Protic ionic liquids for the selective absorption of H2S from CO2: Thermodynamic analysis

The solubilities of H₂S and CO₂ in four protic ionic liquids (PILs)—methyldiethanolammonium acetate, methyldiethanolammonium formate, dimethylethanolammonium acetate, and dimethylethanolammonium formate were determined at 303.2–333.2 K and 0–1.2 bar. It is shown PILs have higher absorption capacity for H₂S than normal ionic liquids (ILs) and the Henry's law constants of H₂S in PILs (3.5–11.5 bar at 303.2 K) are much lower than those in normal ILs. In contrast, the solubility of CO₂ in PILs is found to be a magnitude lower than that of H₂S, implying these PILs have both higher absorption capacity for H₂S and higher ideal selectivity of H₂S/CO₂ (8.9–19.5 at 303.2 K) in comparison with normal ILs. The behavior of H₂S and CO₂ absorption in PILs is further demonstrated based on thermodynamic analysis. The results illustrate that PILs are a kind of promising absorbents for the selective separation of H₂S/CO₂ and believed to have potential use in gas sweetening. © 2014 American Institute of Chemical Engineers AIChE J 60: 4232–4240, 2014     

Highly selective absorption separation of H2S and CO2 from CH4 by novel azole-based protic ionic liquids

Recently, the selective removal of H₂S and CO₂ has been highly desired in natural gas sweetening. Herein, four novel azole-based protic ionic liquids (PILs) were designed and prepared through one-step neutralization reaction. The solubility of H₂S (0–1.0 bar), CO₂ (0–1.0 bar), and CH₄ (0–5.0 bar) was systematically measured at temperatures from 298.2 to 333.2 K. NMR and theoretical calculation were used to investigate the reaction mechanism between these PILs and H₂S. Reaction equilibrium thermodynamic model (RETM) was screened to correlate the H₂S solubility. Impressively, 1,5-diazabicyclo[4,3,0] non-5-ene 1,2,4-1H-imidazolide ([DBNH][1,2,4-triaz]) shows the highest H₂S solubility (1.4 mol/mol or 7.3 mol/kg at 298.2 K and 1.0 bar) and superior H₂S/CH₄ (831) and CO₂/CH₄ (199) selectivities compared with literature results. Considering the excellent absorption capacity of H₂S, high H₂S/CH₄, and CO₂/CH₄ selectivity, acceptable reversibility, as well as facile preparation process, it is believed that azole-based PILs provide an attractive alternative in natural gas upgrading process.     

Exceptionally effective H2S absorption and conversion into thiols in novel superbase protic ionic liquids

We demonstrate an effective strategy for capture and conversion of H₂S in novel superbase protic ionic liquids (SPILs). It is found that the synthesized SPILs with the multiple active sites exhibit the unprecedented H₂S uptake via chemical absorption (up to 1.81 mol mol⁻¹ at 298.2 K and 1 bar). More importantly, H₂S molecule is activated by these SPILs during the absorption process, so that the activated H₂S can be converted further into high value-added thiols in situ with excellent yields under mild conditions (303.2 K and 1 bar) without any solvents and metallic catalysts. Since H₂S-saturated SPILs can be regenerated by chemical conversion of absorbed H₂S into thiols, thereby eliminating the higher input of energy consumption during the process of H₂S stripping. This SPIL-mediated scheme provides an alternative approach for the capture and chemical conversion of H₂S.     

Enhanced gravimetric CO2 capacity and viscosity for ionic liquids with cyanopyrrolide anion

Ionic Liquids (ILs) are considered as alternative solvents for the separation of CO₂ from flue gas due mainly to their CO₂ affinity and thermal stability. The cation architecture in a matrix of ammonium and mostly phosphonium‐based ILs with 2‐cyanopyrrolide as the anion to evaluate its impact on gravimetric CO₂ absorption capacity, viscosity, and thermal stability and the three fundamental properties vital for application realization are systematically investigated. Among the investigated ILs, [P2,2,2,8][2‐CNpyr] demonstrated the lowest viscosity, 95 cP at 40°C, and highest CO₂ uptake, 114 mg CO₂ per g IL at 40°C. Combined effects of asymmetry and the optimized chain lengths also resulted in improved thermal stability for [P2,2,2,8][2‐CNpyr], with a mass loss rate of 1.35 × 10^?6 g h^?1 (0.0067 mass % h^?1) at 80°C. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2280–2285, 2015     

碱性离子液体-NaOH/MEA混合体系的CO2吸收性能

为了改善有机醇胺与无机碱液对生物质燃气中CO2的吸收性能,制备了具有代表性的4种功能化离子液体:[TMG]+ [C3H4N2]-、[TMG]+[TFEA]-、[MEA]+[BF4]-、[MEA]+[CHOO]-,并按一定的比例分别与NaOH溶液和乙醇胺(MEA)溶液复配组成新型CO2吸收剂,以研究其对CO2的吸收特性.实验结果显示,MEA-[TMG]+[C3H4N2]-、MEA-[MEA]+[CHOO]-和NaOH-[MEA]+[CHOO]-对CO2的吸收去除率高于单纯的MEA和NaOH溶液,而MEA-[TMG]+[TFEA]-、MEA-[MEA]+[BF4]-和NaOH-[MEA]+[BF4]-对CO2的去除率则低于单纯碱液吸收剂.同时发现,当离子液体[MEA]+[CHOO]-与MEA的混合比例为2∶3时,混合溶剂对CO2的吸收效果比MEA溶液的显著提高,生物质燃气中CO2去除率从91.3％增加至95.7％.     

Rigorous correlations for predicting the solubility of H2S in methylimidazolium-based ionic liquids

Two general and simple models, a group contribution correlation (model I) and an empirical relation (model II), were proposed to predict the solubility of H₂S in methylimidazolium based ionic liquids (ILs) over wide range of temperatures (303.15-363.15 K) and pressures (60.8-2016.8 kPa). The constants of the suggested functionality relations were found via the Nelder-Mead simplex algorithm. Both correlations were trained with 407 data points of H₂S solubility in 9 methylimidazolium based ILs and tested through 121 H₂S solubility data points of 3 different methylimidazolium based ILs to ensure generality. A comprehensive statistical evaluation showed that both suggested correlations are vigorous and have satisfactory error trends. The dataset was subjected to a statistical outlier diagnostic test and the validity of the database was confirmed. In addition, the sensitivity analysis revealed that the experimental data and both models have the same responses toward pressure and temperature, which indicates the reliability of the proposed correlations.     

Designing amino-based ionic liquids for improved carbon capture: One amine binds two CO2

Generally, amine group captures CO₂ according to 2:1 or 1:1 stoichiometry. Here, we report a kind of improved carbon capture using amino-functionalized ionic liquids (ILs) through 1:2 stoichiometry. A serial of amino-functionalized ILs various with basicity and steric hindrance of anion were designed, prepared, and applied in CO₂ capture. Through a combination of absorption experiment, quantum chemical calculation, spectroscopic investigation and calorimetric method, the results indicated that one amine group could bind two CO₂ through proton transfer (PT) process and intramolecular hydrogen bond formation, which leading to enhanced capacity that breaks through equimolar. The basicity and steric hindrance of anion play a significant role in promoting amine group to capture two CO₂. [P₆₆₆₁₄]₂[Asp] with dual anion was further designed and synthesized to promote PT process, which showed high capacity of 1.96 mol/mol IL at 30°C and 1 atm as well as excellent reversibility. © 2018 American Institute of Chemical Engineers AIChE J, 65: 230–238, 2019     

离子液体中电化学还原CO2研究评述与展望

近百年来,伴随着矿石燃料的大量消耗,CO₂的排放量剧增,引发了全球性的生态环境和社会问题。CO₂同时也是廉价且可再生的碳资源,可作为生产醇、醚、酸、酯等重要化工品的原料。在众多吸引力十足的CO₂利用路线中,作为清洁、可控的反应过程,电化学还原固定CO₂技术在温和条件下生产化学品方面具有独特的优势。离子液体以其特有的性质被广泛用于电化学还原CO₂过程,本文对目前国内外离子液体介质中电化学还原CO₂的研究现状进行了综述,介绍了离子液体介质中电化学还原CO₂的主要反应及基本原理;针对离子液体对CO₂高效活化和转化等关键科学问题进行深入探讨,提出新型功能化离子液体的应用将成为CO₂电化学还原领域的发展方向和热点。     

Cuprous-based composite ionic liquids for the selective absorption of CO: Experimental study and thermodynamic analysis

Three cuprous-based composite ionic liquids (ILs) [EimH][OAc]–xCuOAc (x = 0.5, 0.6, 0.7) were prepared and employed for efficient absorption of CO. It is shown that the cuprous composite IL [EimH][OAc]–0.6CuOAc exhibited the largest absorption capacity for CO (0.031 g/g at 293.15 K and 1 bar) and had a record CO/N₂ selectivity of 967, which is better than most of common ILs and solvents reported in the literature. The results of Fourier transform infrared (FTIR) spectra, electrospray ionization mass spectrometry (ESI-MS) analysis, and theoretical calculations reveal that such superior CO capacity mainly resulted from two kinds of chemical interaction between CO and the active anionic species [Cu(OAc)₂]⁻ in [EimH][OAc]–0.6CuOAc. Furthermore, a “deactivated IL model” was further proposed to accurately describe the absorption behavior of CO in [EimH][OAc]–0.6CuOAc, in which the thermodynamic parameters including Henry's law constants, reaction equilibrium constants, and absorption enthalpies were estimated by the correlation of the experimental solubilities of CO.     

功能型离子液体的合成表征及CO2吸收性能

合成了两种传统型离子液体［bmim］BF₄和［emim］BF₄及含有胺基和羟基的功能型离子液体［NH₂P-mim］Br、［NH₂-e-mim］BF₄、［OH-e-mim］Br,并对合成的离子液体进行IR和¹H NMR表征。常温常压条件下,对所合成的离子液体开展CO₂吸收性能实验,发现胺基改性离子液体［NH₂P-mim］Br、［NH₂-e-mim］BF₄和羟基改性离子液体［OH-e-mim］Br的CO₂饱和吸收量分别是常规离子液体的3～9倍和1～2倍,且含有乙基官能团的离子液体吸收平衡时间普遍较短。最终探讨了温度、CO₂分压等对功能型离子液体吸收CO₂过程的影响。     

肉桂酸型离子液体的合成及其二氧化碳吸收

合成了一系列肉桂酸型功能化离子液体,研究了其CO₂ 吸收性能。结果表明,肉桂酸型功能化离子液体吸收二氧化碳性能良好,其阴离子苯环上的取代基会影响CO₂ 吸收性能。随着温度的升高和压力的降低,其CO₂吸收性能都会降低。同时,该离子液体具有很好的循环稳定性,经过5 次吸收脱附循环,该离子液体仍能保持较高的CO₂ 吸收量。结合红外光谱和其低浓度下CO₂ 的吸收研究发现肉桂酸型离子液体吸收CO₂ 存在着化学作用。     

The effect of protic ionic liquids incorporation on CO2 separation performance of Pebax-based membranes

The separation of carbon dioxide (CO₂) is of great importance for environment protection and gas resource purification. The ionic liquids (ILs)-based gas separation membrane provides a new chance for efficient CO₂ separation, while high permeability and selectivity of membranes is a great challenge. In this study, the influence of two protic ILs with different anion ([TMGH][Im] and [TMGH][PhO]) on the CO₂ separation performance of the prepared ILs/Pebax blended membranes were systematically investigated at different temperature. The results showed the CO₂ permeability exhibits the rising trend for ILs/Pebax blended membranes with the increment of IL content. Especially, the [TMGH][Im] with low viscosity and high CO₂ absorption capacity leads to the blended membranes showing better CO₂ permeability and ideal CO₂ selectivity than that of membranes with [TMGH][PhO] at high IL content. Besides, with operating temperature increasing, the gas permeability of 20% (mass) [TMGH][Im]/Pebax blended membrane increases due to the decreasing viscosity of IL and the rising chain mobility of polymer. Inversely, the gas selectivity shows decreasing trend because CO₂ absorption capacity obviously decreased at higher temperature.     

Novel amino acid ionic liquids prepared via one-step lactam hydrolysis for the highly efficient capture of CO2

This article proposes for the first time the preparation of a series of amino acid ionic liquids (AAILs) via one-step hydrolysis of cheap lactams for the capture of CO₂. The structures of the prepared AAILs are confirmed using NMR, FTIR, and ESI-MS, and their physical properties are also determined. It is found that these AAILs are reversible CO₂ absorbents with very high absorption capacities (0.15 to 0.18 g·g⁻¹ at 313.2 K and 1.0 bar), better than almost all task-specific ionic liquids reported in literatures. The absorption mechanism is also elucidated to be a combination of 1:1 and 2:1 stoichiometric reaction of AAILs with CO₂ from NMR, FTIR, reaction equilibrium thermodynamical modeling and quantum calculations. The AAILs have the advantages of simple synthesis, high yield, and using available cheap raw materials. It is believed that this kind of AAILs have great potentials to be used as efficient CO₂ absorbents.     

Thermodynamic validation of 1‐alkyl‐3‐methylimidazolium carboxylates as task‐specific ionic liquids for H2S absorption

Solubilities of H₂S in five 1‐alkyl‐3‐methylimidazolium carboxylates ionic liquids (ILs) have been measured at temperatures from 293.15 to 333.15 K and pressures up to 350 kPa. It is shown that these ILs have significantly larger absorption capacities for H₂S than those common ILs reported in the literature. The solubility is found to increase dramatically with the increasing alkalinity of the anions and slightly with the increasing length of the alkyl chains on the cations. It is further demonstrated that the absorption isotherms are typically nonideal. With the assumption of complex formation between H₂S and ILs, a reaction equilibrium thermodynamic model is developed to correlate the experimental solubilities. The model favors a reaction mechanism of AB₂ type that two IL molecules interact with one H₂S molecule. Thermodynamic parameters such as Henry's law constants, reaction equilibrium constants, and heat of complex formation are also calculated to evaluate the absorption process of H₂S in these ILs. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2227–2235, 2013     

Performance and pressure drop of CO2 absorption into task-specific and halide-free ionic liquids in a microchannel

The gas–liquid two-phase flow pattern, absorption rate and pressure drop of CO₂ absorbed into the aqueous solution of the task-specific ionic liquids (1-aminopropyl-3-methylimidazole tetrafluoroborate [Apmim][BF₄] and 1-hydroxyethyl-3-methylimidazole tetrafluoroborate [OHemim][BF₄]) and halide-free ionic liquid 1-butyl-3-methylimidazolium methylsulfate [Bmim][CH₃SO₄] were investigated in a microreactor. The absorption mechanism of the three ionic liquids was analyzed employing the ¹³C NMR spectroscopy. The [Apmim][BF₄] was found to have the best ability of CO₂ capture compared with the other two ionic liquids, as chemical absorption occurred between [Apmim][BF₄] and CO₂, while only physical absorption took place between [OHemim][BF₄]/[Bmim][CH₃SO₄] and CO₂. The sequence of CO₂ absorption rate in three ionic liquids aqueous solutions is: [Apmim][BF₄] > [Bmim][CH₃SO₄] > [OHemim][BF₄]. Furthermore, the effects of gas–liquid flow rate and ionic liquids concentration on CO₂ absorption rate and pressure drop were studied, the pressure drop models based on various flow patterns were proposed.     

MDEA-TBEE复合溶液选择性吸收H_2S性能评价

将一种强空间位阻胺TBEE(叔丁氨基乙氧基乙醇)添加于MDEA(N-甲基二乙醇胺)溶液中形成复合溶液MDEA-TBEE,以填料柱为反应器,采用常压吸收-常压再生操作流程,研究了复合溶液从混合气中选择性吸收H2S吸收性能,并与单组分吸收剂MDEA溶液吸收性能作比较,以脱除率、选择性、溶液负载和容量为评价指标,评价了再生温度、原料气CO2/H2S摩尔比、气液比和贫液负载等因素对复合溶液选择性吸收H2S性能的影响。结果表明,复合溶液比MDEA溶液易于再生,H2S脱除率高于MDEA溶液;复合溶液的容量大于MDEA溶液,平均是MDEA的1.25倍;随着气液比增大,H2S脱除率下降,选择性有所上升。     

Efficient capture of CO2 from flue gas at high temperature by tunable polyamine-based hybrid ionic liquids

For an ideal absorbent for CO₂ capture from flue gas, there are some key features including easy preparation, high stability, low absorption enthalpy, high capacity at high temperature and excellent reversibility. Herein, several polyamine-functionalized ionic liquids (ILs) were easily prepared from cheap polyamines and lithium salts, which exhibited significantly improved stability due to the presence of multisite coordinating interactions. The viscosity was reduced by introducing polyalcohol-based ILs, leading to polyamine-based hybrid ILs. Interestingly, these polyamine-based hybrid ILs exhibited high CO₂ capacity (4.09 mmol/g, 0.1 bar) at high temperature (80°C) and excellent reversibility in the presence of H₂O and O₂, which is superior to many other good absorbents. Moreover, these ILs also showed good performance for CO₂ capture from stimulated air (2.10 mmol/g, 380 ppm). We believe that this method with easy preparation, low cost, high efficiency and excellent reversibility has a great potential in the industrial capture of CO₂ from flue gas.     

Gas–liquid mass‐transfer properties in CO2 absorption system with ionic liquids

The deficiency of mass‐transfer properties in ionic liquids (ILs) has become a bottleneck in developing the novel IL‐based CO₂ capture processes. In this study, the liquid‐side mass‐transfer coefficients (k_L) were measured systematically in a stirred cell reactor by the decreasing pressure method at temperatures ranging from 303 to 323 K and over a wide range of IL concentrations from 0 to 100 wt %. Based on the data of k_L, the kinetics of chemical absorption of CO₂ with mixed solvents containing 30 wt % monoethanolamine (MEA) and 0–70 wt % ILs were investigated. The k_L in IL systems is influenced not only by the viscosity but also the molecular structures of ILs. The enhancement factors and the reaction activation energy were quantified. Considering both the mass‐transfer rates and the stability of IL in CO₂ absorption system, the new IL‐based system MEA + [bmim][NO₃] + H₂O is recommended. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2929–2939, 2014     

聚离子液体二氧化碳分离膜材料的研究进展

近年来,全球二氧化碳排放超过370亿吨/年,对气候和自然环境造成严重影响,亟需发展碳捕集、利用与封存技术。气体膜分离是一种条件温和、操作简单的无相变分离技术,随着高渗透性、高选择性膜材料的不断涌现,逐渐成为全球碳捕集技术的主要发展方向。聚离子液体膜材料中含有大量高度亲和二氧化碳的功能基团,有望实现超高渗透选择性,被誉为下一代气体分离膜材料。综述了聚离子液体膜材料的研究进展,以渗透机制为主线重点介绍了面向碳捕集的阳离子型聚离子液体膜材料(主链型和支链型)的设计合成,包括阳离子和阴离子基团的选择,合成途径的选择,以及聚离子液体膜的结构设计优化。讨论了聚离子液体作为二氧化碳分离膜材料的优势和面临的挑战。