Effect of mesopore spatial distribution of HZSM-5 catalyst on zinc state and product distribution in 1-hexene aromatization

doi:10.1016/j.cjche.2023.11.008

摘要/Abstract

摘要： 1-hexene aromatization is a promising technology to convert excess olefin in fluid catalytic cracking (FCC) gasoline to high-value benzene (B), toluene (T), and xylene. Besides, the increasing market demand of xylene has put forward higher requirements for new generation of catalyst. For increasing xylene yield in 1-hexene aromatization, the effect of mesopore structure and spatial distribution on product distribution and Zn loading was studied. Catalysts with different mesopore spatial distribution were prepared by post-treatment of parent HZSM-5 zeolite, including NaOH treatment, tetra-propylammonium hydroxide (TPAOH) treatment, and recrystallization. It was found the evenly distributed mesopore mainly prolongs the catalyst lifetime by enhancing diffusion properties but reduces the aromatics selectivity, as a result of damage of micropores close to the catalyst surface. While the selectivity of high-value xylene can be highly promoted when the mesopore is mainly distributed interior the catalyst. Besides, the state of loaded Zn was also affected by mesopores spatial distribution. On the optimized catalyst, the xylene selectivity was enhanced by 12.4% compared with conventional Zn-loaded parent HZSM-5 catalyst at conversion over 99%. It was attributed to the synergy effect of mesopores spatial distribution and optimized acid properties. This work reveals the role of mesopores in different spatial positions of 1- hexene aromatization catalysts in the reaction process and the influence on metal distribution, as well as their synergistic effect two on the improvement of xylene selectivity, which can improve our understanding of catalyst pore structure and be helpful for the rational design of high-efficient catalyst.

关键词: 1-Hexene aromatization, Alkali treatment, Xylene selectivity, Mesopores, Zinc state

Abstract: 1-hexene aromatization is a promising technology to convert excess olefin in fluid catalytic cracking (FCC) gasoline to high-value benzene (B), toluene (T), and xylene. Besides, the increasing market demand of xylene has put forward higher requirements for new generation of catalyst. For increasing xylene yield in 1-hexene aromatization, the effect of mesopore structure and spatial distribution on product distribution and Zn loading was studied. Catalysts with different mesopore spatial distribution were prepared by post-treatment of parent HZSM-5 zeolite, including NaOH treatment, tetra-propylammonium hydroxide (TPAOH) treatment, and recrystallization. It was found the evenly distributed mesopore mainly prolongs the catalyst lifetime by enhancing diffusion properties but reduces the aromatics selectivity, as a result of damage of micropores close to the catalyst surface. While the selectivity of high-value xylene can be highly promoted when the mesopore is mainly distributed interior the catalyst. Besides, the state of loaded Zn was also affected by mesopores spatial distribution. On the optimized catalyst, the xylene selectivity was enhanced by 12.4% compared with conventional Zn-loaded parent HZSM-5 catalyst at conversion over 99%. It was attributed to the synergy effect of mesopores spatial distribution and optimized acid properties. This work reveals the role of mesopores in different spatial positions of 1- hexene aromatization catalysts in the reaction process and the influence on metal distribution, as well as their synergistic effect two on the improvement of xylene selectivity, which can improve our understanding of catalyst pore structure and be helpful for the rational design of high-efficient catalyst.

Key words: 1-Hexene aromatization, Alkali treatment, Xylene selectivity, Mesopores, Zinc state

Chenhao Wei, Di Gao, Guohao Zhang, Liang Zhao, Jinsen Gao, Chunming Xu. Effect of mesopore spatial distribution of HZSM-5 catalyst on zinc state and product distribution in 1-hexene aromatization[J]. 中国化学工程学报, 2024, 67(3): 16-26.

参考文献

[1] K. Yan, Y.Y. Yang, J.J. Chai, Y.R. Lu, Catalytic reactions of gamma-valerolactone:A platform to fuels and value-added chemicals, Appl. Catal., B 179(2015)292-304.
[2] J. Ren, F. Xin, Y.S. Xu, A review on direct synthesis of dimethoxymethane, Chin. J. Chem. Eng. 50(2022)43-55.
[3] D. Jampaiah, D.Y. Murzin, A.F. Lee, D. Schaller, S.K. Bhargava, B. Tabulo, K. Wilson, Catalytic selective ring opening of polyaromatics for cleaner transportation fuels, Energy Environ. Sci. 15(5)(2022)1760-1804.
[4] M. Raad, A. Astafan, S. Hamieh, J. Toufaily, T. Hamieh, J.D. Comparot, C. Canaff, T.J. Daou, J. Patarin, L. Pinard, Catalytic properties of Ga-containing MFI-type zeolite in cyclohexane dehydrogenation and propane aromatization, J. Catal. 365(2018)376-390.
[5] H.M. Lapa, L.M.D.R.S. Martins, p-Xylene oxidation to terephthalic acid:New trends, Molecules 28(4)(2023)1922.
[6] Y.X. Wang, T. Biddle, C.L. Jiang, T. Luong, R.J. Chen, S. Brown, X.Y. Jie, J.L. Hu, Microwave-driven upcycling of single-use plastics using zeolite catalyst, Chem. Eng. J. 465(2023)142918.
[7] W.W. Kaeding, C. Chu, L.B. Young, B. Weinstein, S.A. Butter, Selective alkylation of toluene with methanol to produce para-xylene, J. Catal. 67(1)(1981)159-174.
[8] L. Young, Shape selective reactions with zeolite catalysts III. Selectivity in xylene isomerization, toluene-methanol alkylation, and toluene disproportionation over ZSM-5 zeolite catalysts, J. Catal. 76(2)(1982)418-432.
[9] J.A. Biscardi, G.D. Meitzner, E. Iglesia, Structure and density of active Zn species in Zn/H-ZSM5 propane aromatization catalysts, J. Catal. 179(1)(1998)192-202.
[10] J. Zhu, W.T. Wu, Y. Chang, X.H. Sun, H.Y. Wang, Application of nano-HZSM-5 catalyst on aromatization of FCC gasoline, Petrol. Sci. Technol. 28(1)(2010)7-12.
[11] H.X. Wang, G. Hu, H. Lei, Y.D. Xu, X.H. Bao, A facile and effective method for the distribution of Mo/HZSM-5 catalyst active centers, Catal. Lett. 89(1)(2003)75-79.
[12] Y.M. Jia, J.W. Wang, K. Zhang, C.M. Ding, Highly shape-selective Zn-P/HZSM-5 zeolite catalyst for methanol conversion to light aromatics, Appl. Organomet. Chem. 34(11)(2020) e5932.
[13] X.H. Yang, F. Wang, R.P. Wei, S. Li, Y.F. Wu, P.X. Shen, H.Z. Wang, L.J. Gao, G.M. Xiao, Synergy effect between hierarchical structured and Sn-modified H[Sn, Al]ZSM-5 zeolites on the catalysts for glycerol aromatization, Microporous Mesoporous Mater. 257(2018)154-161.
[14] Y.B. Xu, Y. Song, X.H. Liu, Z.G. Zhang, Effect of bed height on the performance of a fixed Mo/HZSM-5 bed in direct aromatization of methane, Chem. Eng. Technol. 39(11)(2016)2059-2065.
[15] J.C. Groen, W.D. Zhu, S. Brouwer, S.J. Huynink, F. Kapteijn, J.A. Moulijn, J. Pérez-Ramírez, Direct demonstration of enhanced diffusion in mesoporous ZSM-5 zeolite obtained via controlled desilication, J. Am. Chem. Soc. 129(2)(2007)355-360.
[16] Y.N. Li, S.L. Liu, Z.K. Zhang, S.J. Xie, X.X. Zhu, L.Y. Xu, Aromatization and isomerization of 1-hexene over alkali-treated HZSM-5 zeolites:Improved reaction stability, Appl. Catal., A 338(1-2)(2008)100-113.
[17] H.Y. Long, F.Y. Jin, G. Xiong, X.S. Wang, Effect of lanthanum and phosphorus on the aromatization activity of Zn/ZSM-5 in FCC gasoline upgrading, Microporous Mesoporous Mater. 198(2014)29-34.
[18] L. Lin, X.T. Zhang, N. He, J.X. Liu, Q. Xin, H.C. Guo, Operando dual beam FTIR study of hydroxyl groups and Zn species over defective HZSM-5 zeolite supported zinc catalysts, Catalysts 9(1)(2019)100.
[19] J.E. Gao, C.L. Wei, M. Dong, G.F. Wang, Z.K. Li, Z.F. Qin, J.G. Wang, W.B. Fan, Evolution of Zn species on Zn/HZSM-5 catalyst under H₂ pretreated and its effect on ethylene aromatization, ChemCatChem 11(16)(2019)3892-3902.
[20] J.X. Liu, N. He, W. Zhou, L. Lin, G.D. Liu, C.Y. Liu, J.L. Wang, Q. Xin, G. Xiong, H.C. Guo, Isobutane aromatization over a complete Lewis acid Zn/HZSM-5 zeolite catalyst:Performance and mechanism, Catal. Sci. Technol. 8(16)(2018)4018-4029.
[21] D. Gao, Y.B. Zhi, L.Y. Cao, L. Zhao, J.S. Gao, C.M. Xu, M.Z. Ma, P.F. Hao, Influence of zinc state on the catalyst properties of Zn/HZSM-5 zeolite in 1-hexene aromatization and cyclohexane dehydrogenation, Chin. J. Chem. Eng. 43(2022)124-134.
[22] Q. Li, W.W. Cong, C.Y. Xu, S.G. Zhang, F. Wang, D.Z. Han, G.J. Wang, L.C. Bing, New insight into the inductive effect of various seeds on the template-free synthesis of ZSM-5 zeolite, CrystEngComm 23(48)(2021)8641-8649.
[23] Y. Liu, S.Y. Han, D.D. Guan, S. Chen, Y.H. Wu, Y. Yang, N.Z. Jiang, Rapid green synthesis of ZSM-5 zeolite from leached illite clay, Microporous Mesoporous Mater. 280(2019)324-330.
[24] A. Javdani, J. Ahmadpour, F. Yaripour, Nano-sized ZSM-5 zeolite synthesized via seeding technique for methanol conversions:A review, Microporous Mesoporous Mater. 284(2019)443-458.
[25] T. Biemelt, C. Selzer, F. Schmidt, G. Mondin, A. Seifert, K. Pinkert, S. Spange, T. Gemming, S. Kaskel, Hierarchical porous zeolite ZSM-58 derived by desilication and desilication re-assembly, Microporous Mesoporous Mater. 187(2014)114-124.
[26] K. Tarach, K. Góra-Marek, J. Tekla, K. Brylewska, J. Datka, K. Mlekodaj, W. Makowski, M.C. Igualada López, J. Martínez Triguero, F. Rey, Catalytic cracking performance of alkaline-treated zeolite Beta in the terms of acid sites properties and their accessibility, J. Catal. 312(2014)46-57.
[27] K. Sadowska, A. Wach, Z. Olejniczak, P. Ku strowski, J. Datka, Hierarchic zeolites:zeolite ZSM-5 desilicated with NaOH and NaOH/tetrabutylamine hydroxide, Microporous Mesoporous Mater. 167(2013)82-88.
[28] M.J. Verhoef, P.J. Kooyman, J.C. van der Waal, M.S. Rigutto, J.A. Peters, H. van Bekkum, Partial transformation of MCM-41 material into zeolites:Formation of nanosized MFI type crystallites, Chem. Mater. 13(2)(2001)683-687.
[29] Z. Ma, T.J. Fu, Y.J. Wang, J.A. Shao, Q.A. Ma, C.M. Zhang, L.P. Cui, Z. Li, Silicalite-1 derivational desilication-recrystallization to prepare hollow nano-ZSM-5 and highly mesoporous micro-ZSM-5 catalyst for methanol to hydrocarbons, Ind. Eng. Chem. Res. 58(6)(2019)2146-2158.
[30] S.S. Arzumanov, A.A. Gabrienko, A.V. Toktarev, Z.N. Lashchinskaya, D. Freude, J. Haase, A.G. Stepanov, Propane transformation on Zn-modified zeolite. Effect of the nature of Zn species on alkane aromatization and hydrogenolysis, J. Phys. Chem. C 123(50)(2019)30473-30485.
[31] A. Bonnin, J.D. Comparot, Y. Pouilloux, V. Coupard, D. Uzio, L. Pinard, Mechanisms of aromatization of dilute ethylene on HZSM-5 and on Zn/HZSM-5 catalysts, Appl. Catal., A 611(2021)117974.
[32] A. Shahid, A. Inayat, Y. Avadhut, M. Hartmann, W. Schwieger, A comparative study of the desilication of channel-and cage-like zeolites, Microporous Mesoporous Mater. 341(2022)111903.
[33] D.Z. Zhang, C.Z. Jin, M.M. Zou, S.J. Huang, Mesopore engineering for welldefined mesoporosity in Al-rich aluminosilicate zeolites, Chemistry 25(11)(2019)2675-2683.
[34] S.T. Yang, C.X. Yu, L.L. Yu, S. Miao, M.M. Zou, C.Z. Jin, D.Z. Zhang, L.Y. Xu, S.J. Huang, Bridging dealumination and desilication for the synthesis of hierarchical MFI zeolites, Angew. Chem. Int. Ed. 56(41)(2017)12553-12556.
[35] T.J. Fu, Z. Ma, Y.J. Wang, J. Shao, Q. Ma, C.M. Zhang, L.P. Cui, Z. Li, Si/Al ratio induced structure evolution during desilication-recrystallization of silicalite-1 to synthesize nano-ZSM-5 catalyst for MTH reaction, Fuel Process. Technol. 194(2019)106122.
[36] J.J. Li, M. Liu, X.W. Guo, S. Zeng, S.T. Xu, Y.X. Wei, Z.M. Liu, C.S. Song, Influence of Al coordinates on hierarchical structure and T atoms redistribution during base leaching of ZSM-5, Ind. Eng. Chem. Res. 57(45)(2018)15375-15384.
[37] J. Álvarez-Rodríguez, I. Rodríguez-Ramos, A. Guerrero-Ruiz, A. Arcoya, Surface changes in Ru/KL supported catalysts induced by the preparation method and their effect on the selective hydrogenation of citral, Appl. Catal., A 366(1)(2009)114-121.
[38] A. Godelitsas, T. Armbruster, HEU-type zeolites modified by transition elements and lead, Microporous Mesoporous Mater. 61(1-3)(2003)3-24.
[39] J. Álvarez-Rodríguez, I. Rodríguez-Ramos, A. Guerrero-Ruiz, E. Gallegos-Suarez, A. Arcoya, Influence of the nature of support on Ru-supported catalysts for selective hydrogenation of citral, Chem. Eng. J. 204-206(2012)169-178.
[40] P. He, J.S. Jarvis, S.J. Meng, Q.Y. Li, G.M. Bernard, L.J. Liu, X.H. Mao, Z. Jiang, H.B. Zeng, V.K. Michaelis, H. Song, Co-aromatization of methane with propane over Zn/HZSM-5:The methane reaction pathway and the effect of Zn distribution, Appl. Catal., B 250(2019)99-111.
[41] X.J. Niu, J. Gao, K. Wang, Q. Miao, M. Dong, G.F. Wang, W.B. Fan, Z.F. Qin, J.G. Wang, 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(2017)99-107.
[42] A. Bonnin, Y. Pouilloux, V. Coupard, D. Uzio, L. Pinard, Deactivation mechanism and regeneration study of Zn/HZSM-5 catalyst in ethylene transformation, Appl. Catal., A 611(2021)117976.
[43] X.N. Han, H.Z. Li, H.K. Huang, L. Zhao, L.Y. Cao, Y.X. Wang, J.S. Gao, C.M. Xu, Effect of olefin and aromatics on thiophene adsorption desulfurization over modified NiY zeolites by metal Pd, RSC Adv. 6(78)(2016)75006-75013.
[44] C.L. Wen, J.D. Xu, X.M. Wang, Y. Fan, n-Nonane hydroisomerization over hierarchical SAPO-11-based catalysts with sodium dodecylbenzene sulfonate as a dispersant, Petrol. Sci. 18(2)(2021)654-666.
[45] H.Z. Li, L.X. Dong, L.A. Zhao, L.Y. Cao, J.S. Gao, C.M. Xu, Enhanced adsorption desulfurization performance over mesoporous ZSM-5 by alkali treatment, Ind. Eng. Chem. Res. 56(14)(2017)3813-3821.
[46] T. Pan, Z.J. Wu, K.Y. Zhou, In situ incorporation of Zn into hierarchical ZSM-5 zeolites for olefin hydroisomerization, Ind. Eng. Chem. Res. 59(27)(2020)12371-12380.
[47] W. Qin, Y.W. Zhou, J.D. Rimer, Deleterious effects of non-framework Al species on the catalytic performance of ZSM-5 crystals synthesized at low temperature, React. Chem. Eng. 4(11)(2019)1957-1968.
[48] T. Biligetu, Y. Wang, T. Nishitoba, R. Otomo, S. Park, H. Mochizuki, J.N. Kondo, T. Tatsumi, T. Yokoi, Al distribution and catalytic performance of ZSM-5 zeolites synthesized with various alcohols, J. Catal. 353(2017)1-10.
[49] P. Sazama, B. Wichterlova, J. Dedecek, Z. Tvaruzkova, Z. Musilova, L. Palumbo, S. Sklenak, O. Gonsiorova, FTIR and ²⁷Al MAS NMR analysis of the effect of framework Al-and Si-defects in micro-and micro-mesoporous H-ZSM-5 on conversion of methanol to hydrocarbons, Microporous Mesoporous Mater. 143(1)(2011)87-96.
[50] B. Hu, W.X. Chen, X.J. Wang, G.L. Mao, M.J. Luo, Etching behavior of TEAOH in the post-synthesis of hierarchical SAPO-34, Res. Chem. Intermed. 49(2)(2023)619-634.
[51] L. Treps, C. Demaret, D. Wisser, B. Harbuzaru, A. Methivier, E. Guillon, D.V. Benedis, A. Gomez, T. de Bruin, M. Rivallan, L. Catita, A. Lesage, C. Chizallet, Spectroscopic expression of the external surface sites of H-ZSM-5, J. Phys. Chem. C 125(3)(2021)2163-2181.