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

doi:10.11949/0438-1157.20221230

Abstract

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

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

CLC Number:

TQ 028.2

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.

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.

Figures/Tables 13

Fig.1 Solvent screening steps of COSMO-RS

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

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

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

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

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

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

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

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

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

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

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

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

References 32

1	Umana B, Zhang N, Smith R. Development of vacuum residue hydrodesulphurization-hydrocracking models and their integration with refinery hydrogen networks[J]. Industrial & Engineering Chemistry Research, 2016, 55(8): 2391-2406.
2	Kan T, Sun X Y, Wang H Y, et al. Production of gasoline and diesel from coal tar via its catalytic hydrogenation in serial fixed beds[J]. Energy & Fuels, 2012, 26(6): 3604-3611.
3	Garba M D, Galadima A. Catalytic hydrogenation of hydrocarbons for gasoline production[J]. Journal of Physical Science, 2018, 29(2): 153-176.
4	Dujjanutat P, Kaewkannetra P. Production of bio-hydrogenated kerosene by catalytic hydrocracking from refined bleached deodorised palm/palm kernel oils[J]. Renewable Energy, 2020, 147: 464-472.
5	Sun Y F, Li C S, Zhang A M. Preparation of Ni/CNTs catalyst with high reducibility and their superior catalytic performance in benzene hydrogenation[J]. Applied Catalysis A: General, 2016, 522: 180-187.
6	Wee J H. Applications of proton exchange membrane fuel cell systems[J]. Renewable and Sustainable Energy Reviews, 2007, 11(8): 1720-1738.
7	El Hajj Chehade A M, Daher E A, Assaf J C, et al. Simulation and optimization of hydrogen production by steam reforming of natural gas for refining and petrochemical demands in Lebanon[J]. International Journal of Hydrogen Energy, 2020, 45(58): 33235-33247.
8	Turner J, Sverdrup G, Mann M K, et al. Renewable hydrogen production[J]. International Journal of Energy Research, 2008, 32(5): 379-407.
9	Li Y J, Luo H. Integration of light hydrocarbons cryogenic separation process in refinery based on LNG cold energy utilization[J]. Chemical Engineering Research and Design, 2015, 93: 632-639.
10	Zhu X C, Shi Y X, Li S, et al. Elevated temperature pressure swing adsorption process for reactive separation of CO/CO₂ in H₂-rich gas[J]. International Journal of Hydrogen Energy, 2018, 43(29): 13305-13317.
11	Wu F, Zhao Q H, Tao L F, et al. Solubility of carbon monoxide and hydrogen in methanol and methyl formate: 298—373 K and 0.3—3.3 MPa[J]. Journal of Chemical & Engineering Data, 2019, 64(12): 5609-5621.
12	Yang T X, Chung T S. High performance ZIF-8/PBI nano-composite membranes for high temperature hydrogen separation consisting of carbon monoxide and water vapor[J]. International Journal of Hydrogen Energy, 2013, 38(1): 229-239.
13	刘佳佳, 付雪, 许映杰. 离子液体吸收分离一氧化碳的研究进展[J].化工学报,2020, 71(1):138-147.
	Liu J J, Fu X, Xu Y J. Progress on carbon monoxide removal using ionic liquids [J]. CIESC Journal, 2020, 71(1): 138-147.
14	Ohlin C A, Dyson P J, Laurenczy G. Carbon monoxide solubility in ionic liquids: determination, prediction and relevance to hydroformylation[J]. Chemical Communications, 2004(9): 1070-1071.
15	Raeissi S, Florusse L J, Peters C J. Purification of flue gas by ionic liquids: carbon monoxide capture in[bmim][Tf 2N][J]. AIChE Journal, 2013, 59(10): 3886-3891.
16	Lei Z G, Shen P, Dai C N. Solubility of CO in the mixture of ionic liquid and ZIF: an experimental and modeling study[J]. Journal of Chemical & Engineering Data, 2016, 61(2): 846-855.
17	Tao D J, Chen F F, Tian Z Q, et al. Highly efficient carbon monoxide capture by carbanion-functionalized ionic liquids through C-site interactions[J]. Angewandte Chemie, 2017, 129(24): 6947-6951.
18	Shmukler L E, Fedorova I V, Fadeeva Y A, et al. Alkylimidazolium protic ionic liquids: structural features and physicochemical properties[J]. ChemPhysChem, 2022, 23(4): e202100772.
19	Shmukler L E, Fedorova I V, Fadeeva Y A, et al. The physicochemical properties and structure of alkylammonium protic ionic liquids of R _n H_4- _n NX (n=1—3) family. A mini-review[J]. Journal of Molecular Liquids, 2021, 321: 114350.
20	Bernardino K, Ribeiro M C C. Hydrogen-bonding and symmetry breaking in the protic ionic liquid 1-ethylimidazolium nitrate[J]. Vibrational Spectroscopy, 2022, 120: 103358.
21	Li P F, Shang D W, Tu W H, et al. NH₃ absorption performance and reversible absorption mechanisms of protic ionic liquids with six-membered N-heterocyclic cations[J]. Separation and Purification Technology, 2020, 248: 117087.
22	Huang H Y, Padin J, Yang R T. Comparison of π-complexations of ethylene and carbon monoxide with Cu⁺ and Ag⁺ [J]. Industrial & Engineering Chemistry Research, 1999, 38(7): 2720-2725.
23	Repper S E, Haynes A, Ditzel E J, et al. Infrared spectroscopic study of absorption and separation of CO using copper ( Ⅰ ) -containing ionic liquids[J]. Dalton Transactions, 2017, 46(9): 2821-2828.
24	Tao D J, An X C, Gao Z T, et al. Cuprous-based composite ionic liquids for the selective absorption of CO: experimental study and thermodynamic analysis[J]. AIChE Journal, 2022, 68(5): e17631.
25	刘玉梅. 离子液体强化吸收一氧化碳和醇解反应过程研究[D]. 南昌: 江西师范大学,2019.
	Liu Y M. Study on ionic liquids for intensified CO absorption and alcoholysis reaction processes[D]. Nanchang: Jiangxi Normal University, 2019.
26	Cui G K, Jiang K, Liu H Y, et al. Highly efficient CO removal by active cuprous-based ternary deep eutectic solvents[HDEEA][Cl]+ CuCl + EG[J]. Separation and Purification Technology, 2021, 274: 118985.
27	张志刚, 张德彪, 张亲亲, 等. 基于COSMO-RS方法筛选离子液体分离乙酸乙酯-乙腈共沸物[J]. 化工学报, 2019, 70(1): 146-153.
	Zhang Z G, Zhang D B, Zhang Q Q, et al. Screening of ionic liquids for separation of ethyl acetate-acetonitrile azeotrope based on COSMO-RS[J]. CIESC Journal, 2019, 70(1): 146-153.
28	Klamt A, Schüürmann G. COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient[J]. J. Chem. Soc., Perkin Trans. 2, 1993(5): 799-805.
29	Klamt A. The COSMO and COSMO-RS solvation models[J]. Wiley Interdisciplinary Reviews: Computational Molecular Science, 2011, 1(5): 699-709.
30	Grimme S, Antony J, Ehrlich S, et al. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu[J]. The Journal of Chemical Physics, 2010, 132(15): 154104.
31	杨倩. 离子液体-CO(H₂)体系的UNIFAC模型和实验研究[D]. 北京: 北京化工大学, 2014.
	Yang Q. UNIFAC model for ionic liquid-CO (H₂) systems: an experimental and modeling study[D]. Beijing: Beijing University of Chemical Technology, 2014.
32	Liu H, Liu B, Lin L C, et al. A hybrid absorption–adsorption method to efficiently capture carbon[J]. Nature Communications, 2014, 5: 5147.

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

基于COSMO-RS的离子液体吸收CO的溶剂筛选及H₂/CO分离实验

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