CIESC Journal ›› 2021, Vol. 72 ›› Issue (11): 5664-5674.DOI: 10.11949/0438-1157.20210676

• Separation engineering • Previous Articles     Next Articles

Adsorption behavior of light alkanes/ alkenes on ultramicroporous flexible Cu(Qc)2

Yuning TANG(),Xun WANG,Junjie PENG,Ying WU(),Zhong LI()   

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
  • Received:2021-05-17 Revised:2021-09-27 Online:2021-11-12 Published:2021-11-05
  • Contact: Ying WU,Zhong LI

低碳烷烃烯烃在超微孔柔性Cu(Qc)2上的吸附行为

唐瑜佞(),王勋,彭俊洁,吴颖(),李忠()   

  1. 华南理工大学化学与化工学院,广东 广州 510640
  • 通讯作者: 吴颖,李忠
  • 作者简介:唐瑜佞(1995—),女,硕士研究生,tangyuning123@163.com
  • 基金资助:
    国家自然科学基金项目(21436005)

Abstract:

The adsorption thermodynamics, kinetics and separation behavior of light alkanes/alkenes (CH4/C2H4/C2H6/C3H6/C3H8) on ultramicroporous and flexible metal-organic frameworks (MOFs) Cu(Qc)2 were systematically studied by using combination of experimental and simulation methods. Ultramicroporous and flexible Cu(Qc)2 was synthesized using a room temperature synthesis method for alkanes/alkenes separation. The adsorption isotherms and kinetic curves of these alkanes/alkenes on Cu(Qc)2 were measured. The adsorption behavior of these light hydrocarbons on the Cu(Qc)2 and the deformation of the material structure were studied by means of the Fortcite module of the Materials Studio. The results showed that Cu(Qc)2 had excellent C2H6 /C2H4 adsorption selectivity and adsorption kinetics, while its adsorption selectivity to C3H8 /C3H6 was very weak. At 273 K and 0.1 MPa, the IAST selectivity of Cu(Qc)2 for C2H6/C2H4 reached as high as 4.6. At 298 K and 0.05 MPa, the diffusion time constants of C2H6 and C2H4 on Cu(Qc)2 reached 1.42×10-3 and 1.48×10-3 s-1, respectively, and the activation energy of diffusion was 16.62 and 16.43 kJ/mol, respectively. The application of fixed bed packed with Cu(Qc)2 can realize the complete separation of C2H6/C2H4 binary mixture under normal temperature conditions. The simulation results showed that Cu(Qc)2 was a two-dimensional stack structure, which would undergo different degrees of structural deformation when different molecules were adsorbed. Methane would be ready to diffuse and desorb from the enlarged layer, resulting in a very low adsorption capacity; both C2H6 and C2H4 can be stably adsorbed in the pores in the layer, and the separation driving force mainly comes from the difference in the adsorption heats of the two molecules; C3H8 and C3H6 would be separately adsorbed in two different environments of Cu(Qc)2, and the small difference in adsorption heats of these molecules makes the C3H8/C3H6 adsorption selectivity low.

Key words: Cu(Qc)2, adsorption, separation, alkanes/alkenes, kinetics

摘要:

采用实验研究与分子模拟相结合的方法研究了低碳烷烃烯烃在超微孔柔性Cu(Qc)2上的吸附热力学、动力学和吸附分离机理。用常温合成方法制备了超微孔金属-有机骨架材料Cu(Qc)2,测定了低碳烷烃烯烃(CH4/C2H4/C2H6/C3H6/C3H8)在Cu(Qc)2上的吸附相平衡和吸附动力学。使用Materials Studio中的Fortcite模块模拟低碳烷烃烯烃在超微孔柔性Cu(Qc)2上的吸附机理以及材料的结构形变。结果表明Cu(Qc)2具有优良的C2H6 /C2H4吸附选择性和吸附动力学,而对C3H8 /C3H6的吸附选择性很低。273 K和0.1 MPa下,C2H6/C2H4在Cu(Qc)2上的IAST选择性达4.6。298 K和0.05 MPa下C2H6/C2H4在Cu(Qc)2上的扩散时间常数分别达1.42×10-3和1.48×10-3s-1,扩散活化能分别为16.62 和16.43 kJ/mol。应用装填Cu(Qc)2的固定床可在常温条件下实现C2H6 /C2H4二元混合气的完全分离。模拟结果显示Cu(Qc)2为二维堆叠结构,材料会由于吸附不同分子而发生不同程度的结构形变。甲烷易从变大的层间扩散脱附,导致其在材料上的吸附量很低;C2H6/C2H4两者都能稳定吸附在层中的孔道中,其分离推动力主要来源于两种气体在材料上明显的吸附热差异;C3H8/C3H6会分别吸附在两种不同的环境,吸附热差异小导致Cu(Qc)2对C3H8 /C3H6的吸附选择性低。

关键词: Cu(Qc)2, 吸附, 分离, 烷烃/烯烃, 动力学

CLC Number: