Citation: 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[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026 shu

A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite

Xingyang LI ¹ ,
Tianju LIU ¹ ,
Yang GAO ¹ ,
Dandan ZHANG ¹ ,
Yong ZHOU ^{1, 2,,} ,
Meng PAN ^1,,

1.
School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu, Anhui 241000, China
2.
Eco-materials and Renewable Energy Research Center, School of Physics, Nanjing University, Nanjing 210000, China

Corresponding author: Yong ZHOU, zhouyong1999@nju.edu.cn Meng PAN, panmeng@ahpu.edu.cn
Received Date: 19 January 2024
Revised Date: 19 April 2024

Figures(8)

Combined strategy of alkali treatment and chromium modification was used to synergistically regulate the pore structure and acidic property of the high-silica ZSM-5 zeolite. During the alkaline treatment, the abundant intergrowth boundaries constructed by adjusting the composition of the synthesis gel induced the formation of meso-pores. Thereby, the limitation of the conventional alkali treatment method coming from the framework Si/Al ratio of parent zeolite was circumvented. In the process of chromium modification, the unique hierarchical pore structure promoted the dispersion of chromium species in the catalyst. Thus, a deep modification of the acidic property was realized. As a result, a high-silica hierarchical zeolite catalyst with suitable acidities was obtained. During the catalytic conversion of methanol to propylene, the variation of the pore structure and acidic property caused obvious changes in the coke deposition behavior of the catalyst and the mass transfer of products. Consequently, the prepared catalyst exhibited excellent catalytic stability and a high selectivity towards propylene and total light olefins.
- methanol to propylene,
- hierarchical pore,
- acidity regulation,
- zeolite,
- catalytic performance
1. [1]
  Cui T L, Lv L B, Zhang W B, Li X H, Chen J S. Programmable synthesis of mesoporous ZSM-5 nanocrystals as selective and stable catalysts for the methanol-to-propylene process[J]. Catal. Sci. Technol., 2016,6(14):5262-5266. doi: 10.1039/C6CY00379F
2. [2]
  Kim H Y, Lee B, Lim D J, Choe C G, Lim H K. What is the best green propylene production pathway?: Technical, economic, and environmental assessment[J]. Green Chem., 2021,23(19):7635-7645. doi: 10.1039/D1GC01791H
3. [3]
  Yarulina I, Chowdhury A D, Meirer F, Weckhuysen B M, Gascon J. Recent trends and fundamental insights in the methanol-to-hydrocarbons process[J]. Nat. Catal., 2018,1(6):398-411. doi: 10.1038/s41929-018-0078-5
4. [4]
  Hwang A, Le T T, Shi Z, Dai H, Rimer J D, Bhan A. Effects of diffusional constraints on lifetime and selectivity in methanol-to-olefins catalysis on HSAPO-34[J]. J. Catal., 2019,369:122-132. doi: 10.1016/j.jcat.2018.10.031
5. [5]
  Khanmohammadi M, Amani S, Garmarudi A B, Niaei A. Methanol-to-propylene process: Perspective of the most important catalysts and their behavior[J]. Chin. J. Catal., 2016,37(3):325-339. doi: 10.1016/S1872-2067(15)61031-2
6. [6]
  Zhang W N, Zhi Y C, Huang J D, Wu X Q, Zeng S, Xu S T, Zheng A M, Wei Y X, Liu Z M. Methanol to olefins reaction route based on methylcyclopentadienes as critical intermediates[J]. ACS Catal., 2019,9(8):7373-7379. doi: 10.1021/acscatal.9b02487
7. [7]
  REN K, ZHANG L L, LI Z, FU Y J. Structure-activity relationship and reaction characteristics of propene aromatization catalyzed by ZSM-5[J]. Chinese J. Inorg. Chem., 2022,38(6):1090-1102.
8. [8]
  Yarulina I, De Wispelaere K, Bailleul S, Goetze J, Radersma M, Abou-Hamad E, Vollmer I, Goesten M, Mezari B, Hensen E J M, Martínez-Espín J S, Morten M, Mitchell S, Perez-Ramirez J, Olsbye U, Weckhuysen B M, Van Speybroeck V, Kapteijn F, Gascon J. Structure-performance descriptors and the role of Lewis acidity in the methanol-to-propylene process[J]. Nat. Chem., 2018,10(8):804-812. doi: 10.1038/s41557-018-0081-0
9. [9]
  Li H Y, Wang Y Q, Fan C Y, Sun C, Wang X, Wang C, Zhang X, Wang S H. Facile synthesis of a superior MTP catalyst: Hierarchical micro-meso-macroporous ZSM-5 zeolites[J]. Appl. Catal. A-Gen., 2018,551:34-48. doi: 10.1016/j.apcata.2017.12.007
10. [10]
  Kerstens D, Smeyers B, Van Waeyenberg J, Zhang Q, Yu J H, Sels B F. State of the art and perspectives of hierarchical zeolites: Practical overview of synthesis methods and use in catalysis[J]. Adv. Mater., 2020,32(44)e2004690. doi: 10.1002/adma.202004690
11. [11]
  Bai R S, Song Y, Li Y, Yu J H. Creating hierarchical pores in zeolite catalysts[J]. Trends Chem., 2019,1(6):601-611. doi: 10.1016/j.trechm.2019.05.010
12. [12]
  Qi R Y, Fu T J, Wan W L, Li Z. Pore fabrication of nano-ZSM-5 zeolite by internal desilication and its influence on the methanol to hydrocarbon reaction[J]. Fuel Process. Technol., 2017,155:191-199. doi: 10.1016/j.fuproc.2016.05.046
13. [13]
  Groen J C, Moulijn J A, Pérez-Ramírez J. Desilication: On the controlled generation of mesoporosity in MFI zeolites[J]. J. Mater. Chem., 2006,16(22):2121-2131. doi: 10.1039/B517510K
14. [14]
  Groen J C, Jansen J C, Moulijn J A, Pérez-Ramírez J. Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication[J]. J. Phys. Chem. B, 2004,108(35):13062-13065. doi: 10.1021/jp047194f
15. [15]
  Kalantari N, F Bekheet M, Nezhad P D F, Back J O, Farzi A, Penner S, Delibaş N, Schwarz S, Bernardi J, Salari D, Niaei A. Effect of chromium and boron incorporation methods on structural and catalytic properties of hierarchical ZSM-5 in the methanol-to-propylene process[J]. J. Ind. Eng. Chem., 2022,111:168-182. doi: 10.1016/j.jiec.2022.03.049
16. [16]
  Westgård Erichsen M, Svelle S, Olsbye U. The influence of catalyst acid strength on the methanol to hydrocarbons (MTH) reaction[J]. Catal. Today, 2013,215:216-223. doi: 10.1016/j.cattod.2013.03.017
17. [17]
  Zhang L, Tu R, Ren G Q, Li Z, Zhai S L, Xu Y C, Yu T. Manipulate the acidity of gallium doped silicalite-1 to optimize methanol to propene performance[J]. Chem. Eng. J., 2023,458141447. doi: 10.1016/j.cej.2023.141447
18. [18]
  Yarulina I, Bailleul S, Pustovarenko A, Martinez J R, Wispelaere K D, Hajek J, Weckhuysen B M, Houben K, Baldus M, Van Speybroeck V, Kapteijn F, Gascon J. Suppression of the aromatic cycle in methanol-to-olefins reaction over ZSM-5 by post-synthetic modification using calcium[J]. ChemCatChem, 2016,8(19):3057-3063. doi: 10.1002/cctc.201600650
19. [19]
  Groen J C, Peffer L A A, Moulijn J A, Pérez-Ramírez J. Mesoporosity development in ZSM-5 zeolite upon optimized desilication conditions in alkaline medium[J]. Colloid Surf. A-Physicochem. Eng. Asp., 2004,241(1):53-58.
20. [20]
  Janssens T V W. A new approach to the modeling of deactivation in the conversion of methanol on zeolite catalysts[J]. J. Catal., 2009,264(2):130-137. doi: 10.1016/j.jcat.2009.03.004
21. [21]
  Lee S, Choi M. Unveiling coke formation mechanism in MFI zeolites during methanol-to-hydrocarbons conversion[J]. J. Catal., 2019,375:183-192. doi: 10.1016/j.jcat.2019.05.030
22. [22]
  Armaroli T, Simon L J, Digne M, Montanari T, Bevilacqua M, Valtchev V, Patarin J, Busca G. Effects of crystal size and Si/Al ratio on the surface properties of H-ZSM-5 zeolites[J]. Appl. Catal. A-Gen., 2006,306:78-84. doi: 10.1016/j.apcata.2006.03.030
23. [23]
  Mozgawa W. The relation between structure and vibrational spectra of natural zeolites[J]. J. Mol. Struct., 2001,596(1):129-137.
24. [24]
  Mambrim J S T, Pastore H O, Davanzo C U, Vichi E J S, Nakamura O, Vargas H. Synthesis and characterization of chromium silicalite[J]. Chem. Mater., 1993,5(2):66-173.
25. [25]
  Svelle S, Sommer L, Barbera K, Vennestrøm P N R, Olsbye U, Lillerud K P, Bordiga S, Pan Y H, Beato P. How defects and crystal morphology control the effects of desilication[J]. Catal. Today, 2011,168(1):38-47. doi: 10.1016/j.cattod.2010.12.013
26. [26]
  Groen J C, Peffer L A A, Pérez-Ramı́rez J. Pore size determination in modified micro- and mesoporous materials[J]. Pitfalls and limitations in gas adsorption data analysis. Microporous Mesoporous Mat., 2003,60(1):1-17.
27. [27]
  Zhang R Z, Zhao P R, Han L N, Wang J C, Zhao L F. Seed-assisted template-free synthesis of nano-sized ZSM-5 via two-stage crystallization with related investigation of mechanism[J]. Microporous Mesoporous Mat., 2021,312110754. doi: 10.1016/j.micromeso.2020.110754
28. [28]
  Pan M, Jiang X B, Pang Y H, Pan X F, Zhang Q H, Yang R C, Zheng J J. One-step synthesis of hierarchical ZSM-5 zeolites with low defect density as long-lived MTH catalysts[J]. Appl. Catal. A-Gen., 2023,656:119132-119140. doi: 10.1016/j.apcata.2023.119132
29. [29]
  Verboekend D, Pérez-Ramírez J. Design of hierarchical zeolite catalysts by desilication[J]. Catal. Sci. Technol., 2011,1(6):879-890. doi: 10.1039/c1cy00150g
30. [30]
  Palčić A, Moldovan S, El Siblani H, Vicente A, Valtchev V. Defect sites in zeolites: Origin and healing[J]. Adv. Sci., 2022,9(4)2104414. doi: 10.1002/advs.202104414
31. [31]
  Liu Y H, Zhang Q, Li J Y, Wang X X, Terasaki O, Xu J, Yu J H. Protozeolite-seeded synthesis of single-crystalline hierarchical zeolites with facet-shaped mesopores and their catalytic application in methanol-to-propylene conversion[J]. Angew. Chem. Int. Ed., 2022,61(34)e202205716. doi: 10.1002/anie.202205716
32. [32]
  Kim J, Choi M, Ryoo R. Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process[J]. J. Catal., 2010,269(1):219-228. doi: 10.1016/j.jcat.2009.11.009
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