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Selective Synthesis of para-Xylene in the Alkylation of Toluene via Regulation of MgO Location in Co-modification Over HZSM-5

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Abstract

The alkylation of toluene catalyzed by modified HZSM-5 was an economical and efficient way to produce para-xylene (PX) due to the full utilization of toluene and fewer by-products. It has attracted significant attention in optimizing the modification method for both high activity and PX selectivity. In this study, we employed SiO2 and MgO to co-modify HZSM-5 for the alkylation of toluene with dimethyl carbonate. The catalysts in which SiO2 was deposited first with trimethoxysilane (TMOS) as the precursor, showed significantly higher activity and PX selectivity than that of depositing MgO first. When the content of SiO2 and MgO was both 5%, the conversion of toluene was 12%, with the selectivity of PX up to 85% (400 °C) for the 5Si-5Mg/ZSM-5 catalyst (depositing SiO2 first). However, the conversion and selectivity were only 5% and 56% for the 5Mg-5Si/ZSM-5 catalyst (depositing MgO first). The analysis of structure and acid properties indicated that the pre-deposition of SiO2 can regulate the location of MgO, leading to the suppression of the external acid sites and the inhibition of the pore blockage by MgO. Owing to the pore size of ZSM-5 being slightly smaller than the molecular size of TMOS, TMOS molecules would be embedded in the pore entrance, making SiO2 tend to prevent MgO from entering the micropore of ZSM-5.

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References

  1. Kumar L, Asthana S, Laxman Newalkar B et al (2022) Selective toluene methylation to p-Xylene: current status & future perspective. Catal Rev 24:1–43.

  2. Chakinala N, Chakinala AG (2021) Process design strategies to produce p-Xylene via toluene methylation: a review. Ind Eng Chem Res 60:5331–5351

    Article  CAS  Google Scholar 

  3. Huang X, Wang R, Pan X et al (2020) Catalyst design strategies towards highly shape-selective HZSM-5 for para-xylene through toluene alkylation. Green Energy Environ 5:385–393

    Article  CAS  Google Scholar 

  4. Han H, Yang H, Zhang A et al (2022) Design of highly stable metal/ZSM-5 catalysts for the shape-selective alkylation of toluene with methanol to para-xylene. Inorg Chem Front 9:3348–3358

    Article  CAS  Google Scholar 

  5. Gallego EM, Portilla MT, Paris C et al (2017) “Ab initio” synthesis of zeolites for preestablished catalytic reactions. Science 355:1051–1054

    Article  CAS  PubMed  Google Scholar 

  6. Lobão MWN, Alberton AL, Melo SABV et al (2011) Kinetics of toluene disproportionation: modeling and experiments. Ind Eng Chem Res 51:171–183

    Article  Google Scholar 

  7. Wang D, Zhang J, Dong P et al (2022) Novel short process for p-Xylene production based on the selectivity intensification of toluene methylation with methanol. ACS Omega 7:1211–1222

    Article  CAS  PubMed  Google Scholar 

  8. Kosinov N, Liu C, Hensen EJM et al (2018) Engineering of transition metal catalysts confined in zeolites. Chem Mater 30:3177–3198

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  9. Xue B, Su J, Huang Q et al (2014) Preparation of MgO/MCM-22 catalysts by a novel two-step impregnation and their shape-selective performance in the synthesis of p-xylene. Catal Commun 45:49–53

    Article  CAS  Google Scholar 

  10. Wang C, Zhang L, Huang X et al (2019) Maximizing sinusoidal channels of HZSM-5 for high shape-selectivity to p-xylene. Nat Commun 10:4348

    Article  PubMed  PubMed Central  Google Scholar 

  11. Hou G, Fu T, Li X et al (2022) Creation of silanol nests on HZSM-5 catalyst to boost the alkylation of toluene with methanol for PX synthesis. Appl Catal A-Gen 642:118713

    Article  CAS  Google Scholar 

  12. Xue B, Li Y, Deng L (2009) Selective synthesis of p-xylene by alkylation of toluene with dimethyl carbonate over MgO-modified MCM-22. Catal Commun 10:1609–1614

    Article  CAS  Google Scholar 

  13. Wen Z, Cao F, Liu J-B et al (2023) Shape-selective alkylation of toluene with dimethyl carbonate into p-Xylene over MgO/MCM-22 prepared by a novel pre-impregnation method. Catal Lett. https://doi.org/10.1007/s10562-023-04289-z

    Article  Google Scholar 

  14. Wang C, Huang X, Zhu Y et al (2020) Understanding HZSM-5’s shape-selectivity improvement through tiny autonomous dealumination. Microporous Mesoporous Mater 309:110581

    Article  CAS  Google Scholar 

  15. Alabi W, Atanda L, Jermy R et al (2012) Kinetics of toluene alkylation with methanol catalyzed by pure and hybridized HZSM-5 catalysts. Chem Eng J 195–196:276–288

    Article  Google Scholar 

  16. Niftaliyeva A, Karaduman A, Kalwar NH et al (2021) Synthesis of novel metal/bimetal nanoparticle-modified ZSM-5 zeolite nanocomposite catalysts and application on toluene methylation. Res Chem Intermed 48:145–165

    Article  Google Scholar 

  17. Li X, Tsai S-T, Wu KCW et al (2021) Morphology control of ionic-liquid-templated ZSM-22 and ZSM-5 zeolites using a two-step process and its effect on toluene methylation. Microporous Mesoporous Mater 328:111475

    Article  CAS  Google Scholar 

  18. Chen Q, Liu J, Yang B (2021) Identifying the key steps determining the selectivity of toluene methylation with methanol over HZSM-5. Nat Commun 12:3725

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Zhou J, Liu Z, Wang Y et al (2017) Shape selective catalysis in methylation of toluene: development, challenges and perspectives. Front Chem Sci Eng 12:103–112

    Article  Google Scholar 

  20. Ahn JH, Kolvenbach R, Gutiérrez OY et al (2015) Tailoring p-xylene selectivity in toluene methylation on medium pore-size zeolites. Microporous Mesoporous Mater 210:52–59

    Article  CAS  Google Scholar 

  21. Tan W, Liu M, Zhao Y et al (2014) Para-selective methylation of toluene with methanol over nano-sized ZSM-5 catalysts: synergistic effects of surface modifications with SiO2, P2O5 and MgO. Microporous Mesoporous Mater 196:18–30

    Article  CAS  Google Scholar 

  22. Zhao Y, Ma X, Ren D et al (2021) A strategy to improve the para-selectivity in toluene methylation on P2O5-ZSM-5 modified by the para-xylene placeholder method. React Kinet Mech Catal 132:967–981

    Article  CAS  Google Scholar 

  23. Han H, Zhang A, Ren L et al (2022) Coke-resistant (Pt + Ni)/ZSM-5 catalyst for shape-selective alkylation of toluene with methanol to para-xylene. Chem Eng Sci 252:117529

    Article  CAS  Google Scholar 

  24. Yi D, Meng X, Liu N et al (2019) Catalytic performance of a phosphorus-modified H-IM-5@meso-SiO2 composite in the alkylation of toluene with methanol. New J Chem 43:11758–11770

    Article  CAS  Google Scholar 

  25. Wang S-f, Fan M-h, He Y-t et al (2019) Catalytic conversion of biomass-derived polyols into para-xylene over SiO2-modified zeolites. Chin J Chem Phys 32:513–520

    Article  CAS  Google Scholar 

  26. Xue B, Chen J, Liu N et al (2014) Role of complex equilibrium in the shape-selective performances of MgO/MCM-22 catalysts prepared by complexing impregnation. Catal Commun 56:174–178

    Article  CAS  Google Scholar 

  27. Li G, Wu C, Dong P et al (2020) Core-Shell HZSM-5@silicalite-1 composite: controllable synthesis and catalytic performance in alkylation of toluene with methanol. Catal Lett 150:1923–1931

    Article  CAS  Google Scholar 

  28. Yang G, Tsubaki N, Shamoto J et al (2010) Confinement effect and synergistic function of H-ZSM-5/Cu-ZnO-Al2O3 capsule catalyst for one-step controlled synthesis. J Am Chem Soc 132:8129–8136

    Article  CAS  PubMed  Google Scholar 

  29. Kianfar E (2019) Ethylene to propylene over Zeolite ZSM-5: improved catalyst performance by treatment with CuO. Russ J Appl Chem 92:933–939

    Article  CAS  Google Scholar 

  30. Adel Niaei H, Rostamizadeh M (2020) Adsorption of metformin from an aqueous solution by Fe-ZSM-5 nano-adsorbent: isotherm, kinetic and thermodynamic studies. J Chem Thermodyn 142:106003

    Article  CAS  Google Scholar 

  31. Rahimi S, Rostamizadeh M (2021) Novel Fe/B-ZSM-5 nanocatalyst development for catalytic cracking of plastic to valuable products. J Taiwan Inst Chem Eng 118:131–139

    Article  CAS  Google Scholar 

  32. Mantina M, Chamberlin AC, Valero R, Cramer CJ, Truhlar DG (2009) Consistent van der Waals radii for the whole main group. J Phys Chem A 113:5806–5812

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Yaripour F, Shariatinia Z, Sahebdelfar S et al (2015) Conventional hydrothermal synthesis of nanostructured H-ZSM-5 catalysts using various templates for light olefins production from methanol. J Nat Gas Sci Eng 22:260–269

    Article  CAS  Google Scholar 

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Acknowledgements

The authors thank Shiyanjia Lab (www.shiyanjia.com) for the support of Py-IR test.

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Correspondence to Bing Xue.

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Yan, B., Wu, J., Li, X. et al. Selective Synthesis of para-Xylene in the Alkylation of Toluene via Regulation of MgO Location in Co-modification Over HZSM-5. Catal Lett 154, 2752–2760 (2024). https://doi.org/10.1007/s10562-023-04536-3

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