甲醇制烯烃反应机理及其动力学研究
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摘要
随着全球经济的飞速发展,世界各国对重要的石化原料——乙烯和丙烯的需求迅猛增长。乙烯和丙烯主要来源于石油基原料的蒸汽裂解或催化裂化等过程,随着石油资源的日益短缺,烯烃发展也因此受到制约。鉴于我国缺油少气多煤的能源现状,以煤为原料,走煤-甲醇-烯烃工艺路线符合国家能源政策需要。甲醇制烯烃(Methanol to Olefins,MTO/Methanol to Propylene,MTP)工艺是以甲醇为原料高选择性地生产乙烯、丙烯等低碳烯烃的技术。该工艺开辟了由甲醇(或煤炭、天然气、生物质等非石油基原料)生产乙烯、丙烯的新路线,可有效缓解烯烃供给不足与甲醇产能过剩的矛盾,降低石油资源对外依存度,具有良好的发展前景。本文主要针对SAPO-34催化剂上MTO过程以及ZSM-5催化剂上MTP过程的反应情况,综述了近年来甲醇制烯烃代表性的反应工艺、反应机理以及反应动力学等方面的最新研究进展,并根据其存在的问题分别提出了相应的发展方向。
引文
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[3]文尧顺,南海明,吴秀章,等.甲醇制烯烃反应动力学及反应器模型研究进展[J].化工进展,2014,33(10):2521-2527.
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[6]Nesterenko N,Aguilhon J,Bodart Ph,et al.Zeolites and zeolite-like materials.Chapter 5-Methanol to olefins;an insight into reaction pathways and products formation[M].2016:189-263.
[7]Ye M,Li H,Zhao Y,et al.MTO processes development:the key of mesoscale studies[J].Advances in Chemical Engineering,2015,47;279-335.
[8]Wang S,Chen Y,Wei Z,et al.Polymethylbenzene or alkene cycle?Theoretical study on their contribution to the process of methanol to olefins over H-ZSM-5 zeolite[J].Journal of Physical Chemistry C,2015,119:28482-28498.
[9]Zhang W,Chu Y,Wei Y,et al.Influences of the confinement effect and acid strength of zeolite on the mechanisms of methanol-to-olefins conversion over H-ZSM-5:a theoretical study of alkenesbased cycle[J].Microporous and Mesoporous Materials,2016,231;216-229.
[10]Kumar P,Thybaut J W,Svelle S,et al.Single-event microkinetics for methanol to olefins on H-ZSM-5[J].Industrial&Engineering Chemistry Research,2013,52:1491-1507.
[11]Sedighi M,Bahrami H,Towfighi J.Kinetic modeling formulation of the methanol to olefin process;Parameter estimation[J].Journal of Industrial and Engineering Chemistry,2014,20:3108-3114.
[12]Ying L,Yuan X,Ye M,et al.A seven lumped kinetic model for industrial catalyst in DMTO process[J].Chemical Engineering Research and Design,2015,100:179-191.
[13]Wen M,Ding J,Wang C,et al.High-performance SS-fiber@HZSM-5 core-shell catalyst for methanol-to-propylene:a kinetic and modeling study[J].Microporous and Mesoporous Materials,2016,221:187-196.
[2]胡浩,叶丽萍,应卫勇,等.甲醇制烯烃反应机理和动力学研究进展[J].工业催化,2008,16(3):18-23.
[3]文尧顺,南海明,吴秀章,等.甲醇制烯烃反应动力学及反应器模型研究进展[J].化工进展,2014,33(10):2521-2527.
[4]Wu W,Guo W,Xiao W,et al.Dominant reaction pathway for methanol conversion to propene over high silicon H-ZSM-5[J].Chemical Engineering Science,2011,66:4722-4732.
[5]应磊.SAPO-34及ZSM-5催化剂上甲醇与烯烃转化动力学研究[D].杭州:浙江大学,2015.
[6]Nesterenko N,Aguilhon J,Bodart Ph,et al.Zeolites and zeolite-like materials.Chapter 5-Methanol to olefins;an insight into reaction pathways and products formation[M].2016:189-263.
[7]Ye M,Li H,Zhao Y,et al.MTO processes development:the key of mesoscale studies[J].Advances in Chemical Engineering,2015,47;279-335.
[8]Wang S,Chen Y,Wei Z,et al.Polymethylbenzene or alkene cycle?Theoretical study on their contribution to the process of methanol to olefins over H-ZSM-5 zeolite[J].Journal of Physical Chemistry C,2015,119:28482-28498.
[9]Zhang W,Chu Y,Wei Y,et al.Influences of the confinement effect and acid strength of zeolite on the mechanisms of methanol-to-olefins conversion over H-ZSM-5:a theoretical study of alkenesbased cycle[J].Microporous and Mesoporous Materials,2016,231;216-229.
[10]Kumar P,Thybaut J W,Svelle S,et al.Single-event microkinetics for methanol to olefins on H-ZSM-5[J].Industrial&Engineering Chemistry Research,2013,52:1491-1507.
[11]Sedighi M,Bahrami H,Towfighi J.Kinetic modeling formulation of the methanol to olefin process;Parameter estimation[J].Journal of Industrial and Engineering Chemistry,2014,20:3108-3114.
[12]Ying L,Yuan X,Ye M,et al.A seven lumped kinetic model for industrial catalyst in DMTO process[J].Chemical Engineering Research and Design,2015,100:179-191.
[13]Wen M,Ding J,Wang C,et al.High-performance SS-fiber@HZSM-5 core-shell catalyst for methanol-to-propylene:a kinetic and modeling study[J].Microporous and Mesoporous Materials,2016,221:187-196.