School of Safety Science and Engineering,Henan Polytechnic University
Cultivation Base of State Key Labora⁃tory of Gas Geology and Gas Control,Henan Polytechnic University
Co-construction and Cooperation Between the Provinces and Departments for Safe Production and Clean and Efficient Utilization of Coal Innovation Center,Henan Polytechnic University

为更加经济有效地捕获CO2,减少环境污染,加强资源合理利用,制备不同浓度的[Bmim][BF4]+MBF4(M=Li+,Na+和K+)金属络合离子液体,在压力100~4000kPa,温度30,40,50℃条件下,使用反应釜进行气体吸收试验,测定CO2在金属络合离子液体(metalcomplexionicliq⁃uids,MILs)中的溶解度,并采用密度泛函模拟计算MILs与CO2混合体系的稳定构型的电荷分布、Fukui指数和结合能参数,从微观角度分析MILs吸收CO2机理。结果表明:CO2在MILs中的溶解度随温度升高和压力降低而降低;添加碱金属盐可促进离子液体(ionicliquids,ILs)对CO2的吸收,但当ILs中碱金属盐浓度≥1mol/L时会抑制CO2吸收;0.010mol/L的[Bmim][BF4]+KBF4吸收CO2量最高;密度泛函计算结果显示[Bmim][BF4]+KBF4体系的K+体积大,氢键作用力强,且K+在ILs中溶解度小,造成的空间位阻较小,因而拥有更多的自由体积容纳CO2。与纯ILs相比,MILs具有更高的CO2吸收量,在温室气体治理中具有较好的应用前景。

In order to capture carbon dioxide more economically and effectively,reduce environmental pollu⁃tion,and strengthen the rational use of resources,various concentrations of metal complex ionic liquids [Bmim][BF4]+MBF4(M=Li+,Na+ and K+)were prepared in this paper.Under the pressure range of 100~4 000 kPa,the gas absorption experiment was carried out at 30,40 and 50 ℃ by using a high-pressure reactor,and the solubility of CO2 in metal complex ionic liquids(MILs) was measured.Density functional simulation was used to calculate the charge distribution,Fukui index,and binding energy parameters of the stable con⁃figuration of the mixed system of MILs and CO2,and to analyze the CO2 absorption mechanism of MILs from a microscopic perspective.The experimental results show that the solubility of CO2 in MILs decreases with increasing temperature and decreasing pressure.Adding alkali metal salt can promote the absorption of CO2 by ILs,but when the concentration of alkali metal salt in ILs is ≥1 mol/L,it will inhibit CO2 absorption.Be⁃sides,0.010 mol/L [Bmim][BF4]+KBF4 absorbs the highest amount of CO2.The density functional calcula⁃tion results demonstrate that [Bmim][BF4]+KBF4 has a large K+ volume and strong hydrogen bond force,and the solubility of K+ in the ionic liquid is small,resulting in less steric hindrance,so [Bmim][BF4]+KBF4 has more free volume to accommodate CO2.Overall,MILs have higher CO2 absorption than pure ILs,and have a better application prospects in greenhouse gases management.

国家自然科学基金资助项目(51874124,52074108);河南省科技攻关项目(212102310007);河南省高校重点科研项目(22A620001);河南省高校创新人才项目(22HASTIT012)

0 引言
1 实验
1.1 实验材料
1.2 实验装置及操作步骤
1.3 溶解度计算
2 实验结果与分析
3 模拟计算结果与分析
3.1 稳定构型的电荷分布
3.2 Fukui指数
3.3 结合能
4 结语

王兰云,周华健,张亚娟 .CO2在{[Bmim][BF4]+碱金属盐}金属络合离子液体中的溶解度及溶解机理研究[J].河南理工大学学报(自然科学版),2023,42(6):86-95.doi:10.16186/j.cnki.1673-9787.2021100022

WANG L Y,ZHOU H J,ZHANG Y J.On the solubility and dissolution mechanism of CO2 in {[Bmim][BF4]+alkali metal salt} metal complex ionic liquid[J].Journal of Henan Polytechnic University(Natural Science),2023,42(6):86-95.doi:10.16186/j.cnki.1673-9787.2021100022