skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: High-throughput computational prediction of the cost of carbon capture using mixed matrix membranes
Polymeric membranes are being studied for their potential use in post-combustion carbon capture on the premise that they could dramatically lower costs relative to mature technologies available today. Mixed matrix membranes (MMMs) are advanced materials formed by combining polymers with inorganic particles. Using metal–organic frameworks (MOFs) as the inorganic particles has been shown to improve selectivity and permeability over pure polymers. We have carried out high-throughput atomistic simulations on 112 888 real and hypothetical metal–organic framework structures in order to calculate their CO 2 permeabilities and CO 2 /N 2 selectivities. The CO 2 /H 2 O sorption selectivity of 2 017 real MOFs was evaluated using the H 2 O sorption data of Li et al. (S. Li, Y. G. Chung and R. Q. Snurr, Langmuir , 2016, 32 , 10368–10376). Using experimentally measured polymer properties and the Maxwell model, we predicted the properties of all of the hypothetical mixed matrix membranes that could be made by combining the metal–organic frameworks with each of nine polymers, resulting in over one million possible MMMs. The predicted gas permeation of MMMs was compared to published gas permeation data in order to validate the methodology. We then carried out twelve individually optimized techno-economic evaluations of a three-stage membrane-based capture process. For each evaluation, capture process variables such as flow rate, capture fraction, pressure and temperature conditions were optimized and the resultant cost data were interpolated in order to assign cost based on membrane selectivity and permeability. This work makes a connection from atomistic simulation all the way to techno-economic evaluation for a membrane-based carbon capture process. We find that a large number of possible mixed matrix membranes are predicted to yield a cost of carbon capture less than $50 per tonne CO 2 removed, and a significant number of MOFs so identified have favorable CO 2 /H 2 O sorption selectivity.  more » « less
Award ID(s):
1653375
PAR ID:
10081226
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Energy & Environmental Science
ISSN:
1754-5692
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; (, North American Membrane Society 2023)
    Membrane-based separations offer the potential for the lowest energy demand requirements of all separation options. Among all nanoporous membranes, the carbon molecular sieves (CMS), metal-organic frameworks (MOFs), and mixed-matrix membranes (MMMs) with angstrom level molecular discrimination properties makes them appealing for separating a wide spectrum of gas-pairs. Here we present results of gas selectivity and diffusion of different gases (C2H6, C2H4, C3H8, C3H6, H2, N2, CO2, and CH4) in porous organic cages (POCs) incorporated into fluorinated copolyimides polymers (FCPs). The FCPs were synthesized by the iridization reaction of fluorinated dianhydrides, nonfluorinated dianhydride, and nonfluorinated diamine. Asymmetric hollow fiber membranes formed by the dry-jet/wet-quench spinning process. Once fresh FCP fibers were synthesized, they were crosslinked with POCs, vacuum dried at 90 °C. We investigated the uptake, gas selectivity and diffusion of different gases (C2H6, C2H4, C3H8, C3H6, H2, N2, CO2, and CH4) over synthesized POC-mixed matrixed membranes (POC-MMM) at 25 °C and pressures up to 1 bar. At 1 bar and 25 °C, C2H6, C2H4, C3H8, C3H6 adsorption capacities reached to 42.61, 2.56, 2.77 and 2.65 mmol/g over POC-MMM, respectively, while CO2, CH4, CO, N2 and H2 adsorption capacities of 1.48, 0.84, 0.33, 0.11, and 0.068 mmol/g, respectively. Furthermore, stable CMS membrane were formed by pyrolysis of POC-MMMs under an inert argon atmosphere at 1 atm. To test the gas transport properties of CMS-derived POC/MMM, a lab-scale hollow fiber module with two-five fibers was constructed. The results of longer-term operation of synthesized CMS membrane that was continuously operated for 264 h (10 days) with an equimolar binary H2/CO2, CH4/CO2 and C3H6/C3H8 feed at 25°C and 1 bar feed pressure. The modification yielded promising results in the reduction of physical aging of CMS membranes. 
    more » « less
  2. ; ; (, Journal of Materials Chemistry A)
    null (Ed.)
    Polymer-modification-enabled in situ metal–organic framework formation (PMMOF) is potentially a paradigm-shifting preparation method for polymer/MOF mixed-matrix membranes (MMMs). However, the actual reaction conditions of the in situ formation of MOFs in a confined polymer free volume are expected to be quite different from that in a bulk solution. ZIF-7 is an interesting filler material not only due to its use in selective light gas separations but also for its three different crystal phases. Herein, we carried out systematic investigations on the in situ confined formation of ZIF-7 phases inside a polymer (6FDA-DAM) by PMMOF. The reaction conditions of ZIF-7 in the polymer free volume were deduced based on a bulk-phase ZIF-7 phase diagram constructed by varying the ZIF-7 precursor concentrations and ratios. Based on the understanding of the reaction conditions, the ZIF-7 crystal phases formed inside the polymer during the PMMOF process were controlled, yielding 6FDA-DAM/ZIF-7 MMMs with three different crystal phases. The ZIF-7 phases had significant effects on the gas transport of MMMs with layered ZIF-7-III fillers exhibiting the highest performance enhancement for H 2 /CO 2 separation ( i.e. , H 2 permeability of ∼1630 Barrer and H 2 /CO 2 selectivity of ∼3.8) among other phases. Furthermore, the MMMs obtained by the PMMOF process showed enhanced H 2 /CO 2 separation performance, surpassing the upper bound. 
    more » « less
  3. ; ; (, Science Advances)
    More than 90% of the world’s hydrogen (H2) is produced from fossil fuel sources, which requires energy-intensive separation and purification to produce high-purity H2fuel and to capture the carbon dioxide (CO2) by-product. While membranes can decarbonize H2/CO2separation, their moderate H2/CO2selectivity requires secondary H2purification by pressure swing adsorption. Here, we report hyperselective carbon molecular sieve hollow fiber membranes showing H2/CO2selectivity exceeding 7000 under mixture permeation at 150°C, which is almost 30 times higher than the most selective nonmetallic membrane reported in the literature. The membrane is able to maintain an ultrahigh H2/CO2selectivity over 1400 under mixture permeation at 400°C. Pore structure characterization suggests that highly refined ultramicropores are responsible for effectively discriminating the closely sized H2and CO2molecules in the hyperselective carbon molecular sieve membrane. Modeling shows that the unprecedented H2/CO2selectivity will potentially allow one-step enrichment of fuel-grade H2from shifted syngas for decarbonized H2production. 
    more » « less
  4. ; ; ; ; (, Journal of Polymer Science)
    Abstract Over the last two decades, polymers with superior H2/CO2separation properties at 100–300 °C have gathered significant interest for H2purification and CO2capture. This timely review presents various strategies adopted to molecularly engineer polymers for this application. We first elucidate the Robeson's upper bound at elevated temperatures for H2/CO2separation and the advantages of high‐temperature operation (such as improved solubility selectivity and absence of CO2plasticization), compared with conventional membrane gas separations at ~35 °C. Second, we describe commercially relevant membranes for the separation and highlight materials with free volumes tuned to discriminate H2and CO2, including functional polymers (such as polybenzimidazole) and engineered polymers by cross‐linking, blending, thermal treatment, thermal rearrangement, and carbonization. Third, we succinctly discuss mixed matrix materials containing size‐sieving or H2‐sorptive nanofillers with attractive H2/CO2separation properties. 
    more » « less
  5. ; ; ; (, Membranes)
    null (Ed.)
    Copper-based metal–organic frameworks (MOFs) with different oxidation states and near-uniform particle sizes have been successfully synthesized. Mixed-matrix polyimide membranes incorporating 0.1–7 wt% of Cu(II) benzene-1,2,5-tricarboxylic acid (Cu(II)BTC), Cu(I/II)BTC and Cu(I) 1,2-ethanedisulfonic acid (EDS) (Cu(I)EDS) MOFs were fabricated via non-solvent-induced phase inversion process. These membranes are found to be solvent resistant and mechanically stable. Liquid phase nanofiltration experiments were performed to separate toluene from n-heptane at room temperature. These membranes demonstrate preferential adsorption and permeation of the aromatic toluene over aliphatic n-heptane. The amount of MOF particles incorporated, the oxidation state of the Cu ion and membrane, and barrier layer thickness have a significant impact on the separation factor. Toluene/heptane separation factor at 1.47, 1.67 and 1.79 can be obtained for membranes incorporating 7 wt% Cu(II)BTC, Cu(I/II)BTC and Cu(I)EDS respectively at room temperature. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email