Simultaneous removal of C2H2 and C2H6 for C2H4 purification by robust MOFs featuring a high density of heteroatoms

Xian, Shikai; Peng, Junjie; Pandey, Haardik; Graham, Wells; Yu, Liang; Wang, Hao; Tan, Kui; Thonhauser, Timo; Li, Jing

doi:10.1039/d3ta01598j

Simultaneous removal of C₂H₂ and C₂H₆ for C₂H₄ purification by robust MOFs featuring a high density of heteroatoms

Journal Article · Sat Sep 09 00:00:00 EDT 2023 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d3ta01598j· OSTI ID:2305727

Xian, Shikai ^[1]; Peng, Junjie ^[2]; ^[3]; Graham, Wells ^[3]; Yu, Liang ^[2]; ^[4]; Tan, Kui ^[5]; ^[3]; ^[6]

Shenzhen Polytechnic, Guangdong (China); Rutgers University, Piscataway, NJ (United States); Rutgers University
Foshan University (China)
Wake Forest University, Winston-Salem, NC (United States)
Shenzhen Polytechnic, Guangdong (China)
University of North Texas, Denton, TX (United States)
Rutgers University, Piscataway, NJ (United States); Shenzhen Polytechnic, Guangdong (China)

Simultaneous removal of C₂H₆ and C₂H₂ from C₂H₄ streams is of great importance in the petrochemical industry but remains a challenging task. To address this challenge, we have selected three isoreticular MOFs with high stability, low cost, and desirable scale-up ability, namely, MOF-303, MIL-160, and CAU-23 and assessed their potential in simultaneous removal of acetylene and ethane for ethylene purification. Each MOF exhibits desirable C₂H₂ and C₂H₆ uptake capacity (>5.5 mmol g^–1 and >4 mmol g^–1, respectively), as well as good C₂H₂/C₂H₄ selectivity (>2) and C₂H₆/C₂H₄ selectivity (>1.5). Notably, MOF-303 takes up 4.96 mmol g^–1 C₂H₆ at 298 K and 1 bar, the highest value among the three MOFs, with C₂H₆/C₂H₄ selectivity in the range of 1.55–2.47. MIL-160 possesses a very high C₂H₂ uptake (9.1 mmol g^–1) and C₂H₂/C₂H₄ selectivity, 10.6 (1 : 1, v/v), at 298 K, much higher than those of all other MOFs tested to date for simultaneous removal of C₂H₆ and C₂H₂ from C₂H₄. The results from breakthrough experiments confirm that all three MOFs demonstrate excellent performance for C₂H₄ purification in a ternary mixture of C₂H₆/C₂H₄/C₂H₂ (1 : 1 : 1, v/v/v). Here, for MOF-303, MIL-160, and CAU-23, polymer-grade C₂H₄ up to 0.164, 0.21, and 0.181 mmol g^–1 can be obtained from the equimolar ternary mixture in a single separation step from the breakthrough experiment. Additionally, DFT calculations have been performed to further investigate the mechanism of adsorption/separation for C₂H₆, C₂H₄, and C₂H₂.

View Accepted Manuscript (DOE)

Research Organization:: Wake Forest University, Winston-Salem, NC (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0019902

OSTI ID:: 2305727

Alternate ID(s):: OSTI ID: 2006517

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 39 Vol. 11; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Metal–Organic Framework Materials for the Separation and Purification of Light Hydrocarbons Cui, Wen‐Gang; Hu, Tong‐Liang; Bu, Xian‐He Advanced Materials, Vol. 32, Issue 3 https://doi.org/10.1002/adma.201806445	journal	May 2019
Moisture stability of ethane‐selective Ni(II), Fe(III), Zr(IV)‐based metal–organic frameworks Lv, Daofei; Chen, Jiayu; Chen, Yongwei AIChE Journal, Vol. 65, Issue 8 https://doi.org/10.1002/aic.16616	journal	April 2019
Open Metal Sites within Isostructural Metal-Organic Frameworks for Differential Recognition of Acetylene and Extraordinarily High Acetylene Storage Capacity at Room Temperature Xiang, Shengchang; Zhou, Wei; Zhang, Zhangjing Angewandte Chemie International Edition, Vol. 49, Issue 27 https://doi.org/10.1002/anie.201000094	journal	May 2010
Simultaneous Trapping of C ₂ H ₂ and C ₂ H ₆ from a Ternary Mixture of C ₂ H ₂ /C ₂ H ₄ /C ₂ H ₆ in a Robust Metal-Organic Framework for the Purification of C ₂ H ₄ Hao, Hong-Guo; Zhao, Yun-Feng; Chen, Di-Ming Angewandte Chemie International Edition, Vol. 57, Issue 49 https://doi.org/10.1002/anie.201809884	journal	November 2018
Molecular Sieving of C₂‐C₃ Alkene from Alkyne with Tuned Threshold Pressure in Robust Layered Metal–Organic Frameworks Ke, Tian; Wang, Qingju; Shen, Jin Angewandte Chemie International Edition, Vol. 59, Issue 31 https://doi.org/10.1002/anie.202003421	journal	May 2020
One‐step Ethylene Purification from an Acetylene/Ethylene/Ethane Ternary Mixture by Cyclopentadiene Cobalt‐Functionalized Metal–Organic Frameworks Wang, Yutong; Hao, Chunlian; Fan, Weidong Angewandte Chemie International Edition, Vol. 60, Issue 20 https://doi.org/10.1002/anie.202100782	journal	March 2021
The Hydrogenation of Acetylene Catalyzed by Palladium: Hydrogen Pressure Dependence Molero, H.; Bartlett, B. F.; Tysoe, W. T. Journal of Catalysis, Vol. 181, Issue 1 https://doi.org/10.1006/jcat.1998.2294	journal	January 1999
New Trends in Olefin Production Amghizar, Ismaël; Vandewalle, Laurien A.; Van Geem, Kevin M. Engineering, Vol. 3, Issue 2 https://doi.org/10.1016/J.ENG.2017.02.006	journal	April 2017
Novel glucosamine-based carbon adsorbents with high capacity and its enhanced mechanism of preferential adsorption of C2H6 over C2H4 Wang, Xingjie; Wu, Ying; Peng, Junjie Chemical Engineering Journal, Vol. 358 https://doi.org/10.1016/j.cej.2018.10.109	journal	February 2019
Microporous metal-organic framework with specific functional sites for efficient removal of ethane from ethane/ethylene mixtures Yang, Ling; Wang, Yong; Chen, Yang Chemical Engineering Journal, Vol. 387 https://doi.org/10.1016/j.cej.2020.124137	journal	May 2020
Robust carbazole-based covalent triazine frameworks with defective ultramicropore structure for efficient ethane-selective ethane-ethylene separation Chang, Yanjiao; Huang, Hongliang; Zhu, Hejin Chemical Engineering Journal, Vol. 427 https://doi.org/10.1016/j.cej.2021.131726	journal	January 2022
Ethane selective adsorbent Ni(bdc)(ted)0.5 with high uptake and its significance in adsorption separation of ethane and ethylene Liang, Wanwen; Xu, Feng; Zhou, Xin Chemical Engineering Science, Vol. 148 https://doi.org/10.1016/j.ces.2016.04.016	journal	July 2016
An ethane-trapping MOF PCN-250 for highly selective adsorption of ethane over ethylene Chen, Yongwei; Qiao, Zhiwei; Wu, Houxiao Chemical Engineering Science, Vol. 175 https://doi.org/10.1016/j.ces.2017.09.032	journal	January 2018
An Overview of Metal–Organic Frameworks for Green Chemical Engineering Kong, Xiang-Jing; Li, Jian-Rong Engineering, Vol. 7, Issue 8 https://doi.org/10.1016/j.eng.2021.07.001	journal	August 2021
Applications of metal–organic frameworks for green energy and environment: New advances in adsorptive gas separation, storage and removal Wang, Bin; Xie, Lin-Hua; Wang, Xiaoqing Green Energy & Environment, Vol. 3, Issue 3 https://doi.org/10.1016/j.gee.2018.03.001	journal	July 2018
A combined theoretical and experimental analysis on transient breakthroughs of C2H6/C2H4 in fixed beds packed with ZIF-7 Chen, De-Li; Wang, Ningwei; Xu, Chunhui Microporous and Mesoporous Materials, Vol. 208 https://doi.org/10.1016/j.micromeso.2015.01.019	journal	May 2015
A Microporous Metal–Organic Framework with Lewis Basic Nitrogen Sites for High C ₂ H ₂ Storage and Significantly Enhanced C ₂ H ₂ /CO ₂ Separation at Ambient Conditions Wen, Hui-Min; Wang, Huizhen; Li, Bin Inorganic Chemistry, Vol. 55, Issue 15 https://doi.org/10.1021/acs.inorgchem.6b00748	journal	May 2016
Pore-Space Partition and Optimization for Propane-Selective High-Performance Propane/Propylene Separation Hong, Anh N.; Yang, Huajun; Li, Tong ACS Applied Materials & Interfaces, Vol. 13, Issue 44 https://doi.org/10.1021/acsami.1c10391	journal	July 2021
Selective Adsorption of Ethane over Ethylene in PCN-245: Impacts of Interpenetrated Adsorbent Lv, Daofei; Shi, Renfeng; Chen, Yongwei ACS Applied Materials & Interfaces, Vol. 10, Issue 9 https://doi.org/10.1021/acsami.7b19414	journal	February 2018
Exceptionally High Acetylene Uptake in a Microporous Metal−Organic Framework with Open Metal Sites Xiang, Shengchang; Zhou, Wei; Gallegos, Jose M. Journal of the American Chemical Society, Vol. 131, Issue 34 https://doi.org/10.1021/ja904782h	journal	September 2009
Pore Engineering for One-Step Ethylene Purification from a Three-Component Hydrocarbon Mixture Zhu, Baoyong; Cao, Jian-Wei; Mukherjee, Soumya Journal of the American Chemical Society, Vol. 143, Issue 3 https://doi.org/10.1021/jacs.0c11247	journal	January 2021
Scalable Room-Temperature Synthesis of Highly Robust Ethane-Selective Metal–Organic Frameworks for Efficient Ethylene Purification Geng, Shubo; Lin, En; Li, Xia Journal of the American Chemical Society, Vol. 143, Issue 23 https://doi.org/10.1021/jacs.1c02108	journal	June 2021
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
Boosting Ethane/Ethylene Separation within Isoreticular Ultramicroporous Metal–Organic Frameworks Lin, Rui-Biao; Wu, Hui; Li, Libo Journal of the American Chemical Society, Vol. 140, Issue 40 https://doi.org/10.1021/jacs.8b07563	journal	September 2018
A Robust Ethane-Trapping Metal–Organic Framework with a High Capacity for Ethylene Purification Qazvini, Omid T.; Babarao, Ravichandar; Shi, Zhao-Lin Journal of the American Chemical Society, Vol. 141, Issue 12 https://doi.org/10.1021/jacs.9b00913	journal	March 2019
Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane–Ethylene Separation Yang, Huajun; Wang, Yanxiang; Krishna, Rajamani Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b12924	journal	January 2020
Adsorption on Fe-MOF-74 for C1–C3 Hydrocarbon Separation Verma, Pragya; Xu, Xuefei; Truhlar, Donald G. The Journal of Physical Chemistry C, Vol. 117, Issue 24 https://doi.org/10.1021/jp402884h	journal	June 2013
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
Porous materials with pre-designed single-molecule traps for CO2 selective adsorption Li, Jian-Rong; Yu, Jiamei; Lu, Weigang Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2552	journal	February 2013
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
A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions Pang, Jiandong; Jiang, Feilong; Wu, Mingyan Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8575	journal	June 2015
Efficient purification of ethene by an ethane-trapping metal-organic framework Liao, Pei-Qin; Zhang, Wei-Xiong; Zhang, Jie-Peng Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9697	journal	October 2015
A robust Th-azole framework for highly efficient purification of C2H4 from a C2H4/C2H2/C2H6 mixture Xu, Zhenzhen; Xiong, Xiaohong; Xiong, Jianbo Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16960-9	journal	June 2020
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
A solid solution approach to 2D coordination polymers for CH₄/CO₂and CH₄/C₂H₆gas separation: equilibrium and kinetic studies Horike, Satoshi; Inubushi, Yasutaka; Hori, Takashi Chem. Sci., Vol. 3, Issue 1 https://doi.org/10.1039/C1SC00591J	journal	January 2012
Metal–organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons He, Yabing; Krishna, Rajamani; Chen, Banglin Energy & Environmental Science, Vol. 5, Issue 10 https://doi.org/10.1039/c2ee22858k	journal	January 2012
Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn) Geier, Stephen J.; Mason, Jarad A.; Bloch, Eric D. Chemical Science, Vol. 4, Issue 5 https://doi.org/10.1039/c3sc00032j	journal	January 2013
van der Waals forces in density functional theory: a review of the vdW-DF method Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho Reports on Progress in Physics, Vol. 78, Issue 6 https://doi.org/10.1088/0034-4885/78/6/066501	journal	May 2015
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond Thonhauser, T.; Cooper, Valentino R.; Li, Shen Physical Review B, Vol. 76, Issue 12 https://doi.org/10.1103/PhysRevB.76.125112	journal	September 2007
Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks Thonhauser, T.; Zuluaga, S.; Arter, C. A. Physical Review Letters, Vol. 115, Issue 13 https://doi.org/10.1103/PhysRevLett.115.136402	journal	September 2015
Practical water production from desert air Fathieh, Farhad; Kalmutzki, Markus J.; Kapustin, Eugene A. Science Advances, Vol. 4, Issue 6 https://doi.org/10.1126/sciadv.aat3198	journal	June 2018
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

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Simultaneous removal of C2H2 and C2H6 for C2H4 purification by robust MOFs featuring a high density of heteroatoms

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References (44)

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Simultaneous removal of C₂H₂ and C₂H₆ for C₂H₄ purification by robust MOFs featuring a high density of heteroatoms