Separation of Hydrocarbons by Means of Liquid-Liquid Extraction with Deep Eutectic Solvents

Liquid-liquid equilibria for six ternary systems with choline chloride urea or choline chloride glycerol (molar ratio, 1:2) as selective solvent were experimentally determined at atmospheric pressure and 25°C. Equilibrium data were presented with tie lines. Extraction experiments with three-component systems were performed. The suitability of deep eutectic solvents for the separation of pyridine and toluene from n-hexane, and n-butanol from toluene was evaluated in terms of properties of solvents, solute distribution ratio, and extraction efficiency. Choline chloride glycerol has a better potential for separation of pyridine from its mixture with n-hexane. The equilibrium data were well described with the NRTL model.     

深度共熔溶剂对桉木组分的溶解选择性

制备了不同季铵盐三丁基甲基氯化铵(MTBAC)、四甲基氯化铵(TMAC)、苄基三乙基氯化铵(TEBA)和氯化胆碱(ChCl)分别与DL-乳酸(HL)以摩尔比1:9合成的深度共熔溶剂,并将用于溶解桉木粉中木质素。结果表明,由苄基三乙基氯化铵/DL-乳酸(TEBA/HL)合成的深度共熔溶剂处理桉木粉,在90 ℃下反应10 h,木质素溶解率达92.3wt%,综纤维素溶解率仅为8.3wt%;同时,木质素与综纤维素溶解选择性系数之比K达到158.5,表明TEBA/HL对木质素的溶解选择性最佳。通过红外光谱(FT-IR)分析各分离产物,证明提取物中有木质素特征官能团。通过凝胶渗透色谱(GPC)分析表明分离产物相对分子质量均有所降低。通过固体13C核磁共振谱(CP/MAS 13C NMR)分析90 ℃下TEBA/HL中分离产物结构,证明其结构征符合阔叶材木质素结构特点。     

低共熔溶剂的分子结构及物性估算的研究进展

低共熔溶剂具有熔点低、不挥发、不易燃、溶解性良好、易合成、廉价、低毒、腐蚀性低、生物降解性好等特点,常被作为"绿色"溶剂应用于金属加工和合成反应中。然而,目前对低共熔溶剂的结构和性质的研究只限于少部分具体的低共熔溶剂,没有形成系统全面的理论体系。简述了低共熔溶剂的合成与分类、分子结构和形成机理的研究进展,归纳了低共熔溶剂的物性估算方法,并指出了一些关于低共熔溶剂研究中存在的问题,提出了可能的解决方案。     

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.     

Computer Simulations of Deep Eutectic Solvents: Challenges,Solutions, and Perspectives

Deep eutectic solvents (DESs) are one of the most rapidly evolving types of solvents, appearing in a broad range of applications, such as nanotechnology, electrochemistry, biomass transformation, pharmaceuticals, membrane technology, biocomposite development, modern 3D-printing, and many others. The range of their applicability continues to expand, which demands the development of new DESs with improved properties. To do so requires an understanding of the fundamental relationship between the structure and properties of DESs. Computer simulation and machine learning techniques provide a fruitful approach as they can predict and reveal physical mechanisms and readily be linked to experiments. This review is devoted to the computational research of DESs and describes technical features of DES simulations and the corresponding perspectives on various DES applications. The aim is to demonstrate the current frontiers of computational research of DESs and discuss future perspectives.     

低共熔溶剂在化工分离过程中的应用及研究进展

近年来,低共熔溶剂由于具有廉价、原材料易得、蒸汽压低且更加环境友好的合成过程等特点,越来越成为绿色化学领域的研究热点,特别是低共熔溶剂作为萃取剂在化工分离过程中的应用引起广泛关注。本文主要介绍了低共熔溶剂的组成、性质以及在分离过程中的一些应用和研究进展,最后对其未来的研究方向和存在的问题进行了讨论。     

硫化铜在低共熔溶剂中的合成及光催化研究

在四丁基氯化铵:乙二醇(1:3)低共熔溶剂中,以硫粉和铜粉为原材料,直接反应一步成功合成具有分层结构的微米级球状硫化铜。用XRD表征手段分析了合成的硫化铜的纯度、用SEM、TEM表征手段观察了硫化铜的形貌与微观结构。通过在紫外光下降解染料亚甲基蓝,探究了硫化铜的光催化性能,考察了光催化反应的影响因素。实验表明,合成的硫化铜对亚甲基蓝染料的降解有极佳的催化活性。     

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.     

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.     

Correlation and Prediction of Carbon Dioxide Solubility in n‐Paraffin Systems

This work discusses high‐pressure gas solubility. Reference state is the Henry's law and a two‐parameter corresponding states model is used for the liquid phase. Pure gas is used as the vapor phase for the high‐molecular paraffin's gas‐liquid equilibrium. The systems under study are mixtures of carbon dioxide and normal paraffin up to a chain length of 44 carbon atoms. Correlated liquid compositions are in the 1 % to 3 % average absolute relative deviation range, with a maximum error of about 7 %. Using a known system as reference, the model could be used to predict solubility. In this case average absolute relative deviations are below 6 % in most cases.     

Quantification of Caffeine Interactions in Choline Chloride Natural Deep Eutectic Solvents: Solubility Measurements and COSMO-RS-DARE Interpretation

Solubility of active pharmaceutical ingredients is an important aspect of drug processing and formulation. Although caffeine was a subject of many studies aiming to quantify saturated solutions, many applied solvents suffer from not being environmentally friendly. This work fills this gap by presenting the results of solubility measurements in choline chloride natural deep eutectic solvents, ccNADES, comprising one of seven of the following polyalcohols: glycerol, sorbitol, xylitol, glucose, sucrose, maltose and fructose. The ratio of ccNADES components was optimized for maximizing caffeine solubility at room temperature. Additionally, temperature dependent solubility was measured for the first four systems exhibiting the highest solubility potential, both in their neat forms and in mixtures with water. Results were used for intermolecular interactions assessments using the COSMO-RS-DARE approach, which led to a perfect match between experimental and computed solubility values. An important methodological discussion was provided for an appropriate definition of the systems. Surprising linear trends were observed between the values of fitting parameters and water-ccNADES composition. In addition, comments on selection of the values of the fusion thermodynamic parameters were provided, which led to the conclusion that COSMO-RS-DARE solubility computations can effectively compensate for the inaccuracies of these important physicochemical properties.     

Measurement,Correlation and Thermodynamics of Solubility of 2,6‐Diamino‐3,5‐Dinitropyrazine‐1‐Oxide (LLM‐105) in Eight Solvents

The solubility of insensitive explosive 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) in dimethyl sulphoxide (DMSO), N,N‐dimethylformamide (DMF), N‐methyl‐2‐pyrrolidone (NMP), N,N‐diethylformamide (DEF), 1,4‐dioxane, 1,4‐butyrolactone, ethyl acetate and 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate ([Bmim]CF₃SO₃), were measured by a polythermal method in the temperature range of 293.15 K to 375.15 K at the atmospheric pressure. The solubility of LLM‐105 decreased in the order of DMSO, NMP, DMF, DEF, 1,4‐butyrolactone, [Bmim]CF₃SO₃, 1,4‐dioxane, ethyl acetate. With higher temperature, the solubility of LLM‐105 increased in all solvents. The solubility data was correlated against temperature with the modified Apelblat equation and Ideal solution model. In addition, the dissolution enthalpy, entropy, and mole Gibbs free energy of LLM‐105 in each solvent were also calculated from the experimental solubility data by using van′t Hoff equation with the temperature dependence. The results show that the dissolution process of LLM‐105 in these solvents is endothermic and the mechanism is the entropy‐driving. DMSO is suggested as the appropriate solvent for the cooling crystallization or drowning‐out crystallization of LLM‐105.     

Reaction Mechanism and Kinetics of 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene and Carbon Dioxide in Alkanol Solutions

Carbon dioxide‐binding organic liquids (CO₂BOL) are a new class of solvents with advantageous properties such as high boiling points, low specific heats, high absorption capacities, and easily reversible reactions. In order to implement these solvents in processes, the reaction characteristics must be determined a priori. This work presents an analysis of the rate constants and activation energies of the reaction between carbon dioxide and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in 1‐hexanol and 1‐propanol. The reactions were found to comply with a termolecular reaction mechanism and exhibited pseudo‐first‐order behavior in the presence of excess DBU and 1‐alkanol. It was concluded that DBU‐based CO₂BOL are environmentally friendly and easy‐to‐handle solvents that may provide great flexibility and improvements over conventional carbon dioxide absorption processes.     

The Solubility of Phenanthrene in Toluene: In‐situ ATR‐FTIR,Experimental Measurement,and Thermodynamic Modelling

A comprehensive study of the solubility of phenanthrene in toluene as a model system to investigate the supercritical gas anti‐solvent crystallization process is performed over a wide range of temperatures. The applicability of in‐situ ATR‐FTIR measurements for an improved understanding of the dynamics of the concentration profile of the dissolved compound in the liquid solvent is studied. Experimental determination of the solubility of phenanthrene in toluene was also achieved employing a gravimetric technique over the temperatures range 25 to 65°C. Excellent predictions of the solubility measurements were achieved using Regular Solution Theory and the Flory‐Huggins Correction. Furthermore, this work demonstrated that in‐situ ATR‐FTIR is a valuable technique for monitoring and control of crystallization processes.     

新型制冷剂R134,R134—R134a及R134—R22的热力学性质

采用马丁－侯８１型方程对制冷剂Ｒ１３４、Ｒ１３４－Ｒ１３４ａ及Ｒ１３４－Ｒ２２的热力学性质进行了系统的计算，并绘制了Ｒ１３４的热力学性质图表，为Ｒ１３４在制冷业及相关领域的应用提供了依据。     

Zero‐Trans Cake Shortening: Formulation and Characterization of Physicochemical,Rheological, and Textural Properties

Cake shortening is an important ingredient that imparts taste and texture in the cake as the final product. Hydrogenated shortenings contain high amounts of trans fatty acids, which is considered a risk factor for obesity, cancers, and cardiovascular diseases. In this research, chemically interesterified blends of canola oil (CO) and palm stearin (PS) were recruited in order to formulate zero‐trans shortening, specifically for cake application. The optimization of shortening formulation was performed by Design‐Expert software, considering melting, congelation, textural, and rheological properties of cake shortening as responses. The formulated shortening in the weight ratio of 66.41:33.58 (PS:CO) (%, w/w) was analyzed and compared with two commercial cake shortenings in terms of fatty acid and triacylglycerol composition, slip melting point (SMP), solid fat content (SFC), and rheological and textural properties. The results showed that the formulated zero‐trans cake shortening with 0.2% trans, 47.2% saturated fatty acids, SMP of 40.9 °C, SFC of 10.51% at 37 °C, firmness of 1522.5 g, and linear viscoelastic range of 0.035% had the most acceptable criteria among cake‐shortening samples. The findings of this study offer insights into the relationship between shortening functionality and physicochemical properties and serve as a base for future studies on zero‐trans shortenings formulation.     

Analysis of Physical and Thermodynamic Properties of Poly(2-Phenyl-1,3-Dioxolane-4-Yl-Methyl-Methacrylate-Co-Styrene) Polymer with Inverse Gas Chromatography

In this study, physical and thermodynamic properties of poly(2-phenyl-1,3-dioxolane-4-yl-methyl-methacrylate-co-styrene) (PDMMA-ST) were investigated by using inverse gas chromatography. Two groups of solvents with different chemical natures and polarities were used to obtain information about PDMMA-ST-solvent interactions: alcohols and alkanes. The specific retention volume (V_g ⁰), the sorption enthalpy (ΔH₁ ^S), sorption free energy (ΔG₁ ^S), sorption entropy (ΔS₁ ^S), the weight fraction activity coefficients of solute probes at infinite dilution (Ω ₁ ^∞), and Flory-Huggins interaction parameters (χ ₁₂ ^∞) between polymer and solvents were determined for the interactions of PDMMA-ST with alcohols and alkanes by inverse gas chromatography in the temperature range of 333–473 K. Also, the solubility parameters of PDMMA-ST at infinite dilution were found by plotting the graph of [(δ ₁ ²/RT) - χ ₁₂ ^∞/V₁] versus solubility parameters, δ ₁, of probes.     

Solvent Screening for Solubility Enhancement of Theophylline in Neat,Binary and Ternary NADES Solvents: New Measurements and Ensemble Machine Learning

Theophylline, a typical representative of active pharmaceutical ingredients, was selected to study the characteristics of experimental and theoretical solubility measured at 25 °C in a broad range of solvents, including neat, binary mixtures and ternary natural deep eutectics (NADES) prepared with choline chloride, polyols and water. There was a strong synergistic effect of organic solvents mixed with water, and among the experimentally studied binary systems, the one containing DMSO with water in unimolar proportions was found to be the most effective in theophylline dissolution. Likewise, for NADES, the addition of water (0.2 molar fraction) resulted in increased solubility compared to pure eutectics, with the highest solubilisation potential offered by the composition of choline chloride with glycerol. The ensemble of Statistica Automated Neural Networks (SANNs) developed using intermolecular interactions in pure systems has been found to be a very accurate model for solubility computations. This machine learning protocol was also applied as an extensive screening for potential solvents with higher solubility of theophylline. Such solvents were identified in all three subgroups, including neat solvents, binary mixtures and ternary NADES systems. Some methodological considerations of SANNs applications for future modelling were also provided. Although the developed protocol is focused exclusively on theophylline solubility, it also has general importance and can be used for the development of predictive models adequate for solvent screening of other compounds in a variety of systems. Formulation of such a model offers rational guidance for the selection of proper candidates as solubilisers in the designed solvents screening.     

Evaluation of Phase Morphology,Rheological, and Mechanical Properties Based on Polypropylene Toughened with Poly(ethylene-co-octene)

The influence of blend composition on phase morphology, rheological, and mechanical properties of polypropylene/poly(ethylene-co-octene) blends was studied. Phase morphology of the blends in the whole range of composition was examined using scanning electron microscope. The rheological data were analyzed to yield the variations of rheological properties and insight into the microstructure of PP/POE blends. The finite element code ANSYS was used for the analysis of the interfacial stress and its distribution between dispersed phase and matrix phase.     

Impact of Organic Solvents on Physicochemical Properties of Nanofiltration and Reverse‐Osmosis Membranes

Polymeric membranes subjected to the permeation of n‐hexane were characterized and the influence of pretreatment with ethanol on the properties of the membranes was studied to assess membrane performance and stability. The results suggest that the selectivity of the membrane depends not only on the pore size, but also to a great extent on the interaction between solvent and polymer. An increase in membrane roughness and contact angle was observed for all membranes after pretreatment with ethanol and n‐hexane permeation. Moreover, the surface free energy decreased after solvents exposure, indicating an increase in membrane surface hydrophobicity and polymer swelling. The studied membranes show feasibility of use for the recovery of solvents, if suitable process parameters are selected.