Efficient adsorption separation of methane from C2-C3 hydrocarbons in a Co(II)-nodes metal-organic framework

doi:10.1016/j.cjche.2024.02.001

中国化学工程学报 ›› 2024, Vol. 69 ›› Issue (5): 192-198.DOI: 10.1016/j.cjche.2024.02.001

Efficient adsorption separation of methane from C₂-C₃ hydrocarbons in a Co(II)-nodes metal-organic framework

Jie Zhang¹, Xingzhe Guo², Bing Lin², Guangzu Xiong², Hanshuang Wang¹, Min Zhang¹, Liwen Fan¹, Bingwen Li³, Shuisheng Chen²

1. Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China;
2. Engineering Research Center of Oligosaccharides, Fuyang Normal University, Fuyang 236041, China;
3. Shandong Key Laboratory of Biophysics, Institute of Biophysics, Dezhou University, Dezhou 253023, China

收稿日期:2023-08-29 修回日期:2024-02-01 出版日期:2024-05-28 发布日期:2024-07-01
通讯作者: Xingzhe Guo,E-mail:guoxingzhe2014@gmail.com;Bingwen Li,E-mail:libingwen@dzu.edu.cn;Shuisheng Chen,E-mail:chenss@fynu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (21401099), the Natural Science Foundation of Shanxi Province (202203021212331), Science and Technology Innovation Project of Colleges and Universities of Shanxi Province (2022L532), the National Natural Science Foundation of Anhui Province (2008085MB32 and KJ2021ZD0073), Natural Science Foundation of Shandong Province (ZR2021QB159). This work is also supported by the Talent Program Foundation of Dezhou University (2021xjrc102).

Efficient adsorption separation of methane from C₂-C₃ hydrocarbons in a Co(II)-nodes metal-organic framework

Jie Zhang¹, Xingzhe Guo², Bing Lin², Guangzu Xiong², Hanshuang Wang¹, Min Zhang¹, Liwen Fan¹, Bingwen Li³, Shuisheng Chen²

1. Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China;
2. Engineering Research Center of Oligosaccharides, Fuyang Normal University, Fuyang 236041, China;
3. Shandong Key Laboratory of Biophysics, Institute of Biophysics, Dezhou University, Dezhou 253023, China

Received:2023-08-29 Revised:2024-02-01 Online:2024-05-28 Published:2024-07-01
Contact: Xingzhe Guo,E-mail:guoxingzhe2014@gmail.com;Bingwen Li,E-mail:libingwen@dzu.edu.cn;Shuisheng Chen,E-mail:chenss@fynu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (21401099), the Natural Science Foundation of Shanxi Province (202203021212331), Science and Technology Innovation Project of Colleges and Universities of Shanxi Province (2022L532), the National Natural Science Foundation of Anhui Province (2008085MB32 and KJ2021ZD0073), Natural Science Foundation of Shandong Province (ZR2021QB159). This work is also supported by the Talent Program Foundation of Dezhou University (2021xjrc102).

摘要/Abstract

摘要： Methane (CH₄) as a substitute for other mineral fuels plays a crucial role in reducing energy consumption and preventing environmental pollution. The present study employs a solvothermal method to fabricate a porous framework Co-metal-organic framework (Co-MOF) containing two distinct secondary building units (SBUs): an anionic [Co₂(μ₂-OH)(COO)₄(H₂O)] and a neutral [CoN₂(COO)₂]. Notably, within the anionic SBUs, the coordinated water molecules induce the generation of divergent unsaturated Co(II) centers in the unidirectional porous channels, thereby creating open metal sites. The adsorption performance of Co-MOF towards pure component gases was systematically investigated. The results demonstrated that Co-MOF exhibits superior adsorption capacity for C₂-C₃ hydrocarbons compared to CH₄, which offers the potential for efficient adsorption and separation of CH₄ from C₂-C₃ hydrocarbons. The gas selectivity separation ratios of Co-MOF for C₂H₆/CH₄ and C₃H₈/CH₄ were calculated using the ideal adsorbed solution theory method at 273/298 K and 0.1 MPa. The results revealed that Co-MOF achieved remarkable equilibrium separation selectivity for CH₄ and C₂-C₃ hydrocarbon gases among non-modified MOFs, signifying the potential of the synthesized Co-MOF for efficient recovery and purification of CH₄ from C₂-C₃ hydrocarbons. Breakthrough experiments further demonstrate the ability of Co-MOF to purify methane from C₂-C₃ hydrocarbons in practical gas separation scenarios. Additionally, molecular simulation calculations further substantiate the propensity of anionic SBUs to interact with C₂-C₃ hydrocarbon compounds. This study provides a novel paradigm for the development of porous MOF materials in the application of gas mixture separation.

关键词: Co-MOF, Separation hydrocarbons, Dynamic breakthrough curves, Molecular simulations adsorbent, Monte Carlo simulation

Abstract: Methane (CH₄) as a substitute for other mineral fuels plays a crucial role in reducing energy consumption and preventing environmental pollution. The present study employs a solvothermal method to fabricate a porous framework Co-metal-organic framework (Co-MOF) containing two distinct secondary building units (SBUs): an anionic [Co₂(μ₂-OH)(COO)₄(H₂O)] and a neutral [CoN₂(COO)₂]. Notably, within the anionic SBUs, the coordinated water molecules induce the generation of divergent unsaturated Co(II) centers in the unidirectional porous channels, thereby creating open metal sites. The adsorption performance of Co-MOF towards pure component gases was systematically investigated. The results demonstrated that Co-MOF exhibits superior adsorption capacity for C₂-C₃ hydrocarbons compared to CH₄, which offers the potential for efficient adsorption and separation of CH₄ from C₂-C₃ hydrocarbons. The gas selectivity separation ratios of Co-MOF for C₂H₆/CH₄ and C₃H₈/CH₄ were calculated using the ideal adsorbed solution theory method at 273/298 K and 0.1 MPa. The results revealed that Co-MOF achieved remarkable equilibrium separation selectivity for CH₄ and C₂-C₃ hydrocarbon gases among non-modified MOFs, signifying the potential of the synthesized Co-MOF for efficient recovery and purification of CH₄ from C₂-C₃ hydrocarbons. Breakthrough experiments further demonstrate the ability of Co-MOF to purify methane from C₂-C₃ hydrocarbons in practical gas separation scenarios. Additionally, molecular simulation calculations further substantiate the propensity of anionic SBUs to interact with C₂-C₃ hydrocarbon compounds. This study provides a novel paradigm for the development of porous MOF materials in the application of gas mixture separation.

Key words: Co-MOF, Separation hydrocarbons, Dynamic breakthrough curves, Molecular simulations adsorbent, Monte Carlo simulation

Jie Zhang, Xingzhe Guo, Bing Lin, Guangzu Xiong, Hanshuang Wang, Min Zhang, Liwen Fan, Bingwen Li, Shuisheng Chen. Efficient adsorption separation of methane from C₂-C₃ hydrocarbons in a Co(II)-nodes metal-organic framework[J]. 中国化学工程学报, 2024, 69(5): 192-198.

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Efficient adsorption separation of methane from C₂-C₃ hydrocarbons in a Co(II)-nodes metal-organic framework

Efficient adsorption separation of methane from C₂-C₃ hydrocarbons in a Co(II)-nodes metal-organic framework

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