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Hierarchical ZSM-5 zeolite with radial mesopores: Preparation, formation mechanism and application for benzene alkylation

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Abstract

Hierarchical ZSM-5 zeolite with radial mesopores is controllably synthesized using piperidine in a NaOH solution. The piperidine molecules enter the zeolite micropores and protect the zeolite framework from extensive desilication. The areas containing fewer aluminum atoms contain fewer piperidine protectant molecules and so they dissolve first. Small amounts of mesopores are then gradually generated in areas with more aluminum atoms and more piperidine protectant. In this manner, radial mesopores are formed in the ZSM-5 zeolite with a maximal preservation of the micropores and active sites. The optimal hierarchical ZSM-5 zeolite, prepared with a molar ratio of piperidine to zeolite of 0.03, had a mesopore surface area of 136 m2·g−1 and a solid yield of 80%. The incorporation of the radial mesopores results in micropores that are interconnected which shortened the average diffusion path length. Compared to the parent zeolite, the hierarchical ZSM-5 zeolite possesses more accessible acid sites and has a higher catalytic activity and a longer lifetime for the alkylation of benzene.

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References

  1. Corma A. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chemical Reviews, 1995, 95(3): 559–614

    CAS  Google Scholar 

  2. Cundy C S, Cox P A. The hydrothermal synthesis of zeolites: History and development from the earliest days to the present time. Chemical Reviews, 2003, 103(3): 663–702

    CAS  PubMed  Google Scholar 

  3. Corma A. From microporous to mesoporous molecular sieve materials and their use in catalysis. Chemical Reviews, 1997, 97(6): 2373–2420

    CAS  PubMed  Google Scholar 

  4. Tao Y S, Kanoh H, Abrams L, Kaneko K. Mesopore-modified zeolites: Preparation, characterization, and applications. Chemical Reviews, 2006, 106(3): 896–910

    CAS  PubMed  Google Scholar 

  5. Zheng H, Zhai D, Zhao L, Zhang C, Yu S, Gao J, Xu C. Insight into the contribution of isolated mesopore on diffusion in hierarchical zeolites: The effect of temperature. Industrial & Engineering Chemistry Research, 2018, 57(15): 5453–5463

    CAS  Google Scholar 

  6. Han J, Cho J, Kim J C, Ryoo R. Confinement of supported metal catalysts at high loading in the mesopore network of hierarchical zeolites, with access via the microporous windows. ACS Catalysis, 2018, 8(2): 876–879

    CAS  Google Scholar 

  7. Jia L Y, Raad M, Hamieh S, Toufaily J, Hamieh T, Bettahar M M, Mauviel G, Tarrighi M, Pinard L, Dufour A. Catalytic fast pyrolysis of biomass: Superior selectivity of hierarchical zeolites to aromatics. Green Chemistry, 2017, 19(22): 5442–5459

    CAS  Google Scholar 

  8. Groen J C, Bach T, Ziese U, Paulaime-van Donk A M, de Jong K P, Moulijn J A, Pérez-Ramírez J. Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals. Journal of the American Chemical Society, 2005, 127(31): 10792–10793

    CAS  PubMed  Google Scholar 

  9. Zhang K, Ostraat M L. Innovations in hierarchical zeolite synthesis. Catalysis Today, 2016, 264: 3–15

    CAS  Google Scholar 

  10. Schmidt I, Boisen A, Gustavsson E, Stahl K, Pehrson S, Dahl S, Carlsson A, Jacobsen C J H. Carbon nanotube templated growth of mesoporous zeolite single crystals. Chemistry of Materials, 2001, 13(12): 4416–4418

    CAS  Google Scholar 

  11. Tao Y, Kanoh H, Kaneko K. ZSM-5 monolith of uniform mesoporous channels. Journal of the American Chemical Society, 2003, 125(20): 6044–6045

    CAS  PubMed  Google Scholar 

  12. Zhu K, Egeblad K, Christensen C H. Mesoporous carbon prepared from carbohydrate as hard template for hierarchical zeolites. European Journal of Inorganic Chemistry, 2007, 2007(25): 3955–3960

    Google Scholar 

  13. Xiao F, Wang L, Yin C, Lin K, Di Y, Li J, Xu R, Su D, Schlögl R, Yokoi T, Tatsumi T. Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. Angewandte Chemie International Edition, 2006, 45(19): 3090–3093

    CAS  PubMed  Google Scholar 

  14. Zhao Z, Liu Y, Wu H, Li X, He M, Wu P. Hydrothermal synthesis of mesoporous titanosilicate with the aid of amphiphilic organosilane. Journal of Porous Materials, 2010, 17(4): 399–408

    CAS  Google Scholar 

  15. Liu H, Zhang S, Xie S, Zhang W, Xin W, Liu S, Xu L. Synthesis, characterization, and catalytic performance of hierarchical ZSM-11 zeolite synthesized via dual-template route. Chinese Journal of Catalysis, 2018, 39(1): 167–180

    CAS  Google Scholar 

  16. Wang X, Chen H, Meng F, Gao F, Sun C, Sun L, Wang S, Wang L, Wang Y. CTAB resulted direct synthesis and properties of hierarchical ZSM-11/5 composite zeolite in the absence of template. Microporous and Mesoporous Materials, 2017, 243: 271–280

    CAS  Google Scholar 

  17. Groen J C, Jansen J C, Moulijn J A, Pérez-Ramírez J. Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication. Journal of Physical Chemistry B, 2004, 108(35): 13062–13065

    CAS  Google Scholar 

  18. Groen J C, Peffer L A A, Moulijn J A, Pérez-Ramírez J. Mechanism of hierarchical porosity development in MFI zeolites by desilication: The role of aluminium as a pore-directing agent. Chemistry (Weinheim an der Bergstrasse, Germany), 2005, 11(17): 4983–4994

    CAS  Google Scholar 

  19. Rutkowska M, Pacia I, Basąg S, Kowalczyk A, Piwowarska Z, Duda M, Tarach K A, Góra-Marek K, Michalik M, Díaz U, Chmielarz L. Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH3-SCR and NH3-SCO processes. Microporous and Mesoporous Materials, 2017, 246: 193–206

    CAS  Google Scholar 

  20. Oruji S, Khoshbin R, Karimzadeh R. Preparation of hierarchical structure of Y zeolite with ultrasonic-assisted alkaline treatment method used in catalytic cracking of middle distillate cut: The effect of irradiation time. Fuel Processing Technology, 2018, 176: 283–295

    CAS  Google Scholar 

  21. Groen J C, Sano T, Moulijn J A, Pérez-Ramírez J. Alkalinemediated mesoporous mordenite zeolites for acid-catalyzed conversions. Journal of Catalysis, 2007, 251(1): 21–27

    CAS  Google Scholar 

  22. Pérez-Ramírez J, Abello S, Villaescusa L A, Bonilla A. Toward functional clathrasils: Size- and composition-controlled octadecasil nanocrystals by desilication. Angewandte Chemie International Edition, 2008, 47(41): 7913–7917

    PubMed  Google Scholar 

  23. Verboekend D, Pérez-Ramírez J. Desilication mechanism revisited: Highly mesoporous all-silica zeolites enabled through pore-directing agents. Chemistry (Weinheim an der Bergstrasse, Germany), 2011, 17(4): 1137–1147

    CAS  Google Scholar 

  24. Sadowska K, Wach A, Olejniczak Z, Kustrowski P, Datka J. Hierarchic zeolites: Zeolite ZSM-5 desilicated with NaOH and NaOH/tetrabutylamine hydroxide. Microporous and Mesoporous Materials, 2013, 167(3): 82–88

    CAS  Google Scholar 

  25. 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. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2004, 241(1–3): 53–58

    CAS  Google Scholar 

  26. Pérez-Ramírez J, Verboekend D, Bonilla A, Abello S. Zeolite catalysts with tunable hierarchy factor by pore-growth moderators. Advanced Functional Materials, 2009, 19(24): 3972–3979

    Google Scholar 

  27. Milina M, Mitchell S, Crivelli P, Cooke D, Pérez-Ramírez J. Mesopore quality determines the lifetime of hierarchically structured zeolite catalysts. Nature Communications, 2014, 5(1): 3922–3931

    Google Scholar 

  28. Wang D, Zhang L, Chen L, Wu H, Wu P. Postsynthesis of mesoporous ZSM-5 zeolite by piperidine-assisted desilication and its superior catalytic properties in hydrocarbon cracking. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(7): 3511–3521

    CAS  Google Scholar 

  29. Wang D, Xu L, Wu P. Hierarchical, core-shell meso-ZSM5@mesoporous aluminosilicate-supported Pt nanoparticles for bifunctional hydrocracking. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(37): 15535–15545

    CAS  Google Scholar 

  30. Kalipcilar H, Culfaz A. Influence of nature of silica source on template-free synthesis of ZSM-5. Crystal Research and Technology, 2001, 36(11): 1197–1207

    CAS  Google Scholar 

  31. Sing K S W, Everett D H, Haul R A W, Moscou L, Pierotti R A, Rouquerol J, Siemieniewska V T. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure and Applied Chemistry, 1985, 57(4): 603–619

    CAS  Google Scholar 

  32. Groen J C, Moulijn J A, Pérez-Ramírez J. Desilication: On the controlled generation of mesoporosity in MFI zeolites. Journal of Materials Chemistry, 2006, 16(22): 2121–2131

    CAS  Google Scholar 

  33. Yoo W C, Zhang X, Tsapatsis M, Stein A. Synthesis of mesoporous ZSM-5 zeolites through desilication and re-assembly processes. Microporous and Mesoporous Materials, 2012, 149(1): 147–157

    CAS  Google Scholar 

  34. Pérez-Ramírez J, Abelló S, Bonilla A, Groen J C. Tailored mesoporosity development in zeolite crystals by partial detemplation and desilication. Advanced Functional Materials, 2009, 19(1): 164–172

    Google Scholar 

  35. Gornicka E, Rode J E. Raczynska, E D, Dasiewicz B, Dobrowolski J C. Vibrational Spectroscopy, 2004, 36: 105–115

    CAS  Google Scholar 

  36. Kokotailo G T, Lawton S L, Olson D H, Meier W M. Structure of synthetic zeolite ZSM-5. Nature, 1978, 272(5652): 437–438

    CAS  Google Scholar 

  37. Zhu K, Sun J, Liu J, Wang L, Wan H, Hu J, Wang Y, Peden C H F, Nie Z. Solvent evaporation assisted preparation of oriented nanocrystalline mesoporous MFI zeolites. ACS Catalysis, 2011, 1(7): 682–690

    CAS  Google Scholar 

  38. Liu Y, Zhang W, Liu Z, Xu S, Wang Y, Xie Z, Han X, Bao X. Direct observation of the mesopores in ZSM-5 zeolites with hierarchical porous structures by laser-hyperpolarized 129Xe NMR. Journal of Physical Chemistry C, 2008, 112(39): 15375–15381

    CAS  Google Scholar 

  39. Schumacher R, Karge H G. Sorption kinetics study of the diethylbenzene isomers in MFI-type zeolites. Microporous and Mesoporous Materials, 1999, 30(2–3): 307–314

    CAS  Google Scholar 

  40. Zhou J, Liu Z, Wang Y, Gao H, Li L, Yang W, Xie Z, Tang Y. Enhanced accessibility and utilization efficiency of acid sites in hierarchical MFI zeolite catalyst for effective diffusivity improvement. RSC Advances, 2014, 4(82): 43752–43755

    CAS  Google Scholar 

  41. Yang W, Wang Z, Sun H, Zhang B. Advances in development and industrial applications of ethylbenzene processes. Chinese Journal of Catalysis, 2016, 37(1): 16–26

    CAS  Google Scholar 

  42. Saxena S K, Viswanadham N. Hierarchically nano porous nano crystalline ZSM-5 for improved alkylation of benzene with bioethanol. Applied Materials Today, 2016, 5: 25–32

    Google Scholar 

  43. Lei Z, Liu L, Dai C. Insight into the reaction mechanism and charge transfer analysis for the alkylation of benzene with propylene over H-β zeolite. Molecular Catalysis, 2018, 454: 1–11

    CAS  Google Scholar 

  44. Christensen C H, Johannsen K, Schmidt I, Christensen C H. Catalytic benzene alkylation over mesoporous zeolite single crystals: Improving activity and selectivity with a new family of porous materials. Journal of the American Chemical Society, 2003, 125(44): 13370–13371

    CAS  PubMed  Google Scholar 

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Acknowledgements

The authors acknowledge the financial support from the National Key Research and Development Program of China (Grant No. 2017YFB0702800) and China Postdoctoral Science Foundation (2016M600347).

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Correspondence to Weimin Yang.

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Hierarchical ZSM-5 zeolite with radial mesopores: Preparation, formation mechanism and application for benzene alkylation

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Wang, D., Sun, H., Liu, W. et al. Hierarchical ZSM-5 zeolite with radial mesopores: Preparation, formation mechanism and application for benzene alkylation. Front. Chem. Sci. Eng. 14, 248–257 (2020). https://doi.org/10.1007/s11705-019-1853-9

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