基于COSMO-RS的离子液体吸收CO的溶剂筛选及H2/CO分离实验

doi:10.11949/0438-1157.20221230

摘要/Abstract

摘要：

目前已有的CO吸收方法中，离子液体吸收法由于其独特的优势而备受关注。在本研究中，使用COSMO-RS模型以293.15 K下离子液体对CO的选择性和黏度为指标对350种离子液体进行溶剂筛选，分析了离子液体阴阳离子构型对CO选择性的影响。在此基础上，在实验室合成了离子液体并测定了其黏度随温度的变化曲线。随后通过傅里叶变换红外光谱分析表明质子型离子液体中存在有分子间氢键作用力。使用高压透明蓝宝石釜进行了相平衡实验，测定了溶解度曲线，通过实验分析气液比对分离因子的影响。实验结果表明，在293.15 K、2.1 MPa、气液比为77.75条件下，离子液体对CO/H₂的分离因子可达到109.29。最后，通过FTIR证明了离子液体的稳定性，这意味着该溶剂在工业应用中具有一定的潜力。

关键词: 一氧化碳吸收, 溶剂筛选, 离子液体, 氢气提纯

Abstract:

Among the currently available CO absorption methods, ionic liquid absorption has attracted much attention due to its unique advantages. In this study, 350 ionic liquids were screened as solvents by the COSMO-RS, using the selectivity of CO at 293.15 K and viscosity of ionic liquids as indicators. The effect of the anionic and cationic configurations of the ionic liquids on the selectivity of CO was analyzed. The ionic liquids were synthesized in the laboratory, and their viscosity-temperature curve was measured. Subsequently, Fourier transform infrared spectroscopic analysis showed that there existed intermolecular hydrogen bond force in the proton-type ionic liquid. Phase equilibrium experiments were carried out by using a high-pressure transparent sapphire kettle, solubility curves were determined, and the effect of the gas-to-liquid ratio on the separation factor was analyzed. The results showed that the separation factor of CO/H₂ could reach 109.29 at 293.15 K, 2.1 MPa, and a gas-liquid ratio of 77.75. Finally, the stability of the ionic liquid was demonstrated by FTIR, which implies that the solvent has potential for industrial applications.

Key words: carbon monoxide absorption, solvent screening, ionic liquids, hydrogen purification

中图分类号:

TQ 028.2

霍猛, 彭晓婉, 赵金, 马秋伟, 邓春, 刘蓓, 陈光进. 基于COSMO-RS的离子液体吸收CO的溶剂筛选及H₂/CO分离实验[J]. 化工学报, 2022, 73(12): 5305-5313.

Meng HUO, Xiaowan PENG, Jin ZHAO, Qiuwei MA, Chun DENG, Bei LIU, Guangjin CHEN. COSMO-RS based solvent screening and H₂/CO separation experiments for CO absorption by ionic liquids[J]. CIESC Journal, 2022, 73(12): 5305-5313.

图/表 13

图1 COSMO-RS溶剂筛选步骤

Fig.1 Solvent screening steps of COSMO-RS

图2 313.2 K下CO与H2在[Omim][Tf2N]中的实验和模拟溶解度对比结果

Fig.2 Comparison of experimental and simulated solubility of CO and H2 in [Omim][Tf2N] at 313.2 K

表1 材料名称、纯度和供应商

Table 1 Material name， purity and supplier

名称	纯度/ %（mol）	供应商
1-乙基咪唑盐酸盐	98	河南普赛化工产品有限公司
氯化亚铜	97	上海阿拉丁生化科技股份有限公司
H₂	99.999	北京氦普北分气体工业有限公司
CO	99.999	北京氦普北分气体工业有限公司
H₂/CO混合气	99.999	北京氦普北分气体工业有限公司

图3 293.15 K下CO/H2在离子液体中选择性的预测结果

Fig.3 COSMO-RS predicted results of CO/H2 selectivity in ILs at 293.15 K

图4 [EimH]、[Mmim]和[Bmim]的σ-profiles

Fig.4 σ-profiles of [EimH], [Mmim], and [Bmim]

图6 293.15 K下离子液体黏度的COSMO-RS预测结果

Fig.6 COSMO-RS prediction results of ILs viscosity at 293.15 K

图5 [BF4]、[PF6]和[CuCl2]的σ-profiles

Fig.5 σ-profiles of [BF4], [PF6], and [CuCl2]

图7 [EimH][CuCl2]的FTIR图

Fig.7 FTIR spectrum of [EimH][CuCl2]

图8 常压下离子液体[EimH][CuCl2]黏度随温度变化的黏度-温度曲线

Fig.8 The viscosity-temperature curve of ionic liquid [EimH][CuCl2] at atmospheric pressure as a function of temperature

图9 单组分气体在293.15 K下在[EimH][CuCl2]中的溶解度曲线

Fig.9 Solubility curves of single-component gases in [EimH][CuCl2] at 293.15 K

表2 CO含量为1%（mol）的CO/H2混合气分离实验结果

Table 2 Experimental results of CO/H2 gas mixture separation with 1%（mol） CO

T/K	P_E/MPa	ϕ	气体组分	S_v/(mol·L^-1)	S_c/(mol·bar^-1·L^-1)	β
293.15	2.1	77.75	CO	0.0312	0.8196	109.29
		77.75	H₂	0.1579	0.0075	0.0092
		101.88	CO	0.0313	0.3982	82.12
		101.88	H₂	0.0966	0.0048	0.0122

图10 回收前后[EimH][CuCl2]的FTIR图对比

Fig.10 FTIR comparison of the fresh and recycled [EimH][CuCl2]

图11 [EimH][CuCl2]在宝石釜中解吸的照片

Fig.11 Photographs of [EimH][CuCl2] desorption in the sapphire kettle

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基于COSMO-RS的离子液体吸收CO的溶剂筛选及H₂/CO分离实验

COSMO-RS based solvent screening and H₂/CO separation experiments for CO absorption by ionic liquids

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