Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (4): 520-529.DOI: 10.6023/A20110526 Previous Articles     Next Articles



杨磊a, 吴宇静a, 吴选军a,*(), 蔡卫权b,c   

  1. a 武汉理工大学化学化工与生命科学学院 武汉 430070
    b 广州大学化学化工学院 广州 510006
    c 郑州大学材料科学与工程学院 郑州 450002
  • 投稿日期:2020-11-17 发布日期:2021-02-05
  • 通讯作者: 吴选军

High-throughput Screening of Real Metal-organic Frameworks for Adsorption Separation of C4 Olefins

Lei Yanga, Yujing Wua, Xuanjun Wua,*(), Weiquan Caib,c   

  1. a School of Chemistry, Chemical Engineering & Life Sciences, Wuhan University of Technology, Wuhan 430070, China
    b School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
    c School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, China
  • Received:2020-11-17 Published:2021-02-05
  • Contact: Xuanjun Wu
  • About author:

The conventional separation process of olefin/paraffin with cryogenic and high-pressure distillation usually exhibits high energy consumption and low efficiency. The adsorption separation technology is widely promising in the field of olefin/paraffin separation because of its mild operation conditions and high energy efficiency. In this work, high-throughput screening was adopted to find the optimal adsorbents from 12723 real metal-organic framework (MOF) materials, which is available for adsorption separation of 1,3-butadiene from C4 olefin/paraffin mixture. Firstly, 7681 adsorbents with suitable pore size and specific surface area were selected from the total database according to their structural parameters. Then their mechanical properties were computed by molecular mechanics. The mechanical properties of UIO-66 were used as the threshold to obtain 959 candidate MOFs with stable structure. Secondly, the grand canonical Monte Carlo (GCMC) simulation was performed to calculate the selective adsorption behavior of a quinary equimolar C4 olefin mixture in different candidate MOFs at 298 K and 0.1 MPa. According to their adsorption performance scores (APS) of 1,3-butadiene, the candidate MOFs are ranked to obtain 8 MOFs with the optimal adsorption and separation performance. The structural characteristics of MOFs with high adsorption and separation performance are revealed through quantitative structure-activity relationship, adsorption isotherm and ideal adsorption solution theory. The breakthrough curve simulation further verified that 2-cis-butene could effectively separate from 1,3-butadiene in the fixed bed filled with the optimal adsorbent RIGPEE01. Finally, it is determined that the preferential adsorption mechanism of 1,3-butadiene in RIGPEE01 is mainly due to the strong adsorption sites of Cu(I), π bond coupling effect and the size sieving effect based on the radial distribution function and binding energy analysis. The high-throughput screening method and the molecule-level insights on the olefin separation mechanism of MOFs proposed in this work have laid a theoretical foundation for the further development of new adsorbents for the separation of olefin/paraffin mixtures.

Key words: real metal-organic framework, molecular simulation, high-throughput screening, adsorption separation, 1,3-butadiene