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Extraction of propane and ethane from natural gas on ultramicroporous carbon adsorbent with record selectivity

超微孔碳吸附剂实现天然气中丙烷和乙烷的高选择性提取

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Abstract

The separation of light hydrocarbon mixtures and the extraction of C3H8 and C2H6 from natural gas are of significant importance in natural gas purification and upgrading. Microporous carbon adsorbents are promising in light hydrocarbon separation. However, the fabrication of uniform ultramicropores to boost separation selectivity remains challenging. Herein, we fabricated a series of poly(vinylidene chloride)-resin-derived ultramicroporous carbon adsorbents with a relatively uniform pore size (5.2–5.3 Å) by activator-free pyrolysis. The optimal C-PVDC-800 exhibited record-high ideal adsorption solution theory (IAST) selectivity for C3H8/CH4 (3387) and C2H6/CH4 (75) and Henry’s selectivity for C3H8/CH4 (369) among all reported adsorbents under ambient conditions, combined with ultrahigh uptake of C3H8 (3.9 mmol g−1, 0.05 bar) and C2H6 (2.67 mmol g−1, 0.10 bar) at low partial pressures and 298 K. More importantly, fast gas adsorption kinetics favorable for fixed-bed adsorption applications was realized. Breakthrough experiments and cycling tests further confirm the superb separation performance of the extraction of C3H8 and C2H6 from natural gas.

摘要

轻烃混合物分离以及从天然气中提取C3H8和C2H6对天然气纯化及劣质天然气升级意义重大. 微孔碳吸附剂在轻烃分离中潜力巨大, 然而构筑孔径均一的超微孔从而增强分离选择性仍是巨大挑战. 在本文中, 我们采取无活化剂热解法制备了一系列孔径均一(5.2到5.3 Å)的聚偏二氯乙烯树脂(PVDC)衍生的超微孔碳吸附剂. 与已报道的吸附剂相比, 优选的C-PVDC-800对C3H8/CH4及C2H6/CH4在298 K和1.0 bar下表现出更高的理想吸附溶液理论(IAST)选择性(分别为3387和75), 对C3H8/CH4具有最高的Henry系数选择性(369). 此外, C-PVDC-800在低压下对C3H8和C2H6具有极高的吸附量. 更重要的是, 该材料对所有气体分子都实现了快速的动力学吸附, 有利于应用于固定床吸附过程. 固定床穿透实验及循环测试进一步证实了该材料从天然气中选择性提取C3H8和C2H6的优异性能.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21878260, 21978254, and 22141001).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

    Fuqiang Chen  (陈富强), Kaiqing Guo  (郭凯晴), Xinlei Huang  (黄鑫磊), Zhiguo Zhang  (张治国), Qiwei Yang  (杨启炜), Yiwen Yang  (杨亦文), Qilong Ren  (任其龙) & Zongbi Bao  (鲍宗必)

  2. Institute of Zhejiang University-Quzhou, Quzhou, 324000, China

    Zhiguo Zhang  (张治国), Qiwei Yang  (杨启炜), Yiwen Yang  (杨亦文), Qilong Ren  (任其龙) & Zongbi Bao  (鲍宗必)

  3. Hangzhou Oxygen Plant Group Co., Ltd, Hangzhou, 310014, China

    Kaiqing Guo  (郭凯晴)

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  1. Fuqiang Chen  (陈富强)
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Contributions

Chen F, Guo K, and Bao Z designed the experiments. Chen F, Guo K, and Huang X performed the experiments. Chen F wrote the manuscript under the supervision of Bao Z and Ren Q. All authors contributed to the general discussion.

Corresponding author

Correspondence to Zongbi Bao  (鲍宗必).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Fuqiang Chen received his bachelor’s degree from Heifei University of Technology in 2017. He is currently a PhD candidate under the supervision of Prof. Qilong Ren and Prof. Zongbi Bao. His research interests focus on the design and application of porous adsorbents in the field of gas adsorption separation.

Kaiqing Guo received her master’s degree from Zhejiang University in 2021. She currently works for Hangzhou Oxygen Plant Group Co., Ltd., and is engaged in air separation. Her research interests focus on the application of porous carbons in natural gas purification.

Zongbi Bao received his bachelor and PhD degrees from Zhejiang University in 2003 and 2008, respectively. He then worked as a postdoctoral fellow at Zhejiang University and New Mexico State University from 2009 to 2010 and joined the College of Chemical and Biological Engineering at Zhejiang University in 2011. He obtained the National Excellent Youth Science Fund of National Science Foundation of China in 2017. He is currently a professor of chemical engineering at Zhejiang University. His research interests mainly focus on the development of porous adsorbents (metal-organic frameworks and porous carbons) and their applications in gas adsorption separation.

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Chen, F., Guo, K., Huang, X. et al. Extraction of propane and ethane from natural gas on ultramicroporous carbon adsorbent with record selectivity. Sci. China Mater. 66, 319–326 (2023). https://doi.org/10.1007/s40843-022-2096-8

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