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Enhanced selectivity in mixed matrix membranes for CO2 capture through efficient dispersion of amine-functionalized MOF nanoparticles

Nature Energy volume 2, Article number: 17086 (2017) Cite this article

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Abstract

Mixed matrix membranes (MMMs) for gas separation applications have enhanced selectivity when compared with the pure polymer matrix, but are commonly reported with low intrinsic permeability, which has major cost implications for implementation of membrane technologies in large-scale carbon capture projects. High-permeability polymers rarely generate sufficient selectivity for energy-efficient CO2 capture. Here we report substantial selectivity enhancements within high-permeability polymers as a result of the efficient dispersion of amine-functionalized, nanosized metal–organic framework (MOF) additives. The enhancement effects under optimal mixing conditions occur with minimal loss in overall permeability. Nanosizing of the MOF enhances its dispersion within the polymer matrix to minimize non-selective microvoid formation around the particles. Amination of such MOFs increases their interaction with thepolymer matrix, resulting in a measured rigidification and enhanced selectivity of the overall composite. The optimal MOF MMM performance was verified in three different polymer systems, and also over pressure and temperature ranges suitable for carbon capture.

The current default technology for large-scale CO2 capture and storage (CCS) is based on liquid-phase absorption towers; whilst many projects of this sort are proposed, few reach completion as costs become prohibitive1.Therefore, it is imperative to offer more cost-effective technological solutions. Membrane separation is often considered; however, current commercial membrane technologies are virtually as expensive as adsorption technologies. This is because gas fluxes through selective membranes are so low that hundreds of millions of square metres of commercial membranes are required even for a single 1,000 MW power station2. When combined with membrane costs of ∼US$50 m−2, the capital cost for commercial membrane-based solutions to CCS is not that different from the unpalatably high costs of adsorption towers for CCS. The key to a future membrane-based CCS solution lies in significantly reducing the total membrane areas required, which in turn requires cheap, higher-permeability membrane materials that retain a high selectivity. New research is aimed at developing better performance polymers (in selectivity and permeability); however, the timelines for reducing costs of such polymers may not be compatible with needs to find immediate candidate materials for large-scale membrane-based CCS solutions.

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Figure 1: Fabrication of MMMs in this study.
Figure 2: MOF and MMM physical characterization.
Figure 3: Computational studies of adhesions between PIM-1 and UiO-66 particles.
Figure 4: Gas transport properties.
Figure 5: Mechanical studies of PIM-1 MMMs and demonstration of similar performance in other polymer MMMs.

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Acknowledgements

H.H. thanks JST-PRESTO (JPMJPR141B) and City University of Hong Kong for financial support. E.S. gratefully acknowledges JST-PRESTO (JPMJPR1417) and the Japanese Ministry of Environment as part of the project ‘Low Carbon Technology Research, Development and Demonstration Program’. iCeMS is supported by the World Premier International Research Initiative (WPI), MEXT, Japan.

Author information

Authors and Affiliations

  1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, 606-8501 Kyoto, Japan

    Behnam Ghalei, Kento Sakurai, Yosuke Kinoshita, Kazuki Wakimoto, Ali Pournaghshband Isfahani, Shuhei Furukawa, Susumu Kitagawa & Easan Sivaniah

  2. Department of Energy Science and Technology, Kyoto University, 606-8501 Kyoto, Japan

    Kento Sakurai, Yosuke Kinoshita, Kazuki Wakimoto & Hiromu Kusuda

  3. Department of Chemical Engineering, Barrer Centre, Imperial College, London SW7 2AZ, UK

    Qilei Song

  4. Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China

    Kazuki Doitomi & Hajime Hirao

  5. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore

    Kazuki Doitomi & Hajime Hirao

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  1. Behnam Ghalei
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Contributions

B.G. conceived and designed the research. K.S. and Y.K. synthesized and analysed PIM-1 MMMs, K.W. synthesized and analysed PEBAX MMMs, A.P. synthesized and analysed polyurethane MMMs, S.F. and S.K. evaluated MOF-related data, Q.S. evaluated mixed membrane data, K.D. and H.H. performed simulations and H.K. S.K. and E.S. supervised researchers in the project. All authors discussed the results and commented on the manuscript at all stages.

Corresponding author

Correspondence to Easan Sivaniah.

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Supplementary Figures 1–21, Supplementary Tables 1–10, Supplementary Notes 1–3 and Supplementary References. (PDF 4176 kb)

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Ghalei, B., Sakurai, K., Kinoshita, Y. et al. Enhanced selectivity in mixed matrix membranes for CO2 capture through efficient dispersion of amine-functionalized MOF nanoparticles. Nat Energy 2, 17086 (2017). https://doi.org/10.1038/nenergy.2017.86

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