Separation Performance of BioRenewable Deep Eutectic Solvents (original) (raw)
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Fluid Phase Equilibria, 2018
Solute retention data acquired by gas-liquid chromatography were used to determine the activity coefficients at infinite dilution for 24 organic solutes in the deep eutectic solvent (DES) consisting of tetramethylammonium chloride and glycerol in a molar ratio of 1.001:2. The organic solutes included alk-1anes, alk-1-enes, alk-1-ynes, cycloalkanes, alkanols, alkylbenzenes, ketones, esters and heterocyclics. The measurements were undertaken at four different temperatures, viz T ¼ (313.15, 323.15, 333.15 and 343.15) K with an estimated uncertainty of ±3.8%. From the experimental infinite dilution activity coefficient data, the values of partial molar excess enthalpy at infinite dilution were calculated using Gibbs Helmholtz relationship. Limiting selectivity and capacity values were also calculated from experimental limiting activity coefficients and compared to those of other separation agents, including other deep eutectic solvents, ionic liquids and industrial molecular agents. Results obtained in this study indicate that tetramethylammonium chloride þ glycerol DES can potentially be used as an alternative solvent for nitrogen and sulphur removal from transportation fuels as well as the separation of cycloalkanes, aromatics and esters from light alkanols.
Fluid Phase Equilibria, 2017
The extraction of aromatic hydrocarbons from reformer and pyrolysis gasolines is currently performed by liquid-liquid extraction using organic solvents. Deep eutectic solvents (DES) are being widely studied as environmentally benign alternatives to conventional solvents since DES can be prepared using nontoxic and renewable chemicals. In this work, we have studied for the first time the application of DES in the extraction of aromatic hydrocarbons from reformer and pyrolysis gasolines. We have tested six choline chloride-based DES formed by ethylene glycol, glycerol, levulinic acid, phenylacetic acid, malonic acid, and urea as hydrogen bond donors. COSMO-RS method was employed to predict the performance of the DES in the extraction of aromatics, whereas experimental results indicate that DES formed by choline chloride and levulinic acid has exhibited the most adequate extractive and physical properties. Afterward, the simulation and optimization of the whole process for extraction of aromatics, recovery of extracted hydrocarbons, and regeneration of the solvent have been performed. The proposed process of dearomatization could work at moderate temperatures using a cheap, sustainable, and nontoxic solvent.
Journal of Chemical & Engineering Data, 2018
Choline chloride-based deep eutectic solvent (DES) was tested for the separation of azeotropic mixtures of ethanol−ethyl acetate, n-propanol−n-propyl acetate and nbutanol−n-butyl acetate via liquid−liquid extraction. The mixture of choline chloride with malonic acid with a molar ratio of 1:1 was used. Extraction experiments were conducted with the ternary mixture ethanol−ethyl acetate−DES at temperatures 293.15, 303.15, and 313.15 K and with ternary mixtures npropanol−n-propyl acetate−DES and n-butanol−n-butyl acetate−DES at 293.15, 303.15, 313.15, and 323.15 K. Liquid− liquid tie-lines for studied systems were determined. The extraction performance of DES was characterized with solute distribution coefficients and values of selectively respectively to alcohol. The influence of the alkyl chain length of the alcohol and ester on the phase equilibria was investigated. Experimental data were fitted using the nonrandom two liquids model.
Fluid Phase Equilibria, 2018
Deep eutectic solvents (DESs) are considered as the new ionic liquids (ILs) analogues that have emerged as potential alternative 'green' solvents, for a diversity of applications. In this study, a type III DES based on ammonium salt was investigated as an alternative solvent to currently employed conventional organic solvents in separation processes. Activity coefficients at infinite dilution, g ∞ 13 for 19 organic solutes in the tetramethylammonium chloride þ ethylene glycol DES were measured by the gas-liquid chromatography (GLC) method at four temperatures in the range from (313.15e343.15) K. Experimental measurements were undertaken with an overall uncertainty of ±5.4%. The effect of the structure of the solutes on g ∞ 13 was also investigated. For all investigated solutes, Gibbs helmholtz relationship was utilised to derive partial molar excess enthalpy values at infinite dilution (DH E;ð∞Þ i) from experimental limiting activity coefficient data. From selectivity (S ∞ ij) and capacity (k ∞ j) values at infinte dilution, it was concluded that the investigated DES has the potential to replace a number of industrial solvents for the separation of various industrial mixtures.
The ability of non-toxic and biodegradable deep eutectic solvent (DES) choline chloride + dl-malic acid in molar ratio 1:1, for breaking the azeotropes heptane + methanol and toluene + methanol by means of liquidliquid extraction was evaluated. Ternary liquid-liquid equilibrium experiments were performed at 298.15 K and at atmospheric pressure. Densities, viscosities and refractive indices of DES + methanol and water + DES systems were experimentally determined over a wide temperature range and at atmospheric pressure. Additionally, viscosities of DES + glycerol mixture were determined at temperatures up to 363.15 K to check how much the addition of glycerol decreases high viscosities of DES. The results indicate that addition of small amounts of water or glycerol as a third component significantly decreases viscosity of the investigated deep eutectic solvent. Based on selectivity and distribution ratio values, extraction ability of the investigated deep eutectic solvent, in comparison with conventionally used solvents, yields promising results. Non-random two-liquid (NRTL) and Universal quasichemical (UNIQUAC) models were satisfactorily applied for correlation of experimental phase equilibrium data for two ternary mixtures.
Journal of Chemical & Engineering Data, 2019
Deep eutectic solvent (DES) formed by choline chloride and glutaric acid was tested for the separation of azeotropic mixtures of ethanol− ethyl acetate, n-propanol−n-propyl acetate, n-butanol−n-butyl acetate, ethanol−ethyl propionate, n-propanol−n-propyl propionate, and n-butanol− n-butyl propionate. For this aim, the experimental data of liquid−liquid equilibria (LLE) were obtained at a temperature of 313.15 K and atmospheric pressure. Liquid−liquid tie-lines were determined and analyzed. The extraction performance of DES was characterized with distribution coefficients and values of selectivity with respect to alcohol. The NRTL model for LLE data correlation was used. Perturbed-chain statistical associating fluid theory had also been applied for modeling LLE using a "pseudo-component" approach for the DES. Both models were shown to give reasonable estimates for the selectivity values.
New horizons in the extraction of bioactive compounds using deep eutectic solvents: A review
Analytica chimica acta, 2017
With the rapid development of ionic liquid analogues, termed 'deep eutectic solvents' (DESs), and their application in a wide range of chemical and biochemical processes in the past decade, the extraction of bioactive compounds has attracted significant interest. Recently, numerous studies have explored the extraction of bioactive compounds using DESs from diverse groups of natural sources, including animal and plant sources. This review summarizes the-state-of-the-art effort dedicated to the application of DESs in the extraction of bioactive compounds. The aim of this review also was to introduce conventional and recently-developed extraction techniques, with emphasis on the use of DESs as potential extractants for various bioactive compounds, such as phenolic acid, flavonoids, tanshinone, keratin, tocols, terpenoids, carrageenans, xanthones, isoflavones, α-mangostin, genistin, apigenin, and others. In the near future, DESs are expected to be used extensively for the extrac...
Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications
Sustainable technologies applied to energy-related applications should develop a pivotal role in the next decades. In particular, carbon dioxide capture from flue gases emitted by fossil-fueled power plants should play a pivotal role in controlling and reducing the greenhouse effect. Therefore, the development of new materials for carbon capture purposes has merged as central research line, for which many alternatives have been proposed. Ionic liquids (ILs) have emerged as one of the most promising choices for carbon capture, but in spite of their promising properties, some serious drawbacks have also appeared. Deep eutectic solvents (DESs) have recently been considered as alternatives to ILs that maintain most of their relevant properties, such as task-specific character, and at the same time avoid some of their problems, mainly from economic and environmental viewpoints. DES production from low-cost and natural sources, together with their almost null toxicity and total biodegradability, makes these solvents a suitable platform for developing gas separation agents within the green chemistry framework. Therefore, because of the promising characteristics of DESs as CO 2 absorbents and in general as gas separating agents, the state of the art on physicochemical properties of DESs in relationship to their influence on gas separation mechanisms and on the studies of gas solubility in DESs are discussed. The objective of this review work is to analyze the current knowledge on gas separation using DESs, comparing the capturing abilities and properties of DESs with those of ILs, inferring the weaknesses and strengths of DESs, and proposing future research directions on this subject.
Journal of Agricultural and Food Chemistry, 2017
The green chemistry era has pushed the scientific community to investigate and implement new solvents in the phenolic compounds (PC) extraction, as alternative to the organic solvents which are toxic and may be dangerous. Recently, Deep Eutectic Solvents (DES) have been applied as extraction solvents of PC. They have the advantages to be biodegradable, easy to handle with very low toxicity. Nevertheless, the extraction process is affected by several factors: affinity between DES and the target compounds, the water content, the mole ratio between DES' starting molecules, the liquid:solid ratio between the DES and sample, and the conditions and extraction method. On the other hand, the PC recovery from DES is a challenge; since they can establish a strong hydrogen bonds network. Alternatively, another possibility is to use DES as solvent extraction as well as formulation media. In this way, DES can be suitable for cosmetics, pharmaceutical, or food applications.
Natural Deep Eutectic Solvents − Solvents for the 21st Century
Green technology actively seeks new solvents to replace common organic solvents that present inherent toxicity and have high volatility, leading to evaporation of volatile organic compounds to the atmosphere. Over the past two decades, ionic liquids (ILs) have gained enormous attention from the scientific community, and the number of reported articles in the literature has grown exponentially. Nevertheless, IL "greenness" is often challenged, mainly due to their poor biodegradability, biocompatibility, and sustainability. An alternative to ILs are deep eutectic solvents (DES). Deep eutectic solvents are defined as a mixture of two or more components, which may be solid or liquid and that at a particular composition present a high melting point depression becoming liquids at room temperature. When the compounds that constitute the DES are primary metabolites, namely, aminoacids, organic acids, sugars, or choline derivatives, the DES are so called natural deep eutectic solvents (NADES). NADES fully represent green chemistry principles. Can natural deep eutectic solvents be foreseen as the next generation solvents and can a similar path to ionic liquids be outlined? The current state of the art concerning the advances made on these solvents in the past few years is reviewed in this paper, which is more than an overview on the different applications for which they have been suggested, particularly, biocatalysis, electrochemistry, and extraction of new data. Citotoxicity of different NADES was evaluated and compared to conventional imidazolium-based ionic liquids, and hints at the extraction of phenolic compounds from green coffee beans and on the foaming effect of NADES are revealed. Future perspectives on the major directions toward which the research on NADES is envisaged are here discussed, and these comprised undoubtedly a wide range of chemically related subjects.