催化精馏制备乳酸乙酯绿色工艺的研究
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摘要
本文介绍了一种合成乳酸乙酯的新工艺，即采用催化精馏技术，以乳酸和乙醇为原料、以强酸性离子交换树脂为催化剂催化合成乳酸乙酯，将催化精馏技术应用于乳酸乙酯的合成是一项新的尝试，它的研究对于促进我国乳酸乙酯工业的发展具有重要的意义。
本文探讨了用强酸性离子交换树脂为催化剂合成乳酸乙酯的反应动力学。通过对实验结果的分析，得出如下结论：酯化反应为二级反应，水解反应为零级反应，其反应动力学模型为：其中，且发现在温度较低时这一反应存在诱导期问题。
本文在自行设计安装的高度为1100mm、直径为40mm的催化精馏塔内，用θ网环填料装填催化剂NKC-9构成反应段，考察了回流比、进料位置、进料流量、醇酸比等参数对催化精馏过程的影响，得到了最佳反应条件：回流比为1:1、进料位置为反应段顶部进酸反应段底部进醇、乳酸进料流量为0.6482mol/h、醇酸比为4:1。
在实验结果的基础上，以动力学模型为基础，借助ASPEN软件用平衡级模型进行了催化精馏塔的模拟，塔内温度分布和塔釜、塔顶组成的模拟结果与实验测定结果吻合较好，表明模拟结果是可靠的。对于催化精馏过程合成乳酸乙酯的工业化生产具有一定的指导意义。
研究结果表明，催化精馏技术应用于乳酸乙酯的合成可以提高产品的收率，反应过程对环境无污染，对设备无腐蚀，产品乳酸乙酯又是一种“绿色溶剂”，因此该技术是一项绿色技术，有很好的工业前景。
A new technique is introduced for the synthesis of ethyl lactate. Namely, under ion-exchange resin catalyst a process of catalytic distillation is applied in synthesis of ethyl lactate with lactic acid and ethanol. It is a new try for synthesis of ethyl lactate through catalytic distillation and is very important for the development of ethyl lactate industries if it will be a successful study.
We selected ion-exchange resin as the catalyst of this experiment. Reactive kinetics using ion-exchange resin catalyst is experimentally determined, and the equation of the reaction rate is established. The conclusion is obtained by analyzing the experiment result: the esterification is second-order reaction, and the hydrolysis is zero-order reaction, so the model for reactive kinetics is obtained:
where k+ = 0.06429 Catalytic distillation integrates the reaction and distillation into one reactor and realizes ethyl lactate produced continuously. Catalytic distillation experiments for synthesis of ethyl lactate are carried out in a 1100 mm high and 40mm diameter column filled with the novel catalyst bed-NKC-9 sandwiched between 9 sheets with wire gauze. The effect of reflux ratio, feed location, feed flow rate and the ratio of ethanol to lactate in feeds is investigated. By analyzing the experimental data, the optimum conditions are obtained. That is, the reflux ratio is 1:1, feed locations are lactic acid fed at the top and ethanol at the bottom of the reactive region, lactic acid feed flow rate is 0.6482mol/h, the feed ratio of ethanol to lactic acid is 4:1.
Based on the experiment and the reaction rate equation, ASPEN software is chosen to simulate the temperature, concentration and other profiles of the catalytic distillation column by equilibrium-staged model. The results of the temperature profile along the column height and components of the tower top and bottom are in agree with the experimental data, and are satisfactory. So it provides the basic guideline to industrial production of ethyl lactate used
catalytic distillation.
The study results indicate the catalytic distillation process, in which realistic conversion and higher purity product are obtained, is applied for synthesis of ethyl lactate. The process is little pollution on the environment and little erosion on the equipment, and ethyl lactate is a "green" solvent, so the technology is a "green" technique and will have good prospective applications in the future.
本文探讨了用强酸性离子交换树脂为催化剂合成乳酸乙酯的反应动力学。通过对实验结果的分析，得出如下结论：酯化反应为二级反应，水解反应为零级反应，其反应动力学模型为：其中，且发现在温度较低时这一反应存在诱导期问题。
本文在自行设计安装的高度为1100mm、直径为40mm的催化精馏塔内，用θ网环填料装填催化剂NKC-9构成反应段，考察了回流比、进料位置、进料流量、醇酸比等参数对催化精馏过程的影响，得到了最佳反应条件：回流比为1:1、进料位置为反应段顶部进酸反应段底部进醇、乳酸进料流量为0.6482mol/h、醇酸比为4:1。
在实验结果的基础上，以动力学模型为基础，借助ASPEN软件用平衡级模型进行了催化精馏塔的模拟，塔内温度分布和塔釜、塔顶组成的模拟结果与实验测定结果吻合较好，表明模拟结果是可靠的。对于催化精馏过程合成乳酸乙酯的工业化生产具有一定的指导意义。
研究结果表明，催化精馏技术应用于乳酸乙酯的合成可以提高产品的收率，反应过程对环境无污染，对设备无腐蚀，产品乳酸乙酯又是一种“绿色溶剂”，因此该技术是一项绿色技术，有很好的工业前景。
A new technique is introduced for the synthesis of ethyl lactate. Namely, under ion-exchange resin catalyst a process of catalytic distillation is applied in synthesis of ethyl lactate with lactic acid and ethanol. It is a new try for synthesis of ethyl lactate through catalytic distillation and is very important for the development of ethyl lactate industries if it will be a successful study.
We selected ion-exchange resin as the catalyst of this experiment. Reactive kinetics using ion-exchange resin catalyst is experimentally determined, and the equation of the reaction rate is established. The conclusion is obtained by analyzing the experiment result: the esterification is second-order reaction, and the hydrolysis is zero-order reaction, so the model for reactive kinetics is obtained:
where k+ = 0.06429
Based on the experiment and the reaction rate equation, ASPEN software is chosen to simulate the temperature, concentration and other profiles of the catalytic distillation column by equilibrium-staged model. The results of the temperature profile along the column height and components of the tower top and bottom are in agree with the experimental data, and are satisfactory. So it provides the basic guideline to industrial production of ethyl lactate used
catalytic distillation.
The study results indicate the catalytic distillation process, in which realistic conversion and higher purity product are obtained, is applied for synthesis of ethyl lactate. The process is little pollution on the environment and little erosion on the equipment, and ethyl lactate is a "green" solvent, so the technology is a "green" technique and will have good prospective applications in the future.
引文
[1] Backhaus, A. A. Continuous process for the manufacture of esters. US patent 1,400,849, 1921,December 20
[2] 刘根生．浅述催化精馏技术．兰化科技，1994，12(4)：281-284
[3] Shoernarer. J. D.; Joan. E. M.. In Hydroearhon Process. 1987,55 (5): 57
[4] Michael F. M, Michael F. Doherty. Reactive distillation. Ind. Eng. Chem. Res, 2000, 39:3953-3957
[5] 许锡恩，朱宝福，陈洪钫等．酯化反应的反应精馏过程，石油化工，1985，14，481
[6] 杨梅，韩运华，张启中等．催化精馏合成丙烯酸正丁酯．吉林化工学院学报，2000，17(1)：22-24
[7] 杨志才，崔现宝．乙酸与丁醇酯化反应精馏过程．化工学报，1998，49(1)：39-47
[8] 廖安平，蓝平等．流化催化制备乙酸乙酯研究．化学工程，2000，28(6)：19-33
[9] Maria Pilar Bernal, Joaquin Coronas, et al. Coupling of reaction and separation at the microscopic level: esterificatiom processes in a H-ZSM-5 membrane reactor. Chem. Eng. Sci., 2002,57, 1557-1562
[10] E. Y. Kening, H. Bader, et al. Investigation of ethyl acetate reactive distillation process. Chem. Eng. Sci., 2001,56, 6185-6193
[11] 丁斌，张启忠等．富马酸二甲酯合成新工艺研究．吉林化工学院学报，1998，15(4)：1-5
[12] 廖安平，蓝平等．流化催化制备醋酸异戊酯研究，化学工程，2000，51，Suppl．：117-121
[13] Davis, B.; Jeffereys, G., J. Wans.Inst. Chem.Eng. Sci, 1973,51(4), 267
[14] 姜忠义，王永．酯交换法合成碳酸二甲酯的催化精馏过程．石油化工，2001，30(3)：173-177
[15] 张毅民，博士后出战报告．草酸二乙酯制草酸动力学研究及其工艺条件的选择．天津大学，1998
[16] 周传光等．化学工程，1992，25 (4)：31
[17] 吴燕翔，王良恩等．二对角矩阵及其在催化精馏塔模拟计算中的应用．福州大学学报。2000，28(1)：82—86
[18] Shoemaker, J. D. and Jones, E. M.. Hydrocarbon Processing. 1987,66 (6): 57-58
[19] France Patent No. 1, 410,589(1964); 1,372,964(t 965).
[20] Hoffmann, H.. Chem.Eng. Sci., 1958, 8(1), 113
[21] Belson, D. J.. Ind.Eng. Chem. Res., 29(7), (1990)
[22] 漆志文，孙海军等．反应分离过程模拟．华东理上大学学报，1999，25 (1)：19-23
[23] Smith, L. A.; Jones, E. M.. "Catalytic Distillation -A new Chapter in unit Operations". Paper presented at Spring Meeting of AICHE, Houston (1991).
[24] Smith, L. A. Catalytic distillation process. US patent4, 307,254. 1981, December 22
[25] 李甫，张瑞生，张家庭．催化精馏合成2-羟丙基甲醚．化学反应工程与工艺，2001，17 (4)：338-343
[26] Doherty, M. f. and Buzad, G.. "Reactive Distillation by Design". Ichem E., Symposium, 1992, ser. No.
128, A51
[27] Solokhin A. V, Blagov S. A. Reactive-Distillation is an Advanced Technique of Reaction Process Operation. Chem. Eng. Sci., 1996,51(11): 4443
[28] Sundmacher K., Hoffmann U. Development of a New Catalytic Distillation Process for Fuel Ethers via a Detailed Nonequlibrium Model. Chem. Eng. Sci., 1996, 51(10): 2359
[29] Babcock, P. d. and Clup, C. W.. "Recent Development in Separation Science Ⅳ". P149, Ed. By Norman, 1978
[30] 张瑞生，张家庭等．化学世界，1992，9，385
[31] 刘劲松．催化蒸馏中的热力学行为和回收稀醋酸过程非平衡及模拟的研究．[学位论文]，天津：天津大学，1997
[32] 何寿林，李定或等．反应精馏法合成乙二酸二乙酯的探索．武汉化工学院学报，1997，19(2)：30-33
[33] Quido Smejkal, Jiri Hanika, et al. 2-Methylpropylacetate synthesis in a system of equilibrium reactor and reactive distillation column, Chem. Eng. Sci., 2001,56, 365-370.
[34] 许锡恩，孟祥坤．催化蒸馏过程研究进展．化工进展，1998，NO．1：7-13
[35] 郑宇翔．催化蒸馏过程的研究，[学位论文]，天津：天津大学，1992
[36] BARBOSA D, DOHERTY M F. Design and minimum-reflux calculations for single-feed multicomponent reactive distillation columns. [J]. Chem. Eng Sci., 1988, 43(7): 1523-1537
[37] BARBOSA D, DOHERTY M F. Design and minimum-reflux calculations for double-feed multicomponem reactive distillation columns [J]. Chem. Eng Sci., 1988, 43(7): 2377-2389
[38] Buzad G, Doherty M. F. Design of three-component kinetically controlled reactive distillation columns using fixed-point methods [J]. Chem. Eng. Sci., 1994, 49(12): 1947-1963
[39] Espmosa J, Aguirre P, Perez G. Some aspects in the design of muiticomponent reactive distillation columns including nonreactive species [J]. Chem. Eng. Sci, 1995, 50(3): 496-484
[40] Ung S, Doherty M. F. Synthesis of reactive distillation systems with multiple-equilibrium chemical reaction [J]. Ing. Eng. Chem. Res., 1995, 34(8): 2555-2565
[41] 聂红．催化精馏在精制和化学工业中的应用．石油化工译从，1986，7(6)：33
[42] Zheng Yuxiang, Xu Xien. Study on Catalytic Distillation Process. Presented at the AIChE'92 Annual meeting. Miami beach, Florida, U. S. A. 1992, 11
[43] Minghan Han, Hongfei Lin etc. Characteristics of the Reactive Distillation Column with a Novel Internal. Chemical Engineering Science, 2002, vol.57, pp.1551-1555
[44] USP 4443599(1984).
[45] DeGarmo J L, Parulekar V N, and Pinjala V. Consider Reactive Distillation. Chem. Eng. Prog., 1992, 88(3): 43
[46] Smith L A Jr. Catalytic Distillation System. US Pat: 5262012(1993)
[47] Sundmacher K, and Hoffmann U. Multicomponent Mass and Energy Transport on Different Length
Scales in a Packed Reactive Distillation Column for Heterogeneously Catalyzed Fuel Ether Production. Chem. Eng. Sci., 1994, 49(24A): 4443
[48] Smith L A Jr. Catalytic Distillation Structure. US Pat: 4443559(1984)
[49] Smith L A Jr. Process for Separating Isobutne from C4 Streams. US Pat: 4242530(1980)
[50] Gentry J C, and Binkley M A, et al. Internals for Catalyst-Downcomertray Opertion. US Pat: 5277847(1994)
[51] Yeoman N, Pinaire R, Ulowetz M A, et al. Internals for Distillation Columns including Those for Use in Catalytic Reations. US Pat: 5496446(1996)
[52] Carland R J. Fractionation Tray for Catalytic Distillation. US Pat: 5308451 (1994)
[53] Harandi M N. Fluidized Catalytic Process and Hydration of Olefins. US Pat: 5233101(1993)
[54] Jones E M. Method for Operating a Distillation Column Reactor. US Pat: 5510089(1996)
[55] Dang V Q, Amiglles P, Leonard J, et al. Production of Tertiary Alkyl Ethers by Reactive Distillation. EP: 334702(1989)
[56] Haunschild W M. Catalyst System for Use in a Distillation Column Reactor. US Pat: 4624748(1986)
[57] 崔现宝．醋酸与丁醇酯化反应精馏过程与工艺的研究，[学位论文]，天津：天津大学，1996
[58] 王刚，沙钝等．[J]．哈尔滨师范大学自然科学学报，1997，13 (6)：63-66
[59] 李德昌，黄春林等．改性氧化锆催化合成乳酸乙酯．广西化工。1997，26 (4)：16-18
[60] 郝素娥，金婵等．乳酸乙酯合成的研究．哈尔滨工业大学学报，1999，31 (1)：47-50
[61] 欧阳玉祝．[J]．吉首大学学报(自然科学版)，1998，19(2)：58-60
[62] 刘榕芳，肖秀峰，王清萍等．脱水法合成乳酸乙酯．精细化工，2000，17 (12)：714-716．
[63] 高静，赵学明等．SO_4~(-2)/ZrO_2-TiO_2催化合成乳酸乙酯的研究．四川大学学报，2002，34 (5)：36-38
[64] 粱福沛，吴彦瑜．稀土化合物催化合成乳酸乙酯的研究．广西化工．1995，24 (4)：21-23
[65] 鲁富贵，张深松．H-型强酸性离子交换树脂在合成乳酸乙酯中的应用．河南师范大学学报。89，2：30-35
[66] 李华．固体酸催化合成乳酸乙酯．湖北化工，97，3：31-32
[67] 郑学忠，单颖等．乳酸乙酯生产工艺的改进．河北化工，1990，1：12-13
[68] 陈小嫣，何寿林等．精馏法合成乳酸乙酯的研究．2001，(6)：14-16
[69] 周迎春，王庆革．酯化反应的改进．大学化学，1995，(5)：39-40
[70] Kazuhiro Tanaka, Ryuuhei Yoshikawa, et al. Application of zeolite T membrane to-aided vapor-permeation esterification of lactic acid with ethanol. Chem. Eng. Sci., 200257:1577-1584
[71] United States Patent: 5,723,639
[72] Gorgy Szollosi", Karoly Felfoldi" Jibor Bartokc and Mihaly Bartok. HETEROGENEOUS AS YMMETRIC REACTIONS, 22. β-ISOCINCHONA ALKALOIDS IN ENANTIOSELECTIVEHYDROGENA-TIONS. Reaction kinetics and catalysis letters/Academy of Sciences of the USSR, Hungarian Academy of Sciences
[73] Yulin Huang, Junru Chen, Hua Chen, et al. Enantioselective hydrogenation of ethyl pyruvate catalyzed by PVP-stabilized rhodium nanoclusters. Journal of molecular catalysis. A.chemical, 2001,170,143-146
[74] R. Wandeler, N. Künzle, M. S. Schneider. Continuous Enantioselective Hydrogenation of Ethyl Pyruvate in "Supercritical" Ethane: Relation between Phase Behavior and Catalytic Performance. Journal of Catalysis.
[75] Torok, Bela; Felfoldi, Karoly; Szakonyi, Gerda; Bartok, Mihaly. Sonochemical enantioselective hydrogenation of ethyl pyruvate over platinum catalysts. Ultrasonics Sonochemistry
[76] 廖安平等．催化精馏技术在酯化反应中的应用．化工进展，2001，12：30-35
[77] 范闽光，李景林等．乳酸和乙醇酯化反应动力学．广西大学学报，1991，16(1)：11-15
[78] 鲁富贵，张深松．关于乳酸乙酯合成的研究．河南师范大学学报，1989，2：31-35
[79] Helfferich, F.. "Ion Exchange", 523, McGraw-Hill, New York (1962).
[80] Luis F. Fieser and Mary Fieser: 《Advanced organic Chemistry》, P.360
[81] 中西香尔，P．H．索罗曼：《红外光谱100例》，P．9
[2] 刘根生．浅述催化精馏技术．兰化科技，1994，12(4)：281-284
[3] Shoernarer. J. D.; Joan. E. M.. In Hydroearhon Process. 1987,55 (5): 57
[4] Michael F. M, Michael F. Doherty. Reactive distillation. Ind. Eng. Chem. Res, 2000, 39:3953-3957
[5] 许锡恩，朱宝福，陈洪钫等．酯化反应的反应精馏过程，石油化工，1985，14，481
[6] 杨梅，韩运华，张启中等．催化精馏合成丙烯酸正丁酯．吉林化工学院学报，2000，17(1)：22-24
[7] 杨志才，崔现宝．乙酸与丁醇酯化反应精馏过程．化工学报，1998，49(1)：39-47
[8] 廖安平，蓝平等．流化催化制备乙酸乙酯研究．化学工程，2000，28(6)：19-33
[9] Maria Pilar Bernal, Joaquin Coronas, et al. Coupling of reaction and separation at the microscopic level: esterificatiom processes in a H-ZSM-5 membrane reactor. Chem. Eng. Sci., 2002,57, 1557-1562
[10] E. Y. Kening, H. Bader, et al. Investigation of ethyl acetate reactive distillation process. Chem. Eng. Sci., 2001,56, 6185-6193
[11] 丁斌，张启忠等．富马酸二甲酯合成新工艺研究．吉林化工学院学报，1998，15(4)：1-5
[12] 廖安平，蓝平等．流化催化制备醋酸异戊酯研究，化学工程，2000，51，Suppl．：117-121
[13] Davis, B.; Jeffereys, G., J. Wans.Inst. Chem.Eng. Sci, 1973,51(4), 267
[14] 姜忠义，王永．酯交换法合成碳酸二甲酯的催化精馏过程．石油化工，2001，30(3)：173-177
[15] 张毅民，博士后出战报告．草酸二乙酯制草酸动力学研究及其工艺条件的选择．天津大学，1998
[16] 周传光等．化学工程，1992，25 (4)：31
[17] 吴燕翔，王良恩等．二对角矩阵及其在催化精馏塔模拟计算中的应用．福州大学学报。2000，28(1)：82—86
[18] Shoemaker, J. D. and Jones, E. M.. Hydrocarbon Processing. 1987,66 (6): 57-58
[19] France Patent No. 1, 410,589(1964); 1,372,964(t 965).
[20] Hoffmann, H.. Chem.Eng. Sci., 1958, 8(1), 113
[21] Belson, D. J.. Ind.Eng. Chem. Res., 29(7), (1990)
[22] 漆志文，孙海军等．反应分离过程模拟．华东理上大学学报，1999，25 (1)：19-23
[23] Smith, L. A.; Jones, E. M.. "Catalytic Distillation -A new Chapter in unit Operations". Paper presented at Spring Meeting of AICHE, Houston (1991).
[24] Smith, L. A. Catalytic distillation process. US patent4, 307,254. 1981, December 22
[25] 李甫，张瑞生，张家庭．催化精馏合成2-羟丙基甲醚．化学反应工程与工艺，2001，17 (4)：338-343
[26] Doherty, M. f. and Buzad, G.. "Reactive Distillation by Design". Ichem E., Symposium, 1992, ser. No.
128, A51
[27] Solokhin A. V, Blagov S. A. Reactive-Distillation is an Advanced Technique of Reaction Process Operation. Chem. Eng. Sci., 1996,51(11): 4443
[28] Sundmacher K., Hoffmann U. Development of a New Catalytic Distillation Process for Fuel Ethers via a Detailed Nonequlibrium Model. Chem. Eng. Sci., 1996, 51(10): 2359
[29] Babcock, P. d. and Clup, C. W.. "Recent Development in Separation Science Ⅳ". P149, Ed. By Norman, 1978
[30] 张瑞生，张家庭等．化学世界，1992，9，385
[31] 刘劲松．催化蒸馏中的热力学行为和回收稀醋酸过程非平衡及模拟的研究．[学位论文]，天津：天津大学，1997
[32] 何寿林，李定或等．反应精馏法合成乙二酸二乙酯的探索．武汉化工学院学报，1997，19(2)：30-33
[33] Quido Smejkal, Jiri Hanika, et al. 2-Methylpropylacetate synthesis in a system of equilibrium reactor and reactive distillation column, Chem. Eng. Sci., 2001,56, 365-370.
[34] 许锡恩，孟祥坤．催化蒸馏过程研究进展．化工进展，1998，NO．1：7-13
[35] 郑宇翔．催化蒸馏过程的研究，[学位论文]，天津：天津大学，1992
[36] BARBOSA D, DOHERTY M F. Design and minimum-reflux calculations for single-feed multicomponent reactive distillation columns. [J]. Chem. Eng Sci., 1988, 43(7): 1523-1537
[37] BARBOSA D, DOHERTY M F. Design and minimum-reflux calculations for double-feed multicomponem reactive distillation columns [J]. Chem. Eng Sci., 1988, 43(7): 2377-2389
[38] Buzad G, Doherty M. F. Design of three-component kinetically controlled reactive distillation columns using fixed-point methods [J]. Chem. Eng. Sci., 1994, 49(12): 1947-1963
[39] Espmosa J, Aguirre P, Perez G. Some aspects in the design of muiticomponent reactive distillation columns including nonreactive species [J]. Chem. Eng. Sci, 1995, 50(3): 496-484
[40] Ung S, Doherty M. F. Synthesis of reactive distillation systems with multiple-equilibrium chemical reaction [J]. Ing. Eng. Chem. Res., 1995, 34(8): 2555-2565
[41] 聂红．催化精馏在精制和化学工业中的应用．石油化工译从，1986，7(6)：33
[42] Zheng Yuxiang, Xu Xien. Study on Catalytic Distillation Process. Presented at the AIChE'92 Annual meeting. Miami beach, Florida, U. S. A. 1992, 11
[43] Minghan Han, Hongfei Lin etc. Characteristics of the Reactive Distillation Column with a Novel Internal. Chemical Engineering Science, 2002, vol.57, pp.1551-1555
[44] USP 4443599(1984).
[45] DeGarmo J L, Parulekar V N, and Pinjala V. Consider Reactive Distillation. Chem. Eng. Prog., 1992, 88(3): 43
[46] Smith L A Jr. Catalytic Distillation System. US Pat: 5262012(1993)
[47] Sundmacher K, and Hoffmann U. Multicomponent Mass and Energy Transport on Different Length
Scales in a Packed Reactive Distillation Column for Heterogeneously Catalyzed Fuel Ether Production. Chem. Eng. Sci., 1994, 49(24A): 4443
[48] Smith L A Jr. Catalytic Distillation Structure. US Pat: 4443559(1984)
[49] Smith L A Jr. Process for Separating Isobutne from C4 Streams. US Pat: 4242530(1980)
[50] Gentry J C, and Binkley M A, et al. Internals for Catalyst-Downcomertray Opertion. US Pat: 5277847(1994)
[51] Yeoman N, Pinaire R, Ulowetz M A, et al. Internals for Distillation Columns including Those for Use in Catalytic Reations. US Pat: 5496446(1996)
[52] Carland R J. Fractionation Tray for Catalytic Distillation. US Pat: 5308451 (1994)
[53] Harandi M N. Fluidized Catalytic Process and Hydration of Olefins. US Pat: 5233101(1993)
[54] Jones E M. Method for Operating a Distillation Column Reactor. US Pat: 5510089(1996)
[55] Dang V Q, Amiglles P, Leonard J, et al. Production of Tertiary Alkyl Ethers by Reactive Distillation. EP: 334702(1989)
[56] Haunschild W M. Catalyst System for Use in a Distillation Column Reactor. US Pat: 4624748(1986)
[57] 崔现宝．醋酸与丁醇酯化反应精馏过程与工艺的研究，[学位论文]，天津：天津大学，1996
[58] 王刚，沙钝等．[J]．哈尔滨师范大学自然科学学报，1997，13 (6)：63-66
[59] 李德昌，黄春林等．改性氧化锆催化合成乳酸乙酯．广西化工。1997，26 (4)：16-18
[60] 郝素娥，金婵等．乳酸乙酯合成的研究．哈尔滨工业大学学报，1999，31 (1)：47-50
[61] 欧阳玉祝．[J]．吉首大学学报(自然科学版)，1998，19(2)：58-60
[62] 刘榕芳，肖秀峰，王清萍等．脱水法合成乳酸乙酯．精细化工，2000，17 (12)：714-716．
[63] 高静，赵学明等．SO_4~(-2)/ZrO_2-TiO_2催化合成乳酸乙酯的研究．四川大学学报，2002，34 (5)：36-38
[64] 粱福沛，吴彦瑜．稀土化合物催化合成乳酸乙酯的研究．广西化工．1995，24 (4)：21-23
[65] 鲁富贵，张深松．H-型强酸性离子交换树脂在合成乳酸乙酯中的应用．河南师范大学学报。89，2：30-35
[66] 李华．固体酸催化合成乳酸乙酯．湖北化工，97，3：31-32
[67] 郑学忠，单颖等．乳酸乙酯生产工艺的改进．河北化工，1990，1：12-13
[68] 陈小嫣，何寿林等．精馏法合成乳酸乙酯的研究．2001，(6)：14-16
[69] 周迎春，王庆革．酯化反应的改进．大学化学，1995，(5)：39-40
[70] Kazuhiro Tanaka, Ryuuhei Yoshikawa, et al. Application of zeolite T membrane to-aided vapor-permeation esterification of lactic acid with ethanol. Chem. Eng. Sci., 200257:1577-1584
[71] United States Patent: 5,723,639
[72] Gorgy Szollosi", Karoly Felfoldi" Jibor Bartokc and Mihaly Bartok. HETEROGENEOUS AS YMMETRIC REACTIONS, 22. β-ISOCINCHONA ALKALOIDS IN ENANTIOSELECTIVEHYDROGENA-TIONS. Reaction kinetics and catalysis letters/Academy of Sciences of the USSR, Hungarian Academy of Sciences
[73] Yulin Huang, Junru Chen, Hua Chen, et al. Enantioselective hydrogenation of ethyl pyruvate catalyzed by PVP-stabilized rhodium nanoclusters. Journal of molecular catalysis. A.chemical, 2001,170,143-146
[74] R. Wandeler, N. Künzle, M. S. Schneider. Continuous Enantioselective Hydrogenation of Ethyl Pyruvate in "Supercritical" Ethane: Relation between Phase Behavior and Catalytic Performance. Journal of Catalysis.
[75] Torok, Bela; Felfoldi, Karoly; Szakonyi, Gerda; Bartok, Mihaly. Sonochemical enantioselective hydrogenation of ethyl pyruvate over platinum catalysts. Ultrasonics Sonochemistry
[76] 廖安平等．催化精馏技术在酯化反应中的应用．化工进展，2001，12：30-35
[77] 范闽光，李景林等．乳酸和乙醇酯化反应动力学．广西大学学报，1991，16(1)：11-15
[78] 鲁富贵，张深松．关于乳酸乙酯合成的研究．河南师范大学学报，1989，2：31-35
[79] Helfferich, F.. "Ion Exchange", 523, McGraw-Hill, New York (1962).
[80] Luis F. Fieser and Mary Fieser: 《Advanced organic Chemistry》, P.360
[81] 中西香尔，P．H．索罗曼：《红外光谱100例》，P．9