基于渗流催化剂的轻汽油醚化催化精馏过程研究
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摘要
为了满足生产清洁汽油的要求并且合理利用FCC汽油中的活性烯烃组分,目前的趋势是将其中所含有的活性烯烃成分醚化成高辛烷值的含氧醚类物质。鉴于MTBE采用催化精馏技术实现工业化生产取得的巨大成功,本文对轻汽油醚化催化精馏过程进行了研究。
针对催化精馏技术中最关键的是催化剂装填技术,本文设计了能够在精馏区提供良好的气液接触,在反应区保证液相催化反应效率的催化精馏内构件——渗流型催化剂填装内构件(Seepage Catalyst Packing Internal,SCPI)。
SCPI是由带有防溢流挡板的催化剂网盒和规整填料组成,可以灵活调整催化剂装填区和分离区的尺寸比例从而改变催化剂和规整填料的装填比例来满足不同的催化精馏过程的需要。本文就三组不同比例的SCPI在直径Φ600mm冷模精馏塔内,采用常温下空气—水系统对其流体力学性能进行了测试。并根据实验测得SCPI压降和持液量,结合SCPI的结构建立了流体力学模型。
最后本文中利用化工流程模拟软件Aspen Plus采用平衡级模型RedFrac模块作为反应精馏模型,采用SCPI实验所得到的流体力学数据,对轻汽油醚化的反应精馏过程中C5活性烯烃与甲醇醚化生成TAME反应进行了流程模拟。考察了精馏塔操作条件对醚化反应的影响,最终得出优化反应条件。研究结果可以为轻汽油醚化过程和催化精馏工艺设计提供依据和借鉴。
In order to meet the requirements for production of clean gasoline and make rational use of the active olefin content in FCC gasoline, the best method in Currently is that changing the olefins into high octane ether material by etherification of light FCC. In view of the great success in MTBE producing by catalytic distillation technology, So in this work reactive distillation process used in FCC Light Gasoline Etherification was studied.
In application of the catalytic distillation the most important key is the design of the catalyst packing internal. A seepage catalyst packing internal (SCPI) which can provide a good gas-liquid contact in distillation zone and can also ensure Liquid phase catalytic reaction time is designed in this work.
A seepage catalysts packing internal (SCPI) consist of catalysts container and structured packing which provides the flexibility in varying the ratio of the reaction zone relative to the separation zone according to different catalytic distillation process requirements by changing the size ratio of catalyst container relative to structured packing. Three different ratios SCPI’s hydrodynamics was measured in a cold mould distillation column with 600mm diameter, air and water at normal pressure and room temperature were used as test media. With the experimental results of the pressure drop and liquid holdup and structural mechanism of the SCPI, Modelling for predicting hydrodynamics was presented.
At last, The reactive distillation process used in FCC Light Gasoline Etherification for the production of t-amyl-methyl-ether (TAME) from methanol and isoamylenes was simulated by chemical engineering simulation software Aspen Plus, in which the RadFrac equilibrium stage model was selected as reactive distillation model, The hydromechanical Experimental data of the SCPI was adopted. The operating conditions in reactive distillation which affect Etherification was reviewed, and the final optimized conditions was obtained. This study can provide a basis and reference for Light gasoline etherification process and Catalytic distillation process design.
针对催化精馏技术中最关键的是催化剂装填技术,本文设计了能够在精馏区提供良好的气液接触,在反应区保证液相催化反应效率的催化精馏内构件——渗流型催化剂填装内构件(Seepage Catalyst Packing Internal,SCPI)。
SCPI是由带有防溢流挡板的催化剂网盒和规整填料组成,可以灵活调整催化剂装填区和分离区的尺寸比例从而改变催化剂和规整填料的装填比例来满足不同的催化精馏过程的需要。本文就三组不同比例的SCPI在直径Φ600mm冷模精馏塔内,采用常温下空气—水系统对其流体力学性能进行了测试。并根据实验测得SCPI压降和持液量,结合SCPI的结构建立了流体力学模型。
最后本文中利用化工流程模拟软件Aspen Plus采用平衡级模型RedFrac模块作为反应精馏模型,采用SCPI实验所得到的流体力学数据,对轻汽油醚化的反应精馏过程中C5活性烯烃与甲醇醚化生成TAME反应进行了流程模拟。考察了精馏塔操作条件对醚化反应的影响,最终得出优化反应条件。研究结果可以为轻汽油醚化过程和催化精馏工艺设计提供依据和借鉴。
In order to meet the requirements for production of clean gasoline and make rational use of the active olefin content in FCC gasoline, the best method in Currently is that changing the olefins into high octane ether material by etherification of light FCC. In view of the great success in MTBE producing by catalytic distillation technology, So in this work reactive distillation process used in FCC Light Gasoline Etherification was studied.
In application of the catalytic distillation the most important key is the design of the catalyst packing internal. A seepage catalyst packing internal (SCPI) which can provide a good gas-liquid contact in distillation zone and can also ensure Liquid phase catalytic reaction time is designed in this work.
A seepage catalysts packing internal (SCPI) consist of catalysts container and structured packing which provides the flexibility in varying the ratio of the reaction zone relative to the separation zone according to different catalytic distillation process requirements by changing the size ratio of catalyst container relative to structured packing. Three different ratios SCPI’s hydrodynamics was measured in a cold mould distillation column with 600mm diameter, air and water at normal pressure and room temperature were used as test media. With the experimental results of the pressure drop and liquid holdup and structural mechanism of the SCPI, Modelling for predicting hydrodynamics was presented.
At last, The reactive distillation process used in FCC Light Gasoline Etherification for the production of t-amyl-methyl-ether (TAME) from methanol and isoamylenes was simulated by chemical engineering simulation software Aspen Plus, in which the RadFrac equilibrium stage model was selected as reactive distillation model, The hydromechanical Experimental data of the SCPI was adopted. The operating conditions in reactive distillation which affect Etherification was reviewed, and the final optimized conditions was obtained. This study can provide a basis and reference for Light gasoline etherification process and Catalytic distillation process design.
引文
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[5]张瑞生,韩英,非均相催化精罐过程的模拟计算,化工学报,1989,40(6):69～70
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[22]Gotze L, Bailer O, Moritz P, Scala C V. Reactive distillation with KATAPAK. Catalysis Today. 2001, 69: 201~208
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[32]郝兴仁等,散装结构的催化蒸馏塔,中国专利,1022382A,1993
[33]李艳青,王伟,杨宗仁,国内外TAME生产技术综述,齐鲁石油化工,2000,28(4):309～301
[34]邓诗峰,石油化工,1998,27(2):79～81
[35]焦子华,周传光,赵文,稳态反应精馏过程的数学模拟及算法研究进展,化学工业与工程,2004,21(4):308～312
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[41]杨照,王志祥,反应精馏技术及其应用,化工时刊,2004,12(11):32～35
[42]赵志海,刘耀芳,许锡恩,催化精馏塔内催化剂床层润湿率研究,化学工程,1999,27(6):6～8
[43]X. Xu, Z. Zhihai, S. Tian, Study of catalytic distillation process: prediction of pressure drop and holdup in catalyst bed, Trans.IChemE75(1997) 625
[44]Han, M., Lin, H., Wang, J., Jin, Y, Pressure drop for Two Phase Counter-current Flow in the Packed Column with a Novel Internal, Chem. Eng, J, 2003, 94(3): 179~187
[45]王双成,规整填料层压降的研究,化肥设计,2002,40(2):15～17
[46]王广全,规整填料压降研究新进展,化学工程,2005,33(3):4～7
[47]Bravo J L, Rocha J A, Fair J R, Distillation columns containing structured packings: A comprehensive model for their performance Hydraulic models, Ind. Eng Chem. Res,1993,32(4):641~651.
[48]Fair J R, Seibert A F, Behrens M, et al, Structured packing performances -Experimental evaluation of two Predictive models, Ind. Eng. Chem. Res, 2000, 39(6):1788~1796
[49]Liu Shijie, A continuum model for gas-liquid flow in packed towers, Chem. Eng. Sci, 2001, 56:5945~5953
[50]卢励生,钱恒元,陈大昌,化工炼油机械,1982,(1):12
[51]Bravo J L , Rocha J A, Fair J R. A comprehensive model for the performance of columns containing structured packing . Ind. Chem. Eng. Symp. Ser, 1992, 128: A489
[52]Bird, R. B., Stewart, W. E., Lightfoot, E. N. Transport Phenomena, John Wiley: New York, 1960, 37~42
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[64]A. Kolodziej, M. Jaroszyński, W. Saacki, W. Orlikowski, K. Frczek, M. Klker, E.Y. Kenig and A. Górak, Catalytic distillation for TAME synthesis with structured catalytic packings, Chemical Engineering Research and Design 82(2)(2004),175~184
[65]A. Hoffmann, C. Noeres, A. G′orak, Scale-up of reactive distillation columns with catalytic packings, Chem. Eng. Process, 2004, 43(5): 383~386
[66]姚文生,合成TAME宏观动力学的研究,石油化工,1998,27(6):391～393
[2]Taylor R, Krishna R. Modelling reactive distillation. Chemical Engineering Science, 2000, 55(22): 5183～5229
[3]ShoemarerJ.D.Jones E.M. Jr. Hydroearbon Progressing,1987,66(6):57~60
[4]晋正茂,王维德,反应精馏及其研究进展,化学工业与工程技术,2006,27(3):11～13
[5]张瑞生,韩英,非均相催化精罐过程的模拟计算,化工学报,1989,40(6):69～70
[6]许锡恩,朱宝福,陈洪钫等,反应精馏(Ⅰ),化工学报,1987,2(2):165～175
[7]许锡恩,李家玲,催化精馏进展,石油化工,1989,18(9):642～649
[8]肖剑,张志炳,反应精馏研究进展及应用前景,江苏化工,2002,30(2):21～25
[9]马敬环,刘家祺,李俊台等,反应精馏技术的进展,化学反应工程与工艺,2003,19(1):1～8
[10]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,1999,18(2):8～10
[11]SmithL. A. Jr. Hudd1estonM.N.HydroearbonProeessing, 1982, 61(3): 121~123
[12]Eur. P. 01896834(1985)
[13]张卫祥,新乙烯回收技术扩大中试装置工艺路线,乙烯工业,2002,14(3):33～35
[14]Lebens P J M, Kapteijn F, Sie S T, et al. Potentials of internally finned monoliths as a packing for multifunctional reactors, Chemical Engineering Science, 1999, 54: 1359~1365
[15]Han M H, Lin H F, Wang L W et al, Characteristics of the reactive distillation column with a novel internal. Chemical Engineering Science, 2002, 57:1551~1555
[16]Smith Jr. Catalyst system for separating isobutene from C4 streams. US4215011, 1980-7-29
[17]Chevron Research Company. Staged fluidized-bed distillation-reactor a process for using such reactor. US4471154, 1984-9-11
[18]陈秀松,白泽双,杨代华,CTST反应精馏塔的工业应用,维普通讯,2004,24(3):18～20
[19]Oudshoorn O L, Janissen M, van Kooten W E J, et al. A novel structured catalyst packing for catalytic distillation of ETBE. Chemical Engineering Science, 1999, 54: 1413~1418
[20]Kolodziej A, Jaroszynski M, Hoffmann A, Gorak A. Determination of catalytic packing characteristics for reactive distillation. Catalytic Today, 2001, 69:75~85
[21]Ratheesh R, Kannan A, Holdup and pressure drop studies in structured packings with catalysts. Chemical Engineering Journal.2004, 104: 45~54
[22]Gotze L, Bailer O, Moritz P, Scala C V. Reactive distillation with KATAPAK. Catalysis Today. 2001, 69: 201~208
[23]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,1997,27(1):6～10
[24]Chemical Research & Licensing Company, Catalytic distillation reactor, US5130102, 1992-7-14
[25]齐鲁石油化工公司设计院,催化蒸馏新型设备和催化剂系统,中国专利,N88109705.5,1990-6-6
[26]李鑫钢,高鑫,李永红等,催化剂网盒及催化剂填装结构,中国专利,101219400,2008-9-10
[27]Catalytic Distillation Technologies integrated process for the Production of Tame US Pat App, US57928991, 1998
[28]Smith Jr, Alkylation of organic aromatic compounds, US4849569, 1989-7-18
[29]李吉春,胡劲松,黄星亮等,FCC轻汽油临氢醚化催化剂反应特性的研究,石油炼制与化工,2003,34(5):23～28
[30]李长明,李吉春,黄星亮等,FCC轻汽油醚化催化精馏工艺的研究,石油炼制与化工,2004,35(1):5～9
[31]王天普,王迎春,王伟等,轻汽油醚化技术在FCC汽油改质中的作用,石油炼制与化工,2001,32(8):64～66
[32]郝兴仁等,散装结构的催化蒸馏塔,中国专利,1022382A,1993
[33]李艳青,王伟,杨宗仁,国内外TAME生产技术综述,齐鲁石油化工,2000,28(4):309～301
[34]邓诗峰,石油化工,1998,27(2):79～81
[35]焦子华,周传光,赵文,稳态反应精馏过程的数学模拟及算法研究进展,化学工业与工程,2004,21(4):308～312
[36]Savkovic-Srevanovic J, Misic Vukovic M, Slavrjkov A et al,Proceedings of world congressⅢof chemical engineering, 1986, 12(3), 672~675
[37]盖旭东,孙锦昌,反应精馏过程模拟研究进展,化学工程,1996,24(01):8～11
[38]Krishnamurthy R, Taylor R, Role of iron in multicomponent molybdate catalysts for selective oxidation of propylene, Ind. Eng. Chem. Process, 1985, 24: 513~521
[39]KRISHNA R,TAYLOR R. A, Nonequilibrium stage model of multicomponent separation process, AIChE J, 1985, 31(3): 449~464
[40]WAYBURN T L, SEADER J D, Homotopy-continuationmethods for computer aided process design, Computers and Chemical Engineering, 1987, 11(1): 7~25
[41]杨照,王志祥,反应精馏技术及其应用,化工时刊,2004,12(11):32～35
[42]赵志海,刘耀芳,许锡恩,催化精馏塔内催化剂床层润湿率研究,化学工程,1999,27(6):6～8
[43]X. Xu, Z. Zhihai, S. Tian, Study of catalytic distillation process: prediction of pressure drop and holdup in catalyst bed, Trans.IChemE75(1997) 625
[44]Han, M., Lin, H., Wang, J., Jin, Y, Pressure drop for Two Phase Counter-current Flow in the Packed Column with a Novel Internal, Chem. Eng, J, 2003, 94(3): 179~187
[45]王双成,规整填料层压降的研究,化肥设计,2002,40(2):15～17
[46]王广全,规整填料压降研究新进展,化学工程,2005,33(3):4～7
[47]Bravo J L, Rocha J A, Fair J R, Distillation columns containing structured packings: A comprehensive model for their performance Hydraulic models, Ind. Eng Chem. Res,1993,32(4):641~651.
[48]Fair J R, Seibert A F, Behrens M, et al, Structured packing performances -Experimental evaluation of two Predictive models, Ind. Eng. Chem. Res, 2000, 39(6):1788~1796
[49]Liu Shijie, A continuum model for gas-liquid flow in packed towers, Chem. Eng. Sci, 2001, 56:5945~5953
[50]卢励生,钱恒元,陈大昌,化工炼油机械,1982,(1):12
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