催化精馏技术合成乙酸乙酯工艺研究
|
摘要
乙酸乙酯是一类重要的有机溶剂和有机化工基本原料，广泛用于有机合成、油漆涂料、医药、香料、粘接剂等行业。目前国内乙酸乙酯生产企业大多数还是以酸和醇为原料，浓硫酸为催化剂直接酯化法的传统工艺。虽然该传统生产工艺比较成熟，但由于使用浓硫酸作催化剂，易对设备造成腐蚀，易发生局部脱水、醚化、碳化等副反应，影响最终产品的质量和原料的收率。另一方面，传统生产工艺由于受平衡的限制，原料的单程转化率较低。
本课题研究将催化精馏技术应用于乙酸乙酯的合成。在商品化的强酸性阳离子交换树脂中，筛选出了对乙酸乙酯合成具有良好催化性能的D072型强酸性阳离子交换树脂。研究了D072型强酸性阳离子交换树脂催化合成乙酸乙酯的动力学，在消除内外扩散的条件下，催化剂质量为0．017～0．083g(催化剂)·g~(-1)(乙酸)，温度范围为53．0℃～74．0℃实验条件范围，合成乙酸乙酯动力学方程：-r_A=x~mk_0e~(-Ea/RT)(C_AC_B-C_EC_W/K)=x~(0.5509)×74534584．79×e~(-65588.40/RT)(C_AC_B-C_EC_W／3．94)对动力学方程进行验证，结果表明在实验范围内由动力学方程计算的结果与实际值符合较好，模型的置信度较高均为98％。对D072型强酸性阳离子交换树脂，采用比表面仪、热分析、红外光谱、X射线衍射等进行了表征，初步探讨了对于催化剂催化活性增强和降低的原因。
在原催化精馏技术基础上，改变催化剂加入方式，采用细粉状的强酸性阳离子交换树脂作催化剂并随物料在塔中一起流动，即流化催化精馏技术。以空气-水体系，研究了催化剂细粉存在条件下填料塔的流体力学，结果表明，催化剂细粉对填料塔的压降和持液量没有显著的影响。将催化剂细粉与乙酸进料混合均匀，一同加入到Φ30mm玻璃填料塔内，催化剂与液相混合在塔内流动，并循环使用。考察了催化剂浓度、回流比、进料酸醇摩尔比和进料总流量等条件对流化催化精馏过程的影响。实验结果表明：催化剂质量与乙酸的质量比为0．033g(催化剂)·g~(-1)(乙酸)，回流比为3．0：1．0，进料位置为乙醇Y_6口进料，乙酸Y_2口进料，进料酸醇摩尔比n_酸：n_醇为2．8：1．0，乙醇进料量为1．0mol·h~(-1)，乙酸2．8mol·h~(-1),进料总量为3．8mol·h~(-1)．塔顶有机相组成为：乙酸乙酯90．60％，乙酸0．028％，乙醇2．90％，水6．47％。塔顶产品精制后，可获得99％以上纯度的乙酸乙酯，获得的工艺条件和操作参数，为催化精馏合成乙酸乙酯的工程开发打下了良好的理论基础。
As an important kind of organic dissolvent and chemical raw stuff, ethyl acetate is wildly used in industries such as organic synthesis, paint, coating, medicine, aromatics and binder etc. At present, ethyl acetate is mainly produced by a traditional technology in our country, which ethyl acetate is directly synthesized by acetate acid and alcohol with concentrated sulfuric acid as catalyst. There are still some existing disadvantages though it is a mature technology: on one hand, concentrated sulfuric acid has so strong corrosion that many side reactions occurred on the equipment such as dehydrolysis , etherification, carbonization etc. It will affect product quality and feedstock yield. On the other hand, for the traditional production technology is restricted by balance, the one-way conversion of material is low.
Synthesis of ethyl acetate by catalytic distillation is investigated in this paper. D072 Strong-acidic cation exchange-resin is chosen to synthesis ethyl acetate for is good catalytic properties. On the purpose of synthesis kinetics of ethyl acetate, D072 Strong-acidic cation exchange-resin is adopted. After the influence of internal and external diffusion is eliminated, some parameters can be obtained as follow: the quantity of catalyst is between 0.017～0.083g _((catalyst))·g~(-1)_((acetic add)),the temperature is between 53.0℃～74.0℃,The kinetics equation of ethyl acetate system is :
Meantime , the equations of kinetics are proved having good rightness and high confidence level of 98%. These provide a theoretical principle for design of catalytic distillation tower. D072 Strong-acidic cation exchange-resin is characterized using specific surface area analyzer, IR, XRD et al. preliminary study on the reasons of increase and decrease of catalytic activity for the catalyst of the catalyst are also taken into consideration.
In this paper, the strong-acidic cation exchange-resin powder is developed on the basis of the original catalytic distillation technology. The mode of catalyst entering is changed. The fine catalyst particles mix with liquid phase through flowing down in the column, that is fluidizing catalytic distillation. In the system of air-water, the hydrodynamics of packing column are studied on the presence of the catalyst powder. The results show that the catalyst powder has no noticeable impact to the pressure drop and the liquid holdup of the packing column. The strong-acid cation change-resin powder mixed with acatic acid flows down in the column and recycles between the catalytic distillation column and catalyst recovery. The fluidizing catalytic distillation process is experimentally studied on the esterification of acetate acid by alcohol. The experiments are carried out in a glass column with an inner diameter of 30mm and the catalyst is strong-acidic cation exchange-resin powder. The effects of catalyst concentration, reflux ratio, feed mole ratio of acetate acid to alcohol and total feed flow on the process are experimentally investigated. Based on the analysis, the experiment results indicate that: the feasible technological conditions of ethyl acetate synthesis are inlet amount of acetate acid is 2.8mol·h~(-1) in Y_2, alcohol is 1mol·h~(-1) in Y_2, total amount is 3.8mol·h~(-1), acid/alcohol mole ratio of 2.8:1.0 and reflux ratio of 3.0:1.0, the catalyst concentration is 0.033 g_((catalyst))·g~(-1)_((acetic acid)), The composition of tower top organic phase are ethyl acetate 90.60%, acid 0.028%, alcohol 2.90% and water 6.47%. The product of tower top rectify in the distillation tower distilled in the distillation column directly, the product of athyl acetate can be obtained, the content of ethyl acetate is up to 99%. The technological parameters obtained from experiments afford a good foundation for engineering development of synthesis of ethyl acetate by catalytic distillation.
本课题研究将催化精馏技术应用于乙酸乙酯的合成。在商品化的强酸性阳离子交换树脂中，筛选出了对乙酸乙酯合成具有良好催化性能的D072型强酸性阳离子交换树脂。研究了D072型强酸性阳离子交换树脂催化合成乙酸乙酯的动力学，在消除内外扩散的条件下，催化剂质量为0．017～0．083g(催化剂)·g~(-1)(乙酸)，温度范围为53．0℃～74．0℃实验条件范围，合成乙酸乙酯动力学方程：-r_A=x~mk_0e~(-Ea/RT)(C_AC_B-C_EC_W/K)=x~(0.5509)×74534584．79×e~(-65588.40/RT)(C_AC_B-C_EC_W／3．94)对动力学方程进行验证，结果表明在实验范围内由动力学方程计算的结果与实际值符合较好，模型的置信度较高均为98％。对D072型强酸性阳离子交换树脂，采用比表面仪、热分析、红外光谱、X射线衍射等进行了表征，初步探讨了对于催化剂催化活性增强和降低的原因。
在原催化精馏技术基础上，改变催化剂加入方式，采用细粉状的强酸性阳离子交换树脂作催化剂并随物料在塔中一起流动，即流化催化精馏技术。以空气-水体系，研究了催化剂细粉存在条件下填料塔的流体力学，结果表明，催化剂细粉对填料塔的压降和持液量没有显著的影响。将催化剂细粉与乙酸进料混合均匀，一同加入到Φ30mm玻璃填料塔内，催化剂与液相混合在塔内流动，并循环使用。考察了催化剂浓度、回流比、进料酸醇摩尔比和进料总流量等条件对流化催化精馏过程的影响。实验结果表明：催化剂质量与乙酸的质量比为0．033g(催化剂)·g~(-1)(乙酸)，回流比为3．0：1．0，进料位置为乙醇Y_6口进料，乙酸Y_2口进料，进料酸醇摩尔比n_酸：n_醇为2．8：1．0，乙醇进料量为1．0mol·h~(-1)，乙酸2．8mol·h~(-1),进料总量为3．8mol·h~(-1)．塔顶有机相组成为：乙酸乙酯90．60％，乙酸0．028％，乙醇2．90％，水6．47％。塔顶产品精制后，可获得99％以上纯度的乙酸乙酯，获得的工艺条件和操作参数，为催化精馏合成乙酸乙酯的工程开发打下了良好的理论基础。
As an important kind of organic dissolvent and chemical raw stuff, ethyl acetate is wildly used in industries such as organic synthesis, paint, coating, medicine, aromatics and binder etc. At present, ethyl acetate is mainly produced by a traditional technology in our country, which ethyl acetate is directly synthesized by acetate acid and alcohol with concentrated sulfuric acid as catalyst. There are still some existing disadvantages though it is a mature technology: on one hand, concentrated sulfuric acid has so strong corrosion that many side reactions occurred on the equipment such as dehydrolysis , etherification, carbonization etc. It will affect product quality and feedstock yield. On the other hand, for the traditional production technology is restricted by balance, the one-way conversion of material is low.
Synthesis of ethyl acetate by catalytic distillation is investigated in this paper. D072 Strong-acidic cation exchange-resin is chosen to synthesis ethyl acetate for is good catalytic properties. On the purpose of synthesis kinetics of ethyl acetate, D072 Strong-acidic cation exchange-resin is adopted. After the influence of internal and external diffusion is eliminated, some parameters can be obtained as follow: the quantity of catalyst is between 0.017～0.083g _((catalyst))·g~(-1)_((acetic add)),the temperature is between 53.0℃～74.0℃,The kinetics equation of ethyl acetate system is :
Meantime , the equations of kinetics are proved having good rightness and high confidence level of 98%. These provide a theoretical principle for design of catalytic distillation tower. D072 Strong-acidic cation exchange-resin is characterized using specific surface area analyzer, IR, XRD et al. preliminary study on the reasons of increase and decrease of catalytic activity for the catalyst of the catalyst are also taken into consideration.
In this paper, the strong-acidic cation exchange-resin powder is developed on the basis of the original catalytic distillation technology. The mode of catalyst entering is changed. The fine catalyst particles mix with liquid phase through flowing down in the column, that is fluidizing catalytic distillation. In the system of air-water, the hydrodynamics of packing column are studied on the presence of the catalyst powder. The results show that the catalyst powder has no noticeable impact to the pressure drop and the liquid holdup of the packing column. The strong-acid cation change-resin powder mixed with acatic acid flows down in the column and recycles between the catalytic distillation column and catalyst recovery. The fluidizing catalytic distillation process is experimentally studied on the esterification of acetate acid by alcohol. The experiments are carried out in a glass column with an inner diameter of 30mm and the catalyst is strong-acidic cation exchange-resin powder. The effects of catalyst concentration, reflux ratio, feed mole ratio of acetate acid to alcohol and total feed flow on the process are experimentally investigated. Based on the analysis, the experiment results indicate that: the feasible technological conditions of ethyl acetate synthesis are inlet amount of acetate acid is 2.8mol·h~(-1) in Y_2, alcohol is 1mol·h~(-1) in Y_2, total amount is 3.8mol·h~(-1), acid/alcohol mole ratio of 2.8:1.0 and reflux ratio of 3.0:1.0, the catalyst concentration is 0.033 g_((catalyst))·g~(-1)_((acetic acid)), The composition of tower top organic phase are ethyl acetate 90.60%, acid 0.028%, alcohol 2.90% and water 6.47%. The product of tower top rectify in the distillation tower distilled in the distillation column directly, the product of athyl acetate can be obtained, the content of ethyl acetate is up to 99%. The technological parameters obtained from experiments afford a good foundation for engineering development of synthesis of ethyl acetate by catalytic distillation.
引文
[1]刘明．乙酸乙酯的市场需求与生产方法[J]．化学工业与工程技术，2004，25(5)：54-56
[2]黄焕生，黄科林，杨波，等．乙酸乙酯合成生产技术现状及发展趋势[J]．化工技术与 开发，2007，12(36)：12-16
[3]荣杰．催化反应精馏合成乙酸乙酯新工艺研究[D]．北京：北京化工大学硕士学位论 文，2003
[4]M.A．约翰逊，游一中，刘军伍．气雾剂手册-配方．技术．市场[M]．北京：化学工业出 版社，2004．222
[5]L．J．Calb．涂料助剂大全[M]．上海：上海科学技术文献出版社，2000．330
[6]林翔云．调香术[M]．北京：化学工业出版社，2001．264-266
[7]魏福祥，韩菊，于宝莉．葡萄籽中活性成分提取工艺的研究[J]．精细化工，2001， 18(7)：394-400
[8]王昌利，宋小妹，胡亚迅，等．沙棘果皮总黄酮提取分离工艺研究[J]．中成药，1994， 9：6-8
[9]王丽霞，刘士艳，朱万春，等．乙醇一步法合成乙酸乙酯的MoSx／C催化剂的研究． 分子催化，2007，21：231-232
[10]王大林，姜浩锡，张敏华．乙醇一步法制备乙酸乙酯反应机理的研究．石油化工， 2007，36(10)：1025-1028
[12]李雄．几种工业乙酸乙酯制备方法的技术经济对比[J]．石油化工技术经济，2002， 17(1)：19-22
[13] Xue-Min Yan, Jia-Heng Lei, Dan Liu, et al. Synthesis and catalytic properties of mesoporous phosphotungstic acid/SiO_2 in a self-generated acidic environment byevaporation-induced self-assembly[J] , Materials Research Bulletin, 2007 , 42(11): 1905-1913
[14] Hao-Yu Shen , Zaher M. A. Judeh , Chi Bun Ching, et al. Comparative studies on alkylation of phenol with tert-butyl alcohol in the presence of liquid or solid acid catalysts in ionic liquids[J]. Journal of Molecular Catalysis A: Chemical, 2004, 212(1):??301-308
[15] Bo-Lun Yang, San-Ba Yang and Rui-qing Yao. Synthesis of ethyl tert-butyl ether fromtert-butyl alcohol and ethanol on strong acid cation-exchange resins [J]. Reactive andFunctional Polymers. 2000,44(2): 167-175
[16] Muhammad Umar, Anwar Rasheed Saleemi and Suleman Qaiser. Synthesis of ethyltert-butyl ether with tert-butyl alcohol and ethanol on various ion exchange resincatalysts [J]. Catalysis Communications, 2008,9(5): 721-727
[17]迟卫军．硫酸氢钠催化合成乙酸乙醋的工艺研究[J]．化学与粘合，2007，29(6)： 451-453
[18]尉志苹，王少君，曲丰作．离子液体催化反应精馏合成乙酸乙酯[J]．精细化工中间 体，2007，37(6)：39-41
[19] Kirk,R.E., Othmer, D.F. Encyclopedia of chemical technology[M]. New York: M.Howe-Grant, 1991. 781-812.
[20]蓝平，廖安平，周桂，等．强酸型阳离子交换树脂催化制各乙酸乙酯的研究[J]．河 北化工，1997，(3)：46-47
[21]闫瑞一．催化精馏合成乙酸酯研究[D]．南宁：广西大学硕士学位论文，2005
[22]王爱军，赵地顺，韩文爱，等．TiO_2／SO_4~(2-)-HZSM-5催化合成乙酸乙酯[J]．河北化工， 2003，(4)：26-27
[23]张立，袁兴东．含磺酸基的介孔分子筛SBA-15-SO_3H催化合成乙酸乙酯[J]．抚顺石 油学院学报，2003，23(2)：20-23
[24]曹忠良，汤青云．活性炭负载杂多酸催化合成乙酸乙酯的研究[J]．湖南城市学院学 报，2005，14(3)：58-59
[25]周华，屈小英，余高奇．纳米固体超强酸TiO_2／SO_4~(2-)催化合成乙酸正丁酯[J]．武汉科 技大学学报(自然科学版)，2007，30(6)：629-631
[26]杨春华．固体超强酸S_2O_8~(-2)／Fe_2O_3-TiO_2-Nd_2O_3催化合成乙酸乙酯的研究[J]．技术与 教育，2007，21(1)：9-11
[27]廖安平，蓝平，周桂，等．催化反应精馏技术连续制备乙酸乙酯[J]．现代化工 1997(9)：25-27
[28]叶清，裘兆蓉，郭本炎，等．天然丝光沸石催化反应精馏技术连续合成乙酸乙酯[J]． 精细石油化工进展，2000，1(4)：29-31
[29] Sennewald K, Gehmann K, Schafer.Column for carrying out organic chenical reactions in contact with fme[P], particyluate catalysts, US: 3 579 309,1971.
[30]王龙延．催化蒸馏技术[J]．现代化工，1990，(2)：43-47．
[31] Shoemaker J D, Jones E M Jr. Cumene by catalytic distillation[J]. HydrocarbonProcessing, 1987, 66(6): 57-58
[32] Stadig W P. Catalytic distillation-combining chemical reaction with product separation [J].Chemical Process, 1987, 50(2): 27-32
[33] Zhang Jirui, er al. Process and apparatus for preparation of ethylbenzene by alkylation orbenzene with dilute ethylene contained in dry gas by catalytic distillation[P]. US PatentApplication: 20010018545, 2001
[34] Markus Schmitt , Hans Hasse, Klaus Althaus, et al. Synthesis of n-hexyl acetate byreactive distillation [J]. Chemical Engineering and Processing, 2004,43: 397-409
[35] Smith LA. Method for the preparation of methyl tertiary butyl ether [P]. USP:4978807,1990
[36] Ward DJ. Etherification of isomylenes by catalytic distillation [P]. USP: 5196612, 1993
[37] Lee J. Whauan Swesterberg AW. Circumventing an azeotrope in reactive distillation[J].Industrial and Engineering Chemistry Research, 2000, 39: 1061-1063
[38]许锡恩，李家玲，刘铁涌．催化精馏进展[J]．石油化工，1989，18(9)：642-649
[39]肖剑，刘家祺．催化精馏塔催化剂装填方式研究进展[J]．化工进展，1 999，(2)：8-12
[40] Moritz P and Hasse H . Fluid dynamics in reactive distillation packing Katapsk [J].Chemixal Engineering Science, 1999, 54: 1367-1374
[41] Ellenberger J and Krishna R. Counter-current operation of structure catalytically packeddistillation columns: pressure drop, holdup and mixing[J]. Chemical EngineeringScience, 1999,54: 1339-1345
[42] Gonzalez JC, Subawalla H. Separation of Tert-amyl Alcoholina Reactive DistillationColumn Experimental Demonstration and Simulation of Column [J]. Ind Eng Chem Res,1997, 36: 3845-3853
[43] Degarmo JL, Parulekar VN. Consider Reactive Distillation [J].Chem Eng Prog, 1992, (3):43-50
[44]许锡恩，孟祥坤．催化精馏过程研究进展[J]．化工进展，1998，(1)：7-13
[45]温朗友，闵恩泽，庞桂赐，等．悬浮床催化蒸馏新工艺合成异丙苯[J]．化工学报， 2000，51(1)：115-119
[46] Adams JR. Alkylation of Organic Aromatic Compounds[P]. US, US5019669. 1991
[47]廖安平，蓝平，李媚，等．流化催化精馏制备乙酸乙酯研究[J]．化学工程，2000， 28(6)：19-22
[48]廖安平，蓝平，李媚，等．流化催化精馏制备乙酸丁酯的研究[J]．广西民族学院学 报(自然科学版)，2000，6(1)：23-26
[49]曲宇霞．浆料催化精馏制备乙酸甲酯的研究[D]．天津：天津大学硕士论文，2004
[50] Baur R, Higler A P, Taylor R, et al. Comparison of equilibrium stage and nonequilibriumstage models for reactive distillation[J]. Chemical Engineering Journal, 2000, 76: 33-47
[51] Lee J H AND Dudukovic M P. A comparison of the equilibrium and nonequilibriummodels for a multicomponent reactive distillation column [J]. Computers and ChemicalEngineering, 1998, 23: 159-172
[52] Taylor R and Krishna R. Modeling reactive distillation[J]. Chemical Engineering Science,2000,55:5183-5229
[53]张丹，曲宇霞，许春建，等．合成乙酸甲酯浆料催化精馏过程的模拟研究[J]．石油 化工，2005，34(8)：754-760
[54]齐向娟，李士雨．采用ChemCAD模拟乙酸丁酯催化反应精馏过程[J]．化工设计， 2005，15(6)：8-10
[55] Minghan Han., Hongfei Lin Pressure drop for two phase counter-current flow in apacked column with a novel internal [J]. Chemical Engineering Journal, 2003, 94:179-187
[56] Achim Hoffmann., Christoph Noeres. Scale-up of reactive distillation columns withcatalytic packings[J]. Chemical Engineering and Processing, 2004,43: 383-395
[57] Jinfu Wang , Xudong Ge, Development of a novel catalytic distillation column[J].Chemical Engineering and Processing, 2002,41: 115-121
[58] Matthew J. Okasinski.Simultaneous kinetic resolution of chiral propylene oxide andpropylene glycol in a continuous reactive distillation column[J]. Chemical EngineeringScience, 2003, 58: 1289-1300
[59]王静康．化工设计[M]．北京：化学工业出版社，2000．229-437
[60]于伟民，薛永强，梁西良，等．乙酸乙酯的精致[J]．化学与黏合，2005，27(2)： 108-111
[61]邱学青，蔡进团，徐清才，等．乙酸乙酯提纯新方法研究[J]．化学工程，1997，25(1)： 41-44．
[62]雷良恒．加盐萃取-恒沸精馏联合过程研究[J]．石油化工，1990，19(11)：749-752．
[63]雷良恒，王洪有．提纯乙酸乙酯的加盐萃取恒沸精馏联合流程[P]．中国：CN 1020896，1993，05，26
[64]蒋毅，冉隆林，刘美光，等．一种提纯乙酸乙酯的方法[P]．中国：CN 1210851，1999， 03,17
[65]冉隆林，蒋毅，刘美光，等．一种分离乙酸乙酯的恒沸蒸馏方法[P]．中国：CN 1156718，1997，08，13
[66]周旭，龚峻松，杜大庆．苯乙烯系离子交换树脂中间体的粒度控制[J]．舰船防化， 2006(1)：16-19
[67]周渊，魏荣卿，刘晓宁，等．通过Michael反应制备脂肪磺酸基强酸型阳离子交换树 脂[J]．化工学报，2007，58(7)：1 857-1 862
[68]任立国，高文艺，张晓丽．SO_4~(2-)／ZrO_2固体超强酸催化剂上的酯化反应机理[J]．抚顺 石油学院学报，2003，23(1)：33-36
[69]王爱军，赵地顺，庞登甲．Fe~(3+)／HZSM-5分子筛催化合成乙酸乙酯[J]．河北化工， 2004(3)：30-33
[70]王凯明．固载杂多酸催化合成乙酸乙酯的研究[J]．中国石油大学硕士研究生学位论 文，2004
[71]高丽娟，杨勇．硅钨酸催化合成乙酸乙酯[J]．长春师范学院学报(自然科学版)，2007， 26(3)：51-53
[72]蓝平，唐正姣，吴如春，等．树脂负载金属离子固体酸催化合成乙酸乙酯动力学研 究[J]．化学反应工程与工艺，2003，19(3)：210-215
[73] E.A.El-Sharkawy, Shar S.Al-Shihry. preparation of butyl acetate using solid acid catalysts: textural and structural characterization[J]. Materials Letters, 2004, 58: 2122-2127
[74]周晓颖，汤志刚，丁立，等．阳离子交换树脂作催化剂合成乙酸乙酯的反应动力学 [J]．清华大学学报，2002，42(5)：17-20
[75]蓝丽红，闫瑞一，李媚，等．阳离子交换膜催化合成乙酸丁酯动力学研究[J]．离子 交换与吸附，2006．22(2)：168-174
[76]刘维桥，孙桂大．固体催化剂使用研究方法[M]．北京：中国石化出版社，1999．1-2
[77]张艳丽．新型吸附分离纤维的合成、结构表征及性能研究[D]．郑州：郑州大学博士 学位论文，2007
[78]邓芹英，刘岚，邓惠敏．波谱分析教程[M]．北京：科学出版社，2004．43
[79]李永红，刘家祺，马沛生．萃取反应精馏合成高纯度乙酸乙酯[J]．精细化工， 1996(10)：719-723
[80]廖安平，蓝平，李媚，等．乙酸丁酯制取新工艺[J]．石油化工，2001，30(11)：831-834
[81]王少兵，张凯，张占柱．新型催化精馏元件流体力学性能的研究[J]．石油炼制与化 工，2001，32(10)：36-39
[82]庄志军，刘放，张卫华，等．复合塔流体力学性能研究[J]．吉林化工学院学报，2002， 19(4)：13-16
[83]齐国祯，谢在库，钟思青，等．滴流床的压降和持液量[J]．华东理工大学学报，2006， 32(1)：20-46
[84]程能林．溶剂手册[M]．第三版，北京：化学工业出版社，2002．580-589
[2]黄焕生，黄科林，杨波，等．乙酸乙酯合成生产技术现状及发展趋势[J]．化工技术与 开发，2007，12(36)：12-16
[3]荣杰．催化反应精馏合成乙酸乙酯新工艺研究[D]．北京：北京化工大学硕士学位论 文，2003
[4]M.A．约翰逊，游一中，刘军伍．气雾剂手册-配方．技术．市场[M]．北京：化学工业出 版社，2004．222
[5]L．J．Calb．涂料助剂大全[M]．上海：上海科学技术文献出版社，2000．330
[6]林翔云．调香术[M]．北京：化学工业出版社，2001．264-266
[7]魏福祥，韩菊，于宝莉．葡萄籽中活性成分提取工艺的研究[J]．精细化工，2001， 18(7)：394-400
[8]王昌利，宋小妹，胡亚迅，等．沙棘果皮总黄酮提取分离工艺研究[J]．中成药，1994， 9：6-8
[9]王丽霞，刘士艳，朱万春，等．乙醇一步法合成乙酸乙酯的MoSx／C催化剂的研究． 分子催化，2007，21：231-232
[10]王大林，姜浩锡，张敏华．乙醇一步法制备乙酸乙酯反应机理的研究．石油化工， 2007，36(10)：1025-1028
[12]李雄．几种工业乙酸乙酯制备方法的技术经济对比[J]．石油化工技术经济，2002， 17(1)：19-22
[13] Xue-Min Yan, Jia-Heng Lei, Dan Liu, et al. Synthesis and catalytic properties of mesoporous phosphotungstic acid/SiO_2 in a self-generated acidic environment byevaporation-induced self-assembly[J] , Materials Research Bulletin, 2007 , 42(11): 1905-1913
[14] Hao-Yu Shen , Zaher M. A. Judeh , Chi Bun Ching, et al. Comparative studies on alkylation of phenol with tert-butyl alcohol in the presence of liquid or solid acid catalysts in ionic liquids[J]. Journal of Molecular Catalysis A: Chemical, 2004, 212(1):??301-308
[15] Bo-Lun Yang, San-Ba Yang and Rui-qing Yao. Synthesis of ethyl tert-butyl ether fromtert-butyl alcohol and ethanol on strong acid cation-exchange resins [J]. Reactive andFunctional Polymers. 2000,44(2): 167-175
[16] Muhammad Umar, Anwar Rasheed Saleemi and Suleman Qaiser. Synthesis of ethyltert-butyl ether with tert-butyl alcohol and ethanol on various ion exchange resincatalysts [J]. Catalysis Communications, 2008,9(5): 721-727
[17]迟卫军．硫酸氢钠催化合成乙酸乙醋的工艺研究[J]．化学与粘合，2007，29(6)： 451-453
[18]尉志苹，王少君，曲丰作．离子液体催化反应精馏合成乙酸乙酯[J]．精细化工中间 体，2007，37(6)：39-41
[19] Kirk,R.E., Othmer, D.F. Encyclopedia of chemical technology[M]. New York: M.Howe-Grant, 1991. 781-812.
[20]蓝平，廖安平，周桂，等．强酸型阳离子交换树脂催化制各乙酸乙酯的研究[J]．河 北化工，1997，(3)：46-47
[21]闫瑞一．催化精馏合成乙酸酯研究[D]．南宁：广西大学硕士学位论文，2005
[22]王爱军，赵地顺，韩文爱，等．TiO_2／SO_4~(2-)-HZSM-5催化合成乙酸乙酯[J]．河北化工， 2003，(4)：26-27
[23]张立，袁兴东．含磺酸基的介孔分子筛SBA-15-SO_3H催化合成乙酸乙酯[J]．抚顺石 油学院学报，2003，23(2)：20-23
[24]曹忠良，汤青云．活性炭负载杂多酸催化合成乙酸乙酯的研究[J]．湖南城市学院学 报，2005，14(3)：58-59
[25]周华，屈小英，余高奇．纳米固体超强酸TiO_2／SO_4~(2-)催化合成乙酸正丁酯[J]．武汉科 技大学学报(自然科学版)，2007，30(6)：629-631
[26]杨春华．固体超强酸S_2O_8~(-2)／Fe_2O_3-TiO_2-Nd_2O_3催化合成乙酸乙酯的研究[J]．技术与 教育，2007，21(1)：9-11
[27]廖安平，蓝平，周桂，等．催化反应精馏技术连续制备乙酸乙酯[J]．现代化工 1997(9)：25-27
[28]叶清，裘兆蓉，郭本炎，等．天然丝光沸石催化反应精馏技术连续合成乙酸乙酯[J]． 精细石油化工进展，2000，1(4)：29-31
[29] Sennewald K, Gehmann K, Schafer.Column for carrying out organic chenical reactions in contact with fme[P], particyluate catalysts, US: 3 579 309,1971.
[30]王龙延．催化蒸馏技术[J]．现代化工，1990，(2)：43-47．
[31] Shoemaker J D, Jones E M Jr. Cumene by catalytic distillation[J]. HydrocarbonProcessing, 1987, 66(6): 57-58
[32] Stadig W P. Catalytic distillation-combining chemical reaction with product separation [J].Chemical Process, 1987, 50(2): 27-32
[33] Zhang Jirui, er al. Process and apparatus for preparation of ethylbenzene by alkylation orbenzene with dilute ethylene contained in dry gas by catalytic distillation[P]. US PatentApplication: 20010018545, 2001
[34] Markus Schmitt , Hans Hasse, Klaus Althaus, et al. Synthesis of n-hexyl acetate byreactive distillation [J]. Chemical Engineering and Processing, 2004,43: 397-409
[35] Smith LA. Method for the preparation of methyl tertiary butyl ether [P]. USP:4978807,1990
[36] Ward DJ. Etherification of isomylenes by catalytic distillation [P]. USP: 5196612, 1993
[37] Lee J. Whauan Swesterberg AW. Circumventing an azeotrope in reactive distillation[J].Industrial and Engineering Chemistry Research, 2000, 39: 1061-1063
[38]许锡恩，李家玲，刘铁涌．催化精馏进展[J]．石油化工，1989，18(9)：642-649
[39]肖剑，刘家祺．催化精馏塔催化剂装填方式研究进展[J]．化工进展，1 999，(2)：8-12
[40] Moritz P and Hasse H . Fluid dynamics in reactive distillation packing Katapsk [J].Chemixal Engineering Science, 1999, 54: 1367-1374
[41] Ellenberger J and Krishna R. Counter-current operation of structure catalytically packeddistillation columns: pressure drop, holdup and mixing[J]. Chemical EngineeringScience, 1999,54: 1339-1345
[42] Gonzalez JC, Subawalla H. Separation of Tert-amyl Alcoholina Reactive DistillationColumn Experimental Demonstration and Simulation of Column [J]. Ind Eng Chem Res,1997, 36: 3845-3853
[43] Degarmo JL, Parulekar VN. Consider Reactive Distillation [J].Chem Eng Prog, 1992, (3):43-50
[44]许锡恩，孟祥坤．催化精馏过程研究进展[J]．化工进展，1998，(1)：7-13
[45]温朗友，闵恩泽，庞桂赐，等．悬浮床催化蒸馏新工艺合成异丙苯[J]．化工学报， 2000，51(1)：115-119
[46] Adams JR. Alkylation of Organic Aromatic Compounds[P]. US, US5019669. 1991
[47]廖安平，蓝平，李媚，等．流化催化精馏制备乙酸乙酯研究[J]．化学工程，2000， 28(6)：19-22
[48]廖安平，蓝平，李媚，等．流化催化精馏制备乙酸丁酯的研究[J]．广西民族学院学 报(自然科学版)，2000，6(1)：23-26
[49]曲宇霞．浆料催化精馏制备乙酸甲酯的研究[D]．天津：天津大学硕士论文，2004
[50] Baur R, Higler A P, Taylor R, et al. Comparison of equilibrium stage and nonequilibriumstage models for reactive distillation[J]. Chemical Engineering Journal, 2000, 76: 33-47
[51] Lee J H AND Dudukovic M P. A comparison of the equilibrium and nonequilibriummodels for a multicomponent reactive distillation column [J]. Computers and ChemicalEngineering, 1998, 23: 159-172
[52] Taylor R and Krishna R. Modeling reactive distillation[J]. Chemical Engineering Science,2000,55:5183-5229
[53]张丹，曲宇霞，许春建，等．合成乙酸甲酯浆料催化精馏过程的模拟研究[J]．石油 化工，2005，34(8)：754-760
[54]齐向娟，李士雨．采用ChemCAD模拟乙酸丁酯催化反应精馏过程[J]．化工设计， 2005，15(6)：8-10
[55] Minghan Han., Hongfei Lin Pressure drop for two phase counter-current flow in apacked column with a novel internal [J]. Chemical Engineering Journal, 2003, 94:179-187
[56] Achim Hoffmann., Christoph Noeres. Scale-up of reactive distillation columns withcatalytic packings[J]. Chemical Engineering and Processing, 2004,43: 383-395
[57] Jinfu Wang , Xudong Ge, Development of a novel catalytic distillation column[J].Chemical Engineering and Processing, 2002,41: 115-121
[58] Matthew J. Okasinski.Simultaneous kinetic resolution of chiral propylene oxide andpropylene glycol in a continuous reactive distillation column[J]. Chemical EngineeringScience, 2003, 58: 1289-1300
[59]王静康．化工设计[M]．北京：化学工业出版社，2000．229-437
[60]于伟民，薛永强，梁西良，等．乙酸乙酯的精致[J]．化学与黏合，2005，27(2)： 108-111
[61]邱学青，蔡进团，徐清才，等．乙酸乙酯提纯新方法研究[J]．化学工程，1997，25(1)： 41-44．
[62]雷良恒．加盐萃取-恒沸精馏联合过程研究[J]．石油化工，1990，19(11)：749-752．
[63]雷良恒，王洪有．提纯乙酸乙酯的加盐萃取恒沸精馏联合流程[P]．中国：CN 1020896，1993，05，26
[64]蒋毅，冉隆林，刘美光，等．一种提纯乙酸乙酯的方法[P]．中国：CN 1210851，1999， 03,17
[65]冉隆林，蒋毅，刘美光，等．一种分离乙酸乙酯的恒沸蒸馏方法[P]．中国：CN 1156718，1997，08，13
[66]周旭，龚峻松，杜大庆．苯乙烯系离子交换树脂中间体的粒度控制[J]．舰船防化， 2006(1)：16-19
[67]周渊，魏荣卿，刘晓宁，等．通过Michael反应制备脂肪磺酸基强酸型阳离子交换树 脂[J]．化工学报，2007，58(7)：1 857-1 862
[68]任立国，高文艺，张晓丽．SO_4~(2-)／ZrO_2固体超强酸催化剂上的酯化反应机理[J]．抚顺 石油学院学报，2003，23(1)：33-36
[69]王爱军，赵地顺，庞登甲．Fe~(3+)／HZSM-5分子筛催化合成乙酸乙酯[J]．河北化工， 2004(3)：30-33
[70]王凯明．固载杂多酸催化合成乙酸乙酯的研究[J]．中国石油大学硕士研究生学位论 文，2004
[71]高丽娟，杨勇．硅钨酸催化合成乙酸乙酯[J]．长春师范学院学报(自然科学版)，2007， 26(3)：51-53
[72]蓝平，唐正姣，吴如春，等．树脂负载金属离子固体酸催化合成乙酸乙酯动力学研 究[J]．化学反应工程与工艺，2003，19(3)：210-215
[73] E.A.El-Sharkawy, Shar S.Al-Shihry. preparation of butyl acetate using solid acid catalysts: textural and structural characterization[J]. Materials Letters, 2004, 58: 2122-2127
[74]周晓颖，汤志刚，丁立，等．阳离子交换树脂作催化剂合成乙酸乙酯的反应动力学 [J]．清华大学学报，2002，42(5)：17-20
[75]蓝丽红，闫瑞一，李媚，等．阳离子交换膜催化合成乙酸丁酯动力学研究[J]．离子 交换与吸附，2006．22(2)：168-174
[76]刘维桥，孙桂大．固体催化剂使用研究方法[M]．北京：中国石化出版社，1999．1-2
[77]张艳丽．新型吸附分离纤维的合成、结构表征及性能研究[D]．郑州：郑州大学博士 学位论文，2007
[78]邓芹英，刘岚，邓惠敏．波谱分析教程[M]．北京：科学出版社，2004．43
[79]李永红，刘家祺，马沛生．萃取反应精馏合成高纯度乙酸乙酯[J]．精细化工， 1996(10)：719-723
[80]廖安平，蓝平，李媚，等．乙酸丁酯制取新工艺[J]．石油化工，2001，30(11)：831-834
[81]王少兵，张凯，张占柱．新型催化精馏元件流体力学性能的研究[J]．石油炼制与化 工，2001，32(10)：36-39
[82]庄志军，刘放，张卫华，等．复合塔流体力学性能研究[J]．吉林化工学院学报，2002， 19(4)：13-16
[83]齐国祯，谢在库，钟思青，等．滴流床的压降和持液量[J]．华东理工大学学报，2006， 32(1)：20-46
[84]程能林．溶剂手册[M]．第三版，北京：化学工业出版社，2002．580-589