Asymmetric pore windows in MOF membranes for natural gas valorization

Sheng Zhou; Osama Shekhah; Adrian Ramírez; Pengbo Lyu; Edy Abou-Hamad; Jiangtao Jia; Jiantang Li; Prashant M. Bhatt; Zhiyuan Huang; Hao Jiang; Tian Jin; Guillaume Maurin; Jorge Gascon; Mohamed Eddaoudi

doi:10.1038/s41586-022-04763-5

Asymmetric pore windows in MOF membranes for natural gas valorization

Sheng Zhou, Osama Shekhah, Adrian Ramírez, Pengbo Lyu, Edy Abou-Hamad, Jiangtao Jia, Jiantang Li, Prashant M. Bhatt, Zhiyuan Huang, Hao Jiang, Tian Jin, Guillaume Maurin, Jorge Gascon, Mohamed Eddaoudi^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

178 Scopus citations

Abstract

To use natural gas as a feedstock alternative to coal and oil, its main constituent, methane, needs to be isolated with high purity¹. In particular, nitrogen dilutes the heating value of natural gas and is, therefore, of prime importance for removal². However, the inertness of nitrogen and its similarities to methane in terms of kinetic size, polarizability and boiling point pose particular challenges for the development of energy-efficient nitrogen-removing processes³. Here we report a mixed-linker metal–organic framework (MOF) membrane based on fumarate (fum) and mesaconate (mes) linkers, Zr-fum₆₇-mes₃₃-fcu-MOF, with a pore aperture shape specific for effective nitrogen removal from natural gas. The deliberate introduction of asymmetry in the parent trefoil-shaped pore aperture induces a shape irregularity, blocking the transport of tetrahedral methane while allowing linear nitrogen to permeate. Zr-fum₆₇-mes₃₃-fcu-MOF membranes exhibit record-high nitrogen/methane selectivity and nitrogen permeance under practical pressures up to 50 bar, removing both carbon dioxide and nitrogen from natural gas. Techno-economic analysis shows that our membranes offer the potential to reduce methane purification costs by about 66% for nitrogen rejection and about 73% for simultaneous removal of carbon dioxide and nitrogen, relative to cryogenic distillation and amine-based carbon dioxide capture.

Original language	English (US)
Pages (from-to)	706-712
Number of pages	7
Journal	Nature
Volume	606
Issue number	7915
DOIs	https://doi.org/10.1038/s41586-022-04763-5
State	Published - Jun 23 2022

Bibliographical note

Funding Information:
We gratefully acknowledge funding from King Abdullah University of Science and Technology and the CCF programme 1972. This work was also granted access to the HPC resources of CINES under the allocation A0100907613 made by GENCI.

Funding Information:
We gratefully acknowledge funding from King Abdullah University of Science and Technology and the CCF programme 1972. This work was also granted access to the HPC resources of CINES under the allocation A0100907613 made by GENCI.

Publisher Copyright:
© 2022, The Author(s), under exclusive licence to Springer Nature Limited.

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10.1038/s41586-022-04763-5

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title = "Asymmetric pore windows in MOF membranes for natural gas valorization",

abstract = "To use natural gas as a feedstock alternative to coal and oil, its main constituent, methane, needs to be isolated with high purity1. In particular, nitrogen dilutes the heating value of natural gas and is, therefore, of prime importance for removal2. However, the inertness of nitrogen and its similarities to methane in terms of kinetic size, polarizability and boiling point pose particular challenges for the development of energy-efficient nitrogen-removing processes3. Here we report a mixed-linker metal–organic framework (MOF) membrane based on fumarate (fum) and mesaconate (mes) linkers, Zr-fum67-mes33-fcu-MOF, with a pore aperture shape specific for effective nitrogen removal from natural gas. The deliberate introduction of asymmetry in the parent trefoil-shaped pore aperture induces a shape irregularity, blocking the transport of tetrahedral methane while allowing linear nitrogen to permeate. Zr-fum67-mes33-fcu-MOF membranes exhibit record-high nitrogen/methane selectivity and nitrogen permeance under practical pressures up to 50 bar, removing both carbon dioxide and nitrogen from natural gas. Techno-economic analysis shows that our membranes offer the potential to reduce methane purification costs by about 66% for nitrogen rejection and about 73% for simultaneous removal of carbon dioxide and nitrogen, relative to cryogenic distillation and amine-based carbon dioxide capture.",

author = "Sheng Zhou and Osama Shekhah and Adrian Ram{\'i}rez and Pengbo Lyu and Edy Abou-Hamad and Jiangtao Jia and Jiantang Li and Bhatt, {Prashant M.} and Zhiyuan Huang and Hao Jiang and Tian Jin and Guillaume Maurin and Jorge Gascon and Mohamed Eddaoudi",

note = "Funding Information: We gratefully acknowledge funding from King Abdullah University of Science and Technology and the CCF programme 1972. This work was also granted access to the HPC resources of CINES under the allocation A0100907613 made by GENCI. Funding Information: We gratefully acknowledge funding from King Abdullah University of Science and Technology and the CCF programme 1972. This work was also granted access to the HPC resources of CINES under the allocation A0100907613 made by GENCI. Publisher Copyright: {\textcopyright} 2022, The Author(s), under exclusive licence to Springer Nature Limited.",

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doi = "10.1038/s41586-022-04763-5",

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T1 - Asymmetric pore windows in MOF membranes for natural gas valorization

AU - Zhou, Sheng

AU - Shekhah, Osama

AU - Ramírez, Adrian

AU - Lyu, Pengbo

AU - Abou-Hamad, Edy

AU - Jia, Jiangtao

AU - Li, Jiantang

AU - Bhatt, Prashant M.

AU - Huang, Zhiyuan

AU - Jiang, Hao

AU - Jin, Tian

AU - Maurin, Guillaume

AU - Gascon, Jorge

AU - Eddaoudi, Mohamed

N1 - Funding Information: We gratefully acknowledge funding from King Abdullah University of Science and Technology and the CCF programme 1972. This work was also granted access to the HPC resources of CINES under the allocation A0100907613 made by GENCI. Funding Information: We gratefully acknowledge funding from King Abdullah University of Science and Technology and the CCF programme 1972. This work was also granted access to the HPC resources of CINES under the allocation A0100907613 made by GENCI. Publisher Copyright: © 2022, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2022/6/23

Y1 - 2022/6/23

N2 - To use natural gas as a feedstock alternative to coal and oil, its main constituent, methane, needs to be isolated with high purity1. In particular, nitrogen dilutes the heating value of natural gas and is, therefore, of prime importance for removal2. However, the inertness of nitrogen and its similarities to methane in terms of kinetic size, polarizability and boiling point pose particular challenges for the development of energy-efficient nitrogen-removing processes3. Here we report a mixed-linker metal–organic framework (MOF) membrane based on fumarate (fum) and mesaconate (mes) linkers, Zr-fum67-mes33-fcu-MOF, with a pore aperture shape specific for effective nitrogen removal from natural gas. The deliberate introduction of asymmetry in the parent trefoil-shaped pore aperture induces a shape irregularity, blocking the transport of tetrahedral methane while allowing linear nitrogen to permeate. Zr-fum67-mes33-fcu-MOF membranes exhibit record-high nitrogen/methane selectivity and nitrogen permeance under practical pressures up to 50 bar, removing both carbon dioxide and nitrogen from natural gas. Techno-economic analysis shows that our membranes offer the potential to reduce methane purification costs by about 66% for nitrogen rejection and about 73% for simultaneous removal of carbon dioxide and nitrogen, relative to cryogenic distillation and amine-based carbon dioxide capture.

AB - To use natural gas as a feedstock alternative to coal and oil, its main constituent, methane, needs to be isolated with high purity1. In particular, nitrogen dilutes the heating value of natural gas and is, therefore, of prime importance for removal2. However, the inertness of nitrogen and its similarities to methane in terms of kinetic size, polarizability and boiling point pose particular challenges for the development of energy-efficient nitrogen-removing processes3. Here we report a mixed-linker metal–organic framework (MOF) membrane based on fumarate (fum) and mesaconate (mes) linkers, Zr-fum67-mes33-fcu-MOF, with a pore aperture shape specific for effective nitrogen removal from natural gas. The deliberate introduction of asymmetry in the parent trefoil-shaped pore aperture induces a shape irregularity, blocking the transport of tetrahedral methane while allowing linear nitrogen to permeate. Zr-fum67-mes33-fcu-MOF membranes exhibit record-high nitrogen/methane selectivity and nitrogen permeance under practical pressures up to 50 bar, removing both carbon dioxide and nitrogen from natural gas. Techno-economic analysis shows that our membranes offer the potential to reduce methane purification costs by about 66% for nitrogen rejection and about 73% for simultaneous removal of carbon dioxide and nitrogen, relative to cryogenic distillation and amine-based carbon dioxide capture.

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SN - 0028-0836

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EP - 712

JO - Nature

JF - Nature

IS - 7915

ER -

Asymmetric pore windows in MOF membranes for natural gas valorization

Abstract

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