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Piperazine-immobilized polymeric membranes for CO2 capture: mechanism of preferential CO2 permeation

Polymer Journal volume 53, pages 129–136 (2021)Cite this article

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Abstract

Amines are incorporated into various membranes to improve their CO2 separation performance. With amine-containing polymeric membranes, gas transport properties are often enhanced under humidity, where CO2 migrates through the membranes in the form of bicarbonate ions. Piperazine (Pz) and its derivatives are known to catalyze the conversion of CO2 to bicarbonate ions and have been used in liquid amine scrubbing technology. Piperazines were immobilized in poly(vinyl alcohol) (PVA), and the resulting polymeric membranes showed high CO2 separation performance over H2 and CH4. The gas transport properties were dependent on the chemical structure of the amines. In particular, 3-(1-piperazinyl)-1,2-propanediol (PzPD)-containing polymeric membranes gave excellent CO2 separation performance, and the CO2 permeability and CO2 selectivity over CH4 were 1060 Barrer and 370, respectively, at 50 °C and 90% relative humidity with a transmembrane CO2 pressure of 11 kPa. The interaction between PzPD and CO2 was quantitatively studied by inverse-gate decoupling 13C NMR spectroscopy. CO2 interacted with the secondary amino group on the Pz ring to form a carbamate, which was readily hydrolyzed to produce bicarbonate ions. The hydroxyl group on the C2 carbon of PzPD facilitated the interaction between CO2 and the amine through hydrogen bonding, resulting in enhanced diffusivity of CO2 in the membranes.

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Acknowledgements

This research is supported by JST ALCA Grant Number JPMJAL1403 and JSPS KAKENHI Grant Number JP17K05966, Japan. The WPI-I2CNER is supported by the World Premier International Research Center Initiative (WPI), MEXT, Japan. The authors would like to thank Mr. Tomonori Oda for helping with the membrane preparations and gas separation experiments. HT and KM acknowledge the support of the Kyushu University Future Creators in Science Project (QFC-SP) by the JST Global Science Campus Project, Japan.

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Authors and Affiliations

  1. International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan

    Ikuo Taniguchi, Kae Kinugasa, Mariko Toyoda, Haruno Tanaka & Kanato Mitsuhara

  2. Department of Automotive Science, Graduate School of Integrated Frontier Sciences, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan

    Koki Minezaki

  3. Yatsushiro Senior High School, 856 Nagaikarimachi, Yatsushiro, Kumamoto, 866-0885, Japan

    Haruno Tanaka

  4. Takeo Senior High School, 5540-2 Ooaza, Takeo-cho, Takeo, Saga, 843-0022, Japan

    Kanato Mitsuhara

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  1. Ikuo Taniguchi
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Correspondence to Ikuo Taniguchi.

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Taniguchi, I., Kinugasa, K., Toyoda, M. et al. Piperazine-immobilized polymeric membranes for CO2 capture: mechanism of preferential CO2 permeation. Polym J 53, 129–136 (2021). https://doi.org/10.1038/s41428-020-0389-7

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