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Synthesis of hierarchical ZSM-5 with ultra-small mesopore structure and its catalytic performance during methanol to hydrocarbons

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Abstract

Introduction of mesopore system into zeolite crystals is always deemed to be an effective strategy to improve diffusion and acidic accessibility. In this work, a hierarchically structured ZSM-5 with an ultra-small intracrystalline mesopore structure was prepared by using lysine as a pore-forming agent via a hydrothermal crystallization procedure. The structured and textured properties of the as-synthesized samples were characterized by XRD, SEM, EDS, TEM, NH3-TPD, FT-IR and N2 adsorption–desorption isothermals. The results showed that a purely-phased hierarchical ZSM-5 zeolite with a size of 2–6 nm mesopore can be obtained under the condition of lysine/Al2O3 = 2–8. The addition of lysine in the precursor not only generated an ultra-small mesopore system, but also had a significant effect on the acidity of the synthesized sample: With the increased amount of added lysine, the acid density and acid strength of the as-prepared zeolite catalyst were gradually weakened. The effects of the introduced hierarchical pore structure and the tailored acid sites on the catalytic performance of the catalysts were investigated during methanol dehydration to hydrocarbons reaction. The introduced hierarchical pores and the weakened strong acids significantly improved the stability of the catalyst. Meanwhile, the reduced acid density strongly inhibited hydrogen transfer of light olefins intermediate and then increased the selectivity toward light olefins on the hierarchical zeolite catalysts.

Graphical abstract

To overcome phase separation resulted from brittle combining forces between template and zeolite precursor, lysine, which is easily soluble in water and has a stable structure in the temperature range of ZSM-5 synthesis, served as a mesoporous template, and then, a hierarchical ZSM-5 zeolite was prepared in a hydrothermal method.

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References

  1. Sun MH, Huang SZ, Chen LH, Li Y, Yang XY, Yuan ZY, Su BL (2016) Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine. Chem Soc Rev 45:3479–3563

    Article  CAS  PubMed  Google Scholar 

  2. Rangnekar N, Mittal N, Elyassi B, Caro J, Tsapatsis M (2015) Zeolite membranes–a review and comparison with MOFs. Chem Soc Rev 44:7128–7154

    Article  CAS  PubMed  Google Scholar 

  3. Zhang HB, Hu ZJ, Huang L, Zhang HX, Song KS, Wang L, Shi ZP, Ma JX, Zhuang Y, Shen W, Zhang YH, Xu HL, Tang Y (2015) Dehydration of glycerol to acrolein over hierarchical ZSM-5 zeolites: effects of mesoporosity and acidity. ACS Catal 4:2548–2558

    Article  Google Scholar 

  4. Wang K, Dong M, Niu XJ, Li JF, Qin ZF, Fan WB, Wang JG (2018) Area-controllable synthesis of (001), (101), and (011) planes in ZSM-5 zeolites. Cryst Growth Des 18:7548–7561

    Article  CAS  Google Scholar 

  5. Pan M, Zheng JJ, Liu YJ, Ning WW, Tian HP, Li RF (2019) Construction and practical application of a novel zeolite catalyst for hierarchically cracking of heavy oil. J Catal 369:72–85

    Article  CAS  Google Scholar 

  6. Huang L, Qin F, Huang Z, Zhuang Y, Ma JX, Xu HL (2016) Hierarchical ZSM-5 zeolite synthesized by an ultrasound-assisted method as a long-life catalyst for dehydration of glycerol to acrolein. Ind Eng Chem Res 55:7318–7327

    Article  CAS  Google Scholar 

  7. Zhang JG, Qian WZ, Kong CY, Wei F (2015) Increasing para-Xylene Selectivity in Making Aromatics from Methanol with a Surface-Modified Zn/P/ZSM-5 Catalyst. ACS Catal 5:2982–2988

    Article  CAS  Google Scholar 

  8. Zheng YX, Ning WW, Wang QH, Wei XL, Li XY, Pan M (2023) Hierarchical ZSM-5 zeolite using amino acid as template: Avoiding phase separation and fabricating an ultra-small mesoporous structure. Micropor Mesopor Mater 355:112578–112588

    Article  CAS  Google Scholar 

  9. Pérez-Ramírez J, Verboekend D, BonillaA AbellóS (2009) Zeolite catalysts with tunable hierarchy factor by pore-growth moderators. Adv Funct Mater 19:3972–3979

    Article  Google Scholar 

  10. Chen LH, Sun MH, Wang Z, Yang WM, Xie ZK, Su BL (2020) Hierarchically structured zeolites: from design to application. Chem Rev 120:11194–11294

    Article  CAS  PubMed  Google Scholar 

  11. Shestakova DO, Babina KA, Sladkovskiy DA, Parkhomchuk EV (2022) Seed-assisted synthesis of hierarchical zeolite ZSM-5 in the absence of organic templates. Mater Chem Phy 288:126432–126442

    Article  CAS  Google Scholar 

  12. Bosnar S, Rac V, Stošić D, Travert A, Postole G, Auroux A, Škapin S, Damjanović-Vasilić L, Bronić J, Du XS, Marković S, Pavlović V, Rakić V (2022) Overcoming phase separation in dual templating: A homogeneous hierarchical ZSM-5 zeolite with flower-like morphology, synthesis and in-depth acidity study. Micropor Mesopor Mater 329:111534–111544

    Article  CAS  Google Scholar 

  13. Linares N, Jardim EO, SachseA SE, García-Martínez J (2018) The Energetics of Surfactant-Templating of Zeolites. Angew ChemInt Ed 57:8724–8728

    Article  CAS  Google Scholar 

  14. Fleury G, Mendoza-Castro MJ, Linares N, Roeffaers MBJ, García-Martínez J (2021) Micelle Formation inside Zeolites: A Critical Step in Zeolite Surfactant-Templating Observed by Raman Microspectroscopy. ACS Mater Lett 4:49–54

    Article  PubMed  PubMed Central  Google Scholar 

  15. Meng L, Mezari B, Goesten MG, Hensen EJM (2017) One-step synthesis of hierarchical ZSM-5 using cetyltrimethylammonium as mesoporogen and structure-directing agent. Chem Mater 29:4091–4096

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Wen D, Liu Q, Fei ZY, Yang YR, Zhang ZX, Chen X, Tang JH, Cui MF, Qiao X (2018) Organosilane-assisted synthesis of hierarchical porous ZSM-5 zeolite as a durable catalyst for light-olefins production from chloromethane. Ind Eng ChemRes 57:446–455

    Article  CAS  Google Scholar 

  17. SachseA G-M (2017) Surfactant-templating of zeolites: from design to application. Chem Mater 29:3827–3853

    Article  Google Scholar 

  18. Serrano DP, Escola JM, Sanz R, Garcia RA, PeralA Moreno I, Linares M (2016) Hierarchical ZSM-5 zeolite with uniform s and mesoporeimproved catalytic properties. New J Chem 40:4206–421

    Article  CAS  Google Scholar 

  19. Zhang DZ, Jin CZ, Zou MM, Huang SJ (2019) Mesopore Engineering for Well-Defined Mesoporosity in Al-Rich Aluminosilicate Zeolites. Chem Eur J 25:2675–2683

    Article  CAS  PubMed  Google Scholar 

  20. Han L, Wang R, Wang P, Zheng AG, Guo YQ, Chen Y, Jiang QQ, Lin W (2021) Hierarchical hollow Al-rich nano ZSM-5 crystals for highly selective production of light olefins from naphthenes. Catal Sci Technol 11:6089–6095

    Article  CAS  Google Scholar 

  21. Zheng JJ, Zhang HY, Liu YJ, Wang GS, Kong QL, Pan M, Tian HP, Li RF (2016) Synthesis of Wool-Ball-Like ZSM-5 with Enlarged External Surfaces and Improved Diffusion: A Potential Highly-Efficient FCC Catalyst Component for Elevating Pre-cracking of Large Molecules and Catalytic Longevity. Catal Lett 146:1457–1469

    Article  CAS  Google Scholar 

  22. Wang QH, Zhang LC, Yao ZJ, Guo YN, Gao ZH, Zheng JJ, Li WL, Fan BB, Wang Y, Chen SW, Li RF (2020) Synthesis of loosely aggregating polycrystalline ZSM-5 with luxuriant mesopore structure and its hierarchically cracking for bulky reactants. Mater Chem Phy 243:122610–122617

    Article  CAS  Google Scholar 

  23. Zheng JJ, Zeng QH, Zhang YY, Wang Y, Ma IH, Zhang XW, Sun WF, Li RF (2010) Hierarchical porous zeolite composite with a core—shell structure fabricated using β-zeolite crystals as nutrients as well as cores. Chem Mater 22:6065–6074

    Article  CAS  Google Scholar 

  24. Mallette AJ, Seo S, Rimer JD (2022) Synthesis strategies and design principles for nanosized and hierarchical zeolites. Nat Synth 1:521–534

    Article  Google Scholar 

  25. Zhang M, Ren SY, Guo QX, Shen BJ (2021) Synthesis of hierarchically porous zeolite TS-1 with small crystal size and its performance of 1-hexene epoxidation reaction. Micropor Mesopor Mater 326:111395–111403

    Article  CAS  Google Scholar 

  26. Zhang LC, Sun XB, Pan M, Yang XN, Liu YC, Sun JH, Wang QH, Zheng JJ, Wang Y, Ma JH, Li WL, Li RF (2020) Interfacial effects between carbon nanotube templates and precursors on fabricating a wall-crystallized hierarchical pore system in zeolite crystals. J Mater Sci 55:10412–10426. https://doi.org/10.1007/s10853-020-04708-1

    Article  CAS  Google Scholar 

  27. Valtchev V, Majano G, Mintova S, Pérez-Ramírez J (2013) Tailored crystalline microporous materials by post-synthesis modification. Chem Soc Rev 42:263–290

    Article  CAS  PubMed  Google Scholar 

  28. Ma Q, Fu TJ, Wang YJ, Li H, Cui LP, Li Z (2020) Development of mesoporous ZSM-5 zeolite with microporosity preservation through induced desilication. J Mater Sci 55:11870–11890. https://doi.org/10.1007/s10853-020-04855-5

    Article  CAS  Google Scholar 

  29. Bosnar S, Rac V, Stošić D, Travert A, Postole G, Auroux A, Škapin S, Damjanović-Vasilić L, Bronić J, Du XS, Marković S, Pavlović V, Rakić V (2022) Overcoming phase separation in dual templating: A homogeneous hierarchical ZSM-5 zeolite with flower-like morphology, synthesis and in-depth acidity study. Micropor Mesopor Mater 329:111534–111545

    Article  CAS  Google Scholar 

  30. Zhou J, Hua Z, Liu Z, Wu W, Zhu Y, Shi JL (2011) Direct synthetic strategy of mesoporous ZSM-5 zeolites by using conventional block copolymer templates and the improved catalytic properties. ACS Catal 1:287–291

    Article  CAS  Google Scholar 

  31. Zhang J, Bai S, Chen ZW, Wang YD, Dong L, Zheng HR, Cai FY, Hong M (2017) Core–shell zeolite Y with ant-nest like hollow interior constructed by amino acids and enhanced catalytic activity. J Mater Chem A 5:20757–20764

    Article  CAS  Google Scholar 

  32. Gao BB, Yang M, Qiao YY, Li JZ, Xiang X, Wu PF, Wei YX, Xu ST, Tian P, Liu ZM (2016) A low-temperature approach to synthesize low-silica SAPO-34 nanocrystals and their application in the methanol-to-olefins (MTO) reaction. Catal Sci Technol 6:7569–7578

    Article  CAS  Google Scholar 

  33. Groen JC, Peffer LAA, Pérez-Ramrez J (2003) Pore size determination in modified micro-and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. Micropor Mesopor Mat 60:1–17

    Article  CAS  Google Scholar 

  34. Shirazi L, Jamshidi E, Ghasemi MR (2008) The effect of Si/Al ratio of ZSM-5 zeolite on its morphology, acidity and crystal size. Cryst Res Technol 43:1300–1306

    Article  CAS  Google Scholar 

  35. Ravishankar R, Kirschhock C, Schoeman BJ, Vanoppen P, Grobet PJ, Storck S, Maier WF, Martens JA, SchryverAFC De, Jacobs PA (1998) Physicochemical characterization of silicalite-1 nanophase material. J Phys Chem B 102:2633–2639

    Article  CAS  Google Scholar 

  36. Sun C, Wang YQ, Zhao AJ, Wang X, Wang C, Zhang X, Wang ZY, Zhao JJ, Zhao TT (2020) Synthesis of nano-sized SAPO-34 with morpholine-treated micrometer-seeds and their catalytic performance in methanol-to-olefin reactions. Appl Catal A 589:117314–117324

    Article  CAS  Google Scholar 

  37. Guo L, Zhu WQ, Miao P, Li F, Guo ZH, Sun Q (2018) Intergrowth silicoaluminophosphate molecular sieves synthesized and their catalytic performances for methanol to olefins reaction. Ind Eng Chem Res 57:10398–10402

    Article  CAS  Google Scholar 

  38. Benghalem MA, Pinard L, Comparot J-D, Astafan A, Daou TJ, Belin T (2017) Impact of crystal size on the acidity and the involved interactions studied by conventional and innovative techniques. J Phys Chem C 121:18725–18737

    Article  CAS  Google Scholar 

  39. Akhgar S, Towfighi J, Hamidzadeh M (2020) MTO performance over seed-assisted SAPO-34 zeolites synthesized by reducing template consumption. J Mater Res Technol 9:12126–12136

    Article  CAS  Google Scholar 

  40. Kim S, Park G, Woo MH, Kwak G, Kim SK (2019) Control of hierarchical structure and framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on methanol conversion. ACS Catal 9:2880–2892

    Article  CAS  Google Scholar 

  41. Guisnet M, Magnoux P (2001) Organic chemistry of coke formation. Appl Catal A 212:83–96

    Article  CAS  Google Scholar 

  42. Tian P, Wei YX, YeM LZM (2015) Methanol to olefins (MTO): from fundamentals to commercialization. ACS Catal 5:1922–1938

    Article  CAS  Google Scholar 

  43. Jin YY, Sun Q, Qi GD, Yang CG, Xu J, Chen F, Meng XJ, Deng F, Xiao FS (2013) Solvent-free synthesis of silicoaluminophosphate zeolites. Angew Chem Int Ed 52:9172–9175

    Article  CAS  Google Scholar 

  44. Bjørgen M, Svelle S, Joensen F, Nerlov J, Kolboe S, Bonino F, Palumbo L, Bordiga S, Olsbye U (2007) Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species. J Catal 249:195–207

    Article  Google Scholar 

  45. Svelle S, Joensen F, Nerlov J, Olsbye U, Lillerud KP, Kolboe S, Bjørgen M (2006) Conversi47on of methanol into hydrocarbons over zeolite H-ZSM-5: Ethene formation is mechanistically separated from the formation of higher alkenes. J Am Chem Soc 128:14770–14771

    Article  CAS  PubMed  Google Scholar 

  46. Sun QM, Wang N, Xi DY, Yang M, Yu JH (2014) Organosilane surfactant-directed synthesis of hierarchical porous SAPO-34 catalysts with excellent MTO performance. Chem Comm 50:6502–6505

    Article  CAS  PubMed  Google Scholar 

  47. Wang XT, Li ZB, Gong FF, Ma MM, Zhu YJ (2021) Synthesis of SAPO-34 with modifying Si distribution by seed-assisted method and its excellent catalytic performance for methanol to olefins. Mol Catal 499:111312–111322

    Article  CAS  Google Scholar 

  48. Yang GJ, Wei YX, Xu ST, Chen JR, Li JZ, Liu ZM, Yu IH, Xu RR (2013) Nanosize-enhanced lifetime of SAPO-34 catalysts in methanol-to-olefin reactions. J Phys Chem C 117:8214–8222

    Article  CAS  Google Scholar 

  49. Bakhtiar SUH, Ali S, Wang XT, Yuan FL, Li ZB, Zhu YJ (2019) Synthesis of sub-micrometric SAPO-34 by a morpholine assisted two-step hydrothermal route and its excellent MTO catalytic performance. Dalton Trans 48:2606–2616

    Article  PubMed  Google Scholar 

  50. Hu S, Shan J, Zhang Q, Wang Y, Liu YS, Gong YJ, Wu ZJ, Dou T (2012) Selective formation of propylene from methanol over high-silica nanosheets of MFI zeolite. Appl Catal A 445–446:215–220

    Article  Google Scholar 

  51. Yuan K, Jia XY, Wang S, Fan S, He SP, Wang PF, Dong M, Qin ZF, Fan WB, Wang JG (2023) Effect of crystal size of ZSM-11 zeolite on the catalytic performance and reaction route in methanol to olefins. J Fuel Chem Technol 51:1652–1662

    Article  CAS  Google Scholar 

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Acknowledgement

This work was supported by the National Nature Science Foundation of China (Grant No. U21B20100 and U19B2003) and China Petroleum & Chemical Corporation (121014-2).

Funding

National Natural Science Foundation of China, U21B20100, Ruifeng Li, U19B2003, Ruifeng Li, China Petrochemical Corporation, 121014-2, Jiajun Zheng.

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Authors and Affiliations

  1. Research Centre of Energy Chemical & Catalytic Technology, School of Chemical Engineering and Technology, Taiyuan University of Technology, 79# West Yingze Street, Taiyuan, 030024, China

    Chuyu Jiao, Qirui Jiao, Wei Zhang, Zhuo Ji, Jiajun Zheng, Weijiong Dai, Yan Wang, Meng Pan & Ruifeng Li

  2. School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu, 241000, China

    Meng Pan

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  1. Chuyu Jiao
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Contributions

Chuyu Jiao contributed to writing—carrying out measurements, manuscript composition, original draft and investigation. Qirui Jiao helped in validation and investigation. Wei Zhang helped in validation and investigation. Zhuo Ji helped in validation and investigation. Jiajun Zhen contributed to writing—review & editing, supervision, resources, funding acquisition and conceptualization. Weijiong Dai worked in supervision, resources and funding acquisition. Yan Wang worked in supervision and resources. Meng Pan contributed to writing—experimental design and conceptualization. Ruifeng Li worked in supervision, resources, funding acquisition and conceptualization.

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Correspondence to Jiajun Zheng, Meng Pan or Ruifeng Li.

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Jiao, C., Jiao, Q., Zhang, W. et al. Synthesis of hierarchical ZSM-5 with ultra-small mesopore structure and its catalytic performance during methanol to hydrocarbons. J Mater Sci 59, 16486–16500 (2024). https://doi.org/10.1007/s10853-024-10152-2

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