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化学进展 2009, Vol. 21 Issue (09): 1757-1762 前一篇   后一篇

• 综述与评论 •

甲醇制烯烃反应机理

虞贤波;刘烨;阳永荣;王靖岱*   

  1. (化学工程国家重点实验室(浙江大学),浙江大学化学工程与生物工程学系 |杭州 310027)
  • 收稿日期:2008-11-10 修回日期:2008-12-10 出版日期:2009-09-24 发布日期:2009-09-15
  • 通讯作者: 王靖岱 E-mail:wangjd@cmsce.zju.edu.cn
  • 基金资助:

Mechanisms of Methanol-to-Olefin Reaction

Yu Xianbo ; |Liu Ye ; |Yang Yongrong ; |Wang Jingdai*   

  1. (State Key Laboratory of Chemical Engineering, Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027, China)
  • Received:2008-11-10 Revised:2008-12-10 Online:2009-09-24 Published:2009-09-15
  • Contact: Wang Jingdai E-mail:wangjd@cmsce.zju.edu.cn

本文综述了甲醇制烯烃(MTO)反应机理的研究进展,介绍了MTO反应的5个阶段:二甲醚平衡物的生成,反应诱导期,反应稳定期,二次反应和积碳失活,以及各个阶段存在的反应类型。总结了主要的机理模型及相应的实验论据,讨论了机理模型在各个反应阶段的应用,重点讨论了直接形成机理和hydrocabon pool机理。基于实验论据的支持,认为hydrocabon pool机理能更好地解释MTO反应。同时,对机理研究中采用的理论和试验方法进行了综述。

Researches in mechanism for methanol-to-olefin (MTO) reaction are reviewed in this paper. Five reaction steps, the equilibrium between methanol and dimethyl ether, induction period, post-induction period, secondary reaction and deactivation, are introduced as well as the reaction types in each step. The main mechanism models and their experimental proofs are concluded. The mechanism models, especially the direct mechanism and the hydrocarbon pool theory, are discussed in detail in each reaction step. The hydrocarbon pool theory is thought as the one that can better explain the MTO reaction based on the experimental proof. Meanwhile the research methods, both theoretic and experimental are also reviewed in this paper.

Contents
1 Introduction
2 Mechanisms of methanol to olefin reaction
2.1 Equilibrium between methanol and dimethyl ether
2.2 Induction period
2.3 Post-induction period
2.4 Secondary reaction
2.5 Deactivation
3 Conclusion

中图分类号: 

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[ 1 ]  Meisel S L , McCullough J P , Lechthaler C H , et a1. Chemtech. ,1976 , 6 : 86 —89
[ 2 ]  Chang C D , Silvestri A J . J . Catal . , 1977 , 47 : 249 —259
[ 3 ]  Chang C D. Catal . Today , 1992 , 13 : 103 —111
[ 4 ]  Cosyns J , Chodorge J , Commereuc D. Hydrocarbon Processing ,1998 , 1 : 28 —29
[ 5 ]  HawJ F , Song W G, Marcus D M, et al . Acc. Chem. Res. ,2003 , 36 : 317 —326
[ 6 ]  Stêcker M. Microporous Mesoporous Mater. , 1999 , 29 : 3 —48
[ 7 ]  Chang C D. Catal . Rev. , 1983 , 25 : 1 —118
[ 8 ]  Keil F J . Microporous Mesoporous Mater. , 1999 , 29 : 49 —66
[ 9 ]  Wilson S , Barger P. Microporous Mesoporous Mater. , 1999 , 29 :117 —126
[10 ]  Olsbye U , Bjorgen M, Svelle S. Catalysis Today , 2005 , 106 (1/4) :108 —111
[11 ]  Lesthaeghe D , Speybroeck V V , Marin G B. Ind. Eng. Chem.Res. , 2007 , 46 : 8832 —8838
[12 ]  胡浩(Hu H) , 叶丽萍(Ye L P) , 应卫勇(Ying W Y) 等. 工业催化( Industrial Catalysis) , 2008 , 16 (3) : 18 —23
[13 ]  Chang C D , Howe R F , Yurchak S. Methane Conversion.Amsterdam: Elsevier , 1988. 127
[14 ]  Salvador P , Kladnig W. J . Chem. Soc. Faraday Tyans. 1 , 1977 ,73 : 1153 —1168
[15 ]  NovákováJ , KubelkováL , Dolejˇsek Z. J . Catal . , 1987 , 108 :208 —213
[16 ]  Forester T R , Howe R F. J . Am. Chem. Soc. , 1987 , 109 : 5076 —5082
[17 ]  Kupelková L , Nováková J , Nedomová K. J . Catal . , 1990 , 124 :441 —450
[18 ]  Murray D K, Chang J W, Haw J F. J . Am. Chem. Soc. , 1993 ,115 : 4732 —4741
[19 ]  Salehirad F , Anderson M W. J . Catal . , 1998 , 177 : 189 —207
[20 ]  Wang W, Seiler M, Hunger M. J . Phys. Chem. B , 2001 , 105(50) : 12553 —12558
[21 ]  Wang W, Buchholz A , Hunger M, et a1. J . Am. Chem. Soc. ,2003 , 125 : 15260 —15267
[22 ]  Wang W, Jiang Y, Hunger M. Catal . Today , 2006 , 113 : 102 —114
[23 ]  Jiang Y, Hunger M, Wang W. J . Am. Chem. Soc. , 2006 , 128(35) : 11679 —11692
[24 ]  Wang W, Hunger M. Acc. Chem. Res. , 2008 , 41 (8) : 895 —904
[25 ]  徐柏庆(Xu P Q) , 梁娟(Liang J ) , 陈国权(Chen G Q) 等. 催化学报(Chinese Journal of Catalysis) , 1991 , 12 (4) : 273 —280
[26 ]  Dessau R M. J . Catal . , 1986 , 99 : 111 —116
[27 ]  Cui Z M, Liu Q , Song W G, et al . J . Phys. Chem. C , 2008 , 112 :2685 —2688
[28 ]  Langner B E. Appl . Catal . , 1982 , 2 : 289 —302
[29 ]  Song W G, Marcus D M, Haw J F , et al . J . Am. Chem. Soc. ,2002 , 124 : 3844 —3845
[30 ]  Van den Berg J P , Wolthuizen J P , van Hooff J H C. Proceedings 5th International Zeolite Conference ( Ed. Rees L V) , London , 1980.649
[31 ]  Munson E J , Haw J F. J . Am. Chem. Soc. , 1991 , 113 : 6303 —6305
[32 ]  Ono Y, Mori T. J . Chem. Soc. Faraday Trans. 1 , 1981 , 77 :2209 —2221
[33 ]  Chang C D , Hellring S D , Pearson J A. J . Catal . , 1989 , 115 :282 —285
[34 ]  Cui Z M, Liu Q , Song W G. Angew. Chem. Int . Ed. , 2006 , 45 :6512 —6515
[35 ]  Marcus D M, McLachlan KA , HawJ F , et al . Angew. Chem. Int .Ed. , 2006 , 45 : 3133 —3136
[36 ]  Lesthaeghe D , van Speybroeck V , Marin GB. Angew. Chem. Int .Ed. , 2006 , 45 : 1714 —1719
[37 ]  Mole T, Bett G, Seddon D. J . Catal . , 1983 , 84 : 435 —445
[38 ]  Kolboe S. Acta Chem. Scand. , 1986 , A40 : 711 —713
[39 ]  Dahl I M, Kolboe S. Catal . Lett . , 1993 , 20 : 329 —336
[40 ]  Dahl I M, Kolboe S. J . Catal . , 1994 , 149 : 458 —464
[41 ]  Dahl I M, Kolboe S. J . Catal . , 1996 , 161 : 304 —309
[42 ]  Goguen P W, Xu T, Barich D H , Haw J F , et al . J . Am. Chem.Soc. , 1998 , 120 : 2650 —2651
[43 ]  Xu T, Barich D H , Haw J F , et al . J . Am. Chem. Soc. , 1998 ,120 : 4025 —4026
[44 ]  Mikkelsen a, Kolboe S. Microporous and Mesoporous Materials ,1999 , 29 (1P2) : 173 —184
[45 ]  Song W G, Haw J F , Nicholas J B. J . Am. Chem. Soc. , 2000 ,122 : 10726 —10727
[46 ]  Song W G, Nicholas J B , HawJ F. J . Phys. Chem. B , 2001 , 105 :4317 —4323
[47 ]  Arstad B , Kolboe S. J . Am. Chem. Soc. , 2001 , 123 : 8137 —8138
[48 ]  Song W G, Nicholas J B , Sassi A. Catal . Lett . , 2002 , 81 : 49 —53
[49 ]  Bjorgen M, Bonino F. Kolboe S. J . Am. Chem. Soc. , 2003 , 125(51) : 15863 —15868
[50 ]  Bjorgen M, Olsbye U , Kolbue S , et al . J . Catal . , 2004 , 221 (1) :1 —10
[51 ]  Chua Y T, Stair P C , Nicholas J B. J . Am. Chem. Soc. , 2003 ,125 (4) : 866 —867
[52 ]  Bjørgen M, Svelle S , Joensen F , et al . J . Catal . , 2007 , 249 :195 —207
[53 ]  Song W, Fu H , HawJ F. J . Phys. Chem. B , 2001 , 105 : 12839 —12843
[54 ]  Fu H , Song W G, Marcus D M. J . Phys. Chem. B , 106 (22) :5648 —5652
[55 ]  Marcus D M, Song W G, Abubakar SM. Langmuir , 2004 , 20 (14) :5946 —5951
[56 ]  Svelle S , Olsbye U , Lillerud K P. J . Am. Chem. Soc. , 2006 , 128(17) : 5618 —5619
[57 ]  HawJ F , Nicholas J B , Song W G. J . Am. Chem. Soc. , 2000 ,122 : 4763 —4775
[58 ]  Song W, Nicholas J B , HawJ F. J . Am. Chem. Soc. , 2001 , 123 :121 —129
[59 ]  Sullivan R F , Egan CJ , Langlois G E. J . Am. Chem. Soc. , 1961 ,83 : 1156 —1160
[60 ]  Arstad B , Kolboe S , Swang O. J . Phys. Chem. B , 2002 , 106(49) : 12722 —12726
[61 ]  Arstad B , Kolboe S , Swang O. J . Phys. Chem. B , 2005 , 109(39) : 8914 —8922
[62 ]  Sassi A , Song W G, Wildman M A. J . Phys. Chem. B , 2002 ,106 : 2294 —2303
[63 ]  Song W G, Fu H , Haw J F. J . Am. Chem. Soc. , 2001 , 123 :4749 —4754
[64 ]  Arstad B , Nicholas J B , Haw J F. J . Am. Chem. Soc. , 2004 ,126 : 2991 —3001
[65 ]  Sassi A , Wildman M A , Haw J F. J . Phys. Chem. B , 2002 , 106(34) : 8768 —8773
[66 ]  Cui ZM, Liu Q , Bain S W. J . Catal . , 2008 , 258 : 83 —86
[67 ]  Svelle S , Rønning P O , Kolboe S. J . Catal . , 2004 , 224 ( 1) :115 —123
[68 ]  Svelle S , Rønning P O , Kolboe S. J . Catal . , 2005 , 234 ( 2) :385 —400
[69 ]  Svelle S , Arstad B , Kolboe S. J . Phys. Chem. B , 2003 , 107 (35) :9281 —9289
[70 ]  Svelle S , Kolboe S , Swang O. J . Phys. Chem. B , 2004 , 108 (9) :2953 —2962
[71 ]  Svelle S , Joensen F , Nerlov J . J . Am. Chem. Soc. , 2006 , 128(46) : 14770 —14771
[72 ]  Bjørgen M, Olsbye U , Kolboe S. J . Catal . , 2003 , 215 : 30 —44

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摘要

甲醇制烯烃反应机理