液体酸耦合体系催化C_4烷基化研究进展
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摘要
综述了近十年来液体酸耦合体系催化C_4烃烷基化反应的最新进展,包括液体超强酸、有机酸-杂多酸、离子液体-酸耦合体系,对比了不同催化体系催化C_4烃烷基化反应过程中的烯烃转化率、三甲基戊烷的选择性和烷基化汽油的研究法辛烷值,总结了不同催化体系的优缺点。重点论述了离子液体-酸耦合体系催化剂中组成离子液体的阴阳离子以及耦合酸类型对C_4烃烷基化反应的影响:有机胺类离子液体较咪唑类有着更为优异的烷基化效果,阴离子和改性离子液体通过形成特定的结构来维持反应体系的酸强度、减少副反应,从而延长催化剂的使用寿命,耦合酸为反应提供酸性位点并与离子液体协同催化。离子液体-酸耦合催化体系具有酸耗低、稳定性好、不易失活且可循环使用等优点,是C_4烷基化催化剂未来的发展方向之一。
The progress in the alkylation of C_4 hydrocarbons catalyzed by liquid acid coupling systems,including liquid super acids, organic acid-heteropoly acids, and ionic liquid-acid coupling systems, in last decade is reviewed. The conversion of olefins, selectivity of trimethylpentane and research octane number of alkylated gasoline during the alkylation of C_4 hydrocarbons catalyzed by different catalytic systems were compared. The advantages and disadvantages of different catalytic systems were also summarized. The effects of the anions and cations of ionic liquids and the coupling acid types on the alkylation of C_4 hydrocarbons in ionic liquid-acid coupling catalysts are mainly discussed. Organic amine ionic liquids have superior alkylation effects to imidazoles. Anions and modified ionic liquids could form specific structures to maintain the acid strength of the reaction systems and reduce side reactions so as to extend the life of the catalysts. The coupling acids provide acidic sites for the reaction and cooperate with ionic liquids. Finally, the ionic liquid-acid coupling catalytic system which has the advantages of low acid consumption, good stability, resistant inactivation and easy recycling, is one of the development directions of the C_4 alkylation catalyst in the future.
The progress in the alkylation of C_4 hydrocarbons catalyzed by liquid acid coupling systems,including liquid super acids, organic acid-heteropoly acids, and ionic liquid-acid coupling systems, in last decade is reviewed. The conversion of olefins, selectivity of trimethylpentane and research octane number of alkylated gasoline during the alkylation of C_4 hydrocarbons catalyzed by different catalytic systems were compared. The advantages and disadvantages of different catalytic systems were also summarized. The effects of the anions and cations of ionic liquids and the coupling acid types on the alkylation of C_4 hydrocarbons in ionic liquid-acid coupling catalysts are mainly discussed. Organic amine ionic liquids have superior alkylation effects to imidazoles. Anions and modified ionic liquids could form specific structures to maintain the acid strength of the reaction systems and reduce side reactions so as to extend the life of the catalysts. The coupling acids provide acidic sites for the reaction and cooperate with ionic liquids. Finally, the ionic liquid-acid coupling catalytic system which has the advantages of low acid consumption, good stability, resistant inactivation and easy recycling, is one of the development directions of the C_4 alkylation catalyst in the future.
引文
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[36]MA H,ZHANG R,MENG X H,et al.Solid formation during composite-ionic-liquid-catalyzed isobutane alkylation[J].Energy&Fuels,2014,28(8):5389-5395.
[37]WANG H,MENG X Z,ZHAO G Y,et al.Isobutane/butene alkylation catalyzed by ionic liquids:a more sustainable process for clean oil production[J].Green Chemistry,2017,19(6):1462-1489.
[2]于兆臣,田文君.FCC汽油生产国Ⅵ汽油工艺路线的工业应用[J].炼油技术与工程,2017,47(8):11-15.YU Z C,TIAN W J.Industrial application of process route of FCCgasoline producing GUOⅥgasoline[J].Refining Technology and Engineering,2017,47(8):11-15.
[3]王傲运.离子材料协同酸催化C4烷基化反应研究[D].石家庄:河北科技大学,2016.WANG A Y.Ionic liquid material and acid synergistically catalyzed C4alkylation[D].Shijiazhuang:Hebei University of Science and Technology,2016.
[4]杨为民.碳四烃转化与利用技术研究进展及发展前景[J].化工进展,2015,34(1):1-9.YANG W M.Progress and perspectives on conversion and utilization of C4hydrocarbons[J].Chemical Industry and Engineering Progress,2015,34(1):1-9.
[5]彭凯,张成喜,李永祥,等.异丁烷/丁烯烷基化固体酸催化剂的再生方法研究进展[J].化工进展,2015,34(9):3296-3302.PENG K,ZHANG C X,LI Y X,et al.Advances in regeneration methods of solid acid catalyst for isobutane/butene alkylation[J].Chemical Industry and Engineering Progress,2015,34(9):1-9.
[6]BUI T L T,KORTH W,ASCHAUER S,et al.Alkylation of isobutane with 2-butene using ionic liquids as catalyst[J].Green Chemistry,2009,11(12):1961-1967.
[7]闵恩泽,李成岳.绿色石化技术的科学与工程基础[M].北京:中国石化出版社,2002:298-311.MIN E Z,LI C Y.Science and engineering foundation of green petrochemical technology[M].Beijing:China Petrochemical Press,2002:298-311.
[8]GAN P X,TANG S W.Research progress in ionic liquids catalyzed isobutane/butenealkylation[J].ChineseJournalofChemical Engineering,2016,24(11):1497-1504.
[9]OLAH G A,BATAMACK P,DEFFIEUX D,et al.Acidity dependence of the trifluoromethanesulfonic acid catalyzed isobutane/isobutylene alkylation modified with trifluoroacetic acid or water[J].Applied Catalysis A:General,1996,146(1):107-117.
[10]REN H L,ZHAO G Y,ZHANG S J,et al.Triflic acid catalyzed isobutane alkylation with trifluoroethanol as a promoter[J].Catalysis Communications,2012,18(18):85-88.
[11]ZHAO Z B,SUN W D,YANG X G,et al.Study of the catalytic behaviors of concentrated heteropolyacid solution.I.A novel catalyst for isobutane alkylation with butenes[J].Catalysis Letters,2000,65(1/2/3):115-121.
[12]赵振波.异丁烷-丁烯烷基化杂多酸-醋酸催化机理[J].物理化学学报,2000,16(7):613-620.ZHAO Z B.Active components and mechanism of Isobutane alkylation with butenes in the catalytic system of HPAs+AcOH[J].Acta PhysicoChimica sinica,2000,16(7):613-620.
[13]杨美,钟向宏,陈群.离子液体催化二氧化碳合成环状碳酸酯的研究进展[J].化工进展,2017,36(9):3300-3308.YANG M,ZHONG X H,CHEN Q.Recent progress of the synthesis of cyclic carbonates from CO2and epoxides catalyzed by ionic liquids[J].Chemical Industry and Engineering Progress,2017,36(9):3300-3308.
[14]李海方.离子液体酸催化异丁烷烷基化反应的研究[D].石家庄:河北科技大学,2013.LI H F.Study on isobutane alkylation utilizing ionic liquid/acid as catalyst[D].Shijiazhuang:Hebei University of Science and Technology,2013.
[15]孟祥海,张睿,刘海燕,等.复合离子液体碳四烷基化技术开发与应用[J].中国科学:化学,2018(4):387-396.MENG X H,ZHANG R,LIU H Y,et al.Development and application of composite ionic liquid catalyzed isobutane alkylation technology[J].Scientia Sinica Chimica,2018(4):387-396.
[16]胡静,张涛,张帅,等.[BMim][HSO4]/H2SO4二元体系的黏度及其表面张力[J].石油化工,2017,46(9):1161-1167.HU J,ZHANG T,ZHANG S,et al.Viscosity and surface tensions of[BMim][HSO4]/H2SO4binary system[J].Petrochemical Technology,2017,46(9):1161-1167.
[17]CONG Y,LIU Y,HU R.Isobutane/2-butene alkylation catalyzed by strong acids in the presence of ionic liquid additives[J].Liquid Fuels Technology,2014,32(16):1981-1987.
[18]TANG S W,SCURTO A M,SUBRAMANIAM B.Improved 1-butene/isobutane alkylation with acidic ionic liquids and tunable acid/ionic liquid mixtures[J].Journal of Catalysis,2009,268(2):243-250.
[19]刘鹰,胡瑞生,刘贵丽,等.酸性离子液体催化的异丁烷/丁烯烷基化反应研究[J].分子催化,2010,24(3):217-221.LIU Y,HU R S,LIU G L,et al.Study on the alkylation of isobutane/butene in acidic ionic liquids[J].Journal of Molecular Catalysis,2010,24(3):217-221.
[20]ZHANG Y,ZHANG T,GAN P X,et al.Solubility of isobutane in ionic liquids[BMIm][PF6],[BMIm][BF4],and[BMIm][Tf2N][J].Journal of Chemical&Engineering Data,2015,60(6):1709-1714.
[21]CUI P,ZHAO G Y,REN H L,et al.Ionic liquid enhanced alkylation of iso-butane and 1-butene[J].Catalysis Today,2013,200(1):30-35.
[22]ZHENG W Z,WANG H Y,XIE W X,et al.Understanding interfacial behaviors of isobutane alkylation with C4olefin catalyzed by sulfuric acid or ionic liquids[J].AIChE Journal,2017,64(3):958-959.
[23]WANG P,WANG D X,XU C M,et al.DFT calculations of the alkylation reaction mechanisms of isobutane and 2-butene catalyzed by Br?nsted acids[J].Applied Catalysis A:General,2007,332(1):22-26.
[24]XING X Q,ZHAO G Y,CUI J Z,et al.Isobutane alkylation using acidic ionic liquid catalysts[J].Catalysis Communications,2012,26(26):68-71.
[25]张锁江,刘瑞霞,赵国英,等.一种硫酸和离子液体复合催化剂催化生产烷基化汽油的方法:CN106939173A[P].2017-07-11.ZHANG S J,LIU R X,ZHAO G Y,et al.Method for catalyzing production of alkylated gasoline by using a composite catalyst of sulfuric acid and ionic liquid:CN106939173A[P].2017-07-11.
[26]ZHANG H H,LIU R X,YANG Z Q,et al.Alkylation of isobutane/butene promoted by fluoride-containing ionic liquids[J].Fuel,2018,211:233-240.
[27]张锁江,周志茂,杨飞飞,等.一种含离子液体和硝酸的混酸体系催化合成烷基化油的方法:CN106010636A[P].2016-10-12.ZHANG S J,ZHOU Z M,YANG F F,et al.Method for synthesizing alkylated oil by mixed acid system containing ionic liquid and nitric acid:CN106010636A[P].2016-10-12.
[28]WANG A Y,ZHAO G Y,LIU F F,et al.Anionic clusters enhanced catalytic performance of protic acid ionic liquids for isobutane alkylation[J].Industrial&Engineering Chemistry Research,2016,55(30):8271-8280.
[29]HUANG Q,ZHAO G Y,ZHANG S J,et al.Improved catalytic lifetime of H2SO4for isobutane alkylation with trace amount of ionic liquids buffer[J].Industrial&Engineering Chemistry Research,2015,54(5):1464-1469.
[30]ZHENG W Z,HUANG C Z,SUN W Z,et al.Microstructures of the sulfonic-acid-functionalized ionic liquid/sulfuric acid and their interactions:a perspective from the isobutane alkylation[J].Journal of Physical Chemistry B,2018,122(4):1460-1470.
[31]卢丹,赵国英,任保增,等.醚基功能化离子液体合成及催化烷基化反应[J].化工学报,2015,66(7):2481-2487.LU D,ZHAO G Y,REN B Z,et al.Isobutane alkylation catalyzed by ether functionalized ionic liquids[J].CIESC Journal,2015,66(7):2481-2487.
[32]YU F L,LI G X,GU Y L,et al.Preparation of alkylate gasoline in polyether-based acidic ionic liquids[J].Catalysis Today,2018,310:141-145.
[33]刘鹰,孙宏娟,丛迎楠,等.Cu对离子液体异丁烷/丁烯烷基化反应选择性的影响研究[J].燃料化学学报,2014,42(8):1003-1009.LIU Y,SUN H J,CONG Y N,et al.Study on the selectivity of isobutane/2-butene alkylation catalyzed by ionic liquid with Cu compound[J].Journal of Fuel Chemistry and Technology,2014,42(8):1003-1009.
[34]HU P C,WANG Y D,MENG X H,et al.Isobutane alkylation with 2-butene catalyzed by amide-AlCl3-based ionic liquid analogues[J].Fuel,2017,189:203-209.
[35]LIU Y,LI R,SUN H J,et al.Effects of catalyst composition on the ionic liquid catalyzed isobutane/2-butene alkylation[J].Journal of Molecular Catalysis A Chemical,2015,398:133-139.
[36]MA H,ZHANG R,MENG X H,et al.Solid formation during composite-ionic-liquid-catalyzed isobutane alkylation[J].Energy&Fuels,2014,28(8):5389-5395.
[37]WANG H,MENG X Z,ZHAO G Y,et al.Isobutane/butene alkylation catalyzed by ionic liquids:a more sustainable process for clean oil production[J].Green Chemistry,2017,19(6):1462-1489.