Synthesis of a porous organic polymer via click reaction for efficient CH4/C2H6/C3H8 separation

doi:10.1016/j.cjche.2024.11.013

Abstract

Abstract: Adsorptive separation holds important prospect for the challenging recovery of C₂H₆ and C₃H₈ from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent. In this work, we reported the synthesis of a novel porous organic polymer, FOSU-POP-1 for the separation of CH₄/C₂H₆/C₃H₈. The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer–Emmett–Teller (BET) surface area of 1038 m²·g^-1. Exhibiting stronger affinity towards C₃H₈ and C₂H₆ than CH₄, 2.85 mmol·g^-1 for C₃H₈ and 2.14 mmol·g^-1 for C₂H₆ were achieved on the FOSU-POP-1 at 0.1 MPa, 298 K, with an ideal adsorbed solution theory selectivity of 227 for C₃H₈/CH₄. The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH₄/C₂H₆/C₃H₈ ternary mixture. The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C₃H₈ and C₂H₆. This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH₄/C₂H₆/C₃H₈ mixture.

Key words: Porous organic polymers, Click reaction, Separation, Light hydrocarbon

摘要： Adsorptive separation holds important prospect for the challenging recovery of C₂H₆ and C₃H₈ from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent. In this work, we reported the synthesis of a novel porous organic polymer, FOSU-POP-1 for the separation of CH₄/C₂H₆/C₃H₈. The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer–Emmett–Teller (BET) surface area of 1038 m²·g^-1. Exhibiting stronger affinity towards C₃H₈ and C₂H₆ than CH₄, 2.85 mmol·g^-1 for C₃H₈ and 2.14 mmol·g^-1 for C₂H₆ were achieved on the FOSU-POP-1 at 0.1 MPa, 298 K, with an ideal adsorbed solution theory selectivity of 227 for C₃H₈/CH₄. The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH₄/C₂H₆/C₃H₈ ternary mixture. The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C₃H₈ and C₂H₆. This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH₄/C₂H₆/C₃H₈ mixture.

关键词: Porous organic polymers, Click reaction, Separation, Light hydrocarbon

Xun Wang, Tianjian Lun, Changbin Xu, Haolong Zheng, Daofei Lv, Xin Chen, Jian Yan, Junjie Peng, Feng Xu, Zewei Liu. Synthesis of a porous organic polymer via click reaction for efficient CH₄/C₂H₆/C₃H₈ separation[J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 252-259.

References

[1] D.S. Sholl, R.P. Lively, Seven chemical separations to change the world, Nature 532 (7600) (2016) 435-437.
[2] J.M. Shen, A. Dailly, M. Beckner, Natural gas sorption evaluation on microporous materials, Microporous Mesoporous Mater. 235 (2016) 170-177.
[3] S. Mater, L. Hatch, Chemistry of Petrochemical Processes (second ed.), Gulf Publishing Company, Houston, 2001.
[4] R.B. Eldridge, Olefin/paraffin separation technology: a review, Ind. Eng. Chem. Res. 32 (10) (1993) 2208-2212.
[5] T. Ren, M. Patel, K. Blok, Olefins from conventional and heavy feedstocks: energy use in steam cracking and alternative processes, Energy 31 (4) (2006) 425-451.
[6] D. Ruthven, Principles of Adsorption and Adsorption Processes, John Wiley & Sons, New York, 1984.
[7] R.T. Yang, Adsorbents: Fundamentals and Applications, Wiley, New York, 2003.
[8] S. Hosseinpour, S. Fatemi, Y. Mortazavi, M. Gholamhoseini, M.T. Ravanchi, Performance of CaX zeolite for separation of C₂H₆, C₂H₄, and CH₄ by adsorption process; Capacity, selectivity, and dynamic adsorption measurements, Separ. Sci. Technol. 46 (2) (2010) 349-355.
[9] A.M. Avila, F. Yang, M. Shi, S.M. Kuznicki, Extraction of ethane from natural gas at high pressure by adsorption on Na-ETS-10, Chem. Eng. Sci. 66 (13) (2011) 2991-2996.
[10] J.R. Li, R.J. Kuppler, H.C. Zhou, Selective gas adsorption and separation in metal-organic frameworks, Chem. Soc. Rev. 38 (5) (2009) 1477-1504.
[11] Y.F. Wu, Z.W. Liu, J.J. Peng, X. Wang, X. Zhou, Z. Li, Enhancing selective adsorption in a robust pillared-layer metal-organic framework via channel methylation for the recovery of C₂-C₃ from natural gas, ACS Appl. Mater. Interfaces 12 (46) (2020) 51499-51505.
[12] R.B. Lin, S.C. Xiang, H.B. Xing, W. Zhou, B.L. Chen, Exploration of porous metal-organic frameworks for gas separation and purification, Coord. Chem. Rev. 378 (2019) 87-103.
[13] Y.X. Ye, Y. Xie, Y.S. Shi, L.S. Gong, J. Phipps, A.M. Al-Enizi, A. Nafady, B.L. Chen, S.Q. Ma, A microporous metal-organic framework with unique aromatic pore surfaces for high performance C₂H₆/C₂H₄ separation, Angew. Chem. Int. Ed. 62 (21) (2023) e202302564.
[14] A.E. Amooghin, H. Sanaeepur, R. Luque, H. Garcia, B.L. Chen, Fluorinated metal-organic frameworks for gas separation, Chem. Soc. Rev. 51 (17) (2022) 7427-7508.
[15] W.G. Cui, T.L. Hu, X.H. Bu, Metal-organic framework materials for the separation and purification of light hydrocarbons, Adv. Mater. 32 (3) (2020) e1806445.
[16] H. Li, L.B. Li, R.B. Lin, W. Zhou, Z.J. Zhang, S.C. Xiang, B.L. Chen, Porous metal-organic frameworks for gas storage and separation: status and challenges, EnergyChem 1 (1) (2019) 100006.
[17] D.F. Lv, P.J. Zhou, J.H. Xu, S. Tu, F. Xu, J. Yan, H.X. Xi, W.B. Yuan, Q. Fu, X. Chen, Q.B. Xia, Recent advances in adsorptive separation of ethane and ethylene by C₂H₆-selective MOFs and other adsorbents, Chem. Eng. J. 431 (2022) 133208.
[18] J.X. Wang, C.C. Liang, X.W. Gu, H.M. Wen, C.H. Jiang, B. Li, G.D. Qian, B.L. Chen, Recent advances in microporous metal-organic frameworks as promising adsorbents for gas separation, J. Mater. Chem. A 10 (35) (2022) 17878-17916.
[19] T.H. Lan, L.B. Li, Y. Chen, X.Q. Wang, J.F. Yang, J.P. Li, Opportunities and critical factors of porous metal-organic frameworks for industrial light olefins separation, Mater. Chem. Front. 4 (7) (2020) 1954-1984.
[20] J.T. Li, P.M. Bhatt, J.Y. Li, M. Eddaoudi, Y.L. Liu, Recent progress on microfine design of metal-organic frameworks: structure regulation and gas sorption and separation, Adv. Mater. 32 (44) (2020) e2002563.
[21] Y.B. He, R. Krishna, B.L. Chen, Metal-organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons, Energy Environ. Sci. 5 (10) (2012) 9107-9120.
[22] E.D. Bloch, W.L. Queen, R. Krishna, J.M. Zadrozny, C.M. Brown, J.R. Long, Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites, Science 335 (6076) (2012) 1606-1610.
[23] Y.F. Wu, Y.W. Sun, J. Xiao, X. Wang, Z. Li, Glycine-modified HKUST-1 with simultaneously enhanced moisture stability and improved adsorption for light hydrocarbons separation, ACS Sustainable Chem. Eng. 7 (1) (2019) 1557-1563.
[24] Z. Li, Y.W. Yang, Macrocycle-based porous organic polymers for separation, sensing, and catalysis, Adv. Mater. 34 (6) (2022) e2107401.
[25] D.H. Yang, Y. Tao, X.S. Ding, B.H. Han, Porous organic polymers for electrocatalysis, Chem. Soc. Rev. 51 (2) (2022) 761-791.
[26] Q. Sun, B. Aguila, Y.P. Song, S.Q. Ma, Tailored porous organic polymers for task-specific water purification, Acc. Chem. Res. 53 (4) (2020) 812-821.
[27] Q. Sun, B. Aguila, S.Q. Ma, Opportunities of porous organic polymers for radionuclide sequestration, Trends Chem. 1 (3) (2019) 292-303.
[28] P. Bhanja, A. Modak, A. Bhaumik, Porous organic polymers for CO₂ storage and conversion reactions, ChemCatChem 11 (1) (2019) 244-257.
[29] T. Zhang, G.L. Xing, W.B. Chen, L. Chen, Porous organic polymers: a promising platform for efficient photocatalysis, Mater. Chem. Front. 4 (2) (2020) 332-353.
[30] S.T. Wang, H.T. Li, H.N. Huang, X.H. Cao, X.D. Chen, D.P. Cao, Porous organic polymers as a platform for sensing applications, Chem. Soc. Rev. 51 (6) (2022) 2031-2080.
[31] H.P. Ma, H. Ren, S. Meng, F.X. Sun, G.S. Zhu, Novel porphyrinic porous organic frameworks for high performance separation of small hydrocarbons, Sci. Rep. 3 (2013) 2611.
[32] Q.Y. Liu, L.M. Jiang, J.H. Liu, L.H. Wei, J. Zhang, K.Y. Yuan, Nitrogen-rich triphenylamine-based porous organic polyaminals for the adsorption/separation of C₁-C₃ light hydrocarbons and efficient iodine capture, New J. Chem. 47 (37) (2023) 17567-17577.
[33] P. Pandey, O.K. Farha, A.M. Spokoyny, C.A. Mirkin, M.G. Kanatzidis, J.T. Hupp, S.T. Nguyen, A "click-based" porous organic polymer from tetrahedral building blocks, J. Mater. Chem. 21 (6) (2011) 1700-1703.
[34] J.C. Jiang, Y.B. Zhao, O. Yaghi, Covalent chemistry beyond molecules, J. Am. Chem. Soc. 138 (2016) 3255-3265.
[35] J.T. Fletcher, S.E. Walz, M.E. Keeney, Monosubstituted 1,2,3-triazoles from two-step one-pot deprotection/click additions of trimethylsilylacetylene, Tetrahedron Lett. 49 (49) (2008) 7030-7032.

Synthesis of a porous organic polymer via click reaction for efficient CH₄/C₂H₆/C₃H₈ separation

Synthesis of a porous organic polymer via click reaction for efficient CH₄/C₂H₆/C₃H₈ separation

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