从而使乙烯和丙烯收率增加。在550℃、0.1 MPa、重时空速为0.55 h^(-1)、甲醇与丁烯摩尔比为1的条件下,采用1.5Ag/HZSM-5催化剂时,丙烯收率最高。The thermodynamic calculation of the coupling conversion of methanol and butylene was performed.The effects of reaction temperature,pressure,molar ratio of methanol to butylene and water content on the equilibrium composition of olefin products were discussed.The influences of the pore structures and acidities of the catalysts and the reaction conditions on product distribution were investigated.The results showed that the temperature had the greatest impact on the equilibrium composition of the olefin products.The effect of pressure change on ethylene content was greater than that on propylene content.The moderate ratio of methanol to butylene was favorable to increase the propylene equilibrium composition.The addition of water was not beneficial to the formation of propylene,whereas the proper amount of water added could extend the catalyst life time.The Ag-modified HZSM-5 catalysts were investigated in the coupling reaction.The hydrogen transfer,cyclization and aromatization were effectively suppressed,while the propylene yield was improved by reducing the catalyst acidity appropriately.The highest propylene yield was obtained on the 1.5Ag/HZSM-5 catalyst under the conditions of 550℃,0.1 MPa,WHSV 0.55 h-1,and the molar ratio of methanol to butylene 1.

关 键 词：甲醇 丁烯 耦合反应 丙烯 热力学 HZSM-5分子筛 

分 类 号：TQ021.2[化学工程]