Citation: Kun REN, Liang-Liang ZHANG, Zhong LI, Ting-Jun FU. Structure-Activity Relationship and Reaction Characteristics of Propene Aromatization Catalyzed by ZSM-5[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(6): 1090-1102. doi: 10.11862/CJIC.2022.115 shu

Structure-Activity Relationship and Reaction Characteristics of Propene Aromatization Catalyzed by ZSM-5

State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China

Corresponding author: Zhong LI, lizhong@tyut.edu.cn Ting-Jun FU, futingjun@tyut.edu.cn
Received Date: 7 March 2022
Revised Date: 1 April 2022

Figures(11)

Aromatization of light olefins in methanol to aromatics via a two-step route showed better catalytic stability. To analyze the intrinsic mechanism, a series of ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios and Zn modified were prepared. Then propene aromatization, as the model reaction, was performed to analyze the effects of acidity on aromatization of light olefins and explore the reaction mechanism. The results illustrated that the increased acid density was in favor of the hydrogen transfer process, resulting in an increase of aromatics selectivity from 31.0% to 34.4% with the SiO₂/Al₂O₃ ratio decreased from 150 to 75. Meanwhile, an increase in acid density will cause more propene to directly participate in the hydrogen transfer reaction to produce propane which was enhanced from 28.2% to 36.0%. Further introducing Zn could transform some Brønsted acid sites into Zn-Lewis acid sites, the aromatics selectivity was further significantly increased to 62.4% with the enhancement of the alkenes dehydrogenation aromatization process. Compared with direct methanol aromatization, propene aromatization had a less deep alkylation process, which not only increased the aromatics selectivity, but also inhibited the formation of insoluble coke, and improved the catalytic stability. These results suggested that the pre-conversion of methanol in methanol to light olefins was an important reason for the high catalytic stability of two-step methanol conversions, which inhibited the deep alkylation of aromatics in the subsequent aromatization process.
- light olefins,
- aromatization,
- ZSM-5 zeolites,
- catalytic performance,
- acidic properties
1. [1]
  Ma H, Sun Y, Yu J P, Qiao J R, Jin W Y, Kang G J, Wang Y L, Ma J. Theoretical Study on the Influence of ZSM-5 Zeolite with Different Structures for Methanol to Aromatics[J]. Microporous Mesoporous Mater., 2019,294109838.
2. [2]
  Niziolek A M, Onel O, Guzman Y A, Floudas C A. Biomass-Based Production of Benzene, Toluene, and Xylenes via Methanol: Process Synthesis and Deterministic Global Optimization[J]. Energy Fuels, 2016,30(6):4970-4098. doi: 10.1021/acs.energyfuels.6b00619
3. [3]
  GUO S J, WANG S, LUO Y Y, LUO L, DONG M, QIN Z F, FAN W B, WANG J G. Effect of H-ZSM-5 Zeolite Morphology on the Performance of Bifunctional ZnCr₂O₄/H-ZSM-5 Catalysts in the Direct Conversion of Syngas into Aromatics[J]. Journal of Fuel Chemistry and Technology, 2020,48(8):970-979. doi: 10.3969/j.issn.0253-2409.2020.08.009
4. [4]
  ZHAO Y L. Study on ZSM-5 Modified by Zinc for Methanol to Aromatics. Dalian: Dalian University of Technology, 2020: 1-20
5. [5]
  CHEN S S, ZHANG G S, HUO F, ZHANG J P. Market and Technology Development Trends of Coal-Based Bulk Chemicals[J]. Chemical Industry and Engineering Progress, 2020,39(12):5009-5020.
6. [6]
  CHENG C H, XI N, LI H, YANG Y, DONG P, LI G X. Research Progress on the Reaction Mechanism of Methanol to Hydrocarbons[J]. Fine Chemicals, 2020,37(2):231-241.
7. [7]
  Niu X J, Gao J, Wang K, Miao Q, Dong M, Wang G F, Fan W B, Qin Z F, Wang J G. Influence of Crystal Size on the Catalytic Performance of H-ZSM-5 and Zn/H-ZSM-5 in the Conversion of Methanol to Aromatics[J]. Fuel Process. Technol., 2017,157:99-107. doi: 10.1016/j.fuproc.2016.12.006
8. [8]
  ZHAO Y L, LIU M, LI J J, ZHANG T T, GUO X W. Synthesis of Zn-ZSM-5 Zeolites of Different Thicknesses by Seed-Oriented Strategy for Methanol to Aromatics[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2021,37(2):269-280. doi: 10.3969/j.issn.1001-8719.2021.02.004
9. [9]
  Xing L Y, Wei Z H, Wen Z H, Zhu X D. Catalytic Study for Methanol Aromatization over Hierarchical ZSM-5 Zeolite Synthesized by Kaolin[J]. Pet. Sci. Technol., 2017,35(24):2235-2240. doi: 10.1080/10916466.2017.1381712
10. [10]
  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
11. [11]
  Gao Y, Zheng B H, Wu G, Ma F W, Liu C T. Effect of the Si/Al Ratio on the Performance of Hierarchical ZSM-5 Zeolites for Methanol Aromatization[J]. RSC Adv., 2016,6(87):83581-83588. doi: 10.1039/C6RA17084F
12. [12]
  Su X F, Zhang K, Snatenkova Y, Matieva Z, Bai X F, Kolesnichenko N, Wu W. High-Efficiency Nano [Zn, Al]ZSM-5 Bifunctional Catalysts for Dimethyl ether Conversion to Isoparaffin-Rich Gasoline[J]. Fuel Process. Technol., 2020,198106242. doi: 10.1016/j.fuproc.2019.106242
13. [13]
  Bi Y, Wang Y L, Chen X, Yu Z X, Xu L. Methanol Aromatization over HZSM-5 Catalysts Modified with Different Zinc Salts[J]. Chin. J. Catal., 2014,35(10):1740-1751. doi: 10.1016/S1872-2067(14)60145-5
14. [14]
  Liu M, Cui T, Guo X W, Li J J, Song C S. Stable Zn@ZSM-5 Catalyst via a Dry Gel Conversion Process for Methanol-to-Aromatics Reaction[J]. Microporous Mesoporous Mater., 2021,312110696. doi: 10.1016/j.micromeso.2020.110696
15. [15]
  Fu T J, Shao J, Li Z. Catalytic Synergy between the Low Si/Al Ratio Zn/ZSM-5 and High Si/Al Ratio HZSM-5 for High-Performance Methanol Conversion to Aromatics[J]. Appl. Catal. B, 2021,291120098. doi: 10.1016/j.apcatb.2021.120098
16. [16]
  Shao J, Fu T J, Li Z. The Selective and Stable Synthesis of Aromatics from Methanol via Two-Step Route Using Light Alkenes as Intermediates[J]. Fuel, 2020,280118609. doi: 10.1016/j.fuel.2020.118609
17. [17]
  XIN M D, XING E H, OUYANG Y, XU G T, LUO Y B, SHU X T. Influence of Status of Zn Species in Zn/ZSM-5 on Its Catalytic Performance[J]. China Petroleum Processing Petrochemical Technology, 2019,50(12):42-49. doi: 10.3969/j.issn.1005-2399.2019.12.011
18. [18]
  Pan T, Wu Z J, Zhou K Y. In Situ Incorporation of Zn into Hierarchical ZSM-5 Zeolites for Olefin Hydroisomerization[J]. Ind. Eng. Chem. Res., 2020,59(27):12371-12380. doi: 10.1021/acs.iecr.0c01506
19. [19]
  Wang N, Hou Y L, Sun W J, Cai D L, Chen Z H, Liu L M, Ge B H, Hu L, Qian W Z, Wei F. Modulation of b-Axis Thickness within MFI Zeolite: Correlation with Variation of Product Diffusion and Coke Distribution in the Methanol-to-Hydrocarbons Conversion[J]. Appl. Catal. B, 2019,243:721-733. doi: 10.1016/j.apcatb.2018.11.023
20. [20]
  Zhang Y, Wu S D, Xu X, Jiang H Q. Ethane Aromatization and Evolution of Carbon Deposits over Nanosized and Microsized Zn/ZSM-5 Catalysts[J]. Catal. Sci. Technol., 2020,10(3):835-843. doi: 10.1039/C9CY01903K
21. [21]
  Su X F, Zan W, Bai X F, Wang G L, Wu W. Synthesis of Microscale and Nanoscale ZSM-5 Zeolites: Effect of Particle Size and Acidity of Zn Modified ZSM-5 Zeolites on Aromatization Performance[J]. Catal. Sci. Technol., 2017,7:1943-1952. doi: 10.1039/C7CY00435D
22. [22]
  Wang K, Dong M, Niu X J, Li J F, Qin Z F, Fan W B, Wang J G. Highly Active and Stable Zn/ZSM-5 Zeolite Catalyst for the Conversion of Methanol to Aromatics: Effect of Support Morphology[J]. Catal. Sci. Technol, 2018,8(21):5646-5656. doi: 10.1039/C8CY01734D
23. [23]
  Tamiyakul S, Sooknoi T, Lobban L L, Jongpatiwut S. Generation of Reductive Zn Species over Zn/HZSM-5 Catalysts for n-Pentane Aromatization[J]. Appl. Catal. B, 2016,525(5):190-196.
24. [24]
  Wan Z J, Wu W, Li G, Wang C F, Yang H, Zhang D K. Effect of SiO₂/Al₂O₃ Ratio on the Performance of Nanocrystal ZSM-5 Zeolite Catalysts in Methanol to Gasoline Conversion[J]. Appl. Catal. A, 2016,523:312-320. doi: 10.1016/j.apcata.2016.05.032
25. [25]
  Qiao J, Wang J P, Frenkel A I, Teng J W, Chen X Q, Xiao J X, Zhang T Z, Wang Z D, Yuan Z Q, Yang W M. Methanol to Aromatics: Isolated Zinc Phosphate Groups on HZSM-5 Zeolite Enhance BTX Selectivity and Catalytic Stability[J]. RSC Adv., 2020,105961. doi: 10.1039/C9RA09657D
26. [26]
  Emeis C A. Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts[J]. J. Catal., 1993,141(2):347-354. doi: 10.1006/jcat.1993.1145
27. [27]
  Ma T, Zhang L M, Song Y, Shang Y S, Zhai Y L, Gong Y J. A Comparative Synthesis of ZSM-5 with Ethanol or TPABr Template: Distinction of Brønsted/Lewis Acidity Ratio and Its Impact on n-Hexane Cracking[J]. Catal. Sci. Technol., 2018,8(7):1923-1935. doi: 10.1039/C7CY02418E
28. [28]
  Liu J X, He N, Zhou W, Shu M, Lin L, Wang J L, Si R, Xiong G, Xin Q, Guo H C. Operando Dual Beam FTIR Spectroscopy Unravels the Promotional Effect of Zn on HZSM-5 in iso-Butane Aromatization[J]. Catal. Sci. Technol., 2019,9(7):1609-1620. doi: 10.1039/C9CY00136K
29. [29]
  ZHANG J G, QIAN W Z, TANG X P, SHEN K, WANG T, HUANG X F, WEI F. Influence of Catalyst Acidity on Dealkylation, Isomerization and Alkylation in MTA Process[J]. Acta. Phys-Chim. Sin., 2013,29(6):1281-1288. doi: 10.3866/PKU.WHXB201304101
30. [30]
  CHEN Z P, XU J, BAO X J. Studies on the Reaction Mechanism of Light Olefin Isomerization and Aromatization[J]. Chemical Industry and Engineering Progress, 2015,34(3):617-623.
31. [31]
  Niu X J, Gao J, Miao Q, Dong M, Wang G F, Fan W B, Qin Z F, Wang J G. Influence of Preparation Method on the Performance of Zn-Containing HZSM-5 Catalysts in Methanol-to-Aromatics[J]. Microporous Mesoporous Mater., 2014,197:252-261. doi: 10.1016/j.micromeso.2014.06.027
32. [32]
  Fu T, Guo Y H, Shao J, Ma Q, Li Z. Precisely Regulating Acid Density and Types to Promote the Stable Two-Step Conversion of Methanol to Aromatics via Light Hydrocarbons[J]. Microporous Mesoporous Mater., 2021,320111103. doi: 10.1016/j.micromeso.2021.111103
33. [33]
  Wang N, Hou Y L, Sun W J, Cai D L, Chen Z H, Liu L M, Ge B H, Hu L, Qian W Z, Wei F. Modulation of b-Axis Thickness within MFI Zeolite: Correlation with Variation of Product Diffusion and Coke Distribution in the Methanol-to-Hydrocarbons Conversion[J]. Appl. Catal. B, 2019,243:721-733. doi: 10.1016/j.apcatb.2018.11.023
34. [34]
  Hawkins A P, Zachariou A, Parker S F, Collier P, Howe R F, Lennon D. Studies of Propene Conversion over H-ZSM-5 Demonstrate the Importance of Propene as an Intermediate in Methanol-to-Hydrocarbons Chemistry[J]. Catal. Sci. Technol., 2021,11:2924-2938. doi: 10.1039/D1CY00048A
35. [35]
  Tabor E, Bernauer M, Wichterlová B, Dedecek J. Enhancement of Propene Oligomerization and Aromatization by Proximate Protons in Zeolites; FTIR Study of the Reaction Pathway in ZSM-5[J]. Catal. Sci. Technol., 2019,9:4262-4275. doi: 10.1039/C9CY00929A
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