SiO_2载负废全氟磺酸离子交换膜的制备、表征及其在催化精馏中的应用
|
摘要
全氟磺酸树脂由于具有全氟碳高分子骨架结构而使它有非常好的耐化学腐蚀性和热稳定性，能在200℃下长期使用而不发生脱磺酸反应或其他热降解反应，是目前已知的最强的树脂固体酸催化剂。但由于其比表面积小，使得大量埋没在它内部的酸性中心不能为化学反应利用，此外，非极性溶剂和气态反应物质因不会引起树脂的溶胀，故其重量比活性低。
本论文主要研究了将电解制碱技术中更换下来的大量的全氟磺酸离子交换膜回收制成全氟磺酸树脂溶液，利用溶胶．凝胶法将全氟磺酸树脂分散组装到具有多孔性二氧化硅中，得到全氟磺酸树脂／SiO_2催化剂。
采用FTIR、DSC-TGA、BET、TEM、SEM等技术对其进行表征，发现：全氟磺酸树脂以纳米级状态分散在SiO_2网络或孔道中，由于有效表面积大大增加，充分暴露全氟磺酸树脂的酸性位，使该树脂催化剂的潜力得到发挥，同时还提高了催化剂的机械性能。
采用乙酸丁酯、乙酸异戊酯、邻苯二甲酸二辛酯、癸二酸二辛酯、苯甲醛乙二醇缩醛和苯甲醛丙二醇缩醛等合成反应作为探针来表征催化剂反应活性，发现：全氟磺酸树脂／SiO_2催化剂(NFH)对酯化反应、缩合反应的转化率和选择性都很高，浸渍法得到的负载全氟磺酸树脂催化剂FZG与溶胶—凝胶法负载全氟磺酸树脂催化剂NFH系列比较，由于全氟磺酸树脂分散不均匀，催化效果较差，且与载体结合较差，易流失。与Nafion SAC-13相比，负载量相近的NFH3催化剂在邻苯二甲酸二异辛酯合成反应中的催化效果较好。
建立催化精馏中间采出新工艺，即中间(侧线)采出与催化精馏耦合技术，并尝试将全氟磺酸树脂／SiO_2催化剂用于该工艺中，结果表明：带中间采出的两个填料柱串联的装置邻苯二甲酸二异辛酯酯化率比常规反应精馏柱装置的高出近7％。
As expected due to the fluorocarbon nature of the backbone, perfluorinatedresinsulfonic acids were both chemically stable and thermally stable up to 280~C, atwhich temperature the sulfonic acid groups began to decompose. These materials wereknown to be very strong Bronsted acids. One major drawback of these materials washowever the very low surface area and that the activity of these materials either innon-swelling solvents or in the gas phase was very low. This in tum had limited theutility of these materials.
The used perfluorosulfonic acid ion-exchange membrane was treated into asolution of perfluorosulfonic acid resin to recycle the perfluorosulfonic acidresin(PFIEP). The perfluorosulfonic acid resin/silica composite catalysts(NFH) ofdifferent surface areas and polymer contents were prepared using a sol-gel technique,and characterized by FTIR, DSC-TG A, TEM, SEM, BET measurements. Nanometersized PFIEP particles were entrapped within a highly porous silica network. For thesenanocomposites, PFIEP was highly dispersed within and throughout the porous silicanetwork on the tens of nanometers level, the extent of dispersion of PFIEP within theporous silica framework could be altered. This significantly increased the effectivesurface area of PFIEP particles (within the porous silica). Catalyst NFH showed veryhigh activity in the areas of esterification and condensation reactions. Catalyst NFH3was found to be better than Nation SAC-13 for the systhesis of dioctyl phthalate.
A novel interval withdraw technique for catalytic distillation was explored for thesynthesis of dioctyl phthalate. The results showed that the technique was more efficientthan the conventional process.
本论文主要研究了将电解制碱技术中更换下来的大量的全氟磺酸离子交换膜回收制成全氟磺酸树脂溶液，利用溶胶．凝胶法将全氟磺酸树脂分散组装到具有多孔性二氧化硅中，得到全氟磺酸树脂／SiO_2催化剂。
采用FTIR、DSC-TGA、BET、TEM、SEM等技术对其进行表征，发现：全氟磺酸树脂以纳米级状态分散在SiO_2网络或孔道中，由于有效表面积大大增加，充分暴露全氟磺酸树脂的酸性位，使该树脂催化剂的潜力得到发挥，同时还提高了催化剂的机械性能。
采用乙酸丁酯、乙酸异戊酯、邻苯二甲酸二辛酯、癸二酸二辛酯、苯甲醛乙二醇缩醛和苯甲醛丙二醇缩醛等合成反应作为探针来表征催化剂反应活性，发现：全氟磺酸树脂／SiO_2催化剂(NFH)对酯化反应、缩合反应的转化率和选择性都很高，浸渍法得到的负载全氟磺酸树脂催化剂FZG与溶胶—凝胶法负载全氟磺酸树脂催化剂NFH系列比较，由于全氟磺酸树脂分散不均匀，催化效果较差，且与载体结合较差，易流失。与Nafion SAC-13相比，负载量相近的NFH3催化剂在邻苯二甲酸二异辛酯合成反应中的催化效果较好。
建立催化精馏中间采出新工艺，即中间(侧线)采出与催化精馏耦合技术，并尝试将全氟磺酸树脂／SiO_2催化剂用于该工艺中，结果表明：带中间采出的两个填料柱串联的装置邻苯二甲酸二异辛酯酯化率比常规反应精馏柱装置的高出近7％。
As expected due to the fluorocarbon nature of the backbone, perfluorinatedresinsulfonic acids were both chemically stable and thermally stable up to 280~C, atwhich temperature the sulfonic acid groups began to decompose. These materials wereknown to be very strong Bronsted acids. One major drawback of these materials washowever the very low surface area and that the activity of these materials either innon-swelling solvents or in the gas phase was very low. This in tum had limited theutility of these materials.
The used perfluorosulfonic acid ion-exchange membrane was treated into asolution of perfluorosulfonic acid resin to recycle the perfluorosulfonic acidresin(PFIEP). The perfluorosulfonic acid resin/silica composite catalysts(NFH) ofdifferent surface areas and polymer contents were prepared using a sol-gel technique,and characterized by FTIR, DSC-TG A, TEM, SEM, BET measurements. Nanometersized PFIEP particles were entrapped within a highly porous silica network. For thesenanocomposites, PFIEP was highly dispersed within and throughout the porous silicanetwork on the tens of nanometers level, the extent of dispersion of PFIEP within theporous silica framework could be altered. This significantly increased the effectivesurface area of PFIEP particles (within the porous silica). Catalyst NFH showed veryhigh activity in the areas of esterification and condensation reactions. Catalyst NFH3was found to be better than Nation SAC-13 for the systhesis of dioctyl phthalate.
A novel interval withdraw technique for catalytic distillation was explored for thesynthesis of dioctyl phthalate. The results showed that the technique was more efficientthan the conventional process.
引文
1. Connolly D J, Gresham W F. Fluorocarbon vinyl ether polymers.US 3282875, 1966-10-01.
2. Eisenberg A, Yeager H L, Ed. Perfluorinated Ionomer Membranes,ACS Symposium Series,1982,180. Am Chem Soc. 1982
3. Olah G A, Iyer P S, Prakash G K S. Perfluorinated resinsulfonic acid (Nafion-H(?)) catalysis in synthesis. Synthesis. 1986 (7):513-531.
4. Miyaki H,Ito H,Suzuki K,etal. Cation exchange fluoropolymer membrane.EP 0165466,1984-05-14.
5．方度，杨维驿．全氟离子交换膜——制法、性能与应用．第1版．北京：化学工业出版社，1993
6. Newman M S. Reactions of acetylenic compounds catalyzed by sulfonated polystyrene resins.J Am Chem Soc. 1953 (19): 4740-4742
7. Olah G A, Meidar D. Heterogenous catalysis by solid superacids: 10.mercury impregnated Nafion-H perfluorinated resinsulfonic acid catalyzed hydration of alkynes.Synthesis. 1978(9): 671-672
8. Olah G A, Krishnamurthy V V, Narang S C. Aromatic substitution: mercury(Ⅱ)-promoted azeotropic nitration of aromatics over Nafion-H solid superacidic catalyst.J Org Chem. 1982, 47(3): 596-598
9. Waller F J. Toluic acid.US4356318 and US4463103.1982-10-26,1984-07-31.
10. Lee P C, Meisel D. Catalysis of the hydrogen evolution reaction by colloidal Ag anchored in oerfluosulfonate resin.J Catal. 1981, 70(1): 160-167
11．劳埃德 R B，霍瓦德 E．多孔高度氟化酸性聚合物催化剂及其制备方法．CN1337891A．2002-02-27
12. Grot W G, Pa C F. Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof.US4433082,1984-02-21.
13．王海，王建武，徐柏庆等．全氟磺酸树脂Nafion(?) NR50溶液的制备．应用化学，2001，18(10)：798-301
14. McClure J D,Brandenberger S G..Hydrocarbon conversion process using a supported perfluorinated polymer catalyst.US4038213, 1977-07-26
15. Vaughan R J. Supported catalyst.US 4303551, 1981-12-01
16. Butt Martin H D,Waller F J. Supported perfluorinated ion-exchange polymer.US5094995, 1992-03-10
17. Bucsi Imre, Olah G A. Oligomerization of 2-methylpropene and transformation of 2,4,4-trimethyl-2-pentene over supported and unsupported perfluorinated rensinsulfonic acid catalysts.J Catal. 1992, 137(1): 12-21
18. Harmer M A,Farneth W E, Sun Q. High surface area Nafion resin/silica nanocomposites:a new class of solid acid catalyst.J Am Chem Soc. 1996, 118(33): 7708-7715
19. Sun Q ,Harmer M A. Process for the preparation of a catalytic microcomposite from a silicate and a highly fluorinated ion-exchange resin.WO 9906145, 1999-02-11
20. Torok B,Kiricsi I,Molnar, A,et al. Acidity and catalytic activity of a Nafion-H/silica nanocomposite catalyst compared with a silica-supported Nafion sample. J Catal. 2000, 193(1): 132-138
21. Harmer M A, Sun Q. Sol-gel derived porous microcomposite of perfluorinated ion-exchange polymer and metal oxide.US 6515190, 2003-02-04
22. Heidekum A, Harmer M A, Hoelderich W F. Highly selective Fries rearrangement over zeolites and Nafion in silica composite catalysts:a comparison.J Catal. 1998, 176(1): 260-263
23. Heidekum A,Harmer M A,Hoelderich W F. Nafion/silica composite material reveals high catalytic potential in acylation reactions.J Catal. 1999, 188(1): 230-232
24. Sun Q,Harmer M A,Fameth W E. An extremely active solid acid catalyst,Nafion resin/silica composite,for the Friedel-Crafts benzylation of benzene and p-xylene with benzyl alcohol.Ind Eng Chem Res. 1997, 36(12): 5541-5544
25. Harmer M A, Sun Q. Perfluorinated ion-exchange microcomposite catalysts modified with Lewis acid.US6133493, 2000-10-17
26. Harmer M A, Sun Q. Fluorine-modified perfluorinated ion-exchange microcomposite catalysts. US6248930, 2001-06-19
27. Istvan Palinko, Bela Torok, G.K. Surya Prakasha, etal. Surface characterization of variously treated Nafion(?)-H,Nafion(?)-H supported on silica and Nafion(?)-H silica nanocomposite catalysts by infrared microscopy.Applied Catalysis A: General. 1998,174: 147-153
28. Q.Deng,C.A.Wilkie,R.B.Moore,etal.TGA-FTIR investigation of the thermal degradation of Nafion(?) and Nafion(?)/[silicon oxide]-based nanocomposites.Polymer. 1998,39(24):5961-5972
29. P. Botella, A. Corma, J. M. Lopez-Nieto. The Influence of Textural and Compositional Characteristics of Nafion/Silica Composites on Isobutane/2-Butene Alkylation.Journal of Catalysis. 1999, 185 (2): 371-377
30. Kazuo Okuyama, Xin Chen, Katsumi Takata, etal. Water-tolerant catalysis of a silica composite of a sulfonic acid resin, Aciplex. Applied Catalysis A: General .2000,190: 253-260
31. J.P. Lange, L. Petrus. Solid acid catalysts for converting alkenes and alkanols to carboxylic acids. Applied Catalysis A: General. 2001, 216: 285-294
32. Zhaoyin Hou, Toshio Okuhara. Catalytic synthesis of diphenylmethane from benzene and formalin with water-tolerant solid acids. Applied Catalysis A: General. 2001,216: 147-155
33. M. Schneider, K. Zimmermann, F. Aquino, etal. Industrial application of Nafion-systems in rearrangement-aromatisation, transesterification,alkylation, and ring-closure reactions.Applied Catalysis A: General. 2001,220: 51-58
34. Masahiro Fujiwara, Koji Kuraoka, Tetsuo Yazawa. Preparation of an MCM-41/Nafion(?) composite material: a selective catalyst for α-methylstyrene dimerization.Chem. Commun.. 2000: 1523-1524
35. M. Schneider, K. Zimmermann, F. Aquino. Industrial application of Nafion-systems in rearrangement-aromatisation, transesteritication,alkylation, and ring-closure reactions.Applied Catalysis A: General. 2001, 220 (1-2): 51-58
36．王海，徐柏庆，王建武等．新型固体酸Nafion／SiO_2催化作用Ⅰ苯与丙烯烷基化反应．石油化工．2001，30(10)：741-743
37．陈凯平，张杰，刘兰香．废弃离子交换膜的回收及利用．氯碱工业．2001(1)：15-18
38. Colin Park, Mark A. Keane. Gas phase dehydration of C6 alcohols promoted by Y zeolite and supported nafion catalysts. Journal of Molecular Catalysis A: Chemical. 166(2001): 303-322
39. Mark A. Harmer, Qun Sun. Solid acid catalysis using ion-exchange resins. Applied Catalysis A: General .221 (2001): 45-62
40．王海，徐柏庆，王建武等．新型固体酸Nafion／SiO_2催化作用Ⅱα甲基苯乙烯的二聚反应．石油化工．2002，31(6)：427-430
41．陈凯平，张立新．废弃离子交换膜与全氟磺酸树脂固体超强酸催化剂．氯碱工业．2002，(9)：20-24
42．王海，徐柏庆．氧化硅组装纳米Nafion酸催化合成α生育酚．化学学报．2003，61(10)：1667-1670
43. Francesco Frusteri, Lorenzo Spadaro, Claudia Espro. Liquid-Phase Selective Oxidation of Propane on Silica-Supported Nafion Catalysts. Journal of Natural Gas Chemistry 2002,11(3-4): 180-185
44．凌绍明，隆金桥．Nafion／SiO_2催化合成环己烯．化学世界．2002，43(10)：556-557
45．黄祖良，李红蕾，胡柳等．Nafion／SiO_2催化合成肉桂腈的研究．化工技术与开发．2003．32(3)：6-8
46．周硼，安增建，李文艳等．以Nafion为催化剂的异丁烯齐聚反应的研究．吉林大学学报(理学版)．2003，41(2)：217-220
47. Paolo Beltrame, Giovanni Zuretti. The reaction of naphthalene with benzyl alcohol over a Nafion-silica composite: a kinetic study. Applied Catalysis A: General .2003,248: 75-83
48. Jianxin Mao, Yuichi Kamiya, Toshio Okuhara. Alkylation of 1,3,5-trimethylbenzene with butyrolactone over heteropolyacid catalysts. Applied Catalysis A: General .2003,255:337-344
49. M.C. Laufer, H. Hausmann, and W.F. Holderich. Synthesis of 7-hydroxycoumarins by Pechmann reaction using Nafion resin/silica nanocomposites as catalysts. Journal of Catalysis. 2003,218: 315-320
50. Paolo Beltrame, Giovanni Zuretti.Kinetics of the reaction of naphthalene with benzyl alcohol over a Nafion-silica composite, as a function of temperature.Applied Catalysis A: General.2004,268: 169-174
51．黄祖良，韦国锋，李振中等．大茴香腈的催化合成研究．化学世界．2004，45(6)：312-315
52. Hai Wang, Bo-Qing Xu. Catalytic performance ofNafion/SiO2 nanocomposites for the synthesis of a-tocopherol.Applied Catalysis A: General.2004, 275: 247-255
53. Bulcsu Rac, Gabriele Mulas, Aniko Csongradi,etal.SiO_2-supported dodecatungstophosphoric acid and Nafion-H prepared by ball-milling for catalytic application.Applied Catalysis A: General.2005, 282:255-265
54. Paolo Beltrame, Giovanni Zuretti. Kinetics of the reaction of toluene with benzyl alcohol over a Nafion-silica composite.Applied Catalysis A: General. 2005, 283: 33-38
55. Mercedes Alvaro, Avelino Corma, Debasish Das,etal. "Nafion"-functionalized mesoporous MCM-41 silica shows high activity and selectivity for carboxylic acid esterification and Friedel-Crafts acylation reactions. Journal of Catalysis. 2005,231: 48-55
56. Yijun Liu, Edgar Lotero, James G. Goodwin Jr. A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis. Journal of Catalysis.2006, 242: 278-286
57. Suman L. Jain, Bir Sain. Perfluorinated resinsulphonic acid (Nafion-H1) catalyzed highly efficient oxidations of organic compounds with hydrogen peroxide. Applied Catalysis A: General. 2006,301 (2): 259-264
58. Subramaniam Bala, Lyon Christopher James. Pressure-tuned solid catalyzed heterogeneous chemical reactions. US6924407, 2005, 08-02
59. K.D. Mohl, A. Kienle, K. Sundmacher, et al. A theoretical study of kinetic instabilities in catalytic distillation processes: influence of transport limitations inside the catalyst.Chemical Engineering Science .2001, 56(18): 5239-5254
60. Jiri Hanika, Quido Smejkal and Jiri Kolena. 2-Methylpropylacetate synthesis via catalytic distillation. Catalysis Today. 2001, 66(2-4): 219-223
61．盖旭东，金涌，汪展文等．新型催化精馏塔流体力学特性研究．化学工程．1999，27(1)：6-10
62．肖剑，刘家祺．催化精馏塔催化剂装填技术研究进展．化工进展．1999，(2)：8-11
63．廖安平，蓝平，李媚等．催化精馏技术在酯化反应中的应用．化工进展．2001，(12)：30-32
64. Jie Bao, Buliang Gao, Xiaoqun Wu, et al. Simulation of industrial catalytic-distillation process for production of methyl tert-butyl ether by developing user's model on Aspen plus platform. Chemical Engineering Journal. 2002, 90(3): 253-266
65. Zhiwen Qi, Kai Sundmacher, Erik Stein, et al. Reactive separation of isobutene from C_4 crack fractions by catalytic distillation processes. Separation and Purification Technology. 2002, 26(2-3): 147-163
66．赵贤广，饶骏．国内催化精馏技术研究进展及应用．化学工业与工程技术．2002，23(5)：24-26
67．吴燕翔，王良恩，赵之山等．乙酸甲酯水解催化精馏过程催化剂包内的传质模型(Ⅰ)数学模型．化工学报．2002，53(5)：503-507
68．吴燕翔，王良恩，赵之山等．乙酸甲酯水解催化精馏过程催化剂包内的传质模型(Ⅱ)效率因子的测定与计算．化工学报．2002，53(5)：508-512
69. Hartmut G. Schoenmakers ,Bernd Bessling. Reactive and catalytic distillation from an industrial perspective. Chemical Engineering and Processing. 2003, 42(3): 145-155
70. Zhigang Lei, Chengyue Li, Jianwei Li, et al. Suspension catalytic distillation of simultaneous alkylation and transalkylation for producing cumene. Separation and Purification Technology. 2004, 34(1-3): 265-271
71. C. Noeres, K. Dadhe, R. Gesthuisen,et al. Model-based design, control and optimisation of catalytic distillation processes. Chemical Engineering and Processing. 2004, 43(3): 421-434
72. Yuxiang Zheng, Flora T. T. Ng, Garry L. Rempel. A comparison of a pseudo-homogeneous non-equilibrium model and a three-phase non-equilibrium model for catalytic distillation. Chemical Engineering Journal. 2004, 100(1-3): 119-127
73. F. D. Vargas-Villamil, J. O. Marroquin, C. de la Paz, et al. A catalytic distillation process for light gas oil hydrodesulfurization. Chemical Engineering and Processing. 2004, 43(10): 1309-1316
74. Andrzej Kotodziej, Mieczystaw Jaroszyfiski, Hartmut Schoenmakers, et al. Dynamic tracer study of column packings for catalytic distillation. Chemical Engineering and Processing. 2005, 44(6): 661-670
75. Yongqiang Xu, Yuxiang Zheng, Flora T.T. Ng, et al. A three-phase nonequilibrium dynamic model for catalytic distillation. Chemical Engineering. 2005, 60(20): 5637-5647
76. Deepyaman Seth, Amitava Sarkar, F.T.T. Ng, et al. Uncertainties in the simulation of catalytic distillation process: A systematic grid refinement study. Chemical Engineering Science. 2005, 60(20): 5445-5457
77. Gartside Robert J, Haines Robert I, Skourlis Thomas, et al. Olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps. US 6,759,562. 2004, 07-06
78. Krug Russell R,O'Rear; Dennis J. Process for making a lube base stock from a lower molecular weight feedstock in a catalytic distillation unit. US 6,841,711. 2005, 01-11
79．K．松德马赫尔，A．金勒 编．朱建华译．反应蒸馏．第1版．北京：化学工业出版社，2005
80. Gentry J C ,Binkley M J. Method and apparatus for catalyst downcomer tray operation.US 5277847.1994
81. Smith L A Jr. Catalytic distillation system.US 5262012.1993.
82．郝兴仁，王进善，杨宗仁等．新型催化精馏塔．CN 1042664．1990
83．盖旭东，金涌，汪展文．新型催化精馏塔流体力学特性研究．化学工程，1999，27(1)：6-10
84. Higler A, Krishna R,Ellenberger J, Taylor R.Countercurrent operation of a structured catalytically packed bed reactor:Liquid phase mixing and masstransfer. Chemical Engineering Science,1999,54(24):5145-5152
85. Harandi M N. Fluidizd catalytic process for prducts and hydration of olefins. US 5331011.1993
86．温朗友，闵恩泽，庞桂赐等．悬浮床催化精馏塔新工艺合成异丙苯．化工学报，2000，51(1)：115-119
87．廖安平，蓝平，李媚等．流化催化精馏制备乙酸乙酯的研究．化学工程，2000，28(6)：19-21
88．曹海波，乔旭，曾崇．流化催化精馏合成甲缩醛技术．南京化工大学学报，1998，20(3) 19-22
89. Baur R ,Higler A P,Taylor R and Krishna R. Comparison of equilibrium stage models for reactive distillation. Chemical Engineering Journal,2000,76:33-47
90. Lee J H and Dudukovic M P. A comparison of the equilibrium and nonequilibrium models for a multicomponent reactive distillation column .Computers and Chemical Engineering, 1998,23: 159-172
91. Taylor R and Krishna R. Modelling reactive distillation. Chemical Engineering Science,2000,55:5183-5229
92. Higler A, Krishna R, Taylor R. A Nonequilibrium Cell Model for Multicomponent(Reactive) Separation Processes. American Institute of Chemical Engineers Journal, 1999,45:2357-2370.
93. Higler A, Krishna R, Taylor R. A Non-equilibrium Cell Model for Packed Distillation Columns. The influence of Maldistribution. Industrial and Engineering Chemistry Research, 1999, 38:3988-3999.
94．方永成，江桂秀，万爱媛等．MTBE催化蒸馏数学模型的研究．石油炼制，1989，(2)：22-28
95．鲍杰，严国祥，邬晓风．合成MTBE非均相催化精馏过程数学模拟．化学工程，1994，22(5)：6-12
96．张瑞生，韩英，Hoffmann U．非均相催化精馏过程的模拟计算．化工学报，1989，40(6)：693-703
97．韩英，张瑞生．全回流催化精馏塔的模拟计算．华东化工学院学报，1989，15(3)：331-338
98．朱建华．反应精馏过程的非平衡级模型初探．计算机与应用化学 1994．11(3)167-173
99．郑宇翔．催化精馏过程研究．天津大学学位论文，1992
100．陆茵，吕德伟．串釜式反应精馏的非平衡级模型模拟．宁波大学学报， 1999，12(1)33-39．
101．陈波．催化蒸馏过程研究．非平衡级速率模型中性质参数的评价与选择．天津大学学位论文，1995
102．吴燕翔．醋酸甲酯催化精馏中试过程的研究．浙江大学学位论文，1999
103. Tuchlemski A, Beckmann D. Reactive distillation industrial application. Chemical Engineering Science, 2001, 56(1): 387-394
104. Larry L. Hench, Jon K. West. The Sol-Gel process. Chem. Rev. . 1990, 90: 33-72
105．杨南如，余桂郁．溶胶．凝胶的基本原理与过程．硅酸盐通报，1992，11(2)：56-63．
106．余桂郁，杨南如．溶胶．凝胶法的工艺过程．硅酸盐通报．1993，12(6)：60-69．
107．阎子峰编著，纳米催化技术．北京：化学工业出版社，2003年第1版
108．严继民，张启元．吸附与凝聚(固体的表面与孔)．第1版，北京：科学出版社．1979
109．胡玉才，叶兴凯，吴越．固载杂多酸催化剂气相催化合成乙酸丁酯的研究．精细石油化工，1996，(1)5-9
110．刘庆林，陈洪钫．H_3(PW_(12)O_(40))／PVA催化膜用于酯化反应的研究．石油化工，1997，26(10)676-679
111．楚文玲，杨向光，叶兴凯等．硅钨杂多酸在中孔全硅分子筛HMS上的固载及其催化性能．催化学报，1997，18(3)225-229
112．王廷吉，赵新强，张秉常．SO_4~(2-)-Fe_2O_3／Hβ增强酸催化剂上合成乙酸丁酯．石油化工，1998，27(3)159-163
113．马德，李骏，顾树珍．改性离子交换树脂的表征及催化合成乙酸丁酯的研究．石油化工，1996，25(2)80-84
114．曾庆乐．氯化高锡催化合成乙酸丁酯的研究．化学通报，2000，(1)45-47
115．黄碧纯．固体超强酸SO_4~(2-)-MoO_3-ZrO_2的酸强度与酯化催化性能．工业催化，2000，8(2)61-64
116．胡健平，储伟，邱发礼．固体酸催化乙酸／丁醇酯化反应的研究．精细化工，2000，17(5)269-273
117．马德，黎源．WO_3-YiO_2-SO_4~(2-)固体超强酸的制备及应用研究．精细化工，2002，19(1)36-38
118．常铮，郭灿雄，段雪等．磁性超细固体酸催化剂SO_4~(2-)-ZrO_2／Fe_3O_4的组装及表征．催化学报，2003，24(1)47-51
119．俞善信，唐艳春，梁哲辉。以对甲苯磺酸为催化剂合成乙酸异戊酯．精细石油化工，1996，2：31-32
120．俞善信．硫酸铜的催化酯化作用．精细石油化工，1995，(3)：45-47
121．李毅群，肖小云．十二水合硫酸铁铵催化合成乙酸异戊酯，现代化工，1998， (1) 29-30
122．周建伟．相转移催化合成乙酸异戊酯，化学通报 1999(6)，45-47
123．易兵，郭文辉，龙有前等．氨基磺酸催化合成乙酸异戊酯．化学世界，2001，(3) 148-150
124．翁文，许华丽，李国平等．四氯化锡催化乙酸异戊酯的合成．应用化学，2001，18(3)：244-245
125．廖德仲，何节玉．固体超强酸SO_4~(2-)-MoO_3-TiO_2的制备及其催化酯化性能研究．化学研究与应用．2001，13(3) 290-292
126．訾俊峰，朱蕾．活性炭固载氯化铁催化合成乙酸异戊酯，工业催化，2004，12(9)：31-33
127．杨水金，肖继，梁永光．TiSiW_(12)O_(40)／TiO_2催化合成乙酸异戊酯的研究．化学试剂，2002，24(2)，107-108；121
128．崔秀兰，林明丽，郭海福等．稀土固体超强酸催化合成乙酸异戊酯的研究．化学世界，2003，(1)，27-30
129．林森，郭璇，王国永等．含硅有机锡化合物在酯化反应中的催化性能研究．化学试剂，2006，28(6)，351-353
130．谷珉珉，贾韵仪，姚子鹏．有机化学实验．上海：复旦大学出版社，1991
131．蒋平平，卢冠忠．固体酸催化合成邻苯二甲酸二辛酯．化工进展，2002，21(5)：328-330，348
132．陈其瑞，张美凤，罗明润等．Ln_2O_3／Al_2O_3催化酯化合成邻苯二甲酸二异辛酯．催化学报，1994，15(3)236-238
133．金振兴，张庆勋，刘连利等．固载杂多酸催化剂PW_(12)／SiO_2复相催化酯化合成邻苯二甲酸二异辛酯．精细化工 1996，13(1) 34-36
134．申永存，张良均，邹淑静．邻苯二甲酸二异辛酯(DOP)的非酸催化合成．精细化工 1996，13(4) 21-23
135．梁英，石小鹏，王启慧．固体杂多酸盐TiGeW_(12)O_(40)／TiO_2催化合成DIOP．塑料工业，2004，32(8)58-59
136．王兴平，毛建军，谢飞．以分子筛为催化剂合成邻苯二甲酸二辛酯．现代化工，1997，(6)29
137. YudaoMa,Q.L.Wang,HaoYan,etal. Zeolite-catalyzed esterfication.I.Synthesis of acetates,benzoates and phthalates.Applied Catalysis A:General 139(1996)51-57
138. Guanzhong Lu.Catalytic properties of SO_4~(2-)-/T-M-O superacids in esterfication. Applied Catalysis A:General 133(1995)11-18
139. Z. H. Zhao. Studies on esterification reaction over aluminophosphate and silicoaluminophosphate molecular sieves. Journal of Molecular Catalysis A: Chemical 168(2001) 147-152
140. M.Arabi, M.Mohammadpour Amini,M.Abedini,etal. Esterification of phthalic anhydride with 1-butanol and 2-ethylhexanol catalyzed by heteropolyacids. Journal of Molecular Catalysis A: Chemical 200 (2003) 105-110
141. Firdovsi Tataroglu Sejidov, Yagoub Mansoori and Nadereh Goodarzi. Esterification reaction using solid heterogeneous acid catalysts under solvent-less condition. Journal of Molecular Catalysis A: Chemical 240(2005) 186-190
142. M. Khodadadi Moghaddam and M.R. Gholami. Preparation of Titania based solid strong acid and study of its catalytic activity in esterification of Phthalic anhydride and Sebacic acid. Materials Letters, 2006,60(6) 715-719
143．马雪琴．低温增塑剂癸二酸二异辛酯合成的研究．现代化工，1997，17(7)26-27
144．孟启，朱国彪，孙小强．SnO／沸石催化合成癸二酸二辛酯的研究．精细石油化工进展 2001，2(12)7-9
145．毕韶丹．固体超强酸催化剂在合成癸二酸二异辛酯反应中的研究．辽宁化工，2002，31(4)146-148
146．郑根武，宁立芹．癸二酸二辛酯的开发．现代塑料加工应用，2002，14(2)38-40
147．陈群．SO_4~(2-)／TiO_2-Al_2O_3固体超强酸催化合成癸二酸二异辛酯．精细石油化工进展，2004，5(7) 33-35
148．俞善信，彭红阳．三氯化铁催化合成缩醛(酮)．现代化工，1994，14(12)：29-30．
149．陈翠娟．十二水合硫酸铁铵催化合成缩醛和缩酮．合成材料老化与应用，2001，(2)：20-21．
150．吕月仙．磷钼酸催化法制备某些缩醛(酮)的研究．郑州轻工业学院学报，1999，14(1)：60-63．
151．杨水金，童文龙．H_4SiW_(12)O_(40)／PAn催化剂催化合成苯甲醛乙二醇缩醛．香料香精化妆品，2004，(5)17-19，26．
152．文瑞明，游沛清，罗新湘等．维生素C催化合成缩醛(酮)．石油化工，2002，31(5)：373-375．
153．吴露玲．固体超强酸催化缩醛、酮化反应．科技通报，1995，11(5)：289-291．
154．杨水金．TiSiW_(12)O_(40)／TiO_2催化合成苯甲醛乙二醇缩醛．精细石油化工进展，2004，5(2)：33-35．
155．白爱民，余建勇，杨水金等．SO_4~(2-)／TiO_2-MoO_3催化合成苯甲醛乙二醇缩醛．湖北师范学院学报，2004，24(2)：12-15．
156．但悠梦，米远祝，田大听等．S_2O_8~(2-)／ZrO_2-Al_2O_3固体超强酸催化剂的研制与应用．应用化学，2001，18(10)：840-842．
157．杨水金，夏佳，吕宝兰．磷钨酸催化合成缩醛(酮)．精细化工，2004，21(9)：686-688．
158．魏荣宝，梁娅，薛其峰等．离子交换树脂催化法合成缩醛(酮)．离子交换与吸附，1992，8(2)，171-174
159．杨水金，夏佳，刘江燕等．硅钨杂多酸催化合成缩醛(酮)．精细与专用化学品 2004，12(14)：15-18
160．杨水金，夏佳，孙聚堂．TiSiW_(12)O_(40)／TiO_2催化合成苯甲醛1，2-丙二醇缩醛．化学反应工程与工艺，2003，19(1)：9-13
161．夏佳，杨小山，吴顺红．硫酸根／氧化钛．氧化镧催化合成苯甲醛1，2-丙二醇缩醛．化学工业与工程技术，2004，25(1)：3-5
162．裘兆蓉，王车礼，承民联等．催化精馏中间采出新工艺．CN 02142233．8，2002．
2. Eisenberg A, Yeager H L, Ed. Perfluorinated Ionomer Membranes,ACS Symposium Series,1982,180. Am Chem Soc. 1982
3. Olah G A, Iyer P S, Prakash G K S. Perfluorinated resinsulfonic acid (Nafion-H(?)) catalysis in synthesis. Synthesis. 1986 (7):513-531.
4. Miyaki H,Ito H,Suzuki K,etal. Cation exchange fluoropolymer membrane.EP 0165466,1984-05-14.
5．方度，杨维驿．全氟离子交换膜——制法、性能与应用．第1版．北京：化学工业出版社，1993
6. Newman M S. Reactions of acetylenic compounds catalyzed by sulfonated polystyrene resins.J Am Chem Soc. 1953 (19): 4740-4742
7. Olah G A, Meidar D. Heterogenous catalysis by solid superacids: 10.mercury impregnated Nafion-H perfluorinated resinsulfonic acid catalyzed hydration of alkynes.Synthesis. 1978(9): 671-672
8. Olah G A, Krishnamurthy V V, Narang S C. Aromatic substitution: mercury(Ⅱ)-promoted azeotropic nitration of aromatics over Nafion-H solid superacidic catalyst.J Org Chem. 1982, 47(3): 596-598
9. Waller F J. Toluic acid.US4356318 and US4463103.1982-10-26,1984-07-31.
10. Lee P C, Meisel D. Catalysis of the hydrogen evolution reaction by colloidal Ag anchored in oerfluosulfonate resin.J Catal. 1981, 70(1): 160-167
11．劳埃德 R B，霍瓦德 E．多孔高度氟化酸性聚合物催化剂及其制备方法．CN1337891A．2002-02-27
12. Grot W G, Pa C F. Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof.US4433082,1984-02-21.
13．王海，王建武，徐柏庆等．全氟磺酸树脂Nafion(?) NR50溶液的制备．应用化学，2001，18(10)：798-301
14. McClure J D,Brandenberger S G..Hydrocarbon conversion process using a supported perfluorinated polymer catalyst.US4038213, 1977-07-26
15. Vaughan R J. Supported catalyst.US 4303551, 1981-12-01
16. Butt Martin H D,Waller F J. Supported perfluorinated ion-exchange polymer.US5094995, 1992-03-10
17. Bucsi Imre, Olah G A. Oligomerization of 2-methylpropene and transformation of 2,4,4-trimethyl-2-pentene over supported and unsupported perfluorinated rensinsulfonic acid catalysts.J Catal. 1992, 137(1): 12-21
18. Harmer M A,Farneth W E, Sun Q. High surface area Nafion resin/silica nanocomposites:a new class of solid acid catalyst.J Am Chem Soc. 1996, 118(33): 7708-7715
19. Sun Q ,Harmer M A. Process for the preparation of a catalytic microcomposite from a silicate and a highly fluorinated ion-exchange resin.WO 9906145, 1999-02-11
20. Torok B,Kiricsi I,Molnar, A,et al. Acidity and catalytic activity of a Nafion-H/silica nanocomposite catalyst compared with a silica-supported Nafion sample. J Catal. 2000, 193(1): 132-138
21. Harmer M A, Sun Q. Sol-gel derived porous microcomposite of perfluorinated ion-exchange polymer and metal oxide.US 6515190, 2003-02-04
22. Heidekum A, Harmer M A, Hoelderich W F. Highly selective Fries rearrangement over zeolites and Nafion in silica composite catalysts:a comparison.J Catal. 1998, 176(1): 260-263
23. Heidekum A,Harmer M A,Hoelderich W F. Nafion/silica composite material reveals high catalytic potential in acylation reactions.J Catal. 1999, 188(1): 230-232
24. Sun Q,Harmer M A,Fameth W E. An extremely active solid acid catalyst,Nafion resin/silica composite,for the Friedel-Crafts benzylation of benzene and p-xylene with benzyl alcohol.Ind Eng Chem Res. 1997, 36(12): 5541-5544
25. Harmer M A, Sun Q. Perfluorinated ion-exchange microcomposite catalysts modified with Lewis acid.US6133493, 2000-10-17
26. Harmer M A, Sun Q. Fluorine-modified perfluorinated ion-exchange microcomposite catalysts. US6248930, 2001-06-19
27. Istvan Palinko, Bela Torok, G.K. Surya Prakasha, etal. Surface characterization of variously treated Nafion(?)-H,Nafion(?)-H supported on silica and Nafion(?)-H silica nanocomposite catalysts by infrared microscopy.Applied Catalysis A: General. 1998,174: 147-153
28. Q.Deng,C.A.Wilkie,R.B.Moore,etal.TGA-FTIR investigation of the thermal degradation of Nafion(?) and Nafion(?)/[silicon oxide]-based nanocomposites.Polymer. 1998,39(24):5961-5972
29. P. Botella, A. Corma, J. M. Lopez-Nieto. The Influence of Textural and Compositional Characteristics of Nafion/Silica Composites on Isobutane/2-Butene Alkylation.Journal of Catalysis. 1999, 185 (2): 371-377
30. Kazuo Okuyama, Xin Chen, Katsumi Takata, etal. Water-tolerant catalysis of a silica composite of a sulfonic acid resin, Aciplex. Applied Catalysis A: General .2000,190: 253-260
31. J.P. Lange, L. Petrus. Solid acid catalysts for converting alkenes and alkanols to carboxylic acids. Applied Catalysis A: General. 2001, 216: 285-294
32. Zhaoyin Hou, Toshio Okuhara. Catalytic synthesis of diphenylmethane from benzene and formalin with water-tolerant solid acids. Applied Catalysis A: General. 2001,216: 147-155
33. M. Schneider, K. Zimmermann, F. Aquino, etal. Industrial application of Nafion-systems in rearrangement-aromatisation, transesterification,alkylation, and ring-closure reactions.Applied Catalysis A: General. 2001,220: 51-58
34. Masahiro Fujiwara, Koji Kuraoka, Tetsuo Yazawa. Preparation of an MCM-41/Nafion(?) composite material: a selective catalyst for α-methylstyrene dimerization.Chem. Commun.. 2000: 1523-1524
35. M. Schneider, K. Zimmermann, F. Aquino. Industrial application of Nafion-systems in rearrangement-aromatisation, transesteritication,alkylation, and ring-closure reactions.Applied Catalysis A: General. 2001, 220 (1-2): 51-58
36．王海，徐柏庆，王建武等．新型固体酸Nafion／SiO_2催化作用Ⅰ苯与丙烯烷基化反应．石油化工．2001，30(10)：741-743
37．陈凯平，张杰，刘兰香．废弃离子交换膜的回收及利用．氯碱工业．2001(1)：15-18
38. Colin Park, Mark A. Keane. Gas phase dehydration of C6 alcohols promoted by Y zeolite and supported nafion catalysts. Journal of Molecular Catalysis A: Chemical. 166(2001): 303-322
39. Mark A. Harmer, Qun Sun. Solid acid catalysis using ion-exchange resins. Applied Catalysis A: General .221 (2001): 45-62
40．王海，徐柏庆，王建武等．新型固体酸Nafion／SiO_2催化作用Ⅱα甲基苯乙烯的二聚反应．石油化工．2002，31(6)：427-430
41．陈凯平，张立新．废弃离子交换膜与全氟磺酸树脂固体超强酸催化剂．氯碱工业．2002，(9)：20-24
42．王海，徐柏庆．氧化硅组装纳米Nafion酸催化合成α生育酚．化学学报．2003，61(10)：1667-1670
43. Francesco Frusteri, Lorenzo Spadaro, Claudia Espro. Liquid-Phase Selective Oxidation of Propane on Silica-Supported Nafion Catalysts. Journal of Natural Gas Chemistry 2002,11(3-4): 180-185
44．凌绍明，隆金桥．Nafion／SiO_2催化合成环己烯．化学世界．2002，43(10)：556-557
45．黄祖良，李红蕾，胡柳等．Nafion／SiO_2催化合成肉桂腈的研究．化工技术与开发．2003．32(3)：6-8
46．周硼，安增建，李文艳等．以Nafion为催化剂的异丁烯齐聚反应的研究．吉林大学学报(理学版)．2003，41(2)：217-220
47. Paolo Beltrame, Giovanni Zuretti. The reaction of naphthalene with benzyl alcohol over a Nafion-silica composite: a kinetic study. Applied Catalysis A: General .2003,248: 75-83
48. Jianxin Mao, Yuichi Kamiya, Toshio Okuhara. Alkylation of 1,3,5-trimethylbenzene with butyrolactone over heteropolyacid catalysts. Applied Catalysis A: General .2003,255:337-344
49. M.C. Laufer, H. Hausmann, and W.F. Holderich. Synthesis of 7-hydroxycoumarins by Pechmann reaction using Nafion resin/silica nanocomposites as catalysts. Journal of Catalysis. 2003,218: 315-320
50. Paolo Beltrame, Giovanni Zuretti.Kinetics of the reaction of naphthalene with benzyl alcohol over a Nafion-silica composite, as a function of temperature.Applied Catalysis A: General.2004,268: 169-174
51．黄祖良，韦国锋，李振中等．大茴香腈的催化合成研究．化学世界．2004，45(6)：312-315
52. Hai Wang, Bo-Qing Xu. Catalytic performance ofNafion/SiO2 nanocomposites for the synthesis of a-tocopherol.Applied Catalysis A: General.2004, 275: 247-255
53. Bulcsu Rac, Gabriele Mulas, Aniko Csongradi,etal.SiO_2-supported dodecatungstophosphoric acid and Nafion-H prepared by ball-milling for catalytic application.Applied Catalysis A: General.2005, 282:255-265
54. Paolo Beltrame, Giovanni Zuretti. Kinetics of the reaction of toluene with benzyl alcohol over a Nafion-silica composite.Applied Catalysis A: General. 2005, 283: 33-38
55. Mercedes Alvaro, Avelino Corma, Debasish Das,etal. "Nafion"-functionalized mesoporous MCM-41 silica shows high activity and selectivity for carboxylic acid esterification and Friedel-Crafts acylation reactions. Journal of Catalysis. 2005,231: 48-55
56. Yijun Liu, Edgar Lotero, James G. Goodwin Jr. A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis. Journal of Catalysis.2006, 242: 278-286
57. Suman L. Jain, Bir Sain. Perfluorinated resinsulphonic acid (Nafion-H1) catalyzed highly efficient oxidations of organic compounds with hydrogen peroxide. Applied Catalysis A: General. 2006,301 (2): 259-264
58. Subramaniam Bala, Lyon Christopher James. Pressure-tuned solid catalyzed heterogeneous chemical reactions. US6924407, 2005, 08-02
59. K.D. Mohl, A. Kienle, K. Sundmacher, et al. A theoretical study of kinetic instabilities in catalytic distillation processes: influence of transport limitations inside the catalyst.Chemical Engineering Science .2001, 56(18): 5239-5254
60. Jiri Hanika, Quido Smejkal and Jiri Kolena. 2-Methylpropylacetate synthesis via catalytic distillation. Catalysis Today. 2001, 66(2-4): 219-223
61．盖旭东，金涌，汪展文等．新型催化精馏塔流体力学特性研究．化学工程．1999，27(1)：6-10
62．肖剑，刘家祺．催化精馏塔催化剂装填技术研究进展．化工进展．1999，(2)：8-11
63．廖安平，蓝平，李媚等．催化精馏技术在酯化反应中的应用．化工进展．2001，(12)：30-32
64. Jie Bao, Buliang Gao, Xiaoqun Wu, et al. Simulation of industrial catalytic-distillation process for production of methyl tert-butyl ether by developing user's model on Aspen plus platform. Chemical Engineering Journal. 2002, 90(3): 253-266
65. Zhiwen Qi, Kai Sundmacher, Erik Stein, et al. Reactive separation of isobutene from C_4 crack fractions by catalytic distillation processes. Separation and Purification Technology. 2002, 26(2-3): 147-163
66．赵贤广，饶骏．国内催化精馏技术研究进展及应用．化学工业与工程技术．2002，23(5)：24-26
67．吴燕翔，王良恩，赵之山等．乙酸甲酯水解催化精馏过程催化剂包内的传质模型(Ⅰ)数学模型．化工学报．2002，53(5)：503-507
68．吴燕翔，王良恩，赵之山等．乙酸甲酯水解催化精馏过程催化剂包内的传质模型(Ⅱ)效率因子的测定与计算．化工学报．2002，53(5)：508-512
69. Hartmut G. Schoenmakers ,Bernd Bessling. Reactive and catalytic distillation from an industrial perspective. Chemical Engineering and Processing. 2003, 42(3): 145-155
70. Zhigang Lei, Chengyue Li, Jianwei Li, et al. Suspension catalytic distillation of simultaneous alkylation and transalkylation for producing cumene. Separation and Purification Technology. 2004, 34(1-3): 265-271
71. C. Noeres, K. Dadhe, R. Gesthuisen,et al. Model-based design, control and optimisation of catalytic distillation processes. Chemical Engineering and Processing. 2004, 43(3): 421-434
72. Yuxiang Zheng, Flora T. T. Ng, Garry L. Rempel. A comparison of a pseudo-homogeneous non-equilibrium model and a three-phase non-equilibrium model for catalytic distillation. Chemical Engineering Journal. 2004, 100(1-3): 119-127
73. F. D. Vargas-Villamil, J. O. Marroquin, C. de la Paz, et al. A catalytic distillation process for light gas oil hydrodesulfurization. Chemical Engineering and Processing. 2004, 43(10): 1309-1316
74. Andrzej Kotodziej, Mieczystaw Jaroszyfiski, Hartmut Schoenmakers, et al. Dynamic tracer study of column packings for catalytic distillation. Chemical Engineering and Processing. 2005, 44(6): 661-670
75. Yongqiang Xu, Yuxiang Zheng, Flora T.T. Ng, et al. A three-phase nonequilibrium dynamic model for catalytic distillation. Chemical Engineering. 2005, 60(20): 5637-5647
76. Deepyaman Seth, Amitava Sarkar, F.T.T. Ng, et al. Uncertainties in the simulation of catalytic distillation process: A systematic grid refinement study. Chemical Engineering Science. 2005, 60(20): 5445-5457
77. Gartside Robert J, Haines Robert I, Skourlis Thomas, et al. Olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps. US 6,759,562. 2004, 07-06
78. Krug Russell R,O'Rear; Dennis J. Process for making a lube base stock from a lower molecular weight feedstock in a catalytic distillation unit. US 6,841,711. 2005, 01-11
79．K．松德马赫尔，A．金勒 编．朱建华译．反应蒸馏．第1版．北京：化学工业出版社，2005
80. Gentry J C ,Binkley M J. Method and apparatus for catalyst downcomer tray operation.US 5277847.1994
81. Smith L A Jr. Catalytic distillation system.US 5262012.1993.
82．郝兴仁，王进善，杨宗仁等．新型催化精馏塔．CN 1042664．1990
83．盖旭东，金涌，汪展文．新型催化精馏塔流体力学特性研究．化学工程，1999，27(1)：6-10
84. Higler A, Krishna R,Ellenberger J, Taylor R.Countercurrent operation of a structured catalytically packed bed reactor:Liquid phase mixing and masstransfer. Chemical Engineering Science,1999,54(24):5145-5152
85. Harandi M N. Fluidizd catalytic process for prducts and hydration of olefins. US 5331011.1993
86．温朗友，闵恩泽，庞桂赐等．悬浮床催化精馏塔新工艺合成异丙苯．化工学报，2000，51(1)：115-119
87．廖安平，蓝平，李媚等．流化催化精馏制备乙酸乙酯的研究．化学工程，2000，28(6)：19-21
88．曹海波，乔旭，曾崇．流化催化精馏合成甲缩醛技术．南京化工大学学报，1998，20(3) 19-22
89. Baur R ,Higler A P,Taylor R and Krishna R. Comparison of equilibrium stage models for reactive distillation. Chemical Engineering Journal,2000,76:33-47
90. Lee J H and Dudukovic M P. A comparison of the equilibrium and nonequilibrium models for a multicomponent reactive distillation column .Computers and Chemical Engineering, 1998,23: 159-172
91. Taylor R and Krishna R. Modelling reactive distillation. Chemical Engineering Science,2000,55:5183-5229
92. Higler A, Krishna R, Taylor R. A Nonequilibrium Cell Model for Multicomponent(Reactive) Separation Processes. American Institute of Chemical Engineers Journal, 1999,45:2357-2370.
93. Higler A, Krishna R, Taylor R. A Non-equilibrium Cell Model for Packed Distillation Columns. The influence of Maldistribution. Industrial and Engineering Chemistry Research, 1999, 38:3988-3999.
94．方永成，江桂秀，万爱媛等．MTBE催化蒸馏数学模型的研究．石油炼制，1989，(2)：22-28
95．鲍杰，严国祥，邬晓风．合成MTBE非均相催化精馏过程数学模拟．化学工程，1994，22(5)：6-12
96．张瑞生，韩英，Hoffmann U．非均相催化精馏过程的模拟计算．化工学报，1989，40(6)：693-703
97．韩英，张瑞生．全回流催化精馏塔的模拟计算．华东化工学院学报，1989，15(3)：331-338
98．朱建华．反应精馏过程的非平衡级模型初探．计算机与应用化学 1994．11(3)167-173
99．郑宇翔．催化精馏过程研究．天津大学学位论文，1992
100．陆茵，吕德伟．串釜式反应精馏的非平衡级模型模拟．宁波大学学报， 1999，12(1)33-39．
101．陈波．催化蒸馏过程研究．非平衡级速率模型中性质参数的评价与选择．天津大学学位论文，1995
102．吴燕翔．醋酸甲酯催化精馏中试过程的研究．浙江大学学位论文，1999
103. Tuchlemski A, Beckmann D. Reactive distillation industrial application. Chemical Engineering Science, 2001, 56(1): 387-394
104. Larry L. Hench, Jon K. West. The Sol-Gel process. Chem. Rev. . 1990, 90: 33-72
105．杨南如，余桂郁．溶胶．凝胶的基本原理与过程．硅酸盐通报，1992，11(2)：56-63．
106．余桂郁，杨南如．溶胶．凝胶法的工艺过程．硅酸盐通报．1993，12(6)：60-69．
107．阎子峰编著，纳米催化技术．北京：化学工业出版社，2003年第1版
108．严继民，张启元．吸附与凝聚(固体的表面与孔)．第1版，北京：科学出版社．1979
109．胡玉才，叶兴凯，吴越．固载杂多酸催化剂气相催化合成乙酸丁酯的研究．精细石油化工，1996，(1)5-9
110．刘庆林，陈洪钫．H_3(PW_(12)O_(40))／PVA催化膜用于酯化反应的研究．石油化工，1997，26(10)676-679
111．楚文玲，杨向光，叶兴凯等．硅钨杂多酸在中孔全硅分子筛HMS上的固载及其催化性能．催化学报，1997，18(3)225-229
112．王廷吉，赵新强，张秉常．SO_4~(2-)-Fe_2O_3／Hβ增强酸催化剂上合成乙酸丁酯．石油化工，1998，27(3)159-163
113．马德，李骏，顾树珍．改性离子交换树脂的表征及催化合成乙酸丁酯的研究．石油化工，1996，25(2)80-84
114．曾庆乐．氯化高锡催化合成乙酸丁酯的研究．化学通报，2000，(1)45-47
115．黄碧纯．固体超强酸SO_4~(2-)-MoO_3-ZrO_2的酸强度与酯化催化性能．工业催化，2000，8(2)61-64
116．胡健平，储伟，邱发礼．固体酸催化乙酸／丁醇酯化反应的研究．精细化工，2000，17(5)269-273
117．马德，黎源．WO_3-YiO_2-SO_4~(2-)固体超强酸的制备及应用研究．精细化工，2002，19(1)36-38
118．常铮，郭灿雄，段雪等．磁性超细固体酸催化剂SO_4~(2-)-ZrO_2／Fe_3O_4的组装及表征．催化学报，2003，24(1)47-51
119．俞善信，唐艳春，梁哲辉。以对甲苯磺酸为催化剂合成乙酸异戊酯．精细石油化工，1996，2：31-32
120．俞善信．硫酸铜的催化酯化作用．精细石油化工，1995，(3)：45-47
121．李毅群，肖小云．十二水合硫酸铁铵催化合成乙酸异戊酯，现代化工，1998， (1) 29-30
122．周建伟．相转移催化合成乙酸异戊酯，化学通报 1999(6)，45-47
123．易兵，郭文辉，龙有前等．氨基磺酸催化合成乙酸异戊酯．化学世界，2001，(3) 148-150
124．翁文，许华丽，李国平等．四氯化锡催化乙酸异戊酯的合成．应用化学，2001，18(3)：244-245
125．廖德仲，何节玉．固体超强酸SO_4~(2-)-MoO_3-TiO_2的制备及其催化酯化性能研究．化学研究与应用．2001，13(3) 290-292
126．訾俊峰，朱蕾．活性炭固载氯化铁催化合成乙酸异戊酯，工业催化，2004，12(9)：31-33
127．杨水金，肖继，梁永光．TiSiW_(12)O_(40)／TiO_2催化合成乙酸异戊酯的研究．化学试剂，2002，24(2)，107-108；121
128．崔秀兰，林明丽，郭海福等．稀土固体超强酸催化合成乙酸异戊酯的研究．化学世界，2003，(1)，27-30
129．林森，郭璇，王国永等．含硅有机锡化合物在酯化反应中的催化性能研究．化学试剂，2006，28(6)，351-353
130．谷珉珉，贾韵仪，姚子鹏．有机化学实验．上海：复旦大学出版社，1991
131．蒋平平，卢冠忠．固体酸催化合成邻苯二甲酸二辛酯．化工进展，2002，21(5)：328-330，348
132．陈其瑞，张美凤，罗明润等．Ln_2O_3／Al_2O_3催化酯化合成邻苯二甲酸二异辛酯．催化学报，1994，15(3)236-238
133．金振兴，张庆勋，刘连利等．固载杂多酸催化剂PW_(12)／SiO_2复相催化酯化合成邻苯二甲酸二异辛酯．精细化工 1996，13(1) 34-36
134．申永存，张良均，邹淑静．邻苯二甲酸二异辛酯(DOP)的非酸催化合成．精细化工 1996，13(4) 21-23
135．梁英，石小鹏，王启慧．固体杂多酸盐TiGeW_(12)O_(40)／TiO_2催化合成DIOP．塑料工业，2004，32(8)58-59
136．王兴平，毛建军，谢飞．以分子筛为催化剂合成邻苯二甲酸二辛酯．现代化工，1997，(6)29
137. YudaoMa,Q.L.Wang,HaoYan,etal. Zeolite-catalyzed esterfication.I.Synthesis of acetates,benzoates and phthalates.Applied Catalysis A:General 139(1996)51-57
138. Guanzhong Lu.Catalytic properties of SO_4~(2-)-/T-M-O superacids in esterfication. Applied Catalysis A:General 133(1995)11-18
139. Z. H. Zhao. Studies on esterification reaction over aluminophosphate and silicoaluminophosphate molecular sieves. Journal of Molecular Catalysis A: Chemical 168(2001) 147-152
140. M.Arabi, M.Mohammadpour Amini,M.Abedini,etal. Esterification of phthalic anhydride with 1-butanol and 2-ethylhexanol catalyzed by heteropolyacids. Journal of Molecular Catalysis A: Chemical 200 (2003) 105-110
141. Firdovsi Tataroglu Sejidov, Yagoub Mansoori and Nadereh Goodarzi. Esterification reaction using solid heterogeneous acid catalysts under solvent-less condition. Journal of Molecular Catalysis A: Chemical 240(2005) 186-190
142. M. Khodadadi Moghaddam and M.R. Gholami. Preparation of Titania based solid strong acid and study of its catalytic activity in esterification of Phthalic anhydride and Sebacic acid. Materials Letters, 2006,60(6) 715-719
143．马雪琴．低温增塑剂癸二酸二异辛酯合成的研究．现代化工，1997，17(7)26-27
144．孟启，朱国彪，孙小强．SnO／沸石催化合成癸二酸二辛酯的研究．精细石油化工进展 2001，2(12)7-9
145．毕韶丹．固体超强酸催化剂在合成癸二酸二异辛酯反应中的研究．辽宁化工，2002，31(4)146-148
146．郑根武，宁立芹．癸二酸二辛酯的开发．现代塑料加工应用，2002，14(2)38-40
147．陈群．SO_4~(2-)／TiO_2-Al_2O_3固体超强酸催化合成癸二酸二异辛酯．精细石油化工进展，2004，5(7) 33-35
148．俞善信，彭红阳．三氯化铁催化合成缩醛(酮)．现代化工，1994，14(12)：29-30．
149．陈翠娟．十二水合硫酸铁铵催化合成缩醛和缩酮．合成材料老化与应用，2001，(2)：20-21．
150．吕月仙．磷钼酸催化法制备某些缩醛(酮)的研究．郑州轻工业学院学报，1999，14(1)：60-63．
151．杨水金，童文龙．H_4SiW_(12)O_(40)／PAn催化剂催化合成苯甲醛乙二醇缩醛．香料香精化妆品，2004，(5)17-19，26．
152．文瑞明，游沛清，罗新湘等．维生素C催化合成缩醛(酮)．石油化工，2002，31(5)：373-375．
153．吴露玲．固体超强酸催化缩醛、酮化反应．科技通报，1995，11(5)：289-291．
154．杨水金．TiSiW_(12)O_(40)／TiO_2催化合成苯甲醛乙二醇缩醛．精细石油化工进展，2004，5(2)：33-35．
155．白爱民，余建勇，杨水金等．SO_4~(2-)／TiO_2-MoO_3催化合成苯甲醛乙二醇缩醛．湖北师范学院学报，2004，24(2)：12-15．
156．但悠梦，米远祝，田大听等．S_2O_8~(2-)／ZrO_2-Al_2O_3固体超强酸催化剂的研制与应用．应用化学，2001，18(10)：840-842．
157．杨水金，夏佳，吕宝兰．磷钨酸催化合成缩醛(酮)．精细化工，2004，21(9)：686-688．
158．魏荣宝，梁娅，薛其峰等．离子交换树脂催化法合成缩醛(酮)．离子交换与吸附，1992，8(2)，171-174
159．杨水金，夏佳，刘江燕等．硅钨杂多酸催化合成缩醛(酮)．精细与专用化学品 2004，12(14)：15-18
160．杨水金，夏佳，孙聚堂．TiSiW_(12)O_(40)／TiO_2催化合成苯甲醛1，2-丙二醇缩醛．化学反应工程与工艺，2003，19(1)：9-13
161．夏佳，杨小山，吴顺红．硫酸根／氧化钛．氧化镧催化合成苯甲醛1，2-丙二醇缩醛．化学工业与工程技术，2004，25(1)：3-5
162．裘兆蓉，王车礼，承民联等．催化精馏中间采出新工艺．CN 02142233．8，2002．