Purification of Propylene and Ethylene by a Robust Metal–Organic Framework Mediated by Host–Guest Interactions

Li, Jiangnan; Han, Xue; Kang, Xinchen; Chen, Yinlin; Xu, Shaojun; Smith, Gemma L.; Tillotson, Evan; Cheng, Yongqiang; McCormick McPherson, Laura J.; Teat, Simon J.; Rudić, Svemir; Ramirez‐Cuesta, Anibal J.; Haigh, Sarah J.; Schröder, Martin; Yang, Sihai

doi:10.1002/anie.202103936

Title: Purification of Propylene and Ethylene by a Robust Metal–Organic Framework Mediated by Host–Guest Interactions

Journal Article · Wed Apr 07 00:00:00 EDT 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202103936· OSTI ID:1814002

Li, Jiangnan ^[1]; Han, Xue ^[1]; Kang, Xinchen ^[1]; Chen, Yinlin ^[1]; Xu, Shaojun ^[1]; Smith, Gemma L. ^[1]; Tillotson, Evan ^[1]; Cheng, Yongqiang ^[2]; McCormick McPherson, Laura J. ^[3]; Teat, Simon J. ^[3]; Rudić, Svemir ^[4]; Ramirez‐Cuesta, Anibal J. ^[2]; Haigh, Sarah J. ^[1];

^[1]; Yang, Sihai ^[1]

Univ. of Manchester (United Kingdom)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom)

Industrial purification of propylene and ethylene requires cryogenic distillation and selective hydrogenation over palladium catalysts to remove propane, ethane and/or trace amounts of acetylene. Here, we report the excellent separation of equimolar mixtures of propylene/propane and ethylene/ethane, and of a 1/100 mixture of acetylene/ethylene by a highly robust microporous material, MFM-520, under dynamic conditions. In situ synchrotron single crystal X-ray diffraction, inelastic neutron scattering and analysis of adsorption thermodynamic parameters reveal that a series of synergistic host-guest interactions involving hydrogen bonding and π⋯π stacking interactions underpin the cooperative binding of alkenes within the pore. Notably, the optimal pore geometry of the material enables selective accommodation of acetylene. The practical potential of this porous material has been demonstrated by fabricating mixed-matrix membranes comprising MFM-520, Matrimid and PIM-1, and these exhibit not only a high permeability for propylene (≈1984 Barrer), but also a separation factor of 7.8 for an equimolar mixture of propylene/propane at 298 K.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1814002

Journal Information:: Angewandte Chemie (International Edition), Vol. 60, Issue 28; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

High-Performance Thermally Self-Cross-Linked Polymer of Intrinsic Microporosity (PIM-1) Membranes for Energy Development Li, Fu Yun; Xiao, Youchang; Chung, Tai-Shung Macromolecules, Vol. 45, Issue 3 https://doi.org/10.1021/ma202667y	journal	January 2012
Thermodynamics of mixed-gas adsorption Myers, A. L.; Prausnitz, J. M. AIChE Journal, Vol. 11, Issue 1, p. 121-127 https://doi.org/10.1002/aic.690110125	journal	January 1965
Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites Li, Libo; Lin, Rui-Biao; Krishna, Rajamani Science, Vol. 362, Issue 6413 https://doi.org/10.1126/science.aat0586	journal	October 2018
Membranes for CO ₂ /CH ₄ and CO ₂ /N ₂ Gas Separation Chawla, Muhammad; Saulat, Hammad; Masood Khan, Muhammad Chemical Engineering & Technology, Vol. 43, Issue 2 https://doi.org/10.1002/ceat.201900375	journal	November 2019
Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites Bloch, E. D.; Queen, W. L.; Krishna, R. Science, Vol. 335, Issue 6076, p. 1606-1610 https://doi.org/10.1126/science.1217544	journal	March 2012
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
Zeolitic Imidazolate Frameworks for Kinetic Separation of Propane and Propene Li, Kunhao; Olson, David H.; Seidel, Jonathan Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja9039983	journal	August 2009
Zeolitic Imidazolate Framework/Graphene Oxide Hybrid Nanosheets as Seeds for the Growth of Ultrathin Molecular Sieving Membranes Hu, Yaoxin; Wei, Jing; Liang, Yan Angewandte Chemie International Edition, Vol. 55, Issue 6 https://doi.org/10.1002/anie.201509213	journal	December 2015
Membrane‐Based Olefin/Paraffin Separations Ren, Yanxiong; Liang, Xu; Dou, Haozhen Advanced Science, Vol. 7, Issue 19 https://doi.org/10.1002/advs.202001398	journal	August 2020
Conventional processes and membrane technology for carbon dioxide removal from natural gas: A review Yeo, Zee Ying; Chew, Thiam Leng; Zhu, Peng Wei Journal of Natural Gas Chemistry, Vol. 21, Issue 3 https://doi.org/10.1016/S1003-9953(11)60366-6	journal	May 2012
Physical aging of thin glassy polymer films monitored by gas permeability Huang, Y.; Paul, D. R. Polymer, Vol. 45, Issue 25 https://doi.org/10.1016/j.polymer.2004.10.019	journal	November 2004
A Porous Framework Polymer Based on a Zinc(II) 4,4‘-Bipyridine-2,6,2‘,6‘-tetracarboxylate: Synthesis, Structure, and “Zeolite-Like” Behaviors Lin, Xiang; Blake, Alexander J.; Wilson, Claire Journal of the American Chemical Society, Vol. 128, Issue 33 https://doi.org/10.1021/ja060946u	journal	August 2006
Optimized Separation of Acetylene from Carbon Dioxide and Ethylene in a Microporous Material Lin, Rui-Biao; Li, Libo; Wu, Hui Journal of the American Chemical Society, Vol. 139, Issue 23 https://doi.org/10.1021/jacs.7b03850	journal	June 2017
Enhanced C ₃ H ₆ /C ₃ H ₈ separation performance on MOF membranes through blocking defects and hindering framework flexibility by silicone rubber coating Sheng, Luqian; Wang, Chongqing; Yang, Fan Chemical Communications, Vol. 53, Issue 55 https://doi.org/10.1039/C7CC03887A	journal	January 2017
Flexible Metal-Organic Frameworks with Discriminatory Gate-Opening Effect for the Separation of Acetylene from Ethylene/Acetylene Mixtures: Flexible Metal-Organic Frameworks with Discriminatory Gate-Opening Effect for the Separation of Acetylene from Ethylene/Acetylene Mixtures Li, Libo; Krishna, Rajamani; Wang, Yong European Journal of Inorganic Chemistry, Vol. 2016, Issue 27 https://doi.org/10.1002/ejic.201600182	journal	June 2016
Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1206	journal	February 2011
New low-energy crystal structure for silicon Boyer, L. L.; Kaxiras, Efthimios; Feldman, J. L. Physical Review Letters, Vol. 67, Issue 6 https://doi.org/10.1103/PhysRevLett.67.715	journal	August 1991
Ethane/ethylene and propane/propylene separation in hybrid membrane distillation systems: Optimization and economic analysis Benali, Marzouk; Aydin, Bora Separation and Purification Technology, Vol. 73, Issue 3 https://doi.org/10.1016/j.seppur.2010.04.027	journal	July 2010
Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework Li, Jiangnan; Han, Xue; Zhang, Xinran Nature Chemistry, Vol. 11, Issue 12 https://doi.org/10.1038/s41557-019-0356-0	journal	November 2019
Molecular engineering of PIM-1/Matrimid blend membranes for gas separation Yong, W. F.; Li, F. Y.; Xiao, Y. C. Journal of Membrane Science, Vol. 407-408 https://doi.org/10.1016/j.memsci.2012.03.038	journal	July 2012
Kinetic Separation of Propene and Propane in Metal−Organic Frameworks: Controlling Diffusion Rates in Plate-Shaped Crystals via Tuning of Pore Apertures and Crystallite Aspect Ratios Lee, Chang Yeon; Bae, Youn-Sang; Jeong, Nak Cheon Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja200553m	journal	April 2011
Tuning Gate‐Opening of a Flexible Metal–Organic Framework for Ternary Gas Sieving Separation Dong, Qiubing; Zhang, Xin; Liu, Shuang Angewandte Chemie International Edition, Vol. 59, Issue 50 https://doi.org/10.1002/anie.202011802	journal	October 2020
Exploring the performance limits of MOF/polymer MMMs for O2/N2 separation using computational screening Daglar, Hilal; Erucar, Ilknur; Keskin, Seda Journal of Membrane Science, Vol. 618 https://doi.org/10.1016/j.memsci.2020.118555	journal	January 2021
MOF-Derived Bifunctional Cu ₃ P Nanoparticles Coated by a N,P-Codoped Carbon Shell for Hydrogen Evolution and Oxygen Reduction Wang, Rui; Dong, Xi-Yan; Du, Jiao Advanced Materials, Vol. 30, Issue 6 https://doi.org/10.1002/adma.201703711	journal	December 2017
Thermal/catalytic cracking of hydrocarbons for the production of olefins: A state-of-the-art review I: Thermal cracking review Sadrameli, S. M. Fuel, Vol. 140 https://doi.org/10.1016/j.fuel.2014.09.034	journal	January 2015
Efficient kinetic separation of propene and propane using two microporous metal organic frameworks Peng, Junjie; Wang, Hao; Olson, David H. Chemical Communications, Vol. 53, Issue 67 https://doi.org/10.1039/C7CC03529B	journal	January 2017
Polymer nanosieve membranes for CO₂-capture applications Du, Naiying; Park, Ho Bum; Robertson, Gilles P. Nature Materials, Vol. 10, Issue 5, p. 372-375 https://doi.org/10.1038/nmat2989	journal	April 2011
Materials for next-generation molecularly selective synthetic membranes Koros, William J.; Zhang, Chen Nature Materials, Vol. 16, Issue 3 https://doi.org/10.1038/nmat4805	journal	January 2017
UV-Rearranged PIM-1 Polymeric Membranes for Advanced Hydrogen Purification and Production Li, Fu Yun; Xiao, Youchang; Ong, Yee Kang Advanced Energy Materials, Vol. 2, Issue 12 https://doi.org/10.1002/aenm.201200296	journal	July 2012
Membrane-based gas separation Koros, W. J.; Fleming, G. K. Journal of Membrane Science, Vol. 83, Issue 1, p. 1-80 https://doi.org/10.1016/0376-7388(93)80013-N	journal	August 1993
On-stream modification of MFI zeolite membranes for enhancing hydrogen separation at high temperature Gu, Xuehong; Tang, Zhong; Dong, Junhang Microporous and Mesoporous Materials, Vol. 111, Issue 1-3 https://doi.org/10.1016/j.micromeso.2007.08.039	journal	April 2008
M ₂ ( m -dobdc) (M = Mn, Fe, Co, Ni) Metal–Organic Frameworks as Highly Selective, High-Capacity Adsorbents for Olefin/Paraffin Separations Bachman, Jonathan E.; Kapelewski, Matthew T.; Reed, Douglas A. Journal of the American Chemical Society, Vol. 139, Issue 43 https://doi.org/10.1021/jacs.7b06397	journal	October 2017
Selective Hydrogenation of Ethyne in Ethene‐Rich Streams on Palladium Catalysts. Part 1. Effect of Changes to the Catalyst During Reaction Borodziński, Andrzej; Bond, Geoffrey C. Catalysis Reviews, Vol. 48, Issue 2 https://doi.org/10.1080/01614940500364909	journal	July 2006
Molecular sieving of ethylene from ethane using a rigid metal–organic framework Lin, Rui-Biao; Li, Libo; Zhou, Hao-Long Nature Materials, Vol. 17, Issue 12 https://doi.org/10.1038/s41563-018-0206-2	journal	November 2018
Preparation of carbon molecular sieve membranes on low-cost alumina hollow fibers for use in C3H6/C3H8 separation Kim, Seong-Joong; Lee, Pyung Soo; Chang, Jong-San Separation and Purification Technology, Vol. 194 https://doi.org/10.1016/j.seppur.2017.11.069	journal	April 2018
Effects of Brominating Matrimid Polyimide on the Physical and Gas Transport Properties of Derived Carbon Membranes Xiao, Youchang; Dai, Ying; Chung, Tai-Shung Macromolecules, Vol. 38, Issue 24 https://doi.org/10.1021/ma051354j	journal	November 2005
Beyond Equilibrium: Metal–Organic Frameworks for Molecular Sieving and Kinetic Gas Separation Wang, Yuxiang; Zhao, Dan Crystal Growth & Design, Vol. 17, Issue 5 https://doi.org/10.1021/acs.cgd.7b00287	journal	April 2017
Tuning Gate‐Opening of a Flexible Metal–Organic Framework for Ternary Gas Sieving Separation Dong, Qiubing; Zhang, Xin; Liu, Shuang Angewandte Chemie, Vol. 132, Issue 50 https://doi.org/10.1002/ange.202011802	journal	October 2020
An Ultramicroporous Metal–Organic Framework for High Sieving Separation of Propylene from Propane Liang, Bin; Zhang, Xin; Xie, Yi Journal of the American Chemical Society, Vol. 142, Issue 41 https://doi.org/10.1021/jacs.0c09466	journal	September 2020
Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene Cui, X.; Chen, K.; Xing, H. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf2458	journal	May 2016
An Ideal Molecular Sieve for Acetylene Removal from Ethylene with Record Selectivity and Productivity Li, Bin; Cui, Xili; O'Nolan, Daniel Advanced Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adma.201704210	journal	November 2017
Microporous metal–organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures Hu, Tong-Liang; Wang, Hailong; Li, Bin Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8328	journal	June 2015
Mixed-matrix membranes with soluble porous organic molecular cage for highly efficient C3H6/C3H8 separation Zhang, Qiang; Li, Hongbin; Chen, Si Journal of Membrane Science, Vol. 611 https://doi.org/10.1016/j.memsci.2020.118288	journal	October 2020
Fluorine-containing polyimide/polysilsesquioxane carbon molecular sieve membranes and techno-economic evaluation thereof for C3H6/C3H8 separation Shin, Ju Ho; Yu, Hyun Jung; Park, Junhyung Journal of Membrane Science, Vol. 598 https://doi.org/10.1016/j.memsci.2019.117660	journal	March 2020
A metal-organic framework-based splitter for separating propylene from propane Cadiau, A.; Adil, K.; Bhatt, P. M. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf6323	journal	July 2016
Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework Yang, Sihai; Ramirez-Cuesta, Anibal J.; Newby, Ruth Nature Chemistry, Vol. 7, Issue 2 https://doi.org/10.1038/nchem.2114	journal	December 2014
Zeolitic Imidazolate Framework/Graphene Oxide Hybrid Nanosheets as Seeds for the Growth of Ultrathin Molecular Sieving Membranes Hu, Yaoxin; Wei, Jing; Liang, Yan Angewandte Chemie, Vol. 128, Issue 6 https://doi.org/10.1002/ange.201509213	journal	December 2015
Synergistic sorbent separation for one-step ethylene purification from a four-component mixture Chen, Kai-Jie; Madden, David G.; Mukherjee, Soumya Science, Vol. 366, Issue 6462 https://doi.org/10.1126/science.aax8666	journal	October 2019

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Title: Purification of Propylene and Ethylene by a Robust Metal–Organic Framework Mediated by Host–Guest Interactions

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