异构化制清洁汽油工艺及催化剂

doi:10.16085/j.issn.1000-6613.2016.08.23

摘要/Abstract

摘要： 介绍了异构化工艺制清洁汽油的研究现状，综述了近年来国内外轻石脑油异构化工艺及催化剂的应用与发展。简述了目前国内外主要工业化应用的异构化工艺。从活性金属和载体两方面简单介绍了双功能型金属/酸异构化催化剂的研究与发展。着重阐述了固体超强酸异构化催化剂的特点，详细说明了通过促进剂、载体及活性金属元素的引入等方面对SO₄^2-/ZrO₂型固体超强酸异构化催化剂改性方面的研究进展。通过对目前已商业应用的异构化工艺的对比，对异构化催化剂所面临的主要问题进行探讨。最终指出异构化制清洁汽油将成为我国汽油生产的重要技术手段之一，经济、环保、高效的固体超强酸催化剂将大规模工业应用于异构化催化中。

关键词: 异构化, 催化剂, 轻质烷烃, 固体超强酸, 清洁汽油, 高辛烷值

Abstract: The research status of isomerization process for producing clean gasoline is introduced. The domestic and foreign application and development of light naphtha isomerization and its catalyst in recent years are reviewed. From two sides of active metal and support,the research and development of metal-acid bifunctional catalyst are briefly introduced. The characteristic of solid superacid is mainly expounded. The research progress in modification of SO₄^2-/ZrO₂ solid superacid isomerization catalyst by introducing promoter,support,active metal elements are described in detail. Through the comparison of commercial isomerization process,the problems of isomerization catalyst are discussed. In the future,isomerization process will become the major technology for the production of clean gasoline. Inexpensive,environmental-friendly and efficient solid superacid catalyst will be widely applied in the industrial isomerization process.

Key words: isomerization, catalyst, light paraffin, solid superacid, clean gasoline, high octane number

中图分类号:

TQ426.8

赵文康, 樊洁, 朱博超, 蒙延双, 朱福良, 刘小燕. 异构化制清洁汽油工艺及催化剂[J]. 化工进展, 2016, 35(08): 2455-2463.

ZHAO Wenkang, FAN Jie, ZHU Bochao, MENG Yanshuang, ZHU Fuliang, LIU Xiaoyan. Isomerization process for producing clean gasoline and the catalyst[J]. Chemical Industry and Engineering Progree, 2016, 35(08): 2455-2463.

参考文献

[1] 李劭,王昊,王曼曼. C₅/C₆异构化技术及进展[J]. 当代化工,2014,43(5):858-862.
[2] 徐铁钢,吴显军,王刚,李瑞峰. 轻质烷烃异构化催化剂研究进展[J]. 化工进展,2015,34(2):397-401.
[3] 马爱增,于中伟,张秋平,等. 从石脑油和轻烃资源增产汽油的技术及措施[J]. 石油炼制与化工,2009,40(11):1-7.
[4] HATTORI H. Solid acid catalysts:roles in chemical industries and new concepts[J]. Topics in Catalysis,2010,53(7/8/9/10):432-438.
[5] 龚金双. 2014年中国石油市场回顾与2015年展望[J]. 中国石油和化工经济分析,2015,2:31-35.
[6] 任建生. 轻质烷烃异构化工艺技术[J]. 炼油技术与工程,2013(7):28-31.
[7] CHEKANTSEV N V,GYNGAZOVA M S,IVANCHINA E D. Mathematical modeling of light naphtha (C₅,C₆)isomerization process[J]. Chemical Engineering Journal,2014,238:120-128.
[8] 徐春明,杨朝合. 石油炼制工程[M]. 4版. 北京:石油工业出版社,2009:515-519.
[9] VALAVARASU G,SAIRAM B. Light naphtha isomerization process:a review[J]. Petroleum Science and Technology,2013,31(6):580-595.
[10] 田爱珍,杨周侠,汪毅,等. 轻石脑油异构化工艺技术研究进展[J].应用化工,2015,44(3):558-562.
[11] HIDALGO J,ZBUZEK M,ČERNÝ R,et al. Current uses and trends in catalytic isomerization,alkylation and etherification processes to improve gasoline quality[J]. Open Chemistry,2014,12(1):1-13.
[12] 易玉峰,丁福臣,李术元. 轻质烷烃异构化进展述评[J]. 北京石油化工学院学报,2003,11(1):44 -50.
[13] SULLIVAN D,METRO S,PUJADÓ P R. Isomerization in Petroleum Processing[M]. TREESE S A,JONES D S,PUJADO P R,ed. Handbook of Petroleum Processing. Switzerland:Springer,2015:479-497.
[14] YASAKOVA E A,SITDIKOVA A V,ACHMETOV A F. Tendency of isomerization process development in russia and foreign countries[J]. Oil and Gas Business,2010,1:1-7.
[15] JONES D S J,PUJADÓ P R. Handbook of Petroleum Processing[M]. Springer Science & Business Media,2006:400-415.
[16] 李瑞峰,宋华,李峰,等. 烷烃异构化的研究进展[J]. 辽宁化工,2006,35(8):494-496.
[17] 国海峰,董群,胡云峰. 介孔分子筛在长链正构烷烃异构化中的研究进展[J]. 化学工业与工程,2008,25(4):349-352.
[18] 刘志,马骏. 固体超强酸催化剂的研究与发展[J]. 当代化工,2015,44(10):2384-2387.
[19] WU Y,LIAO S. Review of SO₄²^-/M_xO_y solid superacid catalysts[J]. Frontiers of Chemical Engineering in China,2009,3(3):330-343.
[20] 贾娜. 杂多型和双金属型固体酸的制备及其催化性能研究[D]. 兰州:西北师范大学,2014:10-17.
[21] SHAKUN A N,FEDOROVA M L. Isomerization of light gasoline fractions:the efficiency of different catalysts and technologies[J]. Catalysis in Industry,2014,6(4):298-306.
[22] 于中伟,孙义兰,任坚强,等. 固体超强酸催化C₅/C₆烷烃异构化反应[J]. 石油学报(石油加工),2010(1):89-92.
[23] 张旭,宋华. 固体超强酸催化剂改性的研究进展[J]. 当代化工,2010,39(2):183-185.
[24] 宋华,杨东明,李锋,等. SO₄²^-/M_xO_y 型固体超强酸催化剂的研究进展[J]. 化工进展,2007,26(2):145-151.
[25] 马千里,所艳华,孟凡龙,等. SO₄²^-/M_xO_y型固体超强酸催化剂改性及应用研究进展[J]. 工业催化,2014,22(2):85-91.
[26] TANABE K. Surface and catalytic properties of ZrO₂[J]. Materials Chemistry and Physics,1985,13(3):347-364.
[27] HINO M,ARATA K. Synthesis of solid superacid of tungsten oxide supported on zirconia and its catalytic action for reactions of butane and pentane[J]. Journal of the Chemical Society,Chemical Communications,1988,18:1259-1260.
[28] ARATA K,HINO M. Preparation of superacids by metal oxides and their catalytic action[J]. Materials Chemistry and Physics,1990,26(3):213-237.
[29] ARATA K,HINO M. Solid catalyst treated with anion ⅩⅦ:Benzylation of toluene with benzoyl chloride and benzoic anhydride catalysed by solid superacid of sulfate—supposed alumina[J]. Applied Catalysis,1990,59(1):197-204.
[30] 汪颖军,高志国,所艳华. SO₄²^-/ZrO₂固体超强酸的制备与改性[J]. 石化技术与应用,2015,33(3):269-275.
[31] 汪颖军,刘成双,李小辉. SO₄²^-/ZrO₂催化烷烃异构化反应的研究进展[J]. 石油化工,2010(1):94-99.
[32] ZHAN Li,WANG Lin,CHEN Jianmin. n-Butane isomerization on peroxosulfated zirconia solid superacid catalyst[J]. Journal of Fudan University,1999,38(6):648-651.
[33] 宋国新,王琳,薛华欣,等. S₂O₈^2-和SO₄^2-促进ZrO₂固体超强酸正戊烷反应性能差异的研究[J]. 高等学校化学学报,2003,24(1):130-134.
[34] KUZNETSOVA L I,KAZBANOVA A V,KUZNETSOV P N. The catalytic properties of tungstated zirconia in n-heptane isomerization[J]. Petroleum Chemistry,2012,52(2):86-90.
[35] SHKURENOK V A,SMOLIKOV M D,YABLOKOVA S S,et al. Pt/WO₃/ZrO₂ Catalysts for n-heptane isomerization[J]. Procedia Engineering,2015,113:62-67.
[36] BUSTO M,SHIMIZU K,VERA C R,et al. Influence of hydrothermal aging on the catalytic activity of sulfated zirconia[J]. Applied Catalysis A:General,2008,348(2):173-182.
[37] 焦卫勇,李福祥,周梅梅,等. SO₄^2-/Zr-SBA-15 介孔材料的合成及其催化性能[J]. 石油化工,2010,39(6):620-624.
[38] SUN Y Y,YUAN L,WANG W,et al. Mesostructured sulfated zirconia with high catalytic activity in n-butane isomerization[J]. Catalysis letters,2003,87(1/2):57-61.
[39] REDDY B M,SREEKANTH P M,REDDY V R. Modified zirconia solid acid catalysts for organic synthesis and transformations[J]. Journal of molecular catalysis A:chemical,2005,225(1):71-78.
[40] VIJAY S,WOLF E E. A highly active and stable platinum-modified sulfated zirconia catalyst:1. Preparation and activity for n-pentane isomerization[J]. Applied Catalysis A:General,2004,264(1):117-124.
[41] SMOLIKOV M D,KAZANTSEV K V,ZATOLOKINA E V,et al. Study of n-hexane isomerization on Pt/SO₄²^-/ZrO₂/Al₂O₃ catalysts:effect of the state of platinum on catalytic and adsorption properties[J]. Kinetics and Catalysis,2010,51(4):584-594.
[42] SONG H,WANG N,SONG H L,et al. Effect of Pd content on the isomerization performance over Pd-S₂O₈²^-/ZrO₂-Al₂O₃ catalyst[J]. Research on Chemical Intermediates,2016,42(2):951-962.
[43] PEREZ-LUNA M,ANTONIO J A T,MONTOYA A,et al. n-Hexane isomerization over NiO/SO₄²^-/ZrO₂ catalysts. effect of nickel loading[J]. Catalysis letters,2004,97(1/2):59-64.
[44] SONG H,CUI H,SONG H,et al. The effect of Zn-Fe modified S₂O₈²^-/ZrO₂-Al₂O₃ catalyst for n-pentane hydroisomerization[J]. Research on Chemical Intermediates,2016,42:3029-3038.
[45] KAMOUN N,YOUNES M K,GHORBEL A,et al. Comparative study of aerogels nanostructured catalysts:Ni/ZrO₂-SO₄²^-and Ni/ZrO₂-Al₂O₃-SO₄²^-[J]. Ionics,2015,21(1):221-229.
[46] 曹崇江,陈长林,徐南平. 镓掺杂SO₄^2-/ZrO²的制备及其对正丁烷异构化反应的催化性能[J]. 催化学报,2003,24(6):447-451.
[47] HINO M,ARATA K. Preparation of superacid of ruthenium-sulfated zirconia for reaction of butane to isobutane[J]. Reaction kinetics and catalysis letters,1999,66(2):331-336.
[48] WEI R P,WANG J,GU Y. Usy supported Pt-bearing SO₄²^-/ZrO₂ catalysts promoted by Cr for hydroisomerization of n-heptane[J]. Reaction Kinetics and Catalysis Letters,2007,90(2):315-322.
[49] SILVA-RODRIGO R,CRUZ-DOMÍNGUEZ E L,LUGO-DEL Angel F E,et al. Studies of sulphated mixed oxides(ZrO₂-SO₄^2--La₂O₃)in the isomerization of n-hexane[J]. Catalysis Today,2015,250:197-208.