Citation: ZHANG Jin-Gui, QIAN Wei-Zhong, TANG Xiao-Ping, SHEN Kui, WANG Tong, HUANG Xiao-Fan, WEI Fei. Influence of Catalyst Acidity on Dealkylation, Isomerization and Alkylation in MTA Process[J]. Acta Physico-Chimica Sinica, ;2013, 29(06): 1281-1288. doi: 10.3866/PKU.WHXB201304101 shu

Influence of Catalyst Acidity on Dealkylation, Isomerization and Alkylation in MTA Process

1.
1 Beijing Key Laboratory of Green Reaction Engineering & Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084, P. R. China;
2 Huadian Coal Industry Group Co. Ltd., Beijing, 100031, P. R. China

Received Date: 16 January 2013
Available Online: 10 April 2013
Fund Project: 国家高技术研究发展计划(863)(2012AA051003)资助项目 (863)(2012AA051003)

Relationship between aromatics distribution, in the process of methanol to aromatics (MTA), and the conversion of methanol and the catalyst acidity was investigated over a series of Zn/P/ZSM-5 catalysts with different Si/Al molar ratios and zinc loading. To understand the contribution of aromatization, isomerization, dealkylation and alkylation reactivity of the catalyst to the aromatics distribution, coke deposition degree of Zn/P/ZSM-5 catalyst was tailored as using different feedstocks including methanol, xylene or the mixture of methanol and toluene. With the coke deposition, the amount of different types of acidic sites of catalyst varied significantly, characterized by NH₃-temperature programmed desorption (NH3-TPD) and pyridine-infrared methods. Aromatization, dealkylation, alkylation, and isomerization showed sensitivity to a reduction in the density of strongly acidic sites. Dealkylation reaction was preferentially inhibited just by slightly decreasing the density of strong acid sites. However, aromatization and isomerization reaction were inhibited only when the density of strong acid sites was significantly decreased. In all cases, alkylation was found to be uninfluenced by acidic site density. A Zn/P/ZSM-5 catalyst with Si/Al molar ratio of 14 and 3% (w) Zn loading exhibited aromatics yields of 75% and xylene yields of about 35%, indicating potential for industrial application.
- Methanol,
- ZSM-5 zeolite,
- Aromatization,
- Dealkylation,
- Alkylation,
- Isomerization
1. [1]
  
  (1) Olsbye, U.; Svelle, S.; Bjorgen, M.; Beato, P.; Janssens, T. V.W.; Joensen, F.; Bordiga, S.; Lillerud, K. P. Angew. Chem. Int. Edit. 2012, 51, 2. doi: 10.1002/anie.201107584
2. [2]
  (2) Keil, F. J. Microporous Mesoporous Mat. 1999, 29, 49. doi: 10.1016/S1387-1811(98)00320-5
3. [3]
  (3) Stocker, M. Microporous Mesoporous Mat. 1999, 29, 3. doi: 10.1016/S1387-1811(98)00319-9
4. [4]
  (4) Zaidi, H. A.; Pant, K. K. Catal. Today 2004, 96, 155. doi: 10.1016/j.cattod.2004.06.123
5. [5]
  (5) Freeman, D.;Wells, R. P. K.; Hutchings, G. J. J. Catal. 2002,205, 358. doi: 10.1006/jcat.2001.3446
6. [6]
  (6) Freeman, D.;Wells, R. P. K.; Hutchings, G. J. Chem. Commun.2001, 1754.
7. [7]
  (7) Ni, Y. M.; Peng,W. Y.; Sun, A. M.; Mao,W. L.; Hu, J. L.; Li, T.;Li, G. X. J. Ind. Eng. Chem. 2010, 16, 503. doi: 10.1016/j.jiec.2010.03.011
8. [8]
  (8) Lopez-Sanchez, J. A.; Conte, M.; Landon, P.; Zhou,W.; Bartley,J. K.; Taylor, S. H.; Carley, A. F.; Kiely, C. J.; Khalid, K.;Hutchings, G. J. Catal. Lett. 2012, 142, 1049. doi: 10.1007/s10562-012-0869-2
9. [9]
  (9) Tian, T.; Qian,W. Z.; Sun, Y. J.; Cui, Y.; Lu, Y. Y.;Wei, F.Modern Chemical Industry 2009, 29, 55. [田涛, 骞伟中, 孙玉建, 崔宇, 卢俨俨, 魏飞. 现代化工, 2009, 29, 55.]
10. [10]
  (10) Tian, T.; Qian,W. Z.; Tang, X. P.; Yun, S.;Wei, F. Acta Phys. -Chim. Sin. 2010, 26, 3305. [田涛, 骞伟中, 汤效平,恽松, 魏飞. 物理化学学报, 2010, 26, 3305.] doi: 10.3866/PKU.WHXB20101228
11. [11]
  (11) Wang, J. Y.; Li,W. H.; Hu, J. X. Journal of Fuel Chemistry and Technology 2009, 37, 607. [王金英, 李文怀, 胡津仙. 燃料化学学报, 2009, 37, 607.]
12. [12]
  (12) Kecskemeti, A.; Barthos, R.; Solymosi, F. J. Catal. 2008, 258,111. doi: 10.1016/j.jcat.2008.06.003
13. [13]
  (13) Choudhary, V. R.; Panjala, D.; Banerjee, S. Appl. Catal. A 2002,231, 243. doi: 10.1016/S0926-860X(02)00061-3
14. [14]
  (14) Inoue, Y.; Nakashiro, K.; Ono, Y. Microporous Mat. 1995, 4,379. doi: 10.1016/0927-6513(95)00020-A
15. [15]
  (15) Bjørgen, M.; Svelle, S.; Joensen, F.; Nerlov, J.; Kolboe, S.;Bonino, F.; Palumbo, L.; Bordiga, S.; Olsbye, U. J. Catal. 2007,249, 195. doi: 10.1016/j.jcat.2007.04.006
16. [16]
  (16) Adebajo, M. O.; Long, M. A. Catal. Commun. 2003, 4, 71. doi: 10.1016/S1566-7367(02)00259-5
17. [17]
  (17) Lukyanov, D. B.; Gnep, N. S.; Guisnet, M. R. Ind. Eng. Chem. Res. 1995, 34, 516. doi: 10.1021/ie00041a012
18. [18]
  (18) Olson, D. H.; Kokotailo, G. T.; Lawton, S. L.; Meler,W. M.J. Phys. Chem. 1981, 85, 2238. doi: 10.1021/j150615a020
19. [19]
  (19) Joshi, Y. V.; Thomson, K. T. J. Phys. Chem. C 2008, 112, 12825.doi: 10.1021/jp712071k
20. [20]
  (20) Olson, D. H.; Haag,W. O. ACS Symp. Ser. 1984, 248, 275. doi: 10.1021/symposium
21. [21]
  (21) Mirth, G.; Cejka, J.; Lercher, J. A. J. Catal. 1993, 139, 24. doi: 10.1006/jcat.1993.1003
22. [22]
  (22) Guisnet, M.; Gnep, N. S.; Morin, S. Microporous Mesoporous Mat. 2000, 35 -36, 47.
23. [23]
  (23) Ivanova, I. I.; Corma, A. J. Phys. Chem. B 1997, 101, 547. doi: 10.1021/jp961468k
24. [24]
  (24) Tsai, T.; Liu, S.;Wang, I. Appl. Catal. A 1999, 181, 355. doi: 10.1016/S0926-860X(98)00396-2
25. [25]
  (25) Serra, J. M.; Guillon, E.; Corma, A. J. Catal. 2004, 227, 459.doi: 10.1016/j.jcat.2004.08.006
26. [26]
  (26) Zheng, S. R.; Heydenrych, H. R.; Jentys, A.; Lercher, J. A.J. Phys. Chem. B 2002, 106, 9552. doi: 10.1021/jp014091d
27. [27]
  (27) Bibby, D. M.; Howe, R. F.; Mclellan, G. D. Appl. Catal. A 1992,93, 1. doi: 10.1016/0926-860X(92)80291-J
28. [28]
  (28) Benito, P. L.; Gayubo, A. G.; Aguayo, A. T.; Olazar, M.; Bilbao,J. Ind. Eng. Chem. Res. 1996, 35, 3991. doi: 10.1021/ie950462z
29. [29]
  (29) Biscardi, J. A.; Meitzner, G. D.; Iglesia, E. J. Catal. 1998, 179,192. doi: 10.1006/jcat.1998.2177
30. [30]
  (30) El-Malki, E. M.; Van Santen, R. A.; Sachtler,W. M. H. J. Phys. Chem. B 1999, 103, 4611. doi: 10.1021/jp990116l
31. [31]
  (31) Bhan, A.; Delgass,W. N. Catal. Rev. 2008, 50, 19. doi: 10.1080/01614940701804745
1. [1]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
2. [2]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
3. [3]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
4. [4]
  Zhilian Liu , Wengui Wang , Hongxiao Yang , Yu Cui , Shoufeng Wang . Ideological and Political Education Design for the Synthesis of Irinotecan Drug Intermediate 7-Ethyl Camptothecin. University Chemistry, 2024, 39(2): 89-93. doi: 10.3866/PKU.DXHX202306012
5. [5]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
6. [6]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
7. [7]
  Hongsheng Tang , Yonghe Zhang , Dexiang Wang , Xiaohui Ning , Tianlong Zhang , Yan Li , Hua Li . A Wonderful Journey through the Kingdom of Hazardous Chemicals. University Chemistry, 2024, 39(9): 196-202. doi: 10.12461/PKU.DXHX202403098
8. [8]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
9. [9]
  Lijun Huo , Mingcun Wang , Tianyi Zhao , Mingjie Liu . Exploration of Undergraduate and Graduate Integrated Teaching in Polymer Chemistry with Aerospace Characteristics. University Chemistry, 2024, 39(6): 103-111. doi: 10.3866/PKU.DXHX202312059
10. [10]
  Yanxin Wang , Hongjuan Wang , Yuren Shi , Yunxia Yang . Application of Python for Visualizing in Structural Chemistry Teaching. University Chemistry, 2024, 39(3): 108-117. doi: 10.3866/PKU.DXHX202306005
11. [11]
  Yongming Guo , Jie Li , Chaoyong Liu . Green Improvement and Educational Design in the Synthesis and Characterization of Silver Nanoparticles. University Chemistry, 2024, 39(3): 258-265. doi: 10.3866/PKU.DXHX202309057
12. [12]
  Yingxian Wang , Tianye Su , Limiao Shen , Jinping Gao , Qinghe Wu . Introduction of Chinese Lacquer from the Perspective of Chemistry: Popularizing Chemistry in Lacquer and Inherit Lacquer Art. University Chemistry, 2024, 39(5): 371-379. doi: 10.3866/PKU.DXHX202312015
13. [13]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
14. [14]
  Chengxia Tong , Yajie Li , Jin Yan , Xuejian Qu , Shigang Wei , Yong Fan , Zhiguang Song , Yupeng Guo . The Construction and Practice of a Comprehensive and Three-Dimensional Practical Education Model. University Chemistry, 2024, 39(7): 49-55. doi: 10.12461/PKU.DXHX202404155
15. [15]
  Xu Liu , Chengfang Liu , Jie Huang , Xiangchun Li , Wenyong Lai . Research on the Application of Diversified Teaching Models in the Teaching of Physical Chemistry. University Chemistry, 2024, 39(8): 112-118. doi: 10.3866/PKU.DXHX202402021
16. [16]
  Ruming Yuan , Laiying Zhang , Xiaoming Xu , Pingping Wu , Gang Fu . Application of Mathematica in Visualizing Physical Chemistry Formulas. University Chemistry, 2024, 39(8): 375-382. doi: 10.3866/PKU.DXHX202401030
17. [17]
  Dongxia Zhang , Sijia Hao , Jiarui Wang , Jiwei Wang , Xiaogang Dong , Liang Jiao . Construction and Reflection on the Safety Management of Hazardous Chemicals in University Laboratories. University Chemistry, 2024, 39(10): 229-235. doi: 10.12461/PKU.DXHX202403078
18. [18]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
19. [19]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
20. [20]
  Yuqiao Zhou , Weidi Cao , Shunxi Dong , Lili Lin , Xiaohua Liu . Study on the Teaching Reformation of Practical X-ray Crystallography. University Chemistry, 2024, 39(3): 23-28. doi: 10.3866/PKU.DXHX202303003

Get Citation

PDF

XML

Metrics

PDF Downloads(807)
Abstract views(1116)
HTML views(19)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142