轻汽油醚化的反应精馏技术研究
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摘要
我国的车用汽油约80%来自FCC轻汽油(催化裂化汽油),其中烯烃含量非常高,很难达到车用汽油烯烃含量小于35%(体积分数)的标准,因此如何经济合理地降低FC轻汽油中的烯烃含量而又不降低辛烷值,是当前亟待解决的工艺技术问题。采用反应精馏技术进行轻汽油醚化是实现上述目标的有效途径。反应精馏是指集反应、分离于一体的一种新的化工过程,与传统的固定床反应技术相比具有很多优点,因此对轻汽油醚化的反应精馏技术的研究具有重要意义。
本课题首先对反应精馏技术中的关键问题——催化填料进行了研究。在明确现有催化填料不足的基础上,从两种不同的思路入手,研制出了新型的催化填料,并通过流体力学实验证实。与传统的催化填料相比,所研制的新型催化填料具有制作简单、比表面积大、流通效果好等优点,同时可调节催化剂的填充量和填充密度,实现较大的塔内床层空隙率和较小的压降,从而提高了塔的生产能力,并且催化剂装卸方便,工艺上容易实现。
其次,本课题采用所研制的新型催化填料进行了轻汽油醚化反应精馏过程的实验,考查了各种因素对轻汽油醚化的影响,通过理论与实验相结合,找到了醚化的最佳工艺条件,同时也检验了所研制的新型催化填料的催化分离性能。
最后,本课题应用流程模拟方法对轻汽油的醚化过程进行了计算模拟,并将模拟值与实验值进行了对比,结果基本吻合,证实了在模拟过程中所采用的模型参数的正确性,从而可以为进一步实验及工业放大提供指导。
About 80%of the gas used in cars comes from the FCC light gasoline,which contains a high concentration of olefin,the concentration of olefin in FCC light gasoline is difficultly meet the standards which limits the proportion of olefin less than 35%in volume base,so,how to reduce the olefin concentration reasonably and at the same time not reduce the octane number of gas,is a important technology problem to be resolved.It is a effective way to realize the aim above to eherify FCC light gasoline by Reactive Distillation,Reactive Distillation is refered to one new chemical process which combines the reaction and the distillation.Compared to the traditional fix-bed technology,the Reactive Distillation technology has superiorities, so,the researchment of Reactive Distillation has important significance.
Firstly,one key problem in reactive distillation-the catalytic packing has been studied.After knowing about the defects in current catalytic packing clearly,started from two different thinking,and at the end,invented new catalytic packing.Then,the experimental on fluid hydrodynamics has been done,and the result has proved that compared with current catalytic packings,the new one has several superiorities as: simpler making;bigger surface area;better flowing.Also,the new packing was adjustable at the catalyst amount and catalyst density,guaranteeing bigger bed-gap ratio and smaller pressure-drop at the same time,so to improve the production capacity of the column,and what is more,in the new packing,catalysts is more easy to fill in and out,more easy to do technological operation.
Secondly,experimental on reacted distillation has been done using the new packing that has been invention,by that,the effects of feed location,reaction temperature,alcohol/olefin ratio and reflux ratio on conversion rate have been studied by that,and reasonable results are obtained by integrating theory with experiment,and at the same time,the catalytic-separation performance of the new packing has been tested.
At last,the process simulation has been done used by simulation software-aspen plus.Compared the simulation data with the experimental data,showed that the simulation data and the experimental data anastomoses basically.So The validity of the model is verified and thus can provide guidance for further experimental and industrial scale-up.
本课题首先对反应精馏技术中的关键问题——催化填料进行了研究。在明确现有催化填料不足的基础上,从两种不同的思路入手,研制出了新型的催化填料,并通过流体力学实验证实。与传统的催化填料相比,所研制的新型催化填料具有制作简单、比表面积大、流通效果好等优点,同时可调节催化剂的填充量和填充密度,实现较大的塔内床层空隙率和较小的压降,从而提高了塔的生产能力,并且催化剂装卸方便,工艺上容易实现。
其次,本课题采用所研制的新型催化填料进行了轻汽油醚化反应精馏过程的实验,考查了各种因素对轻汽油醚化的影响,通过理论与实验相结合,找到了醚化的最佳工艺条件,同时也检验了所研制的新型催化填料的催化分离性能。
最后,本课题应用流程模拟方法对轻汽油的醚化过程进行了计算模拟,并将模拟值与实验值进行了对比,结果基本吻合,证实了在模拟过程中所采用的模型参数的正确性,从而可以为进一步实验及工业放大提供指导。
About 80%of the gas used in cars comes from the FCC light gasoline,which contains a high concentration of olefin,the concentration of olefin in FCC light gasoline is difficultly meet the standards which limits the proportion of olefin less than 35%in volume base,so,how to reduce the olefin concentration reasonably and at the same time not reduce the octane number of gas,is a important technology problem to be resolved.It is a effective way to realize the aim above to eherify FCC light gasoline by Reactive Distillation,Reactive Distillation is refered to one new chemical process which combines the reaction and the distillation.Compared to the traditional fix-bed technology,the Reactive Distillation technology has superiorities, so,the researchment of Reactive Distillation has important significance.
Firstly,one key problem in reactive distillation-the catalytic packing has been studied.After knowing about the defects in current catalytic packing clearly,started from two different thinking,and at the end,invented new catalytic packing.Then,the experimental on fluid hydrodynamics has been done,and the result has proved that compared with current catalytic packings,the new one has several superiorities as: simpler making;bigger surface area;better flowing.Also,the new packing was adjustable at the catalyst amount and catalyst density,guaranteeing bigger bed-gap ratio and smaller pressure-drop at the same time,so to improve the production capacity of the column,and what is more,in the new packing,catalysts is more easy to fill in and out,more easy to do technological operation.
Secondly,experimental on reacted distillation has been done using the new packing that has been invention,by that,the effects of feed location,reaction temperature,alcohol/olefin ratio and reflux ratio on conversion rate have been studied by that,and reasonable results are obtained by integrating theory with experiment,and at the same time,the catalytic-separation performance of the new packing has been tested.
At last,the process simulation has been done used by simulation software-aspen plus.Compared the simulation data with the experimental data,showed that the simulation data and the experimental data anastomoses basically.So The validity of the model is verified and thus can provide guidance for further experimental and industrial scale-up.
引文
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[2]王海彦,周定,采用催化裂化轻汽油醚化技术生产清洁汽油,炼油设计,2004,30(2):78-83
[3]李亚军,李吉春,催化裂化轻汽油醚化技术,石化技术与应用,2002,20(3):112-116
[4]IGNATIUS J.,JARVELIN H.,LINDQVIST P.,Use TAME and heavier ethers to improve gasoline properties,Hydrocarbon Processing,1995,74(2):51-53
[5]Ancellotti F et al.J Catal 1977,46-49
[6]Ancellotti F et al.J Mol Catal,1978,4-7
[7]杭道耐,甲基叔丁基醚生产和应用,北京:中国石化出版社,,1993,58-62
[8]Rikol,Krause.Kinetics and thermodynamics of synthesis of tertiary -amylmethyl ether catalyzed by ion-exchange resin.Chinese Chem.Soc,1994,41(2):181-186
[9]Piccoli RL,Lovisi HR.Kinetic and thermo-dynamic study of the liquid-phase etherification of isoamylenes with methanol.In:Eng ChemRes,1995,34(2):510-515
[10]Hofmann H.Berechnung von reaktionen fur gemischtphase-reaktionen Chem.Eng Sic,1958,8(1/2):113-122
[11]Ilie M,Aurelian T,Dan CP,etal.Thermodynamic in study of the methanol addition tolsoamylen.Chem.Eng Process,2005,44:645-651
[12]吕爱梅,王伟,MIO碳五合成TAME宏观动力学研究,科学研究与技术开发,2000,28(3):182-185
[13]姚文生,合成TAME宏观动力学的研究,石油化工,1998,27(6):391-395
[14]孟凡旭,混合进化算法研究甲基叔戊基醚合成反应动力学,化工学报,2003,54(3):54-59
[15]方伯言,杨瑞军,合成甲基叔戊基醚的化学平衡研究,锦州石油化工公司研究院,化工学报,1998,49(3):282-287
[16]刘立新,裂解碳五合成甲基叔戊基醚体系的热力学特征,石油化工,2006,35(7):31-35
[17]郭忠林,刘立新,甲基叔戊基醚合成反应的热力学分析,炼油技术与工程,2006,36(2):140-146
[18]马坚,催化裂化汽油轻馏分醚化分子筛催化剂的研究,PETROL EUM PROCESS IN GAND PETROCHEM ICALS,1999,30(6):112-117
[19]张英强,马坚,催化裂化轻汽油醚化沸石催化剂的研究.炼油设计,2002,32(3):20-23
[20]于永玲,李艳青,醚化用树脂催化剂QRE 02的性能评价,齐鲁石化公司研究院,齐鲁石油化工,2000,24(13):18-24
[21]王海彦,CATAFRACT催化蒸馏深度转化合成TAME全流程技术开发,齐鲁石油化工,1997,25f3):161-165
[22]杜长海,催化精馏专用填料型固体酸,辽宁化工,2006,5:37-41
[23]姚文生,谷素艳,TAME合成原料及产品的气相色谱分析,渤海大学化学化工学院,科学研究与技术开发,2002,34(8):87-95
[24]李艳青,李玉田,轻汽油醚化产物的气相色谱分析,山东化工,2001,30(21):21-25
[25]王海彦,马骏,催化裂化轻汽油及醚化产品的气相色谱分析.分析化学,2000,28(5):65-70
[26]薛慧峰,催化裂化轻汽油及其醚化产品的分析,分析测试学报,2004,23(1):70-73
[27]刘姝,单秀杰,醚化汽油单烃的组成及含氧化合物的测定,色谱,1998,16(2):143-145.
[28]王伟,陈邵安,醚化汽油中醚的测定,石油化工,1998,27(7):529-532
[29]吕振波,王伟,用气相色谱/质谱法分析醚化催化裂化轻汽油的醚及相关烯烃,色谱,1997,15f3):250-255
[30]马骏,王海彦,轻汽油中醚含量的红外分析,当代化工,2001,30(1):58-59
[31]楮庆辉,核磁共振波谱法用于醚化汽油原料烯烃和醚含量的测定,抚顺石油学院学报,1997,17(1):11-13
[32]Chase J D.Catalytic Conversion of Synthetic Gas and A12 cools to Chem.ices.Ed.Herman Richard,1984,307-311
[33]胡竞民,徐宏芬,鲁耘等,碳五馏分醚化多功能催化剂的研究,石油化工,1999,28(6):354-357
[34]Ellenberger,J.Krishna,R.Counter-current operation of structured catalytically packed distillation columns:pressure drop,holdup and mixing.Chemical Engineering Science,1999,54,1339-1345
[35]刘庆林,夏建军,催化反应精馏研究中的若干问题,南京大学学报(自然科学版),2000,36(1):104-110
[36]Sie,S.T.& Krishna,R.Process Development and Scale Up:Ⅲ.Scale up and scale down of trickle-bed processes.Reviews in Chemical Engineering,1998,14,203 -252
[37]Gianetto A,Baldi G,Specchia V,et al.Hydrodynamics and Solid-Liquid Contacting Effectiveness in Trickle Bed Reactors.AIChE,1978,(24):1087
[38]Hitler A P,Krishna R,Ellenberger J.Counter-current operation of a structured catalytically packed bed reactor:Liquid-phase mixing and mass transfer.Chemical EngineeringScience.1999.54(24):5145-5152
[39]O.L.Oudshoorn,M.Janssen,W.E.J.van Kooten,J.C.A novel structured catalyst packing for catalytic distillation of ETBE.US pat.4215011
[40]郝兴仁,王进善,新型催化精馏塔,CN,1042664.1990
[41]张瑞生,高效催化精馏填料,中国专利,1065412,2000-10-15
[42]Jones,Edward M.Jr.Eur.Patent,0461855,1991
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