HZSM-5沸石中Lewis酸与Brönsted酸协同作用下的甲基环己烷开环反应

doi:10.1016/S1872-2067(12)60721-9

催化学报 ›› 2013, Vol. 34 ›› Issue (11): 2153-2159.DOI: 10.1016/S1872-2067(12)60721-9

• 研究论文 • 上一篇

HZSM-5沸石中Lewis酸与Brönsted酸协同作用下的甲基环己烷开环反应

宋晨海^a, 王蒙^a, 赵理^a, 薛念华^a, 彭路明^a, 郭学锋^a, 丁维平^a, 杨为民^b, 谢在库^b

a 南京大学化学化工学院介观化学教育部重点实验室, 江苏南京210093;
b 中国石油化工股份有限公司上海石油化工研究院, 上海201208

收稿日期:2013-09-27 修回日期:2013-10-08 出版日期:2013-10-18 发布日期:2013-10-18
通讯作者: Nianhua Xue,Weiping Ding
基金资助:
国家自然科学基金(21273107,21103087);中央高校基本科研业务费专项资金(1107020524);高等学校博士学科点专项科研基金(20100091120035).

Synergism between the Lewis and Brönsted acid sites on HZSM-5 zeolites in the conversion of methylcyclohexane

Chenhai Song^a, Meng Wang^a, Li Zhao^a, Nianhua Xue^a, Luming Peng^a, Xuefeng Guo^a, Weiping Ding^a, Weimin Yang^b, Zaiku Xie^b

a Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, Jiangsu, China;
b Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China

Received:2013-09-27 Revised:2013-10-08 Online:2013-10-18 Published:2013-10-18
Contact: Nianhua Xue,Weiping Ding
Supported by:
This work was supported by the National Natural Science Foundation of China (21273107, 21103087), the Fundamental Research Funds for the Central Universities (1107020524), and the Specialized Research Fund for the Doctoral Program of Higher Education (20100091120035).

摘要/Abstract

摘要：

由于水蒸气处理HZSM-5生成的骨架外铝在分子筛中体现Lewis酸性, 分子筛中骨架外铝物种的可移动性导致Lewis酸与分子筛本身的Brönsted酸在空间上具有临近性. 当甲基环己烷分子在HZSM-5的笼中转化时, Lewis酸与Brönsted酸的协同作用加快了甲基环己烷分子的转化速率, 且骨架外铝物种浓度越高, 这种协同效应越明显. 而产物的选择性只与催化剂的孔道结构有关, 与水蒸气处理所导致的酸性质的变化无关.

关键词: 甲基环己烷, HZSM-5, 水蒸气处理, 协同效应, Lewis酸, Brönsted酸

Abstract:

Catalytic conversion of methylcyclohexane was studied on four specially designed HZSM-5 zeolites. A careful steam treatment was used to produce pair-sites composed of a Lewis acid site, due to extra-framework Al species from the dealumination by steaming, and a Brö -nsted acid site, due to bridging hydroxyl in the steamed HZSM-5. The spatial proximity of these component acid sites of the pair-site was verified by ¹H double quantum magic spinning NMR. Product selectivities of methylcyclohexane conversion showed the same trend for all the samples, which indicated that the pores of the zeolites were not changed by the steam treatment. The Lewis acid site that was created, however, gave a synergistic effect with the Brönsted acid site in the pair-site, which gave higher conversions and cracking rates of methylcyclohexane. The rate of methylcyclohexane conversion increased with increased concentration of extra-framework Al, which gave more pair-sites.

Key words: Methylcyclohexane, HZSM-5, Steam treatment, Synergistic effect, Lewis acid site, Brönsted acid site

宋晨海, 王蒙, 赵理, 薛念华, 彭路明, 郭学锋, 丁维平, 杨为民, 谢在库. HZSM-5沸石中Lewis酸与Brönsted酸协同作用下的甲基环己烷开环反应[J]. 催化学报, 2013, 34(11): 2153-2159.

Chenhai Song, Meng Wang, Li Zhao, Nianhua Xue, Luming Peng, Xuefeng Guo, Weiping Ding, Weimin Yang, Zaiku Xie. Synergism between the Lewis and Brönsted acid sites on HZSM-5 zeolites in the conversion of methylcyclohexane[J]. Chinese Journal of Catalysis, 2013, 34(11): 2153-2159.

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参考文献

[1] Corma A, Mocholi F, Orchilles V, Koermer G S, Madon R J. Appl Catal, 1990, 67: 307
[2] Mignard S, Caillette P, Marchal N. Chem Ind (Dekker), 1994, 58: 447
[3] Raichle A, Traa Y, Fuder F, Rupp M, Weitkamp J. Angew Chem Int Ed, 2001, 40: 1243
[4] Cerqueira H S, Mihindou-Koumba P C, Magnoux P, Guisnet M. Ind Eng Chem Res, 2001, 40: 1032
[5] Calemma V, Carati A, Flego C, Giardino R, Millini R. Prepr Symp-Am Chem Soc, Div Fuel Chem, 2005, 50: 116
[6] Galperin L B, Jan D Y, McCall M J, Kocal J A, Galperin I, Uop LLC, USA. 2006, p 10 pp.
[7] Calemma V, Carati A, Flego C, Giardino R, Gagliardi F, Millini R, Bullussi G. ChemSusChem, 2008, 1: 548
[8] Castano P, Gayubo A G, Pawelec B, Fierro J L G, Arandes J M. Chem Eng J, 2008, 140: 287
[9] Lecarpentier S, van Gestel J, Thomas K, Gilson J P, Houalla M. J Catal, 2008, 254: 49
[10] Al-Sabawi M, de Lasa H. AIChE J, 2009, 55: 1538
[11] Park J W, Thomas K, van Gestel J, Gilson J P, Collet C, Dath J P, Houalla M. Appl Catal A, 2010, 388: 37
[12] Van Borm R, Reyniers M F, Martens J A, Marin G B. Ind Eng Chem Res, 2010, 49:10486
[13] Shi H, Gutierrez O Y, Haller G L, Mei D H, Rousseau R, Lercher J A. J Catal, 2013, 297: 70
[14] Moraes R, Thomas K, Thomas S, Van Donk S, Grasso G, Gilson J P, Houalla M. J Catal, 2013, 299: 30
[15] Upare D P, Yoon S, Lee C W. Catal Lett, 2012, 142: 744
[16] Moraes R, Thomas K, Thomas S, Van D S, Grasso G, Gilson J P, Houalla M. J Catal, 2012, 286: 62
[17] Nageswara Rao R, You N, Yoon S, Upare D P, Park Y K, Lee C W. Catal Lett, 2011, 141: 1047
[18] Piegsa A, Korth W, Demir F, Jess A. Catal Lett, 2012, 142: 531
[19] Samoila P, Boutzeloit M, Salem I, Uzio D, Mabilon G, Epron F, Marecot P, Especel C. Appl Catal A, 2012, 415-416: 80
[20] Du H, Fairbridge C, Yang H, Ring Z. Appl Catal A, 2005, 294: 1
[21] Yu Z W, Li S H, Wang Q, Zheng A M, Xu J, Chen L, Deng F. J Phys Chem C, 2011, 115: 22320
[22] Feike M, Demco D E, Graf R, Gottwald J, Hafner S, Spiess H W. J Magn Reson Ser A, 1996, 122: 214
[23] Fyfe C A, Gobbi G C, Klinowski J, Thomas J M, Ramdas S. Nature, 1982, 296: 530
[24] Lippmaa E, Maegi M, Samoson A, Engelhardt G, Grimmer A R. J Am Chem Soc, 1980, 102: 4889
[25] Engelhardt G, Lohse U, Lippmaa E, Tarmak M, Magi M Z. Anorg Allg Chem, 1981, 482: 49
[26] Kotrel S, Knozinger H, Gates B C. Microporous Mesoporous Mater, 2000, 35-36: 11
[27] Marques J P, Gener I, Lopes J M, Ribeiro F R, Guisnet M. Appl Catal A, 2006, 301: 96
[28] Maier S M, Jentys A, Lercher J A. J Phys Chem C, 2011, 115: 8005
[29] Mihályi R M, Kollár M, Király P, Karoly Z, Mavrodinova V. Appl Catal A, 2012, 417: 76
[30] Zhu N, Wang Y, Cheng D G, Chen F Q, Zhan X L. Appl Catal A, 2009, 362: 26
[31] Kung H H, Williams B A, Babitz S M, Miller J T, Snurr R Q. Catal Today, 1999, 52: 91
[32] Babitz S M, Williams B A, Miller J T, Snurr R Q, Haag W Q, Kung H H. Appl Catal A, 1999, 179: 71
[33] Williams B A, Babitz S M, Miller J T, Snurr R Q, Kung H H. Appl Catal A, 1999, 177: 161
[34] Zholobenko V L, Kustov L M, Kazansky V B, Loeffler E L, Lohse U, Oehlmann G L. Zeolites, 1991, 11: 132
[35] Zholobenko V L, Kustov L M, Kazansky V B, Loeffler E, Lohser U L, Peuker C, Oehlmann G. Zeolites, 1990, 10: 304
[36] Makarova M A, Dwyer J. J Phys Chem, 1993, 97: 6337
[37] Niwa M, Sota S, Katada N. Catal Today, 2012, 185: 17
[38] Makarova M A, Bates S P, Dwyer J. J Am Chem Soc, 1995, 117: 11309
[39] Van Bokhoven J A, Tromp M, Koningsberger D C, Miller J T, Pieterse J A Z, Lercher J A, Williams B A, Kung H H. J Catal, 2001, 202: 129
[40] Marques J D, Gener I, Ayrault P, Bordado J C, Lopes J M, Ramôa Ribeiro F, Guisnet M. Microporous Mesoporous Mater, 2003, 60: 251
[41] Masuda T, Fujikata Y, Mukai S R, Hashimoto K. Appl Catal A, 1998, 172: 73
[42] Wischert R, Laurent P, Copéret C, Delbecq F, Sautet P. J Am Chem Soc, 2012, 134: 14430
[43] Yu Z W, Li S H, Wang Q, Zheng A M, Jun X, Chen L, Deng F. J Phys Chem C, 2011, 115: 22320
[44] Li S H, Zheng A M, Su Y C, Zhang H L, Chen L, Yang J, Ye C H, Deng F. J Am Chem Soc, 2007, 129: 11161

HZSM-5沸石中Lewis酸与Brönsted酸协同作用下的甲基环己烷开环反应

Synergism between the Lewis and Brönsted acid sites on HZSM-5 zeolites in the conversion of methylcyclohexane

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