Citation: LIU Dong-mei, JIANG Han-bo, QU Sheng-tao, WANG Hai-yan, YANG Zhan-xu, ZHANG Yu-song. Study on the alkylation of thiophene and catalyst deactivation and regeneration with modified HZSM-5 zeolite[J]. Journal of Fuel Chemistry and Technology, ;2018, 46(3): 355-364. shu

Study on the alkylation of thiophene and catalyst deactivation and regeneration with modified HZSM-5 zeolite

1.
School of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Fushun Vocational Technology Institute, Fushun 113122, China

Corresponding author: LIU Dong-mei, ldmwain1234@126.com
Received Date: 27 November 2017
Revised Date: 18 January 2018

Fund Project: Liaoning Province Large-Seale Instrument Equipment Sharing Service Platform Capacity-Building Research Fund Project of China 2016LD0106Ph.D. Start-up Funding 1100130210The project was supported by the Liaoning Education Department of Basic Research Program of China(L2017LQN012) and Ph.D. Start-up Funding (1100130210) and Liaoning Province Large-Seale Instrument Equipment Sharing Service Platform Capacity-Building Research Fund Project of China(2016LD0106)The project was supported by the Liaoning Education Department of Basic Research Program of China L2017LQN012

Figures(6)

HZSM-5 zeolites were treated by different alkalis alone or different combining ways with two kind of alkalis to prepare micro-meso hierarchical pore HZSM-5 catalysts for thiophene alkylation reaction. The result show that mesopores are created in molecular sieves and the acidity of catalysts after treated is modulated by single alkali or different combining methods of double alkalis. Simultaneously, the structure of catalyst obtained by the separate treatment of Na₂CO₃ solution and TPAOH solution is most suitable for the thiophene alkylation reaction. Furthermore, the stability of the thiophene alkylation reaction over the catalyst with the best microstructure was investigated, and the reason of catalyst deactivation and the regeneration conditions were determined. The results show that the catalysts are basically inactivated after thiophene alkylation reaction for 1050 h. During the reaction, the macromolecular compounds such as olefin oligomerization formed by the cyclization, dehydrogenation and aromatics alkylation are deposited on the catalyst, blocking the pore and then covering the active site of the catalyst. From the viewpoint of the high energy consumption in regeneration at high temperature and the adverse effect of repeated high temperature regeneration on the acidity and skeleton structure of the catalyst, the catalyst should be regenerated at the temperature of 550℃.
- alkali modified,
- thiophene alkylation,
- HZSM-5,
- inactivation and regeneration
1. [1]
  SHANG Qi, TANG Da-gang. Control vehicle gasoline harmful substances to reduce vehicle emissions[J]. Envir Sci Res, 2000,13(1):32-35.
2. [2]
  CHANG Zhen-yong. Alkylation process for thiophenic sulfur removal from FCC gasoline[J]. Pet Ref Eng, 2002,32(5):44-46.
3. [3]
  XU Ya-rong, SHEN Ben-xian, XU Xin-liang, ZHU Qing-cai. Quantum chemistry research in alkylation sulfur transfer reaction mechanism of thiophene sulfied in FCC gasoline[J]. Acta Pet Sin(Petrochem Process Sect), 2011,27(5):806-811.
4. [4]
  XU Jun, LONG Jun, ZHANG Jiu-shun, WU Zhi-guo. Alkylation desulfurization of thiophene in FCC gasoline with zeolite catalvst[J]. Pet Ref Chem Ind, 2005,36(82):38-42.
5. [5]
  LI Bai-chun, DU Dong-xue, ZHANG Wen-lin, MIU Xi-ping. Alkylation desulphurization of thiophene in FCC gasoline with zeolite catalyst[J]. Mod Chem Ind, 2015,35(2):113-116.
6. [6]
  WEI Shu-mei, XU Ya-rong, XU Xin-liang, WANG Ji-de. The study of thiophene sulfide alkylation reaction over HY zeolite catalyst in FCC gasoline[J]. Pet Ref Chem Ind, 2012,43(8):63-67.
7. [7]
  PÉREZ-RAMÍREZ J, CHRISTENSEN C H. Chemlnform abstarct:Hierachical zeolites:Enhanced utilization of microporous crystals in catalysis by advances in materials design[J]. Chem Soc Rev, 2008,37(11):2530-2542. doi: 10.1039/b809030k
8. [8]
  XIA Y, MOKAYA R. Are mesoporous silicas and aluminosilicas assembled from zeolite seeds inherently hydrothermally stable? Comparative evaluation of MCM-48 materials assembled from zeolite seeds[J]. J Mater Chem, 2004,14(23):3427-3435. doi: 10.1039/b408960j
9. [9]
  BUEHANAN J M. The chemistry of olefins production by ZSM-5 addition to catalytic cracking units[J]. Catal Today, 2000,55(3):207-212. doi: 10.1016/S0920-5861(99)00248-5
10. [10]
  CHAL R, GÉRARDIN C, BULUT M, VAN DONK DONK S. Overview and industrial assessment of synthesis strategies towards zeolites with mesopores[J]. ChemCatChem, 2011,3(1):67-81. doi: 10.1002/cctc.201000158
11. [11]
  DESSAU R M, VALYOCSIK E W, GEOKE N H. Aluminum zoning in ZSM-5 as revealed by selective silica removal[J]. Zeolites, 1992,12(7):776-779. doi: 10.1016/0144-2449(92)90049-U
12. [12]
  LIETZ G, SCHNABEL K H, PEUKER C, GROSS T. Modifications of HZSM-5 catalysts by NaOH treatment[J]. J Catal, 1994,148(2):562-568. doi: 10.1006/jcat.1994.1242
13. [13]
  TAO Y, KANOH H, KANEKO K. Developments and structures of mesopores in alkaline-treated ZSM-5 zeolites[J]. Adsorption-journal of the International Adsorption Society, 2006,12(5/6):309-316.
14. [14]
  ZHAO Cen, LIU Dong-mei, WEI Min, SUN Zhi-yan, WANG Hai-yan. Preparation and catalytic performance of ZSM-5 molecular sieve with hierarchical pore[J]. J Fuel Chem Technol, 2013,41(10):1256-1261.
15. [15]
  MAO Jing-bo, LIU Min, LI Peng, LIU Yang, GUO Xin-wen. Modification of micrometer-sized TS-1 with tetrapropylammonium hydroxide and its catalytic properties in hydroxylation of phenol and ammoxidation of methyl ethyl ketone[J]. J Fuel Chem Technol, 2008,36(4):484-488.
16. [16]
  YAO Jian-hui, WANG Hai-tao, HOU Kai-hu. The loss and regeneration of Hβ-Al₂O₃alkylation catalyst[J]. Pet Ref Chem Ind, 2013,44(10):71-76. doi: 10.3969/j.issn.1005-2399.2013.10.014
17. [17]
  JIN Shao, FU Ji-quan, ZHANG Ji-rui. The hydrogenation mechanism of benzene and propylene alkylation reaction over deactivation zeolite catalyst[J]. J Fuel Chem Technol, 2002,30(1):58-63.
18. [18]
  GROEN J C, PEFFER L A A, JACOB A, PEREZ-RAMIREZ J. On the introduction of intracrystalline mesoporosity in zeolites upon desilieation in alkaline medium[J]. Mieroporous Mesoporous Materi, 2004,69(1/2):29-34.
19. [19]
  ZENG Shao-huai. Shape-Selective Catalysis[M]. Beijing:Sinopec press, 1994, 1-87.
20. [20]
  LIU Dong-mei, TIE Da-xing, GAO Chen-yi, MAO Yan-hong, WANG Hai-yan, YU Hai-bing. The preparation of micro-mesoporous catalysts by mixed alkali and the catalytic performance of thiophene alkylation[J]. J Fuel Chem Technol, 2017,45(2):200-212.
21. [21]
  LIU Dong-mei, WANG Hai-yan, KONG Fei-fei, MAO Yan-hong, WANG Kun. The performance of micro-mesoporous catalysts by TPAOH treatment and the properties of thiophene alkylation[J]. J Fuel Chem Technol, 2016,44(11):1370-1379. doi: 10.3969/j.issn.0253-2409.2016.11.014
22. [22]
  LI Sha, LI Yu-ping, DI Chun-yu, ZHANG Peng-fei, PAN Rui-li, DOU Tao. Study on the modification of ZSM-5 by the treatment of TPAOH/NaOH mixed alkali system and its catalytic performance[J]. J Fuel Chem Technol, 2012,40(5):583-588.
23. [23]
  LIU Dong-mei, KONG Fei-fei, ZHAI Yu-chun, WANG Hai-yan. Secondary crystallization of Na₂CO₃-modified HZSM-5 zeolites with tetrapropylammonium hydroxide and their catalytic performance in thiophene alkylation reaction[J]. China Pet Process Petrochem Technol, 2015,17(3):77-85.
24. [24]
  ZHAO L, XU C M, GAO S, SHEN B. Effects of concentration on the alkali treatment of ZSM-5 zeolite:A study on dividing points[J]. J Mater Sci, 2010,45(19):5406-5441. doi: 10.1007/s10853-010-4593-2
25. [25]
  SHI Gang, LIN Xiu-ying, FAN Yu, BAO Xiao-jun. ZSM-5 molecular sieve desilicon modification and hydrogenation properties[J]. J Fuel Chem Technol, 2013,41(5):589-600.
26. [26]
  LIU Sheng-lin, GUO Xiao-ye, ZHANG Ze-kai, XIE Su-juan, DAI Hong-yi, XU Long-ya. The influence of MCM-22 molecular sieve mesoporous pore on gasoline alkylation desulfurization[J]. Acta Pet Sin (Pet Process Seet), 2008(Z):88-91.
27. [27]
  YAO Jian-jun, DUAN Yan, HOU Kai-hu. The preparation and performance evaluation of nanocomposite Al₂O₃-Hβ alkylation catalyst[J]. Acta Pet Sin (Pet Process Seet), 2013,29(4):577-583.
28. [28]
  BIAN Jun-jie. Study on the carbon deposition of phenylpropylene alkylation over modified Beta zeolite catalyst [D]. Dalian: Dalian University of Technology, 2002.
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