Modeling vapor–liquid equilibrium and liquid–liquid extraction of deep eutectic solvents and ionic liquids using perturbed-chain statistical associating fluid theory equation of state. Part II

This study aims to use perturbed-chain statistical associating fluid theory (PC-SAFT) to describe the phase behavior of systems containing deep eutectic solvents (DESs) and ionic liquids (ILs). The DESs are based on tetrabutylammonium chloride and tetrabutylammonium bromide as hydrogen bond acceptors, and levulinic acid and diethylene glycol as hydrogen bond donors in the mole ratio of 1:2 and 1:4, respectively. Predictions of phase equilibria by PC-SAFT were compared with the results of COnductor like Screening MOdel for Real Solvents (COSMO-RS) and non-random two-liquid (NRTL). In this work, low viscosity ether- and pyridinium-based ILs [E_nPy][NTf₂] and [C_mPy][NTf₂] were used for vapor–liquid equilibrium systems, while 1-(2-methoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)-amide and 1-propyl-3-methylimidazolium bis{trifluoromethylsulfonyl}imide with n-heptane + thiophene and n-hexane + ethylbenzene were used in the liquid–liquid extraction, respectively. In the last part, the phase behavior of the mixtures of perfluoroalkylalkanes with their linear alkane counterparts was studied and compared with the SAFT-Mie pair potential.     

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.     

Protic ionic liquid-based deep eutectic solvents with multiple hydrogen bonding sites for efficient absorption of NH3

The emerging of ionic liquids (ILs) provides an efficient and sustainable way to separate and recover NH₃ due to their unique properties. However, the solid or highly viscous ILs are not suitable for traditional scrubbing. Therefore, an effective strategy was proposed by combining the protic ILs (PILs) with acidic H and low viscous ethylene glycol (EG) to form IL-based deep eutectic solvents (DESs) for NH₃ absorption. The results indicated that these PIL-based DESs not only have fast absorption rate, but also exhibit exceptional NH₃ capacity and excellent recyclability. The highest mass capacity of 211 mg NH₃/g DES was achieved by [Im][NO₃]/EG with molar ratio of 1:3, and was higher than all the reported ILs and IL-based DESs, which was originated from multiple hydrogen bonding between acidic H and hydroxyl groups of the DESs and NH₃. This work will provide useful idea for designing IL-based solvents for NH₃ separation applications.     

Liquid-Liquid Equilibrium Data for the System N-Octane + Toluene + DES at 293.15 and 313.15 K and Atmospheric Pressure

Deep eutectic solvents (DESs) are promising alternative for ionic liquids due to their low cost and sustainability. Considerable attention is paid on the ability of DES to replace ionic liquids in the separation of organic liquid mixtures via extraction. In this sense, it is important to determine the physicochemical parameters of liquid-liquid equilibrium for the industrially significant mixtures and deep eutectic solvents. In the present work a mixture of n-octane, toluene and DES based on choline chloride and malonic acid was studied at 293.15, 313.15 K and atmospheric pressure. Tie-lines were obtained and ability of deep eutectic solvents to separate aliphatic-aromatic mixture was analyzed. Experimental liquid-liquid equilibrium data were fit with the NRTL model, and interaction parameters of components were obtained and discussed.     

Thermodynamic and molecular insights into natural gas dehydration using choline chloride-based deep eutectic solvents

Deep eutectic solvents (DESs) as promising green drying agents were first proposed to natural gas (NG) dehydration. In this work, choline chloride (ChCl)-based DESs were prepared using ChCl as hydrogen bond acceptor (HBA) and triethylene glycol (TEG), ethylene glycol (EG) or Urea as hydrogen bond donors (HBDs). To explore the potential application, methane (CH₄) dehydration experiment was conducted to verify the dehydration performance using prepared DESs. The thermodynamic properties were predicted by COSMO-RS model (Conductor-like screening model for real solvents). The quantum chemistry calculation was applied to understand the separation mechanism at the molecular level. The absorption performance of H₂O in DESs depends on the weak interaction between Cl atom (or N and O atom) of ChCl and H atom of H₂O as well as the free volume of DESs. Molecular dynamics (MD) simulation discloses the intermolecular interaction between HBA and HBD. This work makes the first multi-scale analysis on NG dehydration using DESs.     

苯甲酸型低共熔溶剂吸收一氧化氮的性能研究

低共熔溶剂（DESs）已被广泛研究并应用于酸性气体的吸收,本研究发现苯甲酸类DESs能够可逆高效地吸收一氧化氮（NO）。以苯甲酸（BA）、硫脲、尿素和咪唑为氢键供体（HBD）,以离子液体为氢键受体（HBA）制备了一系列的DESs。吸收NO的实验结果表明,以氯化四丁基膦（P₄₄₄₄Cl）为HBA和以BA为HBD的DESs表现出较高的NO吸收速率和饱和吸收量。BA/P₄₄₄₄Cl (1∶2) DES在101.3 kPa、303.15 K下,NO吸收量为2.75 mol/mol。热重测试和再生实验的结果表明,BA/P₄₄₄₄Cl (1∶2) DES具有理想的热稳定性和重复使用性。通过FTIR、¹H NMR和高斯模拟计算,探讨了BA/P₄₄₄₄Cl (1∶2) DES对NO的吸收机理,发现NO与BA的含氢氧原子之间存在化学相互作用,且BA的易去质子化性质有利于NO的吸收。     

New Carvone-Based Deep Eutectic Solvents for Siloxanes Capture from Biogas

During biogas combustion, siloxanes form deposits of SiO₂ on engine components, thus shortening the lifespan of the installation. Therefore, the development of new methods for the purification of biogas is receiving increasing attention. One of the most effective methods is physical absorption with the use of appropriate solvents. According to the principles of green engineering, solvents should be biodegradable, non-toxic, and have a high absorption capacity. Deep eutectic solvents (DES) possess such characteristics. In the literature, due to the very large number of DES combinations, conductor-like screening models for real solvents (COSMO-RS), based on the comparison of siloxane activity coefficient of 90 DESs of various types, were studied. DESs, which have the highest affinity to siloxanes, were synthesized. The most important physicochemical properties of DESs were carefully studied. In order to explain of the mechanism of DES formation, and the interaction between DES and siloxanes, the theoretical studies based on σ-profiles, and experimental studies including the ¹H NMR, ¹³C NMR, and FT-IR spectra, were applied. The obtained results indicated that the new DESs, which were composed of carvone and carboxylic acids, were characterized by the highest affinity to siloxanes. It was shown that the hydrogen bonds between the active ketone group (=O) and the carboxyl group (-COOH) determined the formation of stable DESs with a melting point much lower than those of the individual components. On the other hand, non-bonded interactions mainly determined the effective capture of siloxanes with DES.     

CO2 Absorption Mechanism by the Deep Eutectic Solvents Formed by Monoethanolamine-Based Protic Ionic Liquid and Ethylene Glycol

Deep eutectic solvents (DESs) have been widely used to capture CO₂ in recent years. Understanding CO₂ mechanisms by DESs is crucial to the design of efficient DESs for carbon capture. In this work, we studied the CO₂ absorption mechanism by DESs based on ethylene glycol (EG) and protic ionic liquid ([MEAH][Im]), formed by monoethanolamine (MEA) with imidazole (Im). The interactions between CO₂ and DESs [MEAH][Im]-EG (1:3) are investigated thoroughly by applying ¹H and ¹³ C nuclear magnetic resonance (NMR), 2-D NMR, and Fourier-transform infrared (FTIR) techniques. Surprisingly, the results indicate that CO₂ not only binds to the amine group of MEA but also reacts with the deprotonated EG, yielding carbamate and carbonate species, respectively. The reaction mechanism between CO₂ and DESs is proposed, which includes two pathways. One pathway is the deprotonation of the [MEAH]⁺ cation by the [Im]⁻ anion, resulting in the formation of neutral molecule MEA, which then reacts with CO₂ to form a carbamate species. In the other pathway, EG is deprotonated by the [Im]⁻, and then the deprotonated EG, HO-CH₂-CH₂-O⁻, binds with CO₂ to form a carbonate species. The absorption mechanism found by this work is different from those of other DESs formed by protic ionic liquids and EG, and we believe the new insights into the interactions between CO₂ and DESs will be beneficial to the design and applications of DESs for carbon capture in the future.     

Effective separation of aromatic hydrocarbons by pyridine‐based deep eutectic solvents

Many promising qualities of deep‐eutectic solvents made them suitable solvents in separation process. In this work, the pyridine‐based deep eutectic solvents were designed and synthesized with N‐ethylpyridinium bromide and two HBDs (N‐formyl morpholine and levulinic acid). Two ternary systems, benzene + cyclohexane + DES and toluene + n‐heptane + DES, were studied by the liquid‐liquid extraction. The effect of different HBDs, extraction time, volume ratio of DES to system solution, and the initial concentration of aromatic were studied. The DES with N‐formyl morpholine showed better separation performance than that with levulinic acid. The liquid‐liquid extraction equilibrium could be obtained in 10 minutes. The volume ratio of DES to system solution was set as 1:1. Both DESs showed their best separation performance at low temperatures (20°C) and low aromatic concentration system. For the benzene + cyclohexane system, the distribution coefficient of benzene was 1.733 and the selectivity was 23.8 at 20°C. For the toluene + n‐heptane system, the distribution coefficient of toluene was 0.853 and the selectivity was 40.7. Tie‐lines for two ternary systems were obtained, and the Othmer‐Tobias correlation was used to check the reliability of the obtained liquid‐liquid extraction experimental data. The experimental LLE data were correlated using the NRTL model and the calculated data correlated significantly with the experimental data.     

H2S absorption with deep eutectic solvents: Low partial pressure capture and thermodynamic analysis

In the present work, a series of deep eutectic solvents (DESs) based on organic amine as hydrogen bond acceptors (HBAs), and ethylene glycol (EG) as hydrogen bond donor (HBD) were prepared for the H₂S absorption. Thermal decomposition temperature, HBA mass ratios, alkalinity and structure effect on absorption behavior were systematically investigated. The reaction mechanism was demonstrated by FT-IR and ¹H NMR spectroscopy. The reaction equilibrium constants, Henry constant, enthalpy and entropy change were calculated based on the thermodynamic model to reveal the interactions between DESs and H₂S. It was found that H₂S absorption capacities of the most of DESs with HBA/HBD mass ratio of 1:4 was close to 1 mol/mol at 303.15 K and 0.2 bar. The absorption capacity of DESs depends on the alkalinity and structure of HBAs; Additionally, a good linear correlation between the alkalinity of HBA and the absorption equilibrium constant (lnK) of DESs to H₂S was found.     

Development of energy-optimum aromatic extraction processes using ionic liquid [EMIM][NTf2]

There is industrial incentive to extract aromatics from ethylene cracker feeds, but the conventional sulfolane solvent was found not economical by Meindersma and coworkers. Ionic liquids (ILs) have long been considered alternative aromatic extraction solvents. This work develops energy-optimum aromatic extraction processes for an ethylene cracker feed using IL solvents. We avoid pitfalls of using simplified feeds and a priori thermodynamic property estimates, with the largest set of experimentally regressed UNIQUAC binary parameters for the IL, 1-ethyl-3-methylimidazolium bis([trifluoromethyl]sulfonyl)imide ([EMIM][NTf2]). We screen process energy and operating conditions for [EMIM][NTf2] and sulfolane at varying aromatic feed contents and find [EMIM][NTf2] favorable at low aromatic feed contents. Adding light and heavy components of the ethylene cracker feed necessitates process modifications. Our novel steam-assisted extractive distillation developed for [EMIM][NTf2] is also suitable for sulfolane. We show that the [EMIM][NTf2] solvent can reduce 10.7% of energy consumption compared to sulfolane using the same novel process.     

Investigation of CO2 solubility in monoethanolamine hydrochloride based deep eutectic solvents and physical properties measurements

Deep eutectic solvents (DESs) have drawn a growing research interest for applications in a wide range of scientific and industrial arenas. However, a limited effort has been reported in the area of gas separation processes and particularly the carbon dioxide capture. This study introduces a novel set of DESs that were prepared by complexing ethylenediamine (EDA), monoethanolamine (MEA), tetraethylenepentamine (TEPA), triethylenetetramine (TETA) and diethylenetriamine (DETA) as hydrogen bond donors to monoethanolamide hydrochloride (EAHC) salt as a hydrogen bond acceptor. The absorption capacity of CO₂ was evaluated by exploiting a method based on measuring the pressure drop during the absorption process. The solubility of different DESs was studied at a temperature of 313.15 K and initial pressure of 0.8 MPa. The DES systems 1EAHC:9DETA, 1EAHC:9TETA and 1EAHC:9TEPA achieved the highest CO₂ solubility of 0.6611, 0.6572 and 0.7017 mol CO₂·(mole DES)^-1 respectively. The results showed that CO₂ solubility in the DESs increased with increasing the molar ratio of hydrogen bond donor. In addition, the CO₂ solubility increased as the number of amine groups in the solvent increases, therefore, increasing the alkyl chain length in the DESs, resulted in increasing the CO₂ solubility. FTIR analysis confirms the DES synthesis since no new functional group was identified. The FTIR spectra also revealed the carbamate formation in DES-CO₂ mixtures. In addition, the densities and viscosities of the synthesized DESs were also measured. The CO₂ initial investigation of reported DESs shows that these can be potential alternative for conventional solvents in CO₂ capture processes.     

咪唑类离子液体高效吸收二氯甲烷

合成了一系列常规离子液体1-丁基-3-甲基咪唑四氟硼酸盐([Bmim][BF4])、1-丁基-3-甲基咪唑六氟磷酸盐([Bmim][PF6])、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐([Bmim][NTf2])、1-丁基-3-甲基咪唑双氰胺盐([Bmim][DCA])、1-丁基-3-甲基咪唑硫氰酸盐([Bmim][SCN])、1-乙基-3-甲基咪唑硫氰酸盐([Emim][SCN])和N-丁基吡啶硫氰酸盐([BPy][SCN]),用智能重量分析仪(IGA)测定不同温度和分压下离子液体吸收二氯甲烷(DCM)的容量。结果表明,[Bmim][SCN]具有最高的二氯甲烷吸收容量(1.46 g/g, 303.15 K, 60 kPa),5次循环后吸收能力无明显下降,[Bmim][SCN]基本可完全再生,能循环使用。量化计算结果表明[SCN]?可与二氯甲烷形成氢键,增强其对二氯甲烷的吸收能力。     

Effective absorption of SO2 by imidazole-based protic ionic liquids with multiple active sites: Thermodynamic and mechanical studies

In view of the environmental hazards caused by SO₂, the development of efficient SO₂ capture technology has important practical significance. In this work, a low-viscosity protic ionic liquids containing imidazole (Im), ether linkage, and tertiary amine structure was synthesized by acid–base neutralization of tris(3,6-dioxaheptyl)amine (TMEA) and Im for SO₂ absorption. The results showed that the solubility of SO₂ in [TMEA][Im] reached 12.754 mol kg⁻¹ at 298.2 K and 1 bar and the ideal selectivity of SO₂/CO₂ (1/1) is 141.7 at 1 bar. Furthermore, [TMEA][Im] can be reused and the SO₂ absorption performance was not significantly reduced after five cycles. In addition, the absorption of low-concentration SO₂ (2000 ppm) in [TMEA][Im] was also tested. Further spectroscopic research and thermodynamic analysis suggested that the high SO₂ uptake by [TMEA][Im] was caused by the synergistic effect of physical and chemical absorption.     

离子液体/低共熔溶剂用于NH3分离过程的热力学分析

氨气（NH₃）作为一种有害气体,其传统吸收技术存在诸多缺陷,亟需开发性能优越的NH₃吸收剂,以开发新型NH₃分离技术。离子液体和低共熔溶剂作为气体分离过程的潜在吸收剂,因低挥发性、良好的热稳定性以及灵活的可调控性等特点受到越来越多的关注。但离子液体和低共熔溶剂数量众多,筛选困难。采用热力学分析方法分析离子液体和低共熔溶剂用于NH₃分离过程,基于Gibbs自由能变,拟合出分离过程的最佳操作条件,将总能耗和离子液体用量作为筛选标准,筛选出性能良好的[Omim][BF₄]。将[Omim][BF₄]与传统NH₃吸收剂水对比,发现[Omim][BF₄]具有更低的能耗。最后,拟合出筛选标准与离子液体/低共熔溶剂的临界性质间的规律,为开发新的NH₃吸收剂和新的分离技术提供依据。     

低共熔溶剂用于萃取分离的研究进展

作为一种新型的绿色溶剂，低共熔溶剂（DES）拥有与离子液体媲美的优良特性，如挥发性小、可设计性等，且具有成本低廉和制备简单的优势，使得DES正逐步替代传统有机溶剂，在萃取分离应用方面得到广泛的关注。本文综述了近年来国内外有关DES在萃取分离方面的研究报道，阐述了DES直接用于液液萃取、在线生成DES的缔合萃取和通过DES分解完成萃取的应用，并分析比较了各过程的特点和存在的问题；介绍了DES在不同萃取体系中的稳定性和DES的回收方法；总结了DES萃取分离体系的理论发展和萃取机理的研究进展；展望了DES用于萃取分离的工业化前景，指出了目前面临的DES理论、萃取机理、循环稳定性等方面的挑战，分析了进一步的研究趋势。     

High-efficiency separation of oil sands using ChCl-based deep eutectic solvents

Deep eutectic solvents (DESs) are a kind of potential lixiviant for extraction processing. Unlike conventional ionic liquids (ILs), DESs are relatively cheap and environmentally friendly. Herein, three different ChCl-based DESs, namely, choline chloride/urea, choline chloride/ethylene glycol, as well as choline chloride/propandioic acid, were synthesized and used to enhance bitumen recovery from oil sand by petroleum ether extraction. The results showed a multiphase system formed after mixing the components at ~25°C, consisting of sands and clays, a DES layer, and a petroleum ether layer containing the bitumen. These DESs were immiscible with bitumen or petroleum ether. Coupled with a density difference, a clear phase separation was presented between the bitumen–petroleum ether mixture and DES. The DES functioned as a separating agent, keeping the petroleum ether–bitumen mixture and spent sand apart from each other. The results showed that the bitumen recovery was increased by ~12% compared with that without the DESs. We deduced that the enhancement in the separation may result from the reduction of adhesion between bitumen and sand by the DESs. The ChCl-based DESs and petroleum ether could be readily recycled to reduce industrial costs. After 10 cycles, the bitumen recovery remained above 86%.     

Hydrogen bond induced acidic liquids for efficient biodiesel production

In chemical engineering, the Fischer–Speier esterification shows incredible value for biofuel production. However, the transformation suffers from challenges including necessary catalysts that cause corrosion issues in addition to a complex synthesis. Herein, we report a green acidic liquid, [N,N,N-tris(propanesulfonic)aniline][ethanol]₃, which is induced by hydrogen bonding interactions between a hydrogen bond acceptor (HBA) of [N,N,N-tris(propanesulfonic)aniline] and three hydrogen bond donators (HBD) of ethanol, through a one-step reaction. This liquid demonstrates strong Bronsted acidity and hydrogen bond networking to mimic ionic liquids (ILs) or deep-eutectic solvents (DESs). Even under mild conditions, biodiesel was produced with 97.65% of esterification conversion. Exploiting distinguished molecular geometry with a singular methodology, made possible by contributions from HBD, allows for a further reaction of 1,3-propanesulfonate with positively charged amines. This discovery is feasible with a wide range of HBDs as a solvent resulting more commercially accessible products owing to a much greener synthesis when compared with ILs and DESs.     

低共熔溶剂取代危化品的应用进展

危化品在工业生产应用中存在着巨大的危险性和危害性,低共熔溶剂作为一种安全、环保、价格低廉、更具工业化潜力的新型离子液体受到越来越多的关注. 根据低共熔溶剂取代的危化品种类,分析了低共熔溶剂在金属催化剂制备、生物催化转化、气体分离与吸收、有机合成和电化学等反应中的作用. 采用绿色化学原则和葛兰素史克溶剂选择指南等对低共熔溶剂应用中出现的问题和存在的难点做出了展望.     

Gas drying with ionic liquids

The gas drying technology with ionic liquids (ILs) was systematically studied ranging from the molecular level to industrial scale. The COSMO‐RS model was first used to screen the suitable IL and provide theoretical insights at the molecular level. Toward CO₂ gas dehydration, we measured the CO₂ solubility in single [EMIM][Tf₂N] and in the [EMIM][Tf₂N] + H₂O mixture, as well as the vapor‐liquid equilibrium (VLE) of [EMIM][Tf₂N] + H₂O system, to justify the applicability of UNIFAC model. Based on the thermodynamic study, the rigorous equilibrium (EQ) stage mathematical model was established for process simulation. The gas drying experiment with IL was also performed and the water content in gas product can be reduced to 375 ppm. It was confirmed that a less flow rate of absorbent, a higher CO₂ recovery ratio and a much lower energy consumption can be achieved with IL than with the conventional triethylene glycol (TEG). © 2017 American Institute of Chemical Engineers AIChE J, 64: 606–619, 2018