English

Effect of B and Al Distribution in ZSM-5 Zeolite on Methanol to Propylene Reaction Performance

• ZHAI Yanliang ,
• ZHANG Shaolong ,
• ZHANG Luoming ,
• SHANG Yunshan ,
• WANG Wenxuan ,
• SONG Yu ,
• JIANG Caitong ,
• GONG Yanjun ^,

• State Key Laboratory of Heavy Oil Processing, the Key Laboratory of Catalysis of CNPC, College of Chemistry Engineering and Environment, China University of Petroleum, Beijing 102249, P. R. China

Corresponding author: GONG Yanjun, Email: gongyj@cup.edu.cn; Tel.: +86-10-89733066

• Received Date: 24 January 2019
  Accepted Date: 04 March 2019
  Revised Date: 20 February 2019
  Available Online: 15 November 2019
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (U1662116, 21276278)

Abstract: Propylene is widely used as a raw material for producing polypropylene, acrylonitrile, propylene oxide, etc. Typical manufacturing processes for propylene (steam cracking and FCC process) are over-reliant on petroleum resources and cannot meet the rapidly growing global demands. New routes for producing propylene from non-oil resources, particularly methanol-to-propylene (MTP) technology, have attracted increasingly more attention, where a fixed-bed reactor is used and ZSM-5 zeolite is the best alternative catalyst. However, structural optimization of ZSM-5 to enhance the lifetime and propylene selectivity and a deep understanding of the mechanism of the MTP reaction are still considerable challenges. For the conventional ZSM-5 zeolite, carbon deposition preferentially occurs near the outer surface of the zeolite particles because of the high acid density on the external surface, which accelerates the deactivation by blocking the outer pore openings, especially in a long-term MTP reaction. Large amounts of external strong acids also promote secondary reactions, such as hydrogen transfer reactions, resulting in a decrease in propylene selectivity. To study the effects of strong and weak acid distributions of ZSM-5 zeolite on the MTP reaction, two series of boron-modified ZSM-5 zeolites were designed: B-Al-ZSM-5 zeolites by one-step synthesis and Al-ZSM-5@B-ZSM-5 core-shell zeolites by two-step synthesis. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) mapping, N₂ physical adsorption-desorption, temperature-programmed desorption of ammonia (NH₃-TPD) and 1, 3, 5-triisopropylbenzene (TIPB) cracking, and B1-Al-ZSM-5 and Al@B1-ZSM-5, B2-Al-ZSM-5 and Al@B2-ZSM-5, and B3-Al-ZSM-5 and Al@B3-ZSM-5 samples in the two series were found to have similar texture properties, acid amounts and acid strengths, but different B and Al elemental distributions and acid distributions. We used these two sets of samples to compare the effect of different strong and weak acid distributions—a uniform distribution and a gradient distribution of strong and weak acids on the performance of the MTP reaction. The results showed that samples with a uniform distribution of strong and weak acids have higher propylene selectivity due to lower strong and weak acid densities, whereas samples with a gradient acid distribution have a longer catalytic lifetime in the MTP reaction due to the absence of strong acid density and higher weak acid density on the outer surface. The different acid distributions lead to two different carbon deposition modes. Carbon deposition of the sample with the uniform acid distribution preferentially formed on the outer surface, resulting in rapid deactivation by blocking external micropores and leaving the internal active centers not fully utilized. However, for the sample with the gradient acid distribution, the carbon-blocking rate of the external surface considerably decreased, which increased the time that the reactant molecules had to enter the internal micropores. Thus, the utilization rate of the active centers and the catalytic lifetime of the Al-ZSM-5@B-ZSM-5 core-shell sample considerably increased.

Key words:
• B-Al-ZSM-5
•  /  Al-ZSM-5@B-ZSM-5
•  /  Core-shell zeolite
•  /  Acid distribution
•  /  Methanol to propylene

• 1. [1]

     Plotkin, J. S. Catal. Today 2005, 106 (1–4), 10. doi: 10.1016/j.cattod.2005.07.174

  2. [2]

     Sun, C.; Du, J. M.; Liu, J.; Yang, Y. S.; Ren, N.; Shen, W.; Xu, H. L.; Tang, Y. Chem. Commun. 2010, 46 (15), 2671. doi: 10.1039/b925850g

  3. [3]

     Zhao, G. L.; Teng, J. W.; Xie, Z. K.; Jin, W. Q.; Yang, W. M.; Chen, Q. L.; Tang, Y. J. Catal. 2007, 248 (1), 29. doi: 10.1016/j.jcat.2007.02.027

  4. [4]

     Sardesai, A.; Lee, S. Energy Sources 2005, 27 (6), 489. doi: 10.1080/009083190518970

  5. [5]

     Khanmohammadi, M.; Amani, S.; Garmarudi, A. B.; Niaei, A. Chin. J. Catal. 2016, 37 (3), 325. doi: 10.1016/S1872-2067(15)61031-2

  6. [6]

     Yarulina, I.; Chowdhury, A. D.; Meirer, F.; Weckhuysen, B. M.; Gascon, J. Nat. Catal. 2018, 1 (6), 398. doi: 10.1038/s41929-018-0078-5

  7. [7]

     Hu, S.; Gong, Y. J.; Xu, Q. H.; Liu, X. L.; Zhang, Q.; Zhang, L. L.; Dou, T. Catal. Commun. 2012, 28, 95. doi: 10.1016/j.catcom.2012.08.011

  8. [8]

     Teketel, S.; Olsbye, U.; Lillerud, K. P.; Beato, P.; Svelle, S. Appl. Catal. A 2015, 494, 68. doi: 10.1016/j.apcata.2015.01.035

  9. [9]

     Meng, X. J.; Yu, Q. J.; Gao, Y. N.; Zhang, Q.; Li, C. Y.; Cui, Q. K. Catal. Commun. 2015, 61, 67. doi: 10.1016/j.catcom.2014.12.011

  10. [10]

      张兰兰, 宋宇, 李国栋, 张少龙, 尚蕴山, 巩雁军.物理化学学报, 2015, 31 (11), 2139. doi: 10.3866/PKU.WHXB201509281Zhang, L. L.; Song, Y.; Li, G. D.; Zhang, S. L.; Shang, Y. S.; Gong, Y. J. Acta Phys. -Chim. Sin. 2015, 31 (11), 2139. doi: 10.3866/PKU.WHXB201509281

  11. [11]

      张少龙, 张兰兰, 王务刚, 闵媛媛, 马通, 宋宇, 巩雁军, 窦涛.物理化学学报, 2014, 30 (3), 535. doi: 10.3866/PKU.WHXB201401032Zhang, S. L.; Zhang, L. L.; Wang, W. G.; Min, Y. Y.; Ma, T.; Song, Y.; Gong, Y. J.; Dou, T. Acta Phys. -Chim. Sin. 2014, 30 (03), 535. doi: 10.3866/PKU.WHXB201401032

  12. [12]

      Wei, R. C.; Li, C. Y.; Yang, C. H.; Shan, H. H. J. Nat. Gas Chem. 2011, 20 (3), 261. doi: 10.1016/s1003-9953(10)60198-3

  13. [13]

      Chang, C. D.; Chu, C. T.; Socha, R. F. J. Catal. 1984, 86 (2), 289. doi: 10.1016/0021-9517(84)90374-9

  14. [14]

      Gayubo, A. G.; Benito, P. L.; Aguayo, A. T.; Olazar, M.; Bilbao, J. J. Chem. Technol. Biot. 1996, 65 (2), 186. doi: 10.1002/(SICI)1097-4660(199602)65:2<186::AID-JCTB401>3.0.CO;2-J

  15. [15]

      Ong, L. H.; Doemoek, M.; Olindo, R.; van Veen, A. C.; Lercher, J. A. Micropor. Mesopor. Mat. 2012, 164 (SI), 9. doi: 10.1016/j.micromeso.2012.07.033

  16. [16]

      Nayak, V. S.; Choudhary, V. R. Appl. Catal. 1984, 10 (2), 137. doi: 10.1016/0166-9834(84)80098-6

  17. [17]

      毛东森, 郭胜强, 孟涛, 卢冠忠.物理化学学报, 2010, 26 (2), 338. doi: 10.3866/PKU.WHXB20100208Mao, D.; Guo, Q.; Meng, T.; Lu, G. Acta Phys. -Chim. Sin. 2010, 26 (2), 338. doi: 10.3866/PKU.WHXB20100208

  18. [18]

      Zhang, S. L.; Gong, Y. J.; Zhang, L. L.; Liu, Y. S.; Dou, T.; Xu, J.; Deng, F. Fuel Process. Technol. 2015, 129, 130. doi: 10.1016/j.fuproc.2014.09.006

  19. [19]

      Li, J. J.; Liu, M.; Guo, X. W.; Xu, S. T.; Wei, Y. X.; Liu, Z. M.; Song, C. S. ACS Appl. Mater. Inter. 2017, 9 (31), 26096. doi: 10.1021/acsami.7b07806

  20. [20]

      Li, J. J.; Min, L.; Guo, X. W.; Dai, C. Y.; Xu, S. T.; Wei, Y. X.; Liu, Z. M.; Song, C. S. Ind. Eng. Chem. Res. 2018, 57 (24), 8190. doi: 10.1021/acs.iecr.8b00513

  21. [21]

      Papari, S.; Mohammadrezaei, A.; Asadi, M.; Golhosseini, R.; Naderifar, A. Catal. Commun. 2011, 16 (1), 150. doi: 10.1016/j.catcom.2011.09.024

  22. [22]

      Hadi, N.; Niaei, A.; Nabavi, S. R.; Navaei Shirazi, M.; Alizadeh, R. J. Ind. Eng. Chem. 2015, 29, 52. doi: 10.1016/j.jiec.2015.03.017

  23. [23]

      Liu, J.; Zhang, C. X.; Shen, Z. H.; Hua, W. M.; Tang, Y.; Shen, W.; Yue, Y. H.; Xu, H. L. Catal. Commun. 2009, 10 (11), 1506. doi: 10.1016/j.catcom.2009.04.004

  24. [24]

      Zhong, J. W.; Han, J. F.; Wei, Y. X.; Xu, S. T.; He, Y. L.; Zheng, Y. J.; Ye, M.; Guo, X. W.; Song, C. S.; Liu, Z. M. Chem. Commun. 2018, 54 (25), 3146. doi: 10.1039/C7CC09239C

  25. [25]

      Wang, K.; Dong, M.; Niu, X. J.; Li, J. F.; Qin, Z. F.; Fan, W. B.; Wang, J. G. Catal. Sci. Technol. 2018, 8 (21), 5646. doi: 10.1039/C8CY01734D

  26. [26]

      Kong, C. Y.; Zhu, J.; Liu, S. Y.; Wang, Y. RSC Adv. 2017, 7 (63), 39889. doi: 10.1039/C7RA06488H

  27. [27]

      Miyamoto, M.; Kamei, T.; Nishiyama, N.; Egashira, Y.; Ueyama, K. Adv. Mater. 2005, 17 (16), 1985. doi: 10.1002/ADMA.2005.00522

  28. [28]

      Zhu, Z. R.; Chen, Q. L.; Xie, Z. K.; Yang, W. M.; Kong, D. J.; Li, C. J. Mol. Catal. A: Chem. 2006, 248 (1–2), 152. doi: 10.1016/j.molcata.2005.10.023

  29. [29]

      Nunan, J.; Cronin, J.; Cunningham, J. J. Catal. 1984, 87 (1), 77. doi: 10.1016/0021-9517(84)90169-6

  30. [30]

      Rostamizadeh, M.; Taeb, A. J. Ind. Eng. Chem. 2015, 27, 297. doi: 10.1016/j.jiec.2015.01.004

  31. [31]

      Yang, Y. S.; Sun, C.; Du, J. M.; Yue, Y. H.; Hua, W. M.; Zhang, C. L.; Shen, W.; Xu, H. L. Catal. Commun. 2012, 24, 44. doi: 10.1016/j.catcom.2012.03.013

  32. [32]

      Hu, Z. J.; Zhang, H. B.; Wang, L.; Zhang, H. X.; Zhang, Y. H.; Xu, H. L.; Shen, W.; Tang, Y. Catal. Sci. Technol. 2014, 4 (9), 2891. doi: 10.1039/c4cy00376d

  33. [33]

      Li, C. G.; Vidal-Moya, A.; Miguel, P. J.; Dedecek, J.; Boronat, M.; Corma, A. ACS Catal. 2018, 8 (8), 7688. doi: 10.1021/acscatal.8b02112

  34. [34]

      Schmidt, F.; Hoffmann, C.; Giordanino, F.; Bordiga, S.; Simon, P.; Carrillo-Cabrera, W.; Kaskel, S. J. Catal. 2013, 307, 238. doi: 10.1016/j.jcat.2013.07.020

  35. [35]

      Zhao, X. B.; Hong, Y.; Wang, L. Y.; Fan, D.; Yan, N. N.; Liu, X. N.; Tian, P.; Guo, X. W.; Liu, Z. M. Chin. J. Catal. 2018, 39 (8), 1418. doi: 10.1016/S1872-2067(18)63117-1

  36. [36]

      Losch, P.; Boltz, M.; Bernardon, C.; Louis, B.; Palčić, A.; Valtchev, V. Appl. Catal. A 2016, 509, 30. doi: 10.1016/j.apcata.2015.09.037

  37. [37]

      Li, N.; Zhang, Y. Y.; Chen, L.; Au, C. T.; Yin, S. F. Micropor. Mesopor. Mat. 2016, 227, 76. doi: 10.1021/acs.iecr.7b05075

  38. [38]

      Lee, K.; Lee, S.; Jun, Y.; Choi, M. J. Catal. 2017, 347, 222. doi: 10.1016/j.jcat.2017.01.018

  39. [39]

      Zhai, Y. L.; Zhang, S. L.; Shang, Y. S.; Song, Y.; Wang, W. X.; Ma, T.; Zhang, L. M.; Gong, Y. J.; Xu, J.; Deng, F. Catal. Sci. Technol. 2019, 9, 659. doi: 10.1039/C8CY02177E

  40. [40]

      Ghorbanpour, A.; Gumidyala, A.; Grabow, L. C.; Crossley, S. P.; Rimer, J. D. ACS Nano 2015, 9 (4), 4006. doi: 10.1021/acsnano.5b01308

  41. [41]

      Odedairo, T.; Balasamy, R. J.; Al-Khattaf, S. J. Mol. Catal. A: Chem. 2011, 345 (1), 21. doi: 10.1016/j.molcata.2011.05.015

  42. [42]

      Sang, Y.; Xing, A. H.; Wang, C. F.; Han, Z. H.; Wu, Y. L. Catalysts 2017, 7 (6), 171. doi: 10.3390/catal7060171

  43. [43]

      Van Vu, D.; Miyamoto, M.; Nishiyama, N.; Egashira, Y.; Ueyama, K. J. Catal. 2006, 243 (2), 389. doi: 10.1016/j.jcat.2006.07.028

  44. [44]

      Arudra, P.; Bhuiyan, T. I.; Akhtar, M. N.; Aitani, A. M.; Al-Khattaf, S. S.; Hattori, H. ACS Catal. 2014, 4 (11), 4205. doi: 10.1021/cs5009255

  45. [45]

      Yarulina, I.; De Wispelaere, K.; Bailleul, S.; Goetze, J.; Radersma, M.; Abou-Hamad, E.; Vollmer, I.; Goesten, M.; Mezari, B.; Hensen, E. J. M.; et al. Nat. Chem. 2018, 10 (8), 804. doi: 10.1038/s41557-018-0081-0

  46. [46]

      Gao, S. S.; Xu, S. T.; Wei, Y. X.; Qiao, Q. L.; Xu, Z. C.; Wu, X. Q.; Zhang, M. Z.; He, Y. L.; Xu, S. L.; Liu, Z. M. J. Catal. 2018, 367, 306. doi: 10.1016/j.jcat.2018.09.010

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