Light paraffin isomerizadon catalyst and its development

doi:10.16085/j.issn.1000-6613.2015.02.015

Abstract

Abstract: The research status and development trend of light paraffin isomerization is reviewed. Characteristics of the light paraffin isomerization process are summarized. Some commercial catalysts are introduced,and the performance parameters of reaction temperature,RON,antitoxicity are compared. Based on components and support,the development of light paraffin isomerization catalysts is reviewed with respect to Pt/zeolite,Pt/ZrO₂-SO₄,heteropoly acids,Pt/WO₃-ZrO₂,mesoporous materials,Molybdenum based catalysts,ionic liquids,and some problems in the study of catalysts are indicated. In the future,lower reaction temperature and antitoxicity catalyst will be paid increasing attention.

Key words: light paraffin, isomerization, hydrogenation, catalyst, catalyst support

摘要： 综述了轻质烷烃异构化催化剂的研究现状及发展趋势,总结了轻质烷烃异构化反应的特点,介绍了有代表性的氯化铝型、分子筛型、固体超强酸型轻质烷烃异构化工业催化剂,并分别从反应温度、产品辛烷值、抗毒性等方面对比了几种工业催化剂的性能及优缺点。重点从活性组分和载体两方面描述了各类轻质烷烃异构化催化剂的最新研究进展,包括Pt/zeolite、Pt/ZrO₂-SO₄、杂多酸、Pt/WO₃-ZrO₂、介孔材料、钼基催化剂、离子液体等,同时提出了催化剂研究中面临的一些问题。最后指出了低温、高抗毒性的轻质烷烃异构化催化剂将是未来研究的焦点。

关键词: 轻质烷烃, 异构化, 加氢, 催化剂, 催化剂载体

CLC Number:

TQ426.8

XU Tiegang, WU Xianjun, WANG Gang, LI Ruifeng. Light paraffin isomerizadon catalyst and its development[J]. Chemical Industry and Engineering Progree, 2015, 34(02): 397-401.

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(02): 397-401.

References

[1] 姚国欣. 面向21世纪的车用清洁燃料生产技术[J]. 石油炼制与化工,2000,31(1):1-5.
[2] 易玉峰,丁福臣,李术元. 轻质烷烃异构化进展评述[J]. 北京石油化工学院学报,2003,11(1):44-49.
[3] 赵旺华. C₅/C₆异构化技术方案对比与应用分析[J]. 海峡科学,2012,69(9):15-17.
[4] 刘颖涛. C₅/C₆烷烃异构化研究进展[J]. 化学工程师,2004,106(7):52-53.
[5] 郑冬梅. C₅/C₆烷烃异构化生产工艺及进展[J]. 石油化工设计,2004,21(3):1-5.
[6] 张永铭. 引进轻石脑油异构化装置的工艺设计[J]. 石油炼制与化工,2012,43(8):17-21.
[7] 胡云峰. 利用轻石脑油异构化技术生产优质汽油调和组分[J]. 中外能源,2013,18(6):61-64.
[8] 鄢德怀,李德飞. 烷烃临氢异构化技术及进展概述[J]. 2007,36(5):441-443.
[9] 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.
[10] Alvarez F,Ribeiro F R,Perot G,et al. Hydroisomerization and hydrocracking of alkanes:7. Influence of the balance between acid and hydrogenating functions on the transformation of n-decane on PtHY catalysts[J]. Journal of Catalysis,1996,162:179-189.
[11] 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.
[12] Yasakova E A,Sitdikova A V. Tendency of isomerization process development[J]. Oil and Gas Business,2010(1):1-13.
[13] Valavarasu G,Sairam B. Light naphtha isomerization process:A review[J]. Petroleum Science and Technology,2013,31:580-595.
[14] Hidalgo J M,Zbuzek M,Cerny R,et al. Current uses and trends in catalytic isomerization,alkylation and etherification processes to improve gasoline quality[J]. Central European Journal of Chemistry,2014,12(1):1-13.
[15] 温天红,郑晓军,张秋平,等. RISO异构化技术在新疆泽普石化厂的应用[J]. 石油炼制与化工,2007,38(2):30-33.
[16] 胡尧良,韩松,吴正太,等. 载钯分子筛C₅/C₆异构化催化剂工业应用[J]. 催化重整通讯,2004(4):64-65.
[17] 濮仲英,金欣,张秋平,等. 碳五、碳六烷烃异构化方法:中国,1345914[P]. 2002-04-24.
[18] Hanafi S A,Gobara H M,Elmelawy M S. Catalytic behavior of Pt nanoparticles dealuminated Y-zeolite for some n-alkane hydroisomerization[J]. Egyptian Journal of Petroleum,2014,23(2):151-161.
[19] Ramos M J,Lucas A,Jiménez V,et al. Hydroisomerization of different refinery naphtha streams by using a beta zeolite catalyst[J]. Fuel Processing Technology,2008,89(8):721-727.
[20] Chi Kebin,Zhao Zhen,Tian Zhijian,et al. Hydroisomerization performance of platinum supported on ZSM-22/ZSM-23 intergrowth zeolite catalyst[J]. Petroleum Science,2013,10:242-250.
[21] Gopal S,Smirniotis P G. Pt/H-ZSM-12 as a catalyst for the hydroisomerization of C₅-C₇ n-alkanes and simultaneous saturation of benzene[J]. Applied Catalysis A:General,2003,247(1):113-123.
[22] 卢信清,郭玉萍,许春慧,等. 第16届全国催化大会论文集[C]. 沈阳:中国化学会催化委员会,2012.
[23] 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,2010,26(s1):88-92.
[24] 潘晖华,于中伟,濮仲英,等. 一种低碳烷烃异构化催化剂及制备方法:中国,1541764A [P]. 2004-11-03.
[25] Serra J M,Chica A,Corma A. Development of a low temperature light paraffin isomerization catalysts with improved resistance to water and sulphur by combinatorial methods[J]. Applied Catalysis A:General,2003,239:35-42.
[26] Kuang W X,Rives A,Fournier M,et al. Hubaut structure and reactivity of silica-supported 12-tungstophosphoric acid[J]. Applied Catalysis A:General,2003,250(2):221-229.
[27] Miyaji A,Ohnishi R,Okuhar T. Skeletal isomerization of n-heptane over Pd-H₄SiW₁₂O₄₀ supported on SiO₂:Comparative study with typical bifuncitional catalysts[J]. Applied Catalysis A:General,2004,262(2):143-148.
[28] Na K,Okuhara T,Misono M. Skeletal isomerization of n-butane catalyzed by an acidic cesium salt of 12-tungstophosphoric acid[J]. Chemistry Letters,1993,7:1141-1144.
[29] 王清遐,刘晓萍,徐龙伢,等. 一种正构烷烃异构化催化剂及应用:中国,1465436A[P]. 2004-01-07.
[30] Pinto T,Dufaud V,Lefebvre F. Isomerization of n-hexane on heteropolyacids supported on SBA-15.1. monofunctional impregnated catalysts[J]. Applied Catalysis A:General,2014,483:103-109.
[31] 程晓晶,程伟,王雪枫. 直馏汽油在纳米ZSM-5上的异构化反应研究[J]. 石油炼制与化工,2013,44(7):48-52.
[32] Mishra G S,Kumar A. Hydroisomerization of saturated hydrocarbons with novel MCM-41 immobilized Re(Ⅴ) complex catalysts[J]. Applied Catalysis A:General,2012,429(2):1-8.
[33] Song Yueqin,Zhang Juanjuan,Zhou Xiaolong,et al. WO₃ microcrystallites:One of the crucial factors controlling the isomerization activity of Pt/WO₃-ZrO₂[J]. Catalysis Today,2011,166(1):67-72.
[34] Benitez V M,Grau J M,Yori J C,et al. Hydroisomerization of benzene-containing paraffinic feedstocks over Pt/WO₃-ZrO₂ catalysts[J]. Energy & Fuels,2006,20(5):1791-1798.
[35] Xu Jinsuo,Ying Jackie Y. A highly active and selective nanocomposite catalyst for C₇+paraffin isomerization[J]. Angewandte Chemie International Edition,2006,45(40):6700-6704.
[36] 杜宇乔,陈晓蓉,陈长林,等. Pt/Al₂O₃/WO₃/ZrO₂催化剂对正己烷异构化反应的催化性能[J]. Chinese Journal of Catalysis,2006,27(5):397-402.
[37] 普拉泰罗 S,卡拉提 A,贝鲁希G,等. 钼基催化剂及其在正烷烃异构化反应中的应用:中国,1243037A[P]. 2000-02-02.
[38] 王光维,宁春利,赵晓非. 正戊烷异构化双非金属催化剂的研究[J]. 石油学报:石油加工,1998,14(1):52-56.
[39] 杨淑清,竺柏康,郑贤敏,等. 一种催化正构烷烃异构化生产异构烷烃的方法:中国,102924213 A[P]. 2013-02-13.
[40] 罗琛,田志坚,潘晖华,等. 一种正构烷烃异构化催化剂的应用:中国,103373886 A[P]. 2013-10-30.