[1]刘平,冯晓奇,王军,等.正庚烷异构化催化剂的研究进展[J].常州大学学报(自然科学版),2017,(03):25-33.[doi:10.3969/j.issn.2095-0411.2017.03.005]
　LIU Ping,FENG Xiaoqi,WANG Jun,et al.Research of Catalysts for Isomerization of n-Heptane[J].Journal of Changzhou University(Natural Science Edition),2017,(03):25-33.[doi:10.3969/j.issn.2095-0411.2017.03.005]
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正庚烷异构化催化剂的研究进展()
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常州大学学报(自然科学版)[ISSN:2095-0411/CN:32-1822/N]

卷:
期数:
2017年03期
页码:
25-33
栏目:
化学化工
出版日期:
2017-05-28

文章信息/Info

Title:
Research of Catalysts for Isomerization of n-Heptane
作者:
刘平1; 冯晓奇1; 2; 王军3; 李永昕1
1.常州大学 石油化工学院,江苏 常州213164; 2.无锡百川化工股份有限公司,江苏 无锡 214400; 3.南京工业大学 化学化工学院,江苏 南京 210009
Author(s):
LIU Ping1; FENG Xiaoqi1; 2; WANG Jun3; LI Yongxin1
1. School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China; 2. Wuxi Baichuan Chemical Industrial Co. Ltd., Wuxi 214400, China; 3. College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China
关键词:
正庚烷;  异构化;  辛烷值;  双功能催化剂
Keywords:
n-heptane;  isomerization;  octane number;  bifunctional catalyst
分类号:
TQ 426.95
DOI:
10.3969/j.issn.2095-0411.2017.03.005
文献标志码:
A
摘要:
直馏汽油中含有较多的正庚烷,通过异构化反应提高正庚烷的辛烷值是提高汽油质量的重要过程之一。实现正庚烷异构化过程的关键在于开发高效的催化剂。综述了正庚烷异构化催化剂的研究进展,并提出了研究方向。
Abstract:
Straight-run gasoline contains more n-heptane, and isomerization reaction of n-heptane to increase the octane number is one of the important processes to improve the quality of gasoline. The key to realize the isomerization process of n-heptane is to develop efficient catalysts. The catalysts of n-heptane isomerization are reviewed in this paper, and the research direction is put forward.

参考文献/References:

[1]CHICA A, CORMA A. Hydroisomerization of pentane, hexane, and heptane for improving the octane number of gasoline[J]. J Catal, 1999, 187(1): 167-176.
[2]HEPP H J, DREHMAN L E. Isomerization of normal-heptane aluminum chloride hydrocarbon complex catalyst[J]. Ind Eng Chem, 1960, 52(3): 207-210.
[3]CORMA A, PLANELLES J, TOMAS F. The influence of branching isomerization on the product distribution obtained during cracking of normal-heptane on acidic zeolites[J]. J Catal, 1985, 94(2): 445-454.
[4]HECK R H, CHEN N Y. Hydrocracking of normal-butane and normal-heptane over a sulfided nickel erionite catalyst[J]. Appl Catal A, 1992, 86(2): 83-99.
[5]张春勇, 刘靖, 王祥生. 分子筛催化剂在异构化反应中的研究进展[J]. 工业催化, 2004, 12(6): 1-5.
[6]CAMPELO J M, LAFONT F, MARINAS J M. Comparison of the activity and selectivity of Pt/SAPO-5 and Pt/SAPO-11 in n-hexane and n-heptane hydroconversion[J]. Appl Catal A, 1997, 152(1): 53-62.
[7]ABUDAWOOD R H, ALOTAIBI F M, GARFORTH A A. Hydroisomerization of n-heptane over Pt-loaded USY zeolites. Effect of steaming, dealumination, and the resulting structure on catalytic properties[J]. Ind Eng Chem Res, 2011, 50(17): 9918-9924.
[8]REMY M J, STANICA D, PONCELET G, et al. Dealuminated H-Y zeolites: relation between physicochemical properties and catalytic activity in heptane and decane isomerization[J]. J Phys Chem, 1996, 100: 12440-12447.
[9]王军, 林臻, 张玉辉,等. Pt/脱铝Y沸石催化剂上正庚烷加氢异构化[J]. 石油化工, 2001, 30(7): 509-513.
[10]GU Y, WEI R, REN X, et al. Cs salts of 12-tungstophosphoric acid supported on dealuminated USY as catalysts for hydroisomerization of n-heptane[J]. Catal Lett, 2007, 113(1/2): 41-45.
[11]WANG Z B, KAMO A, YONEDA T, et al. Isomerization of n-heptane over Pt-loaded zeolite β catalysts[J]. Appl Catal A, 1997, 159(1/2): 119-132.
[12]CHAO K J, LEU C L. Hydroisomerization of light normal paraffin’s over series of platinum-loaded mordenite and beta catalysts[J]. Appl Catal A, 1996, 143(2): 223-243.
[13]ARRIBAS M A, MARQUEZ F, MARTINEZ A. Activity, selectivity, and sulfur resistance of Pt/WOx-ZrO2 and Pt/Beta catalysts for the simultaneous hydroisomerization of n-heptane and hydrogenation of benzene[J]. J Catal, 2000, 190(2): 309-319.
[14]SANCHEZ P, RAMOS F, ROMERO M J, et al. Hydroisomerization of C6-C8 n-alkanes, cyclohexane and benzene over palladium and platinum beta catalysts agglomerated with bentonite[J]. Appl Catal A, 2006, 314(2): 248-255.
[15]CAMPELO J M, LAFONT F, MARINES J M. Hydroisomerization and hydrocracking of n-heptane on Pt/SAPO-5 and Pt/SAPO-11 catalysts[J]. J Catal, 1995, 156(1): 11-18.
[16]JIN D, LIU Z, ZHENG J, et al. Nonclassical from-shell-to-core growth of hierarchically organized SAPO-11 with enhanced catalytic performance in hydroisomerization of n-heptane[J]. Rsc Adv, 2016, 6(39): 32523-32533.
[17]CUI X, LIU Y, LIU X. Controlling acidic sites to improve hydroisomerization performance of Pt/SAPO-11 catalysts[J]. Catal Lett, 2015, 145(7): 1464-1473.
[18]PEYROVI M H, HAMOULE T. Study of catalytic properties of Pt/Al-HMS catalysts in n-heptane hydroisomerization[J]. Reac Kinet Mech Cat, 2012, 106(1): 233-243.
[19]HAMOULE T, PEYROVI M H, RASHIDZADEH M, et al. Catalytic reforming of n-heptane over Pt/Al-HMS catalysts[J]. Catal Commun, 2011, 16(1): 234-239.
[20]PEYROVI M H, PARSAFARD N, PEYROVI P. Influence of zirconium addition in platinum-hexagonal mesoporous silica(Pt-HMS)catalysts for reforming of n-heptane[J]. Ind Eng Chem Res, 2014, 53(37): 14253-14262.
[21]YANG X, WANG J A, CHEN L, et al. Heteropolyacid grafted Pt/Si-MCM-41 catalyst for C7 skeletal isomerization[J]. Catal Commun, 2012, 28: 202-206.
[22]HIDALGO J M, PINEDA A, ARANCON R A D, et al. Continuous-flow hydroisomerization of C5-C7 alkanes using mechanochemically synthesized supported Pt and Pd-SBA-15 materials[J]. J Flow Chem, 2015, 5(1): 11-16.
[23]WANG Y, CUI Y, SUO Y, et al. Influences of cerium on structure and catalytic performance of n-heptane hydroisomerization of Ni-HPW/MCM-48[J]. J Rare Earth, 2015, 33(1): 46-55.
[24]SUO Y, CHEN G, WANG Y, et al. Hydroisomerization of n-heptane over HPMo-Ni/Ce-MCM-48 catalysts[J]. Asian J Chem, 2014, 26(17): 5505-5508.
[25]LIU D, HU S, LAU R, et al. Hydroconversion of n-heptane over Pt/Al-MCM-41 mesoporous molecular sieves[J]. Chem Eng J, 2009, 151: 308-318.
[26]王道宏, 王延吉, 王日杰, 等. 固体超强酸在催化正己烷异构化反应中失活的研究[J]. 石油学报(石油加工), 2004, 20: 81-87.
[27]YU G X, ZHOU X L, LIU F, et al. Effect of isopropanol aging of Zr(OH)4 on n-hexane isomerization over Pt-SO2-4/Al2O3-ZrO2[J]. Catal Today, 2009, 148: 70-74.
[28]F?TTINGER K, ZORN K, VINEK H. Influence of the sulfate content on the activity of containing sulfated zirconia[J]. Appl Catal A, 2005, 284: 69-75.
[29]IGLESIA E, SOLED S L, KRAMER G M. Isomerization of alkanes on sulfated zirconia: promotion by Pt and by adamantyl hydride transfer species[J]. J Catal, 1993, 144: 238-253.
[30]魏瑞平, 王军, 任晓乾, 等. 正庚烷在超稳Y沸石(USY)负载超强酸催化剂上加氢异构化[J]. 无机化学学报, 2004, 20(12): 1471-1476.
[31]KUZNETSOVA L N, KAZBANOVA A V, KUZNETSOV P N, et al. Activity of the Pt/WO2-4/ZrO2 catalyst in hydroisomerization reaction of n-heptane-benzene mixture[J]. Petrol Chem, 2015, 55(1): 57-62.
[32]KUZNETSOV P N, KAZBANOVA A V, KUZNETSOVA L I, et al. Bulk and surface characterization and isomerization activity of Pt/WO2-4/ZrO2 catalysts of different preparations[J]. Reac Kinet Mech Cat, 2014, 113(1): 69-84.
[33]SHANG S, XU X, XIE P, et al. Influence of preparative method on Al2O3-doped Pt/WO3-ZrO2 catalyst for n-heptane isomerization[J]. Chin J Catal, 2013, 34(5): 898-905.
[34]XU X, LIU T, XIE P, et al. Enhanced catalytic performance over Fe2O3-doped Pt/SO2-`4/ZrO2 in n-heptane hydroisomerization[J]. Catal Commun, 2014, 54: 77-80.
[35]NIE Y, SHANG S, XU X, et al. In2O3-doped Pt/WO3/ZrO2 as a novel efficient catalyst for hydroisomerization of n-heptane[J]. Appl Catal A, 2012, 433: 69-74.
[36]TU X, YUE Y, WANG J, et al. The promoting effect of Ga2O3 on a Pt/WO3/ZrO2 catalyst for n-heptane isomerization[J]. Chin J Catal, 2009, 30(5): 378-380.
[37]Xu J S, Ying J Y. A highly active and selective nanocomposite catalyst for C7+ paraffin isomerization[J]. Angew Chem Int Ed, 2006, 45: 1-5.
[38]SONG J, WANG H, XU B. A novel preparation method of Pt-WO3/ZrO2 for n-heptane isomerization[J]. Chin J Catal, 2004, 25(8): 599-601.
[39]徐平, 徐云鹏, 滕飞, 等. 固体强酸催化剂Pd/WO3-ZrO2的制备及其对正庚烷异构化反应的催化性能[J]. 催化学报, 2005, 26(9): 750-754.
[40]TRAVERS C, ESSAYEM N, DELAGE M, et al. Heteropolyanions based catalysts for paraffins isomerization[J]. Catal Today, 2001, 65: 355-361.
[41]MIYAJI A, ECHIZEN T, NAGATA K, et al. Selective hydroisomerization of n-pentane to isopentane over highly dispersed Pd-H4SiW12O40/SiO2[J]. J Mol Catal A, 2003, 201(1/2): 145-153.
[42]MIYAJI A, OHNISHI R, OKUHARA T. Skeletal isomerization of n-heptane over Pd-H4SiW12O40 supported on SiO2: comparative study with typical bifunctional catalysts[J]. Appl Catal A, 2004, 262(2): 143-148.
[43]SUGII T, OHNISHI R, ZHANG J, et al. Acidity-attenuated heteropolyacid catalysts: acidity measurement using benzonitrile-TPD and catalytic performance in the skeletal isomerization of n-heptane[J]. Catal Today, 2006, 116(2): 179-183.
[44]蒋冬梅, 王军, 朱海鸥, 等. 正庚烷在改性USY负载杂多酸催化剂上加氢异构化反应[J]. 南京工业大学学报, 2003, 25(1): 36-40.
[45]WANG J, JIANG D M, BAEG J O, et al. Hydroisomerization of n-heptane over modified USY-supported H3PW12O40 catalysts: effect of hydrothermal treatment for USY[J]. J Ind Eng Chem, 2004, 10: 454-459.
[46]WEI R P, WANG J, REN X Q, et al. 12-Phosphotungstic acid catalysts supported on β zeolite for hydroisomerization of n-heptane[J]. 分子催化, 2005, 19(4): 251-254.
[47]顾焰波, 魏瑞平, 王军. Pt-SiW/DUSY催化剂上正庚烷临氢异构化反应的研究[J]. 石油学报(石油加工), 2007, 23(4): 14-19.
[48]YANG X K, CHEN L F, WANG J A, et al. Study of the Keggin structure and catalytic properties of Pt-promoted heteropoly compound/Al-MCM-41 hybrid catalysts[J]. Catal Today, 2009, 148: 160-168.
[49]WANG J A, ZHOU X L, CHEN L F, et al. Hydroisomerization of n-heptane on the Pt/H3PW12O40/Zr-MCM-41 catalysts[J]. J Mol Catal A: Chem, 2009, 299: 68-76.
[50]LE VAN MAO R, SABERI M A. Catalysts for the hydroisomerization of n-heptane, prepared according to the concept of ‘triangular’ site configuration[J]. Appl Catal A, 2000, 199(1): 99-107.
[51]SABERI M A, LE VAN MAO R, MARTIN M, et al. Effect of Zn loading of the Pt-Zn-HY trifunctional catalysts on the hydroisomerization of n-heptane[J]. Appl Catal A, 2001, 214(1): 229-236.
[52]RAMOS M J, JIMéNEZ V, FNEZ A, et al. Influence of the addition of a second metal on the catalytic performance of Pt-Beta agglomerated catalyst in the hydroisomerization of n-octane[J]. Catal Lett, 2008, 125: 220-228.
[53]FNEZ A, DE LUCAS A, SáNCHEZ P, et al. Hydroisomerization in liquid phase of a refinery naphtha stream over Pt-Ni/H-beta zeolite catalysts[J]. Chem Eng J, 2008, 136: 267-275.
[54]WEI R P, WANG J, GU Y B. USY supported Pt-bearing SO2-4/ZrO2 catalysis promoted by Cr for hydroisomerization of N-heptane[J]. Catal Lett, 2007, 90(2): 315-322.
[55]WEI R P, WANG J, XIAO G M. Hydroisomerization of n-heptane over Cr promoted Pt-bearing H3PW12O40 catalysts supported on dealuminated USY zeolite[J]. Catal Lett, 2009, 127(3/4): 360-367.
[56]LIU P, WANG J, ZHANG X, et al. Catalytic performances of dealuminated Hβ zeolite supported Pt catalysts doped with Cr in hydroisomerization of n-heptane[J]. Chem Eng J, 2009, 148: 184-190.
[57]LIU P, ZHANG X, YAO Y, et al. Alkaline earth metal ion-exchanged β zeolite supported Pt catalysts for hydroisomerization of n-heptane[J]. Reac Kinet Mech Cat, 2010, 100: 217-226.
[58]ROLDáN R, BEALE A M, SáNCHEZ M, et al. Effect of the impregnation order on the nature of metal particles of bi-functional Pt/Pd-supported zeolite Beta materials and on their catalytic activity for the hydroisomerization of alkanes[J]. J Catal, 2008, 254: 12-26.
[59]SAXENA S K, VISWANADHAM N, GARG M O. Porosity and acidity patterns of steam treated BEA zeolite material for enhanced catalytic isomerization of naphtha[J]. J Ind Eng Chem, 2014, 20(5): 3875-3883.
[60]VISWANADHAM N, KAMBLE R, SAXENA S K, et al. Studies on octane boosting of industrial feedstocks on Pt/H-BEA zeolite[J]. Fuel, 2008, 87: 2394-2400.
[61]沈志虹, 师为, 李红杰. Cr改性USY分子筛提高裂化催化剂的异构化性能[J]. 燃料化学学报, 2005, 33(3): 363-365.
[62]YANG X, MA H, XU Z, et al. Hydroisomerization of n-dodecane over Pt/MeAPO-11(Me=Mg, Mn, Co or Zn)catalysts[J]. Catal Commun, 2007, 8: 1232-1238.
[63]MERABTI R, PINARD L, LEMBERTON J L, et al. Effect of Na exchange of a HBEA zeolite on the activity and the selectivity of a bifunctional Pt-HBEA catalyst for n-hexadecane hydroisomerization. Comparison with a Pt-HZSM-22 catalyst[J]. Reac Kinet Mech Catal, 2010, 100: 1-9.
[64]YAO Y, WANG J, DENG Y, et al. Morphological effect of beta zeolite nanocrystallite aggregates as the support of Pt catalyst for the hydroisomerization of n-heptane[J]. Reac Kinet Mech Cat, 2012, 107(1): 167-177.
[65]KIM J, KIM W, SEO Y, et al. n-Heptane hydroisomerization over Pt/MFI zeolite nanosheets: effects of zeolite crystal thickness and platinum location[J]. J Catal, 2013, 301: 187-197.
[66]张培青, 徐金光, 王祥生, 等. 纳米HZSM-5催化剂催化C8直链烃转化的性能[J]. 催化学报, 2005, 26(3): 216-222.
[67]BELANDRíA L N, GONZàLEZ C S, AGUIRRE F, et al. Synthesis, characterization of FAU/EMT intergrowths and its catalytic performance in n-pentane hydroisomerization reaction[J]. J Mol Catal A: Chem, 2008, 281: 164-172.
[68]张振莉, 周亚松, 李长喜, 等. HZSM-5/Hβ复合分子筛的正辛烷临氢异构化和芳构化性能[J]. 燃料化学学报, 2008, 36(2): 160-165.
[69]LIU P, YAO Y, WANG J. Using β-MCM41 composite molecular sieves as supports of bifunctional catalysts for hydroisomerization of n-heptane[J]. Reac Kinet Mechs Cat, 2010, 101: 465-475.
[70]PARSAFARD N, PEYROVI M H, RASHIDZADEH M. n-Heptane isomerization on a new kind of micro/mesoporous catalyst: Pt supported on HZSM-5/HMS[J]. Micropor Mesopor Mater, 2014, 200: 190-198.
[71]CHEN J, HUA W, YU X, et al. Tailoring the structure of herarchically porous zeolite Beta through modified orientated attachment growth in a dry gel system[J]. Chem Eur J, 2014, 20(45): 14744-14755.
[72]LEVY R B, BOUDART M. Platinum-like behavior of tungsten carbide in surface catalysis[J]. Science, 1973, 181: 547-549.
[73]OLIVIA ALEMAN-VAZQUEZ L, HERNANDEZ-PEREZ F, LUIS CANO-DOMINGUEZ J, et al. Binder effect on the catalytic activity of MoO3 bulk catalyst reduced by H2 for n-heptane hydroisomerization[J]. Fuel, 2014, 117: 463-469.
[74]LEDOUX M J, PHAM-HUU C, DELPORITE P, et al. Evidence for a new very active and selective catalysts for hydrocarbon isomerization: molybdenum oxicarbide[J]. Stud Surf Sci Catal, 1995, 92: 81-86.
[75]PHAM-HUU C, YORK A P E, BENAISSA M, et al. Reactions of n-heptane and methycyclopentane over an oxygen-modified molybdenum carbide catalyst. Study of coke formation, catalyst deactivation, and regeneration[J]. Ind Eng Chem Res, 1995, 34: 1107-1113.
[76]MATSUDA T, HIRATA Y, SUGA S, et al. Effect of H2 reduction on the catalytic properties of molybdenum oxide for the conversions of heptane and 2-propanol[J]. Appl Catal A, 2000, 193(1/2): 185-193.
[77]MATSUDA T, HIRATA Y, SUGA S, et al. Catalytic properties of MoO3 reduced at different temperatures for the conversions of heptane and 2-propanol[J]. Micropor Mesopor Mater, 2001, 42: 345-353.
[78]AL-KANDARI H, AL-KHARAFI F, KATRIB A, et al. Large scale hydroisomerization reactions of n-heptane on partially reduced MoO3/TiO2[J]. Appl Catal A, 2009, 361: 81-85.
[79]AL-KANDARI S, AL-KANDARI H, AL-KHARAFI F. the catalytic reactions of n-pentane and 1-pentene on different molybdenum oxides and metal surfaces[J]. Appl Catal A, 2008, 341: 160-167.
[80]RIBEIRO F H, BETTA R A D, BOUDART M, et al. Reactions of neopentane, methylcyclohexane, and 3, 3-dimethylpentane on tungsten carbides: the effect of surface oxygen on reaction pathways[J]. J Catal, 1991, 130(1): 86-105.
[81]RIBEIRO F H, BOUDART M, BETTA R A D, et al. Catalytic reactions of n-alkanes on β-W2C and WC: the effect of surface oxygen on reaction pathways[J]. J Catal, 1991, 130(2): 498-513.
[82]BENADDA A, KATRIB A, SOBCZAK J W, et al. Hydroisomerization of n-heptane and dehydration of 2-propanol on bulk and supported WO2(Hx)ac on TiO2[J]. Appl Catal A, 2004, 260(2): 175-183.
[83]LAMIC A F, PHAM T L H, POTVIN C, et al. Kinetics of bifunctional isomerization over carbides(Mo, W)[J]. J Mol Catal A: Chem, 2005, 237: 109-114.
[84]LAMIC A F, SHIN C H, DJéGA-MARIADASSOU G, et al. Characterization of Mo2C-WO2 composite catalysts for bifunctional isomerization: a new pulse method to quantify acid sites[J]. Appl Catal A, 2006, 302: 5-13.
[85]CLARK P A, OYAMA S T. Alumina-supported molybdenum phosphide hydroprocessing catalysts[J]. J Catal, 2003, 218: 78-87.
[86]WANG A, QIN M, GUAN J, et al. The synthesis of metal phosphides: reduction of oxide precursors in a hydrogen plasma[J]. Angew Chem Int Ed, 2008, 47: 6052-6054.
[87]LIU P, WU M Y, WANG J, et al. Hydroisomerization of n-heptane over MoP/Hβ catalyst doped with metal additive[J]. Fuel Process Technol, 2015, 131: 311-316.
[88]LIU P, CHANG W T, WANG J, et al. MoP/Hβ catalyst prepared by low-temperature auto-combustion for hydroisomerization of n-heptane[J]. Catal Commun, 2015, 66: 79-82.

备注/Memo

备注/Memo:
收稿日期:2016-12-03。
基金项目:国家自然科学基金资助项目(21406019); 中国博士后科学基金面上资助项目(2016M601794); 江苏省先进催化与绿色制造协同创新中心创新人才项目(ACGM2016-06-14)。
作者简介:刘平(1983—),女,江苏徐州人,博士,讲师,主要从事纳米金属加氢催化剂研究。
更新日期/Last Update: 2017-06-05