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.     

Thermodynamic and molecular insights into the absorption of H2S,CO2, and CH4 in choline chloride plus urea mixtures

Deep eutectic solvents (DESs) are a class of promising media for gas separation. In order to examine the potential application of DESs for natural gas upgrading, the solubilities of H₂S, CO₂, and CH₄ in choline chloride (ChCl) plus urea mixtures were measured in this work. The solubility data were correlated with Henry's law equation to calculate the thermodynamic properties of gas absorption processes, such as Henry's constants and enthalpy changes. Grand-canonical Monte Carlo simulations and quantum chemistry calculations were also performed to examine the mechanism of gas absorption processes. It is found that the absorption of H₂S in ChCl + urea mixtures is governed by the hydrogen-bond interaction between Cl of ChCl and H of H₂S, whereas the absorption of CO₂ and CH₄ in ChCl+urea mixtures is governed by the free volume of solvents. Based on the different behavior of gas absorption, high H₂S/CO₂, H₂S/CH₄, and CO₂/CH₄ selectivities can be achieved by adjusting the ratio of ChCl/urea in mixtures.     

油酚分离过程低共熔溶剂的筛选及萃取性能研究

低温煤焦油中酚类化合物的高效分离在工业上具有重要意义。采用COSMO-RS模型对40种用于间甲酚-异丙苯分离的低共熔溶剂进行筛选,结合σ-profile和σ-potential对筛选得到的低共熔溶剂的高萃取性能进行分析。并采用液液相平衡实验对筛选结果进行验证,优化了萃取工艺条件。结果表明,COSMO-RS模型筛选得到的氯化胆碱(ChCl)∶乙二醇(EG)(1∶2)、ChCl∶丙三醇(Gly)(1∶2)、ChCl∶乳酸(LA)(1∶2)三种低共熔溶剂与间甲酚之间存在较强的氢键相互作用,与异丙苯之间存在排斥作用。液液相平衡实验证实了COSMO-RS筛选结果的可靠性,其中ChCl∶EG(1∶2)具有最高的分配系数和选择性系数,且黏度最低,被选定为最佳的低共熔溶剂。在25℃、ChCl∶EG(1∶2)与模型油质量比为1∶1时,ChCl∶EG(1∶2)对间甲酚萃取率高达98.41%,同时异丙苯夹带量仅为8.41%,并且具有良好的循环使用性能。     

油酚分离过程低共熔溶剂的筛选及萃取性能研究

低温煤焦油中酚类化合物的高效分离在工业上具有重要意义。采用COSMO-RS模型对40种用于间甲酚-异丙苯分离的低共熔溶剂进行筛选,结合σ-profile和σ-potential对筛选得到的低共熔溶剂的高萃取性能进行分析。并采用液液相平衡实验对筛选结果进行验证,优化了萃取工艺条件。结果表明,COSMO-RS模型筛选得到的氯化胆碱(ChCl)∶乙二醇(EG)(1∶2)、ChCl∶丙三醇(Gly)(1∶2)、ChCl∶乳酸(LA)(1∶2)三种低共熔溶剂与间甲酚之间存在较强的氢键相互作用,与异丙苯之间存在排斥作用。液液相平衡实验证实了COSMO-RS筛选结果的可靠性,其中ChCl∶EG(1∶2)具有最高的分配系数和选择性系数,且黏度最低,被选定为最佳的低共熔溶剂。在25℃、ChCl∶EG(1∶2)与模型油质量比为1∶1时,ChCl∶EG(1∶2)对间甲酚萃取率高达98.41%,同时异丙苯夹带量仅为8.41%,并且具有良好的循环使用性能。     

苯酚型低共熔溶剂中硫酸钛作为催化剂高效氧化脱硫

低共熔溶剂广泛应用于氧化脱硫过程,开发新型的低共熔溶剂并进一步提升脱硫效果具有重要的意义。 以氯化胆碱为氢键受体,苯酚为氢键供体合成了ChCl/2Ph型低共熔溶剂。通过FT-IR和¹H NMR证实了苯酚和氯化胆碱之间存在氢键作用。以苯酚型低共熔溶剂为萃取剂,双氧水为氧化剂,硫酸钛为催化剂氧化脱除模拟油中的二苯并噻吩。考察了反应温度、V(ChCl/2Ph)/V(Oil)、n(H₂O₂)/n(S)、催化剂用量以及硫化物类型对脱硫率影响。实验表明最佳反应条件如下：模拟油量为5 ml,V(ChCl/2Ph)/V(Oil)=2∶10, n(H₂O₂)/n(S)=6,催化剂用量为0.01 g,反应温度为40℃,反应时间180 min。在此条件下脱硫率可以达到98.2%。求得体系的表观活化能为41.9 kJ/mol。含有催化剂的低共熔溶剂相可以重复使用5次且活性没有明显降低。机理研究表明形成钛的过氧化物和Br?nsted酸性是具有较高脱硫活性的关键。     

低共熔溶剂萃取精馏分离苯/环己烯共沸物研究

以四丁基溴化铵(TBAB)、氯化胆碱(ChCl)为氢键受体,乙二醇(EG)、乙酰丙酸(LA)为氢键供体合成的TBAB:EG (1:2), TBAB:LA (1:2), ChCl:LA (1:2)三种低共熔溶剂(DES)作为萃取剂,通过萃取精馏分离苯-环己烯共沸体系。实验测量了环己烯-苯-DES三元体系气液相平衡,并对DES组成中氢键供体和氢键受体对分离性能的影响进行探讨。结果表明,DES的分离性能由高到低依次为ChCl:LA (1:2)>TBAB:LA (1:2)>TBAB:EG (1:2);采用NRTL模型关联环己烯-苯-DES三元体系的气液相平衡数据,拟合得到体系二元交互参数;在Aspen Plus V7中针对ChCl:LA (1:2)为溶剂的萃取精馏过程进行建模计算,并将其分离效果与传统溶剂N,N-二甲基乙酰胺(DMAC)进行对比,以DES为溶剂的萃取精馏过程相比于DMAC,回流比由3.8降至0.30,流程整体热负荷减少了16.57%。     

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。     

Deep eutectic solvents for efficient capture of cyclohexane in volatile organic compounds: Thermodynamic and molecular mechanism

Deep eutectic solvents (DESs) as promising green absorbents were first proposed to capture the condensable cyclohexane gas. Choline chloride–ethylene glycol (EG) (Ethaline) and choline chloride–urea (Reline) were prepared using choline chloride as the hydrogen-bond acceptor (HBA) and urea or EG as the hydrogen-bond donor (HBD). To explore the potential application of DESs in condensable gas capture, the COSMO-RS model was used to predict the solubility of cyclohexane in Ethaline and Reline. The thermodynamic properties, that is, Henry's constant and excess enthalpy, were estimated by correlating solubility data with Henry's law equation. Quantum chemical (QC) calculation was applied to understand the absorption mechanism at the molecular level. The results showed that the absorption performance of cyclohexane in Ethaline and Reline was dependent on the weak interaction between O of EG (or N of urea) and H of cyclohexane as well as the free volume effect of DESs.     

Highly selective purification of ferulic acid from wheat bran using deep eutectic solvents modified magnetic nanoparticles

Fe₃O₄ nanoparticles (Fe₃O₄NPs) were prepared by chemical coprecipitation. Deep eutectic solvents (DESs) (ChCl/glycol, 1/2, n/n) were used to modify Fe₃O₄NPs. The obtained Fe₃O₄NPs and DESs–Fe₃O₄NPs were applied for purification of ferulic acid from wheat bran by magnetic solid-phase extraction (MSPE). The satisfactory extraction recoveries for ferulic acid (88.7%) were obtained by changing different washing and eluted solvents. The recovery of the proposed method at three spiked level analysis was 77.9–97.5%, with the relative standard deviation less than 4.5%. DESs–Fe₃O₄NPs showed good performance for ferulic acid and the proposed approach might offer a novel method for purifying complex samples.     

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.     

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.     

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.     

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.     

咪唑类三元低共熔溶剂捕集低压SO2的实验研究

近几年来,以氢键受体（HBA）和氢键供体（HBD）组成的低共熔溶剂（DESs）以其类似于离子液体的性质被认为是一种有潜力的SO₂吸附剂。为制备用于低压SO₂吸收的容量大、价格合理、循环性能好的低共熔溶剂,选用咪唑(Im)作为功能化组分,以价格低廉的甘油(Gly)、PEG200和乙二醇(EG)作为第二HBD,与作为HBA的氯化胆碱(CC)构建CC-GIy-Im、CC-PEG200-Im、CC-EG-Im三元功能化低共熔溶剂,并用于低压SO₂的捕集实验研究。着重考察了第二HBD种类、咪唑含量、温度等因素对DESs吸收SO₂的性能影响。结果表明：在所选的第二HBD中,PEG200的性能最佳,其构建的低共熔溶剂密度、黏度适中,热稳定性好,吸收性好;CC-PEG200-Im（1∶2∶7）在40℃下,对1% SO₂的吸收量达到0.236 g SO₂/g DES;经5次吸收-解吸循环后,低共熔溶剂吸收性能仍然稳定;¹H NMR谱图分析结果表明,CC-PEG200-Im对SO₂的吸收机理为化学吸收。     

Elimination of All Free Glycerol and Reduction of Total Glycerol from Palm Oil-Based Biodiesel Using Non-Glycerol Based Deep Eutectic Solvents

Purification of biodiesel prior to utilizing it as an alternative fuel is an essential industrial practice. Low glycerol content is one of the important pointers needed for passing the EN 14214 and ASTM D6751 international biodiesel standards. In this study, choline chloride (ChCl) as salt and ethylene glycol and 2,2,2-Trifluoroacetamide as hydrogen bond donors (HBDs) were employed to synthesize two ammonium salt-non glycerol based Deep Eutectic Solvents (DES). The physical properties of the synthesized DESs were measured and analyzed. These DESs were utilized to remove all the free glycerol from the palm oil-based biodiesel. The results indicated that all the tested DESs were able to remove all free glycerol successfully. The Central Composite Design (CCD) of the Response Surface Methodology (RSM) was used to to experiment design and optimization of total glycerol removal using ethylene glycol-based DESs and 2,2,2-Trifluoroacetamide-based DESs. The maximum total glycerol removal by ethylene glycol-based DESs was obtained at 0.66 ethylene glycol mole fraction and at DES/biodiesel molar ratio of 3 with removal efficiency of 23.85% as well as by 2,2,2-Trifluoroacetamide-based DESs at 0.60 2,2,2-Trifluoroacetamide mole fraction and at DES/biodiesel molar ratio of 2.93 with removal efficiency of 29.29%. The reusability of these DESs for removing free glycerol and total glycerol content from palm oil-based biodiesel was also investigated. This study proves that both ammonium salt-non glycerol based DESs can be successfully employed to remove the glycerol from palm oil-based biodiesel.     

Spectroscopic study on the intermolecular interaction of SO2 absorption in poly-ethylene glycol+H2O systems

Poly-Ethylene Glycol (PEG) 300+H₂O solutions (PEGWs) has been used as a promising medium for the absorption of SO₂. We investigated the UV, FTIR, ¹H-NMR, and fluorescence spectra in the absorption processes of SO₂ in PEGWs to present an important absorption mechanism. Based on the spectral results, the possibility of intermolecular hydrogen bond formation by hydroxyl oxygen atom in the PEG molecule with hydrogen atom in H₂O and S…O interaction formation by the oxygen atoms in PEG with the sulfur atom in SO₂ are discussed. This shows that the spectral changes may be due to the formation of -CH₂CH₂O(H)…HOH… and -CH₂-CH₂-O(CH₂-CH₂-)…HOH… in PEGWs and the formation of -CH₂CH₂OH…OSO…, and intermolecular S…O interaction between PEG and SO₂ as the formation of -CH₂CH₂OCH₂CH₂O(H)…(O)S(O)… and -CH₂-CH₂-O(CH₂-CH₂-)…(O)S(O)…. The existence of these bonds benefits the absorption and desorption processes of SO₂ in PEGWs.     

Optimization of the chromatographic behaviors of quercetin using choline chloride-based deep eutectic solvents as HPLC mobile-phase additives

Nine types of deep eutectic solvents (DESs) were used as mobile-phase additives to improve the chromatographic behaviors of quercetin. Three variables (temperature, molar ratio and concentration) were studied. According to the ion interaction theory and the hydrogen bond, DESs components can work as ions and play an ion-pairing role with quercetin at the same time. Under the optimum condition, the number of theoretical plates was 6690.8 and the tailing factor was 1.71. Compared with acetic acid (HAc), DESs as mobile-phase additives would not damage the High Performance Liquid Chromatography (HPLC) system. The excellent properties of DESs showed their potential as additives for the determination of quercetin.     

Exploration of deep eutectic solvent‐based mesoporous silica spheres as high‐performance size exclusion chromatography packing materials

Choline chloride (ChCl) with three alcohol‐based deep eutectic solvents (DESs) was applied as a new type of green solvent for the modification of mesoporous silica spheres. The mesoporous silica spheres were characterized by field emission scanning electron microscopy and Brunauer–Emmett–Teller surface area analysis. Many uniform and mesoporous silica spheres were obtained with a ChCl–1,2‐butanediol DES as a reactant. The DES‐modified mesoporous silica spheres were used for the adsorption of polysaccharides (alginic acid, fucoidan, and laminarin). The adsorption results show that the ChCl–1,2‐butanediol DES‐based silica spheres had stable interactions with the target compounds. A comparison of the three sorbents as size exclusion chromatography packing materials showed that the ChCl–1,2‐butanediol DES‐based silica spheres produced good resolution of the three test polysaccharides and exhibited the best separation capability. This was attributed to the uniform mesoporous structure of the ChCl–1,2‐butanediol DES‐based silica spheres. Therefore, more DESs should be applied to the preparation of mesoporous silica spheres in future studies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42203.     

Removal of Dibenzothiophene from Diesels by Extraction and Catalytic Oxidation with Acetamide‐Based Deep Eutectic Solvents

A series of acetamide‐based deep eutectic solvents (DESs) with different proportions were prepared. Extraction and catalytic oxidation desulfurization (ECODS) of the acetamide‐based DESs were investigated and the process was optimized. Such DESs with a molar ratio of acetamide and p‐TsOH of 1/3 (C₂H₅NO/3p‐TsOH) exhibits such a remarkable catalytic activity that the dibenzothiophene (DBT) removal could reach 100 % under optimized conditions. C₂H₅NO/3p‐TsOH was used for the oxidative desulfurization of actual commercial diesel. The sulfur removal of diesel achieved up to 98 %. C₂H₅NO/3p‐TsOH could be recycled six times and the desulfurization activity was slightly decreased. Evaluation of the mechanism indicated that oxidative desulfurization (ODS) was realized via dual activation of acetamide‐based DESs. A novel and effective way for deep desulfurization of diesel is provided.     

Random forest models to predict the densities and surface tensions of deep eutectic solvents

The use of machine learning in physicochemical properties modeling has great potential to accelerate the application of emerging materials. Deep eutectic solvents (DESs), an emerging class of solvents, are promising for applications as inexpensive “designer” solvents. Due to the unique structure of DESs, the hydrogen bond donor and hydrogen bond acceptor can be varied to create a mixture with specific physical properties. In this work, we proposed random forest (RF) models to predict the densities and the surface tensions of DESs, which are essential for the separation process. In the proposed models, the structural information and the calculated critical properties were used as two different types of features, respectively. The results demonstrate that the RF models predict the densities and surface tensions of DESs with high accuracy, with absolute average relative deviation (AARD%) less than 1% in the prediction of density and 3% in the prediction of surface tension.