Insights into the confinement effect on isobutane alkylation with C4 olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

doi:10.1016/j.cjche.2021.08.005

中国化学工程学报 ›› 2022, Vol. 47 ›› Issue (7): 174-184.DOI: 10.1016/j.cjche.2021.08.005

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Insights into the confinement effect on isobutane alkylation with C₄ olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

Shuo Li¹, Jianlin Cao², Xiang Feng², Yupeng Du¹, De Chen³, Chaohe Yang², Wenhua Wang¹, Wanzhong Ren¹

1. College of Chemistry & Chemical Engineering, Yantai University, Yantai 264005, China;
2. State Key Laboratory of Heavy Oil Processing, School of Chemical Engineering, China University of Petroleum, Qingdao 266580, China;
3. Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim 7491, Norway

收稿日期:2021-04-13 修回日期:2021-08-06 出版日期:2022-07-28 发布日期:2022-08-19
通讯作者: Xiang Feng,E-mail:xiangfeng@upc.edu.cn;Chaohe Yang,E-mail:yangch@upc.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (21978325, 21776312, 21908186), the Independent Innovation Foundation of Qingdao (17-1-1-18-jch), the Fundamental Research Funds for the Central Universities (18CX02014A), and the Fundamental Research Funds for the Central Universities and the Opening Fund of State Key Laboratory of Heavy Oil Processing (SKLOP202003002).

Insights into the confinement effect on isobutane alkylation with C₄ olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

Shuo Li¹, Jianlin Cao², Xiang Feng², Yupeng Du¹, De Chen³, Chaohe Yang², Wenhua Wang¹, Wanzhong Ren¹

1. College of Chemistry & Chemical Engineering, Yantai University, Yantai 264005, China;
2. State Key Laboratory of Heavy Oil Processing, School of Chemical Engineering, China University of Petroleum, Qingdao 266580, China;
3. Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim 7491, Norway

Received:2021-04-13 Revised:2021-08-06 Online:2022-07-28 Published:2022-08-19
Contact: Xiang Feng,E-mail:xiangfeng@upc.edu.cn;Chaohe Yang,E-mail:yangch@upc.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (21978325, 21776312, 21908186), the Independent Innovation Foundation of Qingdao (17-1-1-18-jch), the Fundamental Research Funds for the Central Universities (18CX02014A), and the Fundamental Research Funds for the Central Universities and the Opening Fund of State Key Laboratory of Heavy Oil Processing (SKLOP202003002).

摘要/Abstract

摘要： Elucidating the confinement effect harbours tremendous significance for isobutane alkylation with C₄ olefin. Herein, the confinement effect over zeolite catalysts was elucidated by combining DFT calculations, experiments (using the novel Beta zeolite exposing only external surfaces (Beta-E) and conventional Beta-I zeolite with both external and internal surfaces) and multi-techniques (e.g., TGA-DTG, HRTEM, SEM and XRD). It is found that the main active sites for C₄ alkylation reaction are located on internal surface rather than external surface. On the external surface, the hydride transfer reaction does not occur because the H-shared intermediate cannot be formed without the confinement effect. Moreover, the external surface has stronger selectivity for C₄ olefin adsorption than isobutane, leading to enhanced oligomerization reactions. Therefore, the suitable micropore with confinement effect is essential for zeolite-catalyzed C₄ alkylation. The atomic-scale insights of this work are of great referential importance to the design of highly effective zeolite catalyst.

关键词: C₄ alkylation, Surface, Zeolite, Catalysis, DFT calculation

Abstract: Elucidating the confinement effect harbours tremendous significance for isobutane alkylation with C₄ olefin. Herein, the confinement effect over zeolite catalysts was elucidated by combining DFT calculations, experiments (using the novel Beta zeolite exposing only external surfaces (Beta-E) and conventional Beta-I zeolite with both external and internal surfaces) and multi-techniques (e.g., TGA-DTG, HRTEM, SEM and XRD). It is found that the main active sites for C₄ alkylation reaction are located on internal surface rather than external surface. On the external surface, the hydride transfer reaction does not occur because the H-shared intermediate cannot be formed without the confinement effect. Moreover, the external surface has stronger selectivity for C₄ olefin adsorption than isobutane, leading to enhanced oligomerization reactions. Therefore, the suitable micropore with confinement effect is essential for zeolite-catalyzed C₄ alkylation. The atomic-scale insights of this work are of great referential importance to the design of highly effective zeolite catalyst.

Key words: C₄ alkylation, Surface, Zeolite, Catalysis, DFT calculation

Shuo Li, Jianlin Cao, Xiang Feng, Yupeng Du, De Chen, Chaohe Yang, Wenhua Wang, Wanzhong Ren. Insights into the confinement effect on isobutane alkylation with C₄ olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study[J]. 中国化学工程学报, 2022, 47(7): 174-184.

参考文献

[1] Y. Li, R.X. Liu, G.Y. Zhao, Z.M. Zhou, J.P. Zhang, C.Y. Shi, X.M. Liu, X.P. Zhang, S.J. Zhang, Simulation and optimization of fixed bed solid acid catalyzed isobutane/2-butene alkylation process, Fuel 216(2018)686-696
[2] Y. Liu, G.Q. Wu, X.Y. Pang, R.S. Hu, Kinetics study on alkylation of isobutane with deuterated 2-butene in composite ionic liquids, Chem. Eng. J. 387(2020)123407
[3] W.Z. Zheng, P. Cao, Y. Yuan, C.Z. Huang, Z.N. Wang, W.Z. Sun, L. Zhao, Experimental and modeling study of isobutane alkylation with C4 olefin catalyzed by Brønsted acidic ionic liquid/sulfuric acid, Chem. Eng. J. 377(2019)119578
[4] K.T. Jin, T. Zhang, S.J. Yuan, S.W. Tang, Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22 zeolite, Chin. J. Chem. Eng. 26(1)(2018)127-136
[5] P.C. Hu, Z.T. Wu, J.L. Wang, Y.Q. Huang, Y. Deng, S.F. Zhou, Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl3 based ionic liquid analog, Chin. J. Chem. Eng. 27(8)(2019)1857-1862
[6] F. Kirsch, Isoparaffin-olefin alkylations with crystalline aluminosilicates I. Early studies?C4-olefins, J. Catal. 27(1)(1972)142-150
[7] X. Huang, R.Z. Wang, X. Pan, C.F. Wang, M.H. Fan, Y.F. Zhu, Y.G. Wang, J. Peng, Catalyst design strategies towards highly shape-selective HZSM-5 for Para-xylene through toluene alkylation, Green Energy Environ. 5(4)(2020)385-393
[8] A. Feller, A. Guzman, I. Zuazo, J.A. Lercher, On the mechanism of catalyzed isobutane/butene alkylation by zeolites, J. Catal. 224(1)(2004)80-93
[9] A. Feller, J.A. Lercher, Chemistry and technology of isobutane/alkene alkylation catalyzed by liquid and solid acids. Advances in Catalysis. Amsterdam:Elsevier, 2004:229-295
[10] A. Guzman, I. Zuazo, A. Feller, R. Olindo, C. Sievers, J.A. Lercher, Influence of the activation temperature on the physicochemical properties and catalytic activity of La-X zeolites for isobutane/cis-2-butene alkylation, Microporous Mesoporous Mater. 97(1-3)(2006)49-57
[11] K. Yoo, E.C. Burckle, P.G. Smirniotis, Isobutane/2-butene alkylation using large-pore zeolites:influence of pore structure on activity and selectivity, J. Catal. 211(1)(2002)6-18
[12] R. Klingmann, R. Josl, Y. Traa, R. Gläser, J. Weitkamp, Hydrogenative regeneration of a Pt/La-Y zeolite catalyst deactivated in the isobutane/n-butene alkylation, Appl. Catal. A:Gen. 281(1-2)(2005)215-223
[13] H.H. Zhang, J.K. Xu, H.G. Tang, Z.Q. Yang, R.X. Liu, S.J. Zhang, Isobutane/2-butene alkylation reaction catalyzed by Cu-modified and rare earth X-type zeolite, Ind. Eng. Chem. Res. 58(22)(2019)9690-9700
[14] X. Feng, D. Lin, D. Chen, C.H. Yang, Rationally constructed Ti sites of TS-1 for epoxidation reactions, Sci. Bull.(2021)
[15] C. Sievers, I. Zuazo, A. Guzman, R. Olindo, H. Syska, J.A. Lercher, Stages of aging and deactivation of zeolite LaX in isobutane/2-butene alkylation, J. Catal. 246(2)(2007)315-324
[16] M.J. Janik, R.J. Davis, M. Neurock, A density functional theory study of the alkylation of isobutane with butene over phosphotungstic acid, J. Catal. 244(1)(2006)65-77
[17] D. Lin, X.H. Zheng, X. Feng, N. Sheng, Z.N. Song, Y.B. Liu, X.B. Chen, Z.P. Cai, D. Chen, C.H. Yang, Enhancing the dynamic electron transfer of Au species on wormhole-like TS-1 for boosting propene epoxidation performance with H₂ and O₂, Green Energy Environ. 5(4)(2020)433-443
[18] A.J. Jones, R.T. Carr, S.I. Zones, E. Iglesia, Acid strength and solvation in catalysis by MFI zeolites and effects of the identity, concentration and location of framework heteroatoms, J. Catal. 312(2014)58-68
[19] A.J. Jones, S.I. Zones, E. Iglesia, Implications of transition state confinement within small voids for acid catalysis, J. Phys. Chem. C 118(31)(2014)17787-17800
[20] R. Gounder, E. Iglesia, The catalytic diversity of zeolites:confinement and solvation effects within voids of molecular dimensions, Chem Commun (Camb)49(34)(2013)3491-3509
[21] V. Nieminen, M. Sierka, D.Y. Murzin, J. Sauer, Stabilities of C3-C5 alkoxide species inside H-FER zeolite:a hybrid QM/MM study, J. Catal. 231(2)(2005)393-404
[22] C. Tuma, J. Sauer, Protonated isobutene in zeolites:tert-butyl cation or alkoxide?Angew. Chem. Int. Ed. 44(30)(2005)4769-4771
[23] G. Sastre, A. Corma, The confinement effect in zeolites, J. Mol. Catal. A:Chem. 305(1-2)(2009)3-7
[24] D. Lesthaeghe, V. van Speybroeck, M. Waroquier, Theoretical evaluation of zeolite confinement effects on the reactivity of bulky intermediates, Phys Chem Chem Phys 11(26)(2009)5222-5226
[25] M. Al-Eid, L.H. Ding, Q. Saleem, H. Badairy, H. Sitepu, A. Al-Malki, A facile method to synthesize hierarchical nano-sized zeolite beta, Microporous Mesoporous Mater. 279(2019)99-106
[26] Z.N. Song, J.C. Yuan, Z.P. Cai, D. Lin, X. Feng, N. Sheng, Y.B. Liu, X.B. Chen, X. Jin, D. Chen, C.H. Yang, Engineering three-layer core-shell S-1/TS-1@dendritic-TiO₂-SiO₂ supported Au catalysts towards improved performance for propene epoxidation with H₂ and O₂, Green Energy Environ. 5(4)(2020)473-483
[27] A. Janda, B. Vlaisavljevich, L.C. Lin, B. Smit, A.T. Bell, Effects of zeolite structural confinement on adsorption thermodynamics and reaction kinetics for monomolecular cracking and dehydrogenation of n-butane, J Am Chem Soc 138(14)(2016)4739-4756
[28] Y.Y. Chu, B. Han, A.M. Zheng, F. Deng, Influence of acid strength and confinement effect on the ethylene dimerization reaction over solid acid catalysts:a theoretical calculation study, J. Phys. Chem. C 116(23)(2012)12687-12695
[29] Y.Y. Chu, B. Han, A.M. Zheng, X.F. Yi, F. Deng, Pore selectivity for olefin protonation reactions confined inside mordenite zeolite:a theoretical calculation study, J. Phys. Chem. C 117(5)(2013)2194-2202
[30] B. Gil, K. Kałahurska, A. Kowalczyk, A study of the external and internal sites of 2D and 3D zeolites through the FTIR investigation of the adsorption of ammonia and pivalonitrile, Appl. Catal. A:Gen. 578(2019)63-69
[31] Y.Y. Chu, G.C. Li, L. Huang, X.F. Yi, H.Q. Xia, A.M. Zheng, F. Deng, External or internal surface of H-ZSM-5 zeolite, which is more effective for the Beckmann rearrangement reaction?Catal. Sci. Technol. 7(12)(2017)2512-2523
[32] S. Li, J.L. Cao, Y.B. Liu, X. Feng, X.B. Chen, C.H. Yang, Effect of acid strength on the formation mechanism of tertiary butyl carbocation in initial C4 alkylation reaction over H-BEA zeolite:a density functional theory study, Catal. Today 355(2020)171-179
[33] B. Delley, From molecules to solids with the DMol₃ approach, J. Chem. Phys. 113(18)(2000)7756-7764
[34] Y. Zhao, D.G. Truhlar, A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions, J Chem Phys 125(19)(2006)194101
[35] C. Kumsapaya, K. Bobuatong, P. Khongpracha, Y. Tantirungrotechai, J. Limtrakul, Mechanistic investigation on 1, 5-to 2, 6-dimethylnaphthalene isomerization catalyzed by acidic β zeolite:ONIOM study with an M06-L functional, J. Phys. Chem. C 113(36)(2009)16128-16137
[36] J. Fu, X. Feng, Y.B. Liu, H.H. Shan, C.H. Yang, Mechanistic insights into the pore confinement effect on bimolecular and monomolecular cracking mechanisms of n-octane over HY and HZSM-5 zeolites:A DFT study, J. Phys. Chem. C 122(23)(2018)12222-12230
[37] S. Fischer, M. Karplus, Conjugate peak refinement:an algorithm for finding reaction paths and accurate transition states in systems with many degrees of freedom, Chem. Phys. Lett. 194(3)(1992)252-261
[38] C. Peng, R. Guo, X. Feng, X.C. Fang, Tailoring the structure of Co-Mo/mesoporous γ-Al₂O₃ catalysts by adding multi-hydroxyl compound:a 3000?kt/a industrial-scale diesel ultra-deep hydrodesulfurization study, Chem. Eng. J. 377(2019)119706
[39] C. Wattanakit, S. Nokbin, B. Boekfa, P. Pantu, J. Limtrakul, Skeletal isomerization of 1-butene over ferrierite zeolite:a quantum chemical analysis of structures and reaction mechanisms, J. Phys. Chem. C 116(9)(2012)5654-5663
[40] C. Liu, R.A. van Santen, A. Poursaeidesfahani, T.J.H. Vlugt, E.A. Pidko, E.J.M. Hensen, Hydride transfer versus deprotonation kinetics in the isobutane-propene alkylation reaction:a computational study, ACS Catal. 7(12)(2017)8613-8627
[41] A. Astafan, M.A. Benghalem, Y. Pouilloux, J. Patarin, N. Bats, C. Bouchy, T.J. Daou, L. Pinard, Particular properties of the coke formed on nano-sponge*BEA zeolite during ethanol-to-hydrocarbons transformation, J. Catal. 336(2016)1-10
[42] L.H. Ding, Y. Zheng, Effect of template concentration and gel dilution on crystallization and particle size of zeolite beta in the absence of alkali cations, Microporous Mesoporous Mater. 103(1-3)(2007)94-101
[43] X. Feng, D. Chen, X.G. Zhou, Thermal stability of TPA template and size-dependent selectivity of uncalcined TS-1 supported Au catalyst for propene epoxidation with H₂ and O₂, RSC Adv. 6(50)(2016)44050-44056
[44] Z.H. Liu, X.L. Dong, Y.H. Zhu, A.H. Emwas, D.L. Zhang, Q.W. Tian, Y. Han, Investigating the influence of mesoporosity in zeolite beta on its catalytic performance for the conversion of methanol to hydrocarbons, ACS Catal. 5(10)(2015)5837-5845
[45] K. Möller, B. Yilmaz, R.M. Jacubinas, U. Müller, T. Bein, One-step synthesis of hierarchical zeolite beta via network formation of uniform nanocrystals, J. Am. Chem. Soc. 133(14)(2011)5284-5295
[46] M. Díaz, E. Epelde, J. Valecillos, S. Izaddoust, A.T. Aguayo, J. Bilbao, Coke deactivation and regeneration of HZSM-5 zeolite catalysts in the oligomerization of 1-butene, Appl. Catal. B:Environ. 291(2021)120076
[47] Y. Ro, M.Y. Gim, J.W. Lee, E.J. Lee, I.K. Song, Alkylation of isobutane/2-butene over modified FAU-type zeolites, J Nanosci Nanotechnol 18(9)(2018)6547-6551

Insights into the confinement effect on isobutane alkylation with C₄ olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

Insights into the confinement effect on isobutane alkylation with C₄ olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

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