基于辅助化学反应直接强化的乙酸甲酯水解反应精馏过程基础研究
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摘要
反应精馏将化学反应和精馏分离两种过程耦合在同一设备内进行,利用精馏分离作用提高反应过程的效果,已成为化工行业的关键过程强化技术,并得到了很好的应用。然而,反应精馏技术的优点往往因为体系特殊的物理和化学性质而受到限制。为此,本文研究利用辅助化学反应来直接强化反应精馏过程,通过引入辅助反应改变原有反应精馏体系的诸多性质,例如共沸物组成、体系的最轻与最重组分以及化学反应速率等,最终从精馏和化学反应两个方面同时对原有反应精馏过程进行强化；以乙酸甲酯水解反应精馏过程为例,研究了以甲醇脱水为辅助反应的过程强化机理,并以此开发了乙酸甲酯回收利用新工艺。主要研究工作摘要如下：
基于化工过程模拟软件gPROMS发展了反应精馏过程分析和模拟计算平台。构建了反应精馏过程平衡级和非平衡级模型；拓展了拟弧长延拓算法,可搜索体系的分岔点以及多稳态,可对包括反应精馏在内的化工过程进行分岔计算。利用外部测试函数与gPROMS进行对接的方式来确定分岔点的精确数值,并计算雅克比矩阵的特征值来判断平衡点的稳定性。以CSTR反应器、共沸精馏以及乙酸甲酯反应精馏过程为例,详细描述了该平台的结构与使用方法。
基于剩余曲线图的概念建立了针对包含两个反应和多个组分体系强化机理的分析方法。分别从精馏和化学反应两个方面,分析了甲醇脱水反应来强化乙酸甲酯水解反应精馏过程的强化机理。结果表明,甲醇脱水反应的引入可以为体系提供额外的水,从而避免了在进料中因加入过量的水而导致下游分离能耗升高等问题。同时,由于不停地将甲醇转化成水,使得水解反应平衡向正反应方向移动,极大地提高了乙酸甲酯的水解率。此外,进料中以及乙酸甲酯水解得到的甲醇,可以通过脱水反应转换为副产品二甲醚。
利用所开发的模拟计算平台,对甲醇脱水反应强化的乙酸甲酯水解反应精馏过程进行了概念设计。考察了各种操作参数,如操作压力、反应区间、进料位置、回流比以及催化剂用量对体系的影响。结果表明,在优化条件下,当进料为等摩尔的甲醇和乙酸甲酯时,甲醇和乙酸甲酯可以完全转化,塔顶和塔底分别得到高纯度的二甲醚和乙酸,也验证了辅助化学反应的强化效果。同时,由于甲醇脱水反应的速率过慢,需在反应精馏塔前设置预反应器,将部分甲醇提前脱水,以降低反应精馏塔的能耗。
利用甲醇脱水反应强化乙酸甲酯水解反应精馏的优势,针对目前聚乙烯醇生产废液回收利用所存在的问题,设计出了两种新的工艺流程。考察了各种操作参数对新工艺的影响,从而得出优化的操作条件。与传统工艺流程相比,新的工艺流程更为简化,能耗更低,设备更少。同时,通过甲醇脱水反应可以生产出高附加值的产品二甲醚。
Reactive distillation (RD) is an integration of distillation and reaction, which takes the advantage of distillation to improve the effect of chemical reaction. It has been an important intensification technology and successfully applied in the chemical industry. However, RD processes may be inhibited by their particular properties of the reaction systems. In this dissertation, the concept of RD intensified by an auxiliary reaction is studied. By introducing an auxiliary reaction, the characteristics of original system such as composition of azeotrope, reaction rates, alternative lightest and heaviest components are modified, which will intensify the system in the respect of distillation and chemical reaction. The methyl acetate (MeOAc) hydrolysis intensified by methanol (MeOH) dehydration is studied as an example where the latter serves as the auxiliary reaction. The main research works are listed as follows:
The platform of analysis and simulation for the process of RD was developed based on the process simulator gPROMS. In the platform, the equilibrium and non-equilibrium models of RD were established while the arc-length continuation was extended to search the bifurcation points and multiply steady states for the chemical process including RD. The stability analysis of solutions was realized by evaluating the eigenvalues of the Jacobian matrix that was accessible to users in gPROMS. The examples of a classic adiabatic CSTR, a homogenous azeotropic distillation and methyl acetate synthesis by RD were used to specify the configuration and application of platform.
A residue curve maps (RCMs) was developed to analyze the mechanism of intensification for the case with two chemical reactions and multiple components. The mechanism of intensification of MeOAc hydrolysis intensified by MeOH dehydration was studied in the respect of distillation and chemical reaction. The results show that, extra water can be supplied for the system by introducing MeOH dehydration, which avoids excessive water in the feed and high energy consumption in the downstream separation. Meanwhile, converting MeOH into H2O in the dehydration reaction facilitate the chemical equilibrium to forward direction, which enhance the conversion of MeOAc. Furthermore, MeOH as the product in the MeOAc hydrolysis reaction can be transferred into dimethyl ether as the byproduct.
The conceptual design of MeOAc hydrolysis intensified by MeOH dehydration in the RD was implemented based on the developed platform. The effect of operating parameters such as pressure, reaction zone, feed stage, reflux ration and catalyst loading on the process were analyzed. The results reveal that, in the case of equal mole of MeOH and MeOAc as feed, MeOH and MeOAc can achieve100%conversion in the RD column while pure dimethyl ether and acetic acid are the top and bottom product, respectively. Thus, the effect of intensification is proved. Furthermore, as the rate MeOH dehydration is low, a pre-reactor was set before the RD column to convert MeOH into water in advance so that the energy consumption of RD column could be saved.
As the advantange of effect of intenficaiton, two novel processes of recovery of MeOAc in the production of poly vinyl alcohol were developed. The optimal conditons were obtained by analysis of various operating parameters. Compared with traditional processes, high MeOAc conversion and high purity products could be reached and the equipment costs and energy consumption are significantly reduced with the help of these new processes. Furthermore, high purity DME could be produced as a more valuable product.
基于化工过程模拟软件gPROMS发展了反应精馏过程分析和模拟计算平台。构建了反应精馏过程平衡级和非平衡级模型；拓展了拟弧长延拓算法,可搜索体系的分岔点以及多稳态,可对包括反应精馏在内的化工过程进行分岔计算。利用外部测试函数与gPROMS进行对接的方式来确定分岔点的精确数值,并计算雅克比矩阵的特征值来判断平衡点的稳定性。以CSTR反应器、共沸精馏以及乙酸甲酯反应精馏过程为例,详细描述了该平台的结构与使用方法。
基于剩余曲线图的概念建立了针对包含两个反应和多个组分体系强化机理的分析方法。分别从精馏和化学反应两个方面,分析了甲醇脱水反应来强化乙酸甲酯水解反应精馏过程的强化机理。结果表明,甲醇脱水反应的引入可以为体系提供额外的水,从而避免了在进料中因加入过量的水而导致下游分离能耗升高等问题。同时,由于不停地将甲醇转化成水,使得水解反应平衡向正反应方向移动,极大地提高了乙酸甲酯的水解率。此外,进料中以及乙酸甲酯水解得到的甲醇,可以通过脱水反应转换为副产品二甲醚。
利用所开发的模拟计算平台,对甲醇脱水反应强化的乙酸甲酯水解反应精馏过程进行了概念设计。考察了各种操作参数,如操作压力、反应区间、进料位置、回流比以及催化剂用量对体系的影响。结果表明,在优化条件下,当进料为等摩尔的甲醇和乙酸甲酯时,甲醇和乙酸甲酯可以完全转化,塔顶和塔底分别得到高纯度的二甲醚和乙酸,也验证了辅助化学反应的强化效果。同时,由于甲醇脱水反应的速率过慢,需在反应精馏塔前设置预反应器,将部分甲醇提前脱水,以降低反应精馏塔的能耗。
利用甲醇脱水反应强化乙酸甲酯水解反应精馏的优势,针对目前聚乙烯醇生产废液回收利用所存在的问题,设计出了两种新的工艺流程。考察了各种操作参数对新工艺的影响,从而得出优化的操作条件。与传统工艺流程相比,新的工艺流程更为简化,能耗更低,设备更少。同时,通过甲醇脱水反应可以生产出高附加值的产品二甲醚。
Reactive distillation (RD) is an integration of distillation and reaction, which takes the advantage of distillation to improve the effect of chemical reaction. It has been an important intensification technology and successfully applied in the chemical industry. However, RD processes may be inhibited by their particular properties of the reaction systems. In this dissertation, the concept of RD intensified by an auxiliary reaction is studied. By introducing an auxiliary reaction, the characteristics of original system such as composition of azeotrope, reaction rates, alternative lightest and heaviest components are modified, which will intensify the system in the respect of distillation and chemical reaction. The methyl acetate (MeOAc) hydrolysis intensified by methanol (MeOH) dehydration is studied as an example where the latter serves as the auxiliary reaction. The main research works are listed as follows:
The platform of analysis and simulation for the process of RD was developed based on the process simulator gPROMS. In the platform, the equilibrium and non-equilibrium models of RD were established while the arc-length continuation was extended to search the bifurcation points and multiply steady states for the chemical process including RD. The stability analysis of solutions was realized by evaluating the eigenvalues of the Jacobian matrix that was accessible to users in gPROMS. The examples of a classic adiabatic CSTR, a homogenous azeotropic distillation and methyl acetate synthesis by RD were used to specify the configuration and application of platform.
A residue curve maps (RCMs) was developed to analyze the mechanism of intensification for the case with two chemical reactions and multiple components. The mechanism of intensification of MeOAc hydrolysis intensified by MeOH dehydration was studied in the respect of distillation and chemical reaction. The results show that, extra water can be supplied for the system by introducing MeOH dehydration, which avoids excessive water in the feed and high energy consumption in the downstream separation. Meanwhile, converting MeOH into H2O in the dehydration reaction facilitate the chemical equilibrium to forward direction, which enhance the conversion of MeOAc. Furthermore, MeOH as the product in the MeOAc hydrolysis reaction can be transferred into dimethyl ether as the byproduct.
The conceptual design of MeOAc hydrolysis intensified by MeOH dehydration in the RD was implemented based on the developed platform. The effect of operating parameters such as pressure, reaction zone, feed stage, reflux ration and catalyst loading on the process were analyzed. The results reveal that, in the case of equal mole of MeOH and MeOAc as feed, MeOH and MeOAc can achieve100%conversion in the RD column while pure dimethyl ether and acetic acid are the top and bottom product, respectively. Thus, the effect of intensification is proved. Furthermore, as the rate MeOH dehydration is low, a pre-reactor was set before the RD column to convert MeOH into water in advance so that the energy consumption of RD column could be saved.
As the advantange of effect of intenficaiton, two novel processes of recovery of MeOAc in the production of poly vinyl alcohol were developed. The optimal conditons were obtained by analysis of various operating parameters. Compared with traditional processes, high MeOAc conversion and high purity products could be reached and the equipment costs and energy consumption are significantly reduced with the help of these new processes. Furthermore, high purity DME could be produced as a more valuable product.
引文
[1]Backhaus A A. Method for the production of esters:U.S. Patent 1,400,852[P].1921-12-20
[2]Stankiewicz A, Moulin J A. Process intensification[J]. Chemical Engineering and Processing: Process Intensification,2000:22-34.
[3]Stankiewicz A. Reactive separations for process intensification:an industrial perspective [J]. Chemical Engineering and Processing:Process Intensification,2003,42(3):137-144
[4]Li X, Kraslawski A. Conceptual process synthesis:past and current trends[J]. Chemical Engineering and Processing:Process Intensification,2004,43(5):583-594
[5]Siirola J J. Strategic process synthesis:advances in the hierarchical approach[J]. Computers & Chemical engineering,1996,20:S1637-S1643
[6]Harmsen G J. Reactive distillation:the front-runner of industrial process intensification:a full review of commercial applications, research, scale-up, design and operation[J]. Chemical Engineering and Processing:Process Intensification,2007,46(9):774-780
[7]Kolah A K, Qi Z W, Mahajani S M. Dimerized isobutene:An alternative to MTBE. Chemical Innovation[J].2001,31(3):15-21
[8]Marker T L, Funk G A, Barger P T, et al. Two-stage process for producing diisopropyl ether using catalytic distillation:U.S. Patent 5,504,258[P].1996-4-2
[9]Kamath R S, Qi Z W, Sundmacher K, Aghalayam P, Mahajani S M. Process analysis for dimerization of isobutene by reactive distillation[J]. Industrial & Engineering Chemistry Research,2006,45(5):1575-1582
10] Hu M, Zhou X-G, Yuan W-K. Simulation and optimization of a coupled reactor/column system for trioxane synthesis[J]. Chemical Engineering Science,1999,10:1353-1358
11] Podrebarac G G, Ng F T T, Rempel G L. The production of diacetone alcohol with catalytic distillation:Part Ⅰ:Catalytic distillation experiments[J]. Chemical Engineering Science, 1998,53(5):1067-1075
12] Taylor R, Krishna R. Modelling reactive distillation[J]. Chemical Engineering Science,2000, 55(22):5183-5229
13] Tang Y T, Chen Y W, Huang H P, Yu C C, Hung S B, Lee M J. Design of reactive distillations for acetic acid esterification[J]. AIChE Journal,2005,51(6):1683-1699
[14]王良恩,刘家祺.催化精馏技术在乙酸甲酯水解工艺中的应用[J].福建化工,2001(3)：1-4
15] Ciric A R, Miao P. Steady state multiplicities in an ethylene glycol reactive distillation column[J]. Industrial & Engineering Chemistry Research,1994,33(11):2738-2748
16] Ciric A R, Gu D. Synthesis of nonequilibrium reactive distillation processes by MINLP optimization[J]. AIChE Journal,1994,40(9):1479-1487
17] Monroy-Loperena R, Alvarez-Ramirez J. On the steady-state multiplicities for an ethylene glycol reactive distillation column[J]. Industrial & Engineering Chemistry Research,1999, 38(2):451-455
[18]Steyer F, Qi Z W, Sundmacher K. Synthesis of cylohexanol by three-phase reactive distillation:influence of kinetics on phase equilibria[J]. Chemical Engineering Science, 2002,57(9):1511-1520
[19]Arganbright R P. Hydroisomerization process:U.S. Patent 5,087,780[P].1992-2-11
[20]Masamoto J, Matsuzaki K. Development of methylal synthesis by reactive distillation[J]. Journal of Chemical Engineering of Japan,1994,27(1):1-5
[21]Kolah A K, Mahajani S M, Sharma M M. Acetalization of formaldehyde with methanol in batch and continuous reactive distillation columns[J]. Industrial & Engineering Chemistry Research,1996,35(10):3707-3720
[22]Zhang X, Zhang S, Jian C. Synthesis of methylal by catalytic distillation[J]. Chemical Engineering Research and Design,2011,75(6):573-580
[23]Neumann R, Sasson Y. Recovery of dilute acetic acid by esterification in a packed chemorectification column[J]. Industrial & Engineering Chemistry Process Design and Development,1984,23(4):654-659
[24]Xu Z, Afacan A, Chuang K T. Removal of acetic acid from water by catalytic distillation. Part 1:Experimental studies[J]. The Canadian Journal of Chemical Engineering,1999,77(4): 676-681
[25]Xu Z, Afacan A, Chuang K T. Removal of acetic acid from water by catalytic distillation. Part 2:Modeling and simulation studies[J]. The Canadian Journal of Chemical Engineering, 1999,77(4):682-687
[26]Scates M O, Parker S E, Lacy J B, et al. Recovery of acetic acid from dilute aqueous streams formed during a carbonylation process:U.S. Patent 5,599,976[P].1997-2-4
[27]Saha B, Chopade S P, Mahajani S M. Recovery of dilute acetic acid through esterification in a reactive distillation column[J]. Catalysis Today,2000,60(1):147-157
[28]Bock H, Wozny G, Gutsche B. Design and control of a reaction distillation column including the recovery system[J]. Chemical Engineering and Processing:Process Intensification,1997,36(2):101-109
[29]Chopade S P, Sharma M M. Reaction of ethanol and formaldehyde:use of versatile cation-exchange resins as catalyst in batch reactors and reactive distillation columns[J]. Reactive and Functional Polymers,1997,31(1):53-65
[30]Chopade S P, Sharma M M. Acetalization of ethylene glycol with formaldehyde using cation-exchange resins as catalysts:batch versus reactive distillation[J]. Reactive and Functional Polymers,1997,34(1):37-45
[31]Sharma M M. Some novel aspects of cationic ion-exchange resins as catalysts[J]. Reactive and Functional Polymers,1995,26(1):3-23
[32]Hildreth J M. Removal of. alpha.-methyl styrene from cumene:U.S. Patent 5,905,178[P]. 1999-5-18
[33]Krishnamurthy R, Taylor R. A nonequilibrium stage model of multicomponent separation processes. Part Ⅰ:Model description and method of solution[J]. AIChE Journal,1985,31(3): 449-456
[34]Krishna R, Wesselingh J A. The Maxwell-Stefan approach to mass transfer[J]. Chemical Engineering Science,1997,52(6):861-911
[35]Van Baten J M, Ellenberger J, Krishna R. Hydrodynamics of reactive distillation tray column with catalyst containing envelopes:experiments vs. CFD simulations[J]. Catalysis Today,2001,66(2):233-240
[36]Perez-Cisneros E, Schenk M, Gani R, Pilavachi P A. Aspects of simulation, design and analysis of reactive distillation operations[J]. Computers & Chemical Engineering,1996,20: S267-S272
[37]Chen F, Huss R S, Malone M F, et al. Simulation of kinetic effects in reactive distillation[J]. Computers & Chemical Engineering,2000,24(11):2457-2472
[38]鲍杰,严国祥.合成MTBE非均相催化精馏过程数学模拟[J].化学工程,1994,22(5)：6-12
[39]刘劲松,白鹏,朱思强.反应精馏过程的研究进展[J].化学工业与工程,2002,19(1)：101-106
[40]Kreul L U, Gorak A, Barton P I. Modeling of homogeneous reactive separation processes in packed columns[J]. Chemical Engineering Science,1999,54(1):19-34
[41]Baur R, Higler A P, Taylor R, Krishna R. Comparison of equilibrium stage and nonequilibrium stage models for reactive distillation[J]. Chemical Engineering Journal, 2000,76(1):33-47
[42]Lee J H, Dudukovic M P. A comparison of the equilibrium and nonequilibrium models for a multicomponent reactive distillation column[J]. Computers & Chemical Engineering,1998, 23(1):159-172
[43]Sundmacher K, Uhde G, Hoffmann U. Multiple reactions in catalytic distillation processes for the production of the fuel oxygenates MTBE and TAME:Analysis by rigorous model and experimental validation[J]. Chemical Engineering Science,1999,54(13):2839-2847
[44]Mohl K D, Kienle A, Gilles E D. Multiple steady states in a reactive distillation column for the production of the fuel ether TAME I. Theoretical analysis[J]. Chemical Engineering & Technology,1998,21(2):133-136
[45]Mohl K D, Kienle A, Gilles E D, Rapmund P, Sundmacher K, Hoffmann U. Nonlinear dynamics of reactive distillation processes for the production of fuel ethers[J]. Computers & Chemical engineering,1997,21:S989-S994
[46]Belck L H. Continuous reactions in distillation equipment[J]. AIChE Journal,1955,4: 467-470
[47]Hu M, Zhou X-G, Yuan W-K. Simulation and optimization of a coupled reactor/column system for trioxane synthesis[J]. Chemical Engineering Science,1999,10:1353-1358
[48]Suzuki I, Yagi H, Komatsu H, et al. Calculation of multicomponent distillation accompanied by a chemical reaction[J]. Journal of Chemical Engineering of Japan,1971,4(1):26-33
[49]周传光,郑世清.部分牛顿法模拟反应精馏过程[J].化学工程,1993,21(3)：30-3
[50]Chang Y A, Seader J D. Simulation of continuous reactive distillation by a homotopy-continuation method[J]. Computers & Chemical Engineering,1988,12(12): 1243-1255.
[51]Giessler S, Danilov R Y, Pisarenko R Y, et al. Feasibility study of reactive distillation using the analysis of the statics[J]. Industrial & Engineering Chemistry Research,1998,37(11): 4375-4382
[52]Giessler S, Danilov R Y, Pisarenko R Y, et al. Feasible separation modes for various reactive distillation systems[J]. Industrial & Engineering Chemistry Research,1999,38(10): 4060-4067
[53]Ung S, Doherty M F. Calculation of residue curve maps for mixtures with multiple equilibrium chemical reactions[J]. Industrial & Engineering Chemistry Research,1995, 34(10):3195-3202
[54]Chadda N, Malone M F, Doherty M F. Effect of chemical kinetics on feasible splits for reactive distillation[J]. AIChE journal,2001,47(3):590-601
[55]Frey T, Stichlmair J. Reactive azeotropes in kinetically controlled reactive distillation[J]. Chemical Engineering Research and Design,1999,77(7):613-618
[56]Frey T, Stichlmair J. Thermodynamic fundamentals of reactive distillation[J]. Chemical Engineering & Technology,1999,22(1):11-18
[57]Bessling B, Schembecker G, Simmrock K H. Design of processes with reactive distillation line diagrams[J]. Industrial & Engineering Chemistry Research,1997,36(8):3032-3042
[58]Bessling B, Loning J M, Ohligschlager A, et al. Investigations on the synthesis of methyl acetate in a heterogeneous reactive distillation process[J]. Chemical Engineering & Technology,1998,21(5):393-400
[59]Ciric A R, Gu D. Synthesis of nonequilibrium reactive distillation processes by MINLP optimization[J]. AIChE Journal,1994,40(9):1479-1487
[60]Poth N., Frey T. and Stichlmair J. MINLP optimization of kinetically controlled reactive distillation processes[J]. Computer-Aided Chemical Engineering,2001,9:79-84
[61]Cardoso M F, Salcedo R L, de Azevedo S F, Barbosa D. Optimization of reactive distillation processes with simulated annealing[J]. Chemical Engineering Science,2000,50(21): 5059-5078
[62]Pekkanen M. A local optimization method for the design of reactive distillation[J]. Computers & Chemical Engineering,1995,19:235-240
[63]Seferlis P, Grievink J. Optimal design and sensitivity analysis of reactive distillation units Using collocation models[J]. Industrial & Engineering Chemistry Research,2001,40(7): 1673-1685
[64]Russel B M, Henriksen J P, Jorgensen S B, et al. Integration of design and control through model analysis[J]. Computers & Chemical Engineering,2002,26(2):213-225
[65]Bansal V, Perkins J D, Pistikopoulos E N, et al. Simultaneous design and control optimisation under uncertainty [J]. Computers & Chemical Engineering,2000,24(2): 261-266
[66]Bansal V, Sakizlis V, Ross R, et al. New algorithms for mixed-integer dynamic optimization[J]. Computers & Chemical Engineering,2003,27(5):647-668
[67]Georgiadis M C, Schenk M, Pistikopoulos E N, et al. The interactions of design control and operability in reactive distillation systems [J]. Computers & Chemical Engineering,2002, 26(4):735-746
[68]Sander S, Flisch C, Geissler E, et al. Methyl acetate hydrolysis in a reactive divided wall column[J]. Chemical Engineering Research and Design,2007,85(1):149-154
[69]Gao X, Li X, Li H. Hydrolysis of methyl acetate via catalytic distillation:Simulation and design of new technological process[J]. Chemical Engineering and Processing:Process Intensification,2010,49(12):1267-1276
[70]Tung S T, Yu C C. Effects of relative volatility ranking to the design of reactive distillation[J]. AIChE Journal,2007,53(5):1278-1297
[71]Tang Y T, Chen Y W, Huang H P, et al. Design of reactive distillations for acetic acid esterification[J]. AIChE Journal,2005,51(6):1683-1699
[72]Fuchigami Y. Hydrolysis of methyl acetate in distillation column packed with reactive packing of ion exchange resin[J]. Journal of Chemical Engineering of Japan,1990,23(3): 354-359
[73]Kim K J, Roh H D. Reactive distillation process and equipment for the production of acetic acid and methanol from methyl acetate hydrolysis:U.S. Patent 5,770,770[P].1998-6-23
[74]Wang J, Ge X, Wang Z, et al. Experimental studies on the catalytic distillation for hydrolysis of methyl acetate[J]. Chemical Engineering & Technology,2001,24(2):155-159
[75]Xiao J, Liu J, Li J, et al. Increase MeOAc conversion in PVA production by replacing the fixed bed reactor with a catalytic distillation column[J]. Chemical Engineering Science, 2001,56(23):6553-6562
[76]Lee M M. Method and apparatus of methyl acetate hydrolysis:U.S. Patent Application 09/878,153[P].2001-6-11
[77]Musser M T. Cyclohexanol and cyclohexanone[J]. Ullmann's Encyclopedia of Industrial Chemistry,2005
[78]Steyer F, Qi Z W, Sundmacher K. Synthesis of cylohexanol by three-phase reactive distillation:influence of kinetics on phase equilibria[J]. Chemical Engineering Science, 2002,57(9):1511-1520
[79]Gani R, J(?)rgensen S B. Multiplicity in numerical solution of non-linear models:separation processes[J]. Computers & Chemical Engineering,1994,18:S55-S61
[80]Kovach J W, Seider W D. Heterogeneous azeotropic distillation:experimental and simulation results[J]. AIChE journal,1987,33(8):1300-1314
[81]Vadapalli A, Seader J D. A generalized framework for computing bifurcation diagrams using process simulation programs[J]. Computers & Chemical Engineering,2001,25(2):445-464
[82]Kannan A, Joshi M R, Reddy G R, et al. Multiple-steady-states identification in homogeneous azeotropic distillation using a process simulator [J]. Industrial & Engineering Chemistry Research,2005,44(12):4386-4399
[83]Bekiaris N, Morari M. Multiple steady states in distillation:oo/oo predictions, extensions, and implications for design, synthesis, and simulation[J]. Industrial & Engineering Chemistry Research,1996,35(11):4264-4280
[84]Yang B, Wu J, Zhao G, et al. Multiplicity analysis in reactive distillation column using ASPEN PLUS[J]. Chinese Journal of Chemical Engineering,2006,14(3):301-308
[85]Carlos Cardenas-Guerra J, Lopez-Arenas T, Lobo-Oehmichen R, et al. A reactive distillation process for deep hydrodesulfurization of diesel:Multiplicity and operation aspects [J]. Computers & Chemical Engineering,2010,34(2):196-209
[86]Seydel R, Hlavacek V. Role of continuation in engineering analysis [J]. Chemical Engineering Science,1987,42(6):1281-1295
[87]Keller, H. B. Numerical solution of bifurcation and nonlinear eigenvalue problems. Applications of Bifurcation Theory, P. Rabinowitz, editor, Acacemic Press, New York,359
[88]Seydel R. Numerical computation of branch points in nonlinear equations[J]. Numerische Mathematik,1979,33(3):339-352
[89]Anderson E, Bai Z, Bischof C, et al. LAPACK users'guide, Release 2.0[J]. SIAM, Philadelphia,1995,326:327
[90]Singh B P, Singh R, Kumar M V P, et al. Steady state analysis of reactive distillation using homotopy continuation[J]. Chemical Engineering Research and Design,2005,83(8): 959-968
[91]Venimadhavan G, Malone M F, Doherty M F. A novel distillate policy for batch reactive distillation with application to the production of butyl acetate[J]. Industrial & Engineering Chemistry Research,1999,38(3):714-722
[92]Song W, Venimadhavan G, Manning J M, et al. Measurement of residue curve maps and heterogeneous kinetics in methyl acetate synthesis[J]. Industrial & Engineering Chemistry Research,1998,37(5):1917-1928
[93]Popken T, Gotze L, Gmehling J. Reaction kinetics and chemical equilibrium of homogeneously and heterogeneously catalyzed acetic acid esterification with methanol and methyl acetate hydrolysis[J]. Industrial & Engineering chemistry research,2000,39(7): 2601-2611
[94]Dirk-Faitakis C B, An W, Lin T B, et al. Catalytic distillation for simultaneous hydrolysis of methyl acetate and etherification of methanol [J]. Chemical Engineering and Processing: Process Intensification,2009,48(5):1080-1087
[95]Ung S, Doherty M F. Vapor-liquid phase equilibrium in systems with multiple chemical reactions[J]. Chemical Engineering Science,1995,50(1):23-48
[96]Song W, Huss R S, Doherty M F, et al. Discovery of a reactive azeotrope[J]. Nature,1997, 388(6642):561-563
[97]Al-Arfaj M A, Luyben W L. Comparative control study of ideal and methyl acetate reactive distillation[J]. Chemical Engineering Science,2002,57(24):5039-5050
[98]Huss R S, Chen F, Malone M F, et al. Reactive distillation for methyl acetate production[J]. Computers & Chemical Engineering,2003,27(12):1855-1866
[99]Lin Y D, Chen J J H, Cheng J K, et al. Process alternatives for methyl acetate conversion using reactive distillation.1. Hydrolysis[J]. Chemical Engineering Science,2008,63(6): 1668-1682
100] Xu Y, Zheng Y, Ng F T T, et al. A three-phase nonequilibrium dynamic model for catalytic distillation[J]. Chemical Engineering Science,2005,60(20):5637-5647
[101]Onda K, Takeuchi H, Okumoto Y. Mass transfer coefficients between gas and liquid phases in packed columns[J]. Journal of Chemical Engineering of Japan,1968,1(1):56-62
[102]Zheng Y, Xu X. Study on catalytic distillation process, Part 1. Mass transfer characteristics in catalytic bed within the column[J]. Chemical Engineering Research & Design,1992, 70(A5):459-464
[103]Dorn C, Lee M, Morari M. Stability and transient behavior of homogeneous azeotropic distillation[J]. Computers & Chemical Engineering,1999,23:S191-S194
[2]Stankiewicz A, Moulin J A. Process intensification[J]. Chemical Engineering and Processing: Process Intensification,2000:22-34.
[3]Stankiewicz A. Reactive separations for process intensification:an industrial perspective [J]. Chemical Engineering and Processing:Process Intensification,2003,42(3):137-144
[4]Li X, Kraslawski A. Conceptual process synthesis:past and current trends[J]. Chemical Engineering and Processing:Process Intensification,2004,43(5):583-594
[5]Siirola J J. Strategic process synthesis:advances in the hierarchical approach[J]. Computers & Chemical engineering,1996,20:S1637-S1643
[6]Harmsen G J. Reactive distillation:the front-runner of industrial process intensification:a full review of commercial applications, research, scale-up, design and operation[J]. Chemical Engineering and Processing:Process Intensification,2007,46(9):774-780
[7]Kolah A K, Qi Z W, Mahajani S M. Dimerized isobutene:An alternative to MTBE. Chemical Innovation[J].2001,31(3):15-21
[8]Marker T L, Funk G A, Barger P T, et al. Two-stage process for producing diisopropyl ether using catalytic distillation:U.S. Patent 5,504,258[P].1996-4-2
[9]Kamath R S, Qi Z W, Sundmacher K, Aghalayam P, Mahajani S M. Process analysis for dimerization of isobutene by reactive distillation[J]. Industrial & Engineering Chemistry Research,2006,45(5):1575-1582
10] Hu M, Zhou X-G, Yuan W-K. Simulation and optimization of a coupled reactor/column system for trioxane synthesis[J]. Chemical Engineering Science,1999,10:1353-1358
11] Podrebarac G G, Ng F T T, Rempel G L. The production of diacetone alcohol with catalytic distillation:Part Ⅰ:Catalytic distillation experiments[J]. Chemical Engineering Science, 1998,53(5):1067-1075
12] Taylor R, Krishna R. Modelling reactive distillation[J]. Chemical Engineering Science,2000, 55(22):5183-5229
13] Tang Y T, Chen Y W, Huang H P, Yu C C, Hung S B, Lee M J. Design of reactive distillations for acetic acid esterification[J]. AIChE Journal,2005,51(6):1683-1699
[14]王良恩,刘家祺.催化精馏技术在乙酸甲酯水解工艺中的应用[J].福建化工,2001(3)：1-4
15] Ciric A R, Miao P. Steady state multiplicities in an ethylene glycol reactive distillation column[J]. Industrial & Engineering Chemistry Research,1994,33(11):2738-2748
16] Ciric A R, Gu D. Synthesis of nonequilibrium reactive distillation processes by MINLP optimization[J]. AIChE Journal,1994,40(9):1479-1487
17] Monroy-Loperena R, Alvarez-Ramirez J. On the steady-state multiplicities for an ethylene glycol reactive distillation column[J]. Industrial & Engineering Chemistry Research,1999, 38(2):451-455
[18]Steyer F, Qi Z W, Sundmacher K. Synthesis of cylohexanol by three-phase reactive distillation:influence of kinetics on phase equilibria[J]. Chemical Engineering Science, 2002,57(9):1511-1520
[19]Arganbright R P. Hydroisomerization process:U.S. Patent 5,087,780[P].1992-2-11
[20]Masamoto J, Matsuzaki K. Development of methylal synthesis by reactive distillation[J]. Journal of Chemical Engineering of Japan,1994,27(1):1-5
[21]Kolah A K, Mahajani S M, Sharma M M. Acetalization of formaldehyde with methanol in batch and continuous reactive distillation columns[J]. Industrial & Engineering Chemistry Research,1996,35(10):3707-3720
[22]Zhang X, Zhang S, Jian C. Synthesis of methylal by catalytic distillation[J]. Chemical Engineering Research and Design,2011,75(6):573-580
[23]Neumann R, Sasson Y. Recovery of dilute acetic acid by esterification in a packed chemorectification column[J]. Industrial & Engineering Chemistry Process Design and Development,1984,23(4):654-659
[24]Xu Z, Afacan A, Chuang K T. Removal of acetic acid from water by catalytic distillation. Part 1:Experimental studies[J]. The Canadian Journal of Chemical Engineering,1999,77(4): 676-681
[25]Xu Z, Afacan A, Chuang K T. Removal of acetic acid from water by catalytic distillation. Part 2:Modeling and simulation studies[J]. The Canadian Journal of Chemical Engineering, 1999,77(4):682-687
[26]Scates M O, Parker S E, Lacy J B, et al. Recovery of acetic acid from dilute aqueous streams formed during a carbonylation process:U.S. Patent 5,599,976[P].1997-2-4
[27]Saha B, Chopade S P, Mahajani S M. Recovery of dilute acetic acid through esterification in a reactive distillation column[J]. Catalysis Today,2000,60(1):147-157
[28]Bock H, Wozny G, Gutsche B. Design and control of a reaction distillation column including the recovery system[J]. Chemical Engineering and Processing:Process Intensification,1997,36(2):101-109
[29]Chopade S P, Sharma M M. Reaction of ethanol and formaldehyde:use of versatile cation-exchange resins as catalyst in batch reactors and reactive distillation columns[J]. Reactive and Functional Polymers,1997,31(1):53-65
[30]Chopade S P, Sharma M M. Acetalization of ethylene glycol with formaldehyde using cation-exchange resins as catalysts:batch versus reactive distillation[J]. Reactive and Functional Polymers,1997,34(1):37-45
[31]Sharma M M. Some novel aspects of cationic ion-exchange resins as catalysts[J]. Reactive and Functional Polymers,1995,26(1):3-23
[32]Hildreth J M. Removal of. alpha.-methyl styrene from cumene:U.S. Patent 5,905,178[P]. 1999-5-18
[33]Krishnamurthy R, Taylor R. A nonequilibrium stage model of multicomponent separation processes. Part Ⅰ:Model description and method of solution[J]. AIChE Journal,1985,31(3): 449-456
[34]Krishna R, Wesselingh J A. The Maxwell-Stefan approach to mass transfer[J]. Chemical Engineering Science,1997,52(6):861-911
[35]Van Baten J M, Ellenberger J, Krishna R. Hydrodynamics of reactive distillation tray column with catalyst containing envelopes:experiments vs. CFD simulations[J]. Catalysis Today,2001,66(2):233-240
[36]Perez-Cisneros E, Schenk M, Gani R, Pilavachi P A. Aspects of simulation, design and analysis of reactive distillation operations[J]. Computers & Chemical Engineering,1996,20: S267-S272
[37]Chen F, Huss R S, Malone M F, et al. Simulation of kinetic effects in reactive distillation[J]. Computers & Chemical Engineering,2000,24(11):2457-2472
[38]鲍杰,严国祥.合成MTBE非均相催化精馏过程数学模拟[J].化学工程,1994,22(5)：6-12
[39]刘劲松,白鹏,朱思强.反应精馏过程的研究进展[J].化学工业与工程,2002,19(1)：101-106
[40]Kreul L U, Gorak A, Barton P I. Modeling of homogeneous reactive separation processes in packed columns[J]. Chemical Engineering Science,1999,54(1):19-34
[41]Baur R, Higler A P, Taylor R, Krishna R. Comparison of equilibrium stage and nonequilibrium stage models for reactive distillation[J]. Chemical Engineering Journal, 2000,76(1):33-47
[42]Lee J H, Dudukovic M P. A comparison of the equilibrium and nonequilibrium models for a multicomponent reactive distillation column[J]. Computers & Chemical Engineering,1998, 23(1):159-172
[43]Sundmacher K, Uhde G, Hoffmann U. Multiple reactions in catalytic distillation processes for the production of the fuel oxygenates MTBE and TAME:Analysis by rigorous model and experimental validation[J]. Chemical Engineering Science,1999,54(13):2839-2847
[44]Mohl K D, Kienle A, Gilles E D. Multiple steady states in a reactive distillation column for the production of the fuel ether TAME I. Theoretical analysis[J]. Chemical Engineering & Technology,1998,21(2):133-136
[45]Mohl K D, Kienle A, Gilles E D, Rapmund P, Sundmacher K, Hoffmann U. Nonlinear dynamics of reactive distillation processes for the production of fuel ethers[J]. Computers & Chemical engineering,1997,21:S989-S994
[46]Belck L H. Continuous reactions in distillation equipment[J]. AIChE Journal,1955,4: 467-470
[47]Hu M, Zhou X-G, Yuan W-K. Simulation and optimization of a coupled reactor/column system for trioxane synthesis[J]. Chemical Engineering Science,1999,10:1353-1358
[48]Suzuki I, Yagi H, Komatsu H, et al. Calculation of multicomponent distillation accompanied by a chemical reaction[J]. Journal of Chemical Engineering of Japan,1971,4(1):26-33
[49]周传光,郑世清.部分牛顿法模拟反应精馏过程[J].化学工程,1993,21(3)：30-3
[50]Chang Y A, Seader J D. Simulation of continuous reactive distillation by a homotopy-continuation method[J]. Computers & Chemical Engineering,1988,12(12): 1243-1255.
[51]Giessler S, Danilov R Y, Pisarenko R Y, et al. Feasibility study of reactive distillation using the analysis of the statics[J]. Industrial & Engineering Chemistry Research,1998,37(11): 4375-4382
[52]Giessler S, Danilov R Y, Pisarenko R Y, et al. Feasible separation modes for various reactive distillation systems[J]. Industrial & Engineering Chemistry Research,1999,38(10): 4060-4067
[53]Ung S, Doherty M F. Calculation of residue curve maps for mixtures with multiple equilibrium chemical reactions[J]. Industrial & Engineering Chemistry Research,1995, 34(10):3195-3202
[54]Chadda N, Malone M F, Doherty M F. Effect of chemical kinetics on feasible splits for reactive distillation[J]. AIChE journal,2001,47(3):590-601
[55]Frey T, Stichlmair J. Reactive azeotropes in kinetically controlled reactive distillation[J]. Chemical Engineering Research and Design,1999,77(7):613-618
[56]Frey T, Stichlmair J. Thermodynamic fundamentals of reactive distillation[J]. Chemical Engineering & Technology,1999,22(1):11-18
[57]Bessling B, Schembecker G, Simmrock K H. Design of processes with reactive distillation line diagrams[J]. Industrial & Engineering Chemistry Research,1997,36(8):3032-3042
[58]Bessling B, Loning J M, Ohligschlager A, et al. Investigations on the synthesis of methyl acetate in a heterogeneous reactive distillation process[J]. Chemical Engineering & Technology,1998,21(5):393-400
[59]Ciric A R, Gu D. Synthesis of nonequilibrium reactive distillation processes by MINLP optimization[J]. AIChE Journal,1994,40(9):1479-1487
[60]Poth N., Frey T. and Stichlmair J. MINLP optimization of kinetically controlled reactive distillation processes[J]. Computer-Aided Chemical Engineering,2001,9:79-84
[61]Cardoso M F, Salcedo R L, de Azevedo S F, Barbosa D. Optimization of reactive distillation processes with simulated annealing[J]. Chemical Engineering Science,2000,50(21): 5059-5078
[62]Pekkanen M. A local optimization method for the design of reactive distillation[J]. Computers & Chemical Engineering,1995,19:235-240
[63]Seferlis P, Grievink J. Optimal design and sensitivity analysis of reactive distillation units Using collocation models[J]. Industrial & Engineering Chemistry Research,2001,40(7): 1673-1685
[64]Russel B M, Henriksen J P, Jorgensen S B, et al. Integration of design and control through model analysis[J]. Computers & Chemical Engineering,2002,26(2):213-225
[65]Bansal V, Perkins J D, Pistikopoulos E N, et al. Simultaneous design and control optimisation under uncertainty [J]. Computers & Chemical Engineering,2000,24(2): 261-266
[66]Bansal V, Sakizlis V, Ross R, et al. New algorithms for mixed-integer dynamic optimization[J]. Computers & Chemical Engineering,2003,27(5):647-668
[67]Georgiadis M C, Schenk M, Pistikopoulos E N, et al. The interactions of design control and operability in reactive distillation systems [J]. Computers & Chemical Engineering,2002, 26(4):735-746
[68]Sander S, Flisch C, Geissler E, et al. Methyl acetate hydrolysis in a reactive divided wall column[J]. Chemical Engineering Research and Design,2007,85(1):149-154
[69]Gao X, Li X, Li H. Hydrolysis of methyl acetate via catalytic distillation:Simulation and design of new technological process[J]. Chemical Engineering and Processing:Process Intensification,2010,49(12):1267-1276
[70]Tung S T, Yu C C. Effects of relative volatility ranking to the design of reactive distillation[J]. AIChE Journal,2007,53(5):1278-1297
[71]Tang Y T, Chen Y W, Huang H P, et al. Design of reactive distillations for acetic acid esterification[J]. AIChE Journal,2005,51(6):1683-1699
[72]Fuchigami Y. Hydrolysis of methyl acetate in distillation column packed with reactive packing of ion exchange resin[J]. Journal of Chemical Engineering of Japan,1990,23(3): 354-359
[73]Kim K J, Roh H D. Reactive distillation process and equipment for the production of acetic acid and methanol from methyl acetate hydrolysis:U.S. Patent 5,770,770[P].1998-6-23
[74]Wang J, Ge X, Wang Z, et al. Experimental studies on the catalytic distillation for hydrolysis of methyl acetate[J]. Chemical Engineering & Technology,2001,24(2):155-159
[75]Xiao J, Liu J, Li J, et al. Increase MeOAc conversion in PVA production by replacing the fixed bed reactor with a catalytic distillation column[J]. Chemical Engineering Science, 2001,56(23):6553-6562
[76]Lee M M. Method and apparatus of methyl acetate hydrolysis:U.S. Patent Application 09/878,153[P].2001-6-11
[77]Musser M T. Cyclohexanol and cyclohexanone[J]. Ullmann's Encyclopedia of Industrial Chemistry,2005
[78]Steyer F, Qi Z W, Sundmacher K. Synthesis of cylohexanol by three-phase reactive distillation:influence of kinetics on phase equilibria[J]. Chemical Engineering Science, 2002,57(9):1511-1520
[79]Gani R, J(?)rgensen S B. Multiplicity in numerical solution of non-linear models:separation processes[J]. Computers & Chemical Engineering,1994,18:S55-S61
[80]Kovach J W, Seider W D. Heterogeneous azeotropic distillation:experimental and simulation results[J]. AIChE journal,1987,33(8):1300-1314
[81]Vadapalli A, Seader J D. A generalized framework for computing bifurcation diagrams using process simulation programs[J]. Computers & Chemical Engineering,2001,25(2):445-464
[82]Kannan A, Joshi M R, Reddy G R, et al. Multiple-steady-states identification in homogeneous azeotropic distillation using a process simulator [J]. Industrial & Engineering Chemistry Research,2005,44(12):4386-4399
[83]Bekiaris N, Morari M. Multiple steady states in distillation:oo/oo predictions, extensions, and implications for design, synthesis, and simulation[J]. Industrial & Engineering Chemistry Research,1996,35(11):4264-4280
[84]Yang B, Wu J, Zhao G, et al. Multiplicity analysis in reactive distillation column using ASPEN PLUS[J]. Chinese Journal of Chemical Engineering,2006,14(3):301-308
[85]Carlos Cardenas-Guerra J, Lopez-Arenas T, Lobo-Oehmichen R, et al. A reactive distillation process for deep hydrodesulfurization of diesel:Multiplicity and operation aspects [J]. Computers & Chemical Engineering,2010,34(2):196-209
[86]Seydel R, Hlavacek V. Role of continuation in engineering analysis [J]. Chemical Engineering Science,1987,42(6):1281-1295
[87]Keller, H. B. Numerical solution of bifurcation and nonlinear eigenvalue problems. Applications of Bifurcation Theory, P. Rabinowitz, editor, Acacemic Press, New York,359
[88]Seydel R. Numerical computation of branch points in nonlinear equations[J]. Numerische Mathematik,1979,33(3):339-352
[89]Anderson E, Bai Z, Bischof C, et al. LAPACK users'guide, Release 2.0[J]. SIAM, Philadelphia,1995,326:327
[90]Singh B P, Singh R, Kumar M V P, et al. Steady state analysis of reactive distillation using homotopy continuation[J]. Chemical Engineering Research and Design,2005,83(8): 959-968
[91]Venimadhavan G, Malone M F, Doherty M F. A novel distillate policy for batch reactive distillation with application to the production of butyl acetate[J]. Industrial & Engineering Chemistry Research,1999,38(3):714-722
[92]Song W, Venimadhavan G, Manning J M, et al. Measurement of residue curve maps and heterogeneous kinetics in methyl acetate synthesis[J]. Industrial & Engineering Chemistry Research,1998,37(5):1917-1928
[93]Popken T, Gotze L, Gmehling J. Reaction kinetics and chemical equilibrium of homogeneously and heterogeneously catalyzed acetic acid esterification with methanol and methyl acetate hydrolysis[J]. Industrial & Engineering chemistry research,2000,39(7): 2601-2611
[94]Dirk-Faitakis C B, An W, Lin T B, et al. Catalytic distillation for simultaneous hydrolysis of methyl acetate and etherification of methanol [J]. Chemical Engineering and Processing: Process Intensification,2009,48(5):1080-1087
[95]Ung S, Doherty M F. Vapor-liquid phase equilibrium in systems with multiple chemical reactions[J]. Chemical Engineering Science,1995,50(1):23-48
[96]Song W, Huss R S, Doherty M F, et al. Discovery of a reactive azeotrope[J]. Nature,1997, 388(6642):561-563
[97]Al-Arfaj M A, Luyben W L. Comparative control study of ideal and methyl acetate reactive distillation[J]. Chemical Engineering Science,2002,57(24):5039-5050
[98]Huss R S, Chen F, Malone M F, et al. Reactive distillation for methyl acetate production[J]. Computers & Chemical Engineering,2003,27(12):1855-1866
[99]Lin Y D, Chen J J H, Cheng J K, et al. Process alternatives for methyl acetate conversion using reactive distillation.1. Hydrolysis[J]. Chemical Engineering Science,2008,63(6): 1668-1682
100] Xu Y, Zheng Y, Ng F T T, et al. A three-phase nonequilibrium dynamic model for catalytic distillation[J]. Chemical Engineering Science,2005,60(20):5637-5647
[101]Onda K, Takeuchi H, Okumoto Y. Mass transfer coefficients between gas and liquid phases in packed columns[J]. Journal of Chemical Engineering of Japan,1968,1(1):56-62
[102]Zheng Y, Xu X. Study on catalytic distillation process, Part 1. Mass transfer characteristics in catalytic bed within the column[J]. Chemical Engineering Research & Design,1992, 70(A5):459-464
[103]Dorn C, Lee M, Morari M. Stability and transient behavior of homogeneous azeotropic distillation[J]. Computers & Chemical Engineering,1999,23:S191-S194