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化学进展 2009, Vol. 21 Issue (0708): 1636-1643 前一篇   后一篇

• 综述与评论 •

环氧乙烷胺化制乙醇胺*

冯汝明1,2,3**;刘仲能1;顾荣2;曹勇3;谢在库1   

  1. （1.中国石油化工股份有限公司上海石油化工研究院  |上海 201208；2.中国石油化工股份有限公司上海高桥石化公司  |上海 200137；3.复旦大学化学系  |上海 200433）
  • 收稿日期:2008-09-09 修回日期:2008-11-03 出版日期:2009-08-24 发布日期:2009-06-30
  • 通讯作者: 冯汝明 E-mail:fengrm@sript.com.cn
  • 基金资助:

    博士后科学基金

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Amination of Ethylene Oxide to Ethanolamine

Feng Ruming1,2,3**; |Liu Zhongneng1; |Gu Rong2; |Cao Yong3 |Xie Zaiku1   

  1. (1. Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China|2. Shanghai Gao Qiao Petrochemical Corporation, SINOPEC, Shanghai 200137, China|3. Chemistry Department of Fudan University, Shanghai 200433, China)
  • Received:2008-09-09 Revised:2008-11-03 Online:2009-08-24 Published:2009-06-30
  • Contact: Feng Ruming E-mail:fengrm@sript.com.cn

环氧乙烷选择性胺化制乙醇胺成为近年来胺化反应的热点课题。乙醇胺主要由氨水法与液氨法两种制备方法合成，它们分属于典型的均相催化与多相催化。本文从热力学、动力学、反应机理等方面对氨水法的研究进展进行了系统地综述，并部分探讨了工业上氨水法的工艺条件。并且从催化剂的种类、表面酸碱性质以及孔径结构等方面对液氨法的新认识进行了系统地阐述，并探讨了选择性胺化反应的未来研究方向。

关键词： 环氧乙烷, 氨, 乙醇胺, 选择性胺化

The selective amination of ethylene oxide to ethanolamine has become a hot spot in amination reactions in recent years. The preparation of ethanolamine is mainly composed of aqueous ammonia and liquid ammonia methods, which belong to typical homogeneous catalysis and heterogeneous catalysis respectively. This article intends to review the progress in aqueous ammonia method from thermodynamics, kinetics and reaction mechanism aspects. The engineering condition of aqueous ammonia method in industry is also partly discussed. The latest knowledge of catalyst species, surface acid-base property and pore structure in the catalyst is summarized in terms of liquid ammonia method. A prospection on the future research of selective amination is also discussed.

Contents
1 Homogeneous catalysis system
1.1 Reaction between aqueous ammonia and EO (aqueous ammonia method)
1.2 Thermodynamic research
1.3 Kinetics research
1.4 Influences affecting the product distribution
1.5 Mechanism
2 Heterogeneous catalysis system
2.1 Reaction between liquid ammonia and EO (liquid ammonia method)
2.2 Strong-acid ion exchange resigns
2.3 Supported heteropoly acids
2.4 Microporous solid acid materials
3 Conclusion

Key words: ethylene oxide(EO), ammonia, ethanolamine, selective amination

中图分类号: 

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[ 1 ] 　Setoyama T. Catal . Today , 2006 , 116 : 250 —262
[ 2 ] 　Tsuneki H. Shokubai , 2005 , 17 : 196 —200
[ 3 ] 　孙英杰( Sun Y J ) . 精细与专用化学品( Fine and Specialty Chemicals) , 2005 , 13 : 1 —6
[ 4 ] 　秦伟程(Qin W C) . 化学品科技市场( Chemical Technology Market) , 2004 , 11 : 19 —25
[ 5 ] 　Willis S B , Henry J D. US 4355181 , 1982
[ 6 ] 　Weaver D G, Smart J L. Ind. Eng. Chem. , 1959 , 51 : 894 —900
[ 7 ] 　张欣豪(Zhang X H) , 吴云东(Wu Y D) . 化学进展( Progress in Chemistry) , 2008 , 20 : 1 —7
[ 8 ] 　Frauenkron M, Melder J P , Ruider G, et al . Ullmann's Encyclopedia of Industrial Chemistry Online , 2001 , 1 —30
[ 9 ] 　Vamling L , Cider L. Ind. Eng. Chem. Prod. Res. Dev. 1986 ,25 : 424 —430
[10 ] 　Johnson F L. US 4438281 , 1984
[11 ] 　Grice N J , Knifton J F. US 4939301 , 1990
[12 ] 　Corbin D R , Schwarz S , Sonnichsen GC. Catal . Today , 1997 , 37 :71 —85
[13 ] 　Tsuneki H , Kirishiki M, Arita Y, et al . US 6559342 , 2003
[14 ] 　Tsuneki H , Takeda K, Morishita F. US 6566556 , 2003
[15 ] 　Tsuneki H. US 6455016 , 2002
[16 ] 　Knorr L. Chem. Bev. , 1897 , 30 : 909 —911
[17 ] 　Knorr L. Chem. Bev. , 1899 , 32 : 729 —731
[18 ] 　Carleton E. The Chemistry of Petroleum Derivatives. New York: The Chemical Catalog Co. inc. ,1934. 1 : 541 —544
[19 ] 　Carleton E. The Chemistry of Petroleum Derivatives. New York: The Chemical Catalog Co. inc. , 1937. 2 : 563 —567
[20 ] 　Miller S A. Ethylene and Its Industrial Derivatives. London: Ernest Benn , 1969. 22 : 632 —635
[21 ] 　Schwoegler E J , Olin J F. US 2373199 , 1945
[22 ] 　Schwoegler E J . US 2337004 , 1943
[23 ] 　魏海国(Wei H G) . 浙江大学硕士学位论文(Master Dissertation of Zhejiang University) , 1993
[24 ] 　罗铭芳(Luo M F) . 天津大学硕士学位论文(Master Dissertation of Tianjin University) , 2004
[25 ] 　Duldner I. Rev. Chim. (Bucharest) , 1970 , 21 : 3 —7
[26 ] 　Parker R E , Isaacs N S. Chem. Rev. , 1959 , 59 : 737 —799
[27 ] 　Miki M, Ito T, Hatta M, Okabe T. Yukagaku , 1966 , 15 : 215 —220
[28 ] 　Potter C , Mclaughlin R R. Can. J . Res. Sect . B , 1947 , 25 :405 —409
[29 ] 　Stoyanov A D , Boeva R S , Kotov S V. Zh. Prikl . Khim.(Leningrad) , 1983 , 56 : 1966 —1969
[30 ] 　Johnson F L. US 438281 , 1984
[31 ] 　You P K, Kil P T. Hwaha Konghak , 1985 , 23 : 409 —415
[32 ] 　程华农(Cheng H N) , 孙昌青(Sun C Q) , 孙杰(Sun J ) , 岳金彩( Yue J C) 等. 青岛科技大学学报(Journal of Qingdao University of Science and Technology) , 2007 , 28 : 125 —128
[33 ] 　程华农(Cheng H N) , 毛文峰(Mao WF) , 魏凤(Wei F) , 岳金彩(Yue J C) 等. 计算机与应用化学(Computers and Applied Chemistry) , 2006 , 23 : 69 —72
[34 ] 　Eastham AM, Darwent B B , Beaubien P E. Can. J . Chem. , 1951 ,29 : 575 —584
[35 ] 　Eastham AM, Darwent B B , Beaubien P E. Can. J . Chem. , 1951 ,29 : 585 —596
[36 ] 　Ferrero P , Berbe F , Flamme L R. Bull . Soc. Chim. , 1947 , 56 :349 —368
[37 ] 　Reich H , Fleury R. Chimia , 1966 , 20 : 29 —31
[38 ] 　Societe C , SociétéA. GB 655580 , 1948
[39 ] 　Lowe A J , Butler D , Meade E M. GB 760215 , 1952
[40 ] 　Societe C , SociétéA. GB 642950 , 1950
[41 ] 　Nygarrd D M, Diguilio R M. US 6063965 , 2000
[42 ] 　Diguilio R M, Mckinney M W. EP 6075168 , 2000
[43 ] 　Hammer H , Reutemann W. US 5545757 , 1996
[44 ] 　Kautter C T. US 2051486 , 1936
[45 ] 　Ferrero P , Berbe F , Flamme L R. Bull . Soc. Chim. , 1947 , 56 :349 —368
[46 ] 　Goetze W, Wolf P , Schulz G, Luedemann H. US 3723530 , 1973
[47 ] 　Ahmed M, Nelson J R , Gibson C A. US 4845296 , 1989
[48 ] 　Melder J P , Schulz G. US 6469214 , 2002
[49 ] 　Frauenkron M, Müller U , Harder W, Unger J , et al . US 7119231 ,2006
[50 ] 　Reynhart A F A. US 2186392 , 1940
[51 ] 　Watanabe H , Matsumura M, Ohkawa T, Suzuki K. US 5633408 ,1997
[52 ] 　Washington S J , Grant T F. US 5334763 , 1994
[53 ] 　Ruider G, Ross K H. WO 0032553 , 2000
[54 ] 　Garg D , Shah S N , Okasinski M J , Drayton2Elder A S. US 6846959 , 2005
[55 ] 　Ruider G, Ross K H , Melder J P , et al . US 6323371 , 2001
[56 ] 　Chakraborti A K, Rudrawar S , Kondaskar A. Eur. J . Org. Chem. ,2004 , 3597 —3600
[57 ] 　Holubka J W, Bah R D , Andrés J L. Macromolecules , 1992 , 25 :1189 —1192
[58 ] 　DelBene J E , Frisch M J , Raghavachari K, Pople J A. J . Phys.Chem. , 1982 , 86 : 1529 —1534
[59 ] 　Aue D H , Webb HM, Davidson WR. J . Am. Chem. Soc. , 1980 ,102 : 5151 —5157
[60 ] 　ShibaevA Y, Astra’eva N V , Tereshchenko G G. Zh. Obshch.Khim. , 1984 , 54 : 2744 —2748
[61 ] 　Somorjai GA. Top. Catal . , 2008 , 48 : 1 —7
[62 ] 　Weibull B J G. SE 158167 , 1957
[63 ] 　Weibull B J G, Thorsell L U F , Lindstrom S O. US 3697598 , 1972
[64 ] 　Weibull B J G, Thorsell L U F , Lindstrêm S O. SE 355570 , 1973
[65 ] 　Weibull B J G. Presented at the Swedish Symposium on Catalysis ,Lund , 1970
[66 ] 　Veefkind V A , Lercher J A. J . Catal . , 1998 , 180 : 258 —269
[67 ] 　Veefkind V A , Lercher J A. Appl . Catal . A: Gen. , 1999 , 181 :245 —255
[68 ] 　Veefkind V A , Smidt M L , Lercher J A. Appl . Catal . A: Gen. ,2000 , 194P195 : 319 —332
[69 ] 　Kiyoura T, Ishikawa J , Phala H. J . Catal . , 1997 , 170 : 204 —206
[70 ] 　Segawa K, Shimura T. Appl . Catal . A: Gen. , 2000 , 194P195 :309 —317
[71 ] 　Segawa K, Mizuno S , Sugiura M, Nakata S. Stud. Surf . Sci .Catal . , 1996 , 101 : 267 —276
[72 ] 　Segawa K, Mizuno S , Fujimoto Y, Yamamoto H. Stud. Surf . Sci .Catal . , 1994 , 83 : 273 —278
[73 ] 　Segawa K, Mizuno S , Maruyama Y, Nakata S. Stud. Surf . Sci .Catal . , 1994 , 84 : 1943 —1950
[74 ] 　De Oliveira Nunes M H , da Silva V T, Schmal M. Catal . Lett . ,2004 , 97 : 1 —8
[75 ] 　Zhang Y C , Bai G Y, Yan X L , et al . Catal . Comm. , 2007 , 8 :1102 —1106
[76 ] 　Malinonskii M S. J . Applied Chem. (USSR) , 1947 , 20 : 630 —634
[77 ] 　Sile M. Latv. PSR Zinat . Akad. Vestis , Kim. Serv. , 1972 , 1 :54 —60
[78 ] 　Sile M. Latv. PSR Zinat . , Akad. Vestis , Kim. Serv. , 1972 , 2 :218 —223
[79 ] 　Tsuneki H , Moriya A , Baba H. US 6169207 , 2001
[80 ] 　Tsuneki H , Moriya A , Baba H. EP 0941986 , 1999
[81 ] 　Moriya A , Tsuneki H. EP 0652207 , 1995
[82 ] 　Moriya A , Tsuneki H. US 5880058 , 1999
[83 ] 　Curini M, Epifano F , Marcotullio M C , Rosati O. Eur. J . Org.Chem. ,2001 , 4149 —4152
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摘要

环氧乙烷胺化制乙醇胺*