Abstract
Hierarchical ZSM-5 zeolites were successfully prepared with one-step hydrothermal method by adding MTES to the zeolite precursor. The mesoporous structure of zeolite was formed via organosilane interacts with nanoparticles to form a covalent bond of Si–R, and then the alkyl group was removed by calcination. The influence of methyltriethoxysilane on the mesopores, acidity, morphology of the zeolites, and the catalytic performance of the samples was investigated. A mesoporous size about 6.5 nm was formed in the sample, meanwhile, the Brønsted acid density of zeolite was decreased. The yield of the aromatic compound was increased by about 10% after the introduction of the mesoporous structure. The catalyst’s carbon deposition resistance was improved due to a significant decrease of the Brønsted acid density of zeolite, and the catalyst life (methanol conversion rate > 95%) was extended from 41 to 76 h.
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References
Xu C, Jiang B, Liao Z, Wang J, Huang Z, Yang Y (2017) Effect of metal on the methanol to aromatics conversion over modified ZSM-5 in the presence of carbon dioxide. RSC Adv 7:10729–10736
Bhan A, Nicholas DW (2008) Propane aromatization over HZSM-5 and Ga/HZSM-5 catalysts. Catal Rev 50:19–151
Davis ME (2010) Ordered porous materials for emerging applications. Nature 33:245–245
Li J, Wang L, Zhang D, Qian J, Liu L, Xing J (2019) Effect of ZSM-5 acid modification on aromatization performance of methanol. Chin J Fuel Chem Technol 47:957–963
Bi Y, Wang Y, Chen X, Yu Z, Xu L (2014) Methanol aromatization over HZSM-5 catalysts modified with different zinc salts. Chin J Catal 35:1740–1751
Niu X, Gao J, Wang K, Miao Q, Dong M, Wang G, Fan W, Qin Z, Wang J (2017) Influence of crystal size on the catalytic performance of H-ZSM-5 and Zn/H-ZSM-5 in the conversion of methanol to aromatics. Fuel Process Technol 157:9–107
Stepacheva AA, Doluda VYu, Lakina NV, Molchanov VP, Sidorov AI, Matveeva VG, Sulman MG, Sulman EM (2018) Catalytic performance of the modified H-ZSM-5 zeolite in methanol transformation to hydrocarbons. Reac Kinet Mech Cat 124:807–832
Schulz H (2010) “Coking” of zeolites during methanol conversion: Basic reactions of the MTO-, MTP- and MTG-processes. Catal Today 154:183–194
Keil FJ (1999) Methanol-to-hydrocarbons: process technology. Microporous Mesoporous Mater 29:49–66
Barbera K, Bonino F, Bordiga S, Janssens TVW, Beato P (2011) Structure–deactivation relationship for ZSM-5 catalysts governed by framework defects. J Catal 280:196–205
Gia-Thanh V, Trong-On D (2007) A new route for the synthesis of uniform nanozeolites with hydrophobic external surface in organic solvent medium. J Am Chem Soc 129:3810–3811
Tosheva L, Valtchev VP (2005) Nanozeolites: synthesis, crystallization mechanism and application. Chem mater 36:2494–2513
Svetlana M, Jean-Pierre G, Valentin V (2013) Advances in nanosized zeolites. Nanoscale 5:6693–6703
Ferdi S (2003) Endo- and exotemplating to create high-surface-area inorganic materials. Angew Chem Int Ed 42:3604–3622
Feliczak-Guzik A (2018) Hierarchical zeolites: synthesis and catalytic properties. Microporous Mesoporous Mater 259:33–45
Jin L, Liu S, Xie T, Wang Y, Guo X, Hu H (2014) Synthesis of hierarchical ZSM-5 by cetyltrimethylammonium bromide assisted self-assembly of zeolite seeds and its catalytic performances. Reac Kinet Mech Cat 113(575):584
Mitchell S, Pinar AB, Kenvin J, Crivelli P, Kärger J, Pérezramírez J (2015) Structural analysis of hierarchically organized zeolites. Nat Commun 6:8633–8644
Wang L, Yin C, Shan Z, Liu S, Du Y, Xiao FS (2009) Bread-template synthesis of hierarchical mesoporous ZSM-5 zeolite with hydrothermally stable mesoporosity. Colloid Surf A 340:126–130
Mitchell S, Michels NL, Kunze K, Pérezramírez J (2012) Visualization of hierarchically structured zeolite bodies from macro to nano length scales. Nat Chem 4:825–831
Hu H, Lyu J, Rui J, Jie C, Zhang Q, Wang Q, Han W, Li X (2016) The effect of Si/Al ratio on the catalytic performance of hierarchical porous ZSM-5 for catalyzing benzene alkylation with methanol. Catal Sci Technol 6:2647–2652
Serrano DP, Escola JM, Pizarro P (2013) Synthesis strategies in the search for hierarchical zeolites. Chem Soc Rev 42:4004–4035
Groen JC, Moulijn JA (2006) Desilication: on the controlled generation of mesoporosity in MFI zeolites. J Mater Chem 16:2121–2131
Shetti VN, Kim J, Srivastava R, Choi M, Ryoo R (2008) Assessment of the mesopore wall catalytic activities of MFI zeolite with mesoporous/microporous hierarchical structures. J Catal 254:296–303
Qiu SR, Wierzbicki A, Salter EA, Zepeda S, Orme CA, Hoyer JR, Nancollas GH, Cody AM, De Yoreo JJ (2005) Modulation of calcium oxalate monohydrate crystallization by citrate through selective binding to atomic steps. J Am Chem Soc 127:9036–9044
Choi M, Cho HS, Srivastava R, Venkatesan C, Choi DH, Ryoo R (2006) Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity. Nat Mater 5:718–723
Zhang Y, Zhu K, Zhou XG, Yuan W (2014) Synthesis of hierarchically porous ZSM-5 zeolites by steam-assisted crystallization of dry gel silanized with short-chain organosilane. New J Chem 38:5808–5816
Xue Z, Ma J, ZhengJ ZT, Kang Y, Li R (2012) Hierarchical structure and catalytic properties of a microspherical zeolite with intracrystalline mesopores. Acta Mater 60:5712–5722
Chen H, Yang M, Shang W, Tong Y, Ma X (2018) Organosilane surfactant-directed synthesis of hierarchical ZSM-5 zeolites with improved catalytic performance in MTP reaction. Ind Eng Chem Res 57:10956–10966
Choi M, Na K, Kim J, Sakamoto Y, Terasaki O, Ryoo R (2009) Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature 461:246–249
Srivastava R, Iwasa N, Fujita S, Arai M (2008) Direct synthesis of mesoporous ZSM-5 zeolite by a dual-functional surfactant approach. Chem Eur J 14:9507–9511
Kai L, You H, Jia G, Zheng Y, Huang Y, Song Y, Mei Y, Zhang L, Zhang H (2010) Hierarchically nanostructured coordination polymer: facile and rapid fabrication and tunable morphologies. Cryst Growth Des 10:790–797
Bai YD, Zheng JJ, Fan BB (2015) One step synthesis of SAPO-34 molecular with hierarchical porosity. Chin J Inorg Chem 31:1505–1510
Yu Q, Qiang Z, Liu J, Li C, Cui Q (2013) Inductive effect of various seeds on the organic template-free synthesis of zeolite ZSM-5. CrystEngComm 15:7680–7687
Singh BK, Xu D, Lu H, Jian D, Che S (2014) Synthesis of single-crystalline mesoporous ZSM-5 with three-dimensional pores via the self-assembly of a designed triply branched cationic surfactant. Chem Mater 26:7183–7188
Ying W, Wang R, Xu D, Sun C, Ling N, Fu W, Zeng S, Shang J, Zhang Z, Qiu S (2016) The synthesis and properties of MFI zeolites with microporous, mesoporous and macroporous hierarchical structures by a gel-casting technique. New J Chem 40:4398–4405
Li H, Wang Y, Meng F, Fei G, Chao S, Fan C, Xiao W, Wang S (2017) Controllable fabrication of single-crystalline, ultrafine and high-silica hierarchical ZSM-5 aggregates via solid-like state conversion. RSC Adv 7:25605–25620
Kim J, Choi M, Ryoo R (2010) Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process. J Catal 269:219–228
Davis TM, Drews TO, Ramanan H, He C, Dong J, Schnablegger H, Katsoulakis MA, Kokkoli E, McCormick AV, Penn RL, Tsapatsis M (2006) Mechanistic principles of nanoparticle evolution to zeolite crystals. Nat Mater 5:400–408
Serrano DP, Aguado J, Escola JM, Rodriguez JM, Peral A (2008) Effect of the organic moiety nature on the synthesis of hierarchical ZSM-5 from silanized protozeolitic units. J Mater Chem 18:4210–4218
Serrano DP, Pinnavaia TJ, Aguado J, Escola JM, Peral A, Villalba L (2014) Hierarchical ZSM-5 zeolites synthesized by silanization of protozeolitic units: mediating the mesoporosity contribution by changing the organosilane type. Catal Today 227:15–25
Choudhary TV, Kinage A, Banerjee S, Choudhary VR (2006) Influence of Si/Ga and Si/Al ratios on propane aromatization over highly active H-GaAlMFI. Catal Commun 7:166–169
Gao Y, Zheng B, Wu G, Ma F, Liu C (2016) Effect of the Si/Al ratio on the performance of hierarchical ZSM-5 zeolites for methanol aromatization. RSC Adv 6:83581–83588
Fu W, Zhang L, Wu D, Yu Q, Tang T, Tang T (2016) Mesoporous zeolite ZSM-5 supported Ni2P catalysts with high activity in the hydrogenation of phenanthrene and 4,6-dimethyldibenzothiophene. Ind Eng Chem Res 55:7085–7095
Koekkoek AJJ, Tempelman CHL, Degirmenci V, Guo M, Feng Z, Li C, Hensen EJM (2011) Hierarchical zeolites prepared by organosilane templating: a study of the synthesis mechanism and catalytic activity. Catal Today 168:96–111
Song Y, Zhu X, Song Y, Wang Q, Xu L (2006) An effective method to enhance the stability on-stream of butene aromatization: post-treatment of ZSM-5 by alkali solution of sodium hydroxide. Appl Catal A 302:69–77
Bleken FL, Janssens TVW, Svelle S, Olsbye U (2012) Product yield in methanol conversion over ZSM-5 is predominantly independent of coke content. Microporous Mesoporous Mater 164:190–198
Mores D, Kornatowski J, Olsbye U, Weckhuysen BM (2011) Coke formation during the methanol-to-olefin conversion. in situ microspectroscopy on individual H-ZSM-5 crystals with different Bronsted acidity. Chem Eur J 17:2874–2884
Guisnet M (2009) Prevention of zeolite deactivation by coking. J Mol Catal A 305:69–83
Xiao W, Fei W, Xiao G (2015) Performance of hierarchical HZSM-5 zeolites prepared by NaOH treatments in the aromatization of glycerol. RSC Adv 5:63697–63704
Acknowledgements
The project was supported by the National Natural Science Foundation of China (Grant No. 21606117), Natural Science Foundation of Liaoning Province (Grant Nos. 2015020623, 201602380), Innovation Team Project of Liaoning Province (Grant Nos. 2018-479-14, LT2015001).
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Li, J., Wang, L., Zhang, D. et al. One-step synthesis of hierarchical ZSM-5 zeolites and their catalytic performance on the conversion of methanol to aromatics. Reac Kinet Mech Cat 130, 519–530 (2020). https://doi.org/10.1007/s11144-020-01786-9
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DOI: https://doi.org/10.1007/s11144-020-01786-9