Investigation of the CO2-solubility in deep eutectic solvents using COSMO-RS and molecular dynamics methods (original) (raw)
Related papers
Scientific Reports
In this study, CO2 solubility in different choline chloride-based deep eutectic solvents (DESs) has been investigated using the Quantitative Structure–Property Relationship (QSPR). In this regard, the effect of different structures of the hydrogen bond donor (HBD) in choline chloride (ChCl) based deep eutectic solvents (DESs) has been studied in different temperatures and different molar ratios of ChCl as hydrogen bond acceptor (HBA) to HBD. 12 different datasets with 390 data on the CO2 solubility were chosen from the literature for the model development. Eight predictive models, which contain the pressure and one structural descriptor, have been developed at the fixed temperature (i.e. 293, 303, 313, or 323 K), and the constant molar ratio of ChCl to HBD equal to 1:3 or 1:4. Moreover, two models were also introduced, which considered the effects of pressure, temperature, and HBD structures, simultaneously in the molar ratios equal to 1:3 or 1:4. Two additional datasets were used o...
Mathematical Modeling of the Solubility of Carbon Dioxide in Deep Eutectic Solvents
The increase in energy consumption, along with an increase in human population and industrial activities after the industrial revolution, has caused to increase in the consumption of fossil fuels. Carbon dioxide from fossil fuels has the most significant effect on the production of greenhouse gases and global warming. The absorption of CO2 emitted into the atmosphere is the most crucial method to reduce carbon dioxide in the air. Recently, a new solvent has been developed to absorb greenhouse gases under the name of deep eutectic solvents (DES). These solvents are biodegradable, non-toxic, or low-toxic compounds that are easily obtained. A mathematical model based on the Peng-Robinson (PR) equation of state (EOS) with three different mixing rules Modified van der Waal's (M1), Quadratic (M2) and Wong Sandler (M3) was developed to correlate the CO2 solubility in six types of DESs. The model was validated and compare with the obtained experimental data reported in the literature at temperatures (293.15-333.15) K and pressure (0.405-30.408) bar. The experimental and calculated data of PR EOS with three mixing rules were generally in a good agreement by obtaining % AARD a round (0.08-8.08), (0.05-7.58) and (0.09-6.56) for M1, M2 and M3 respectively, and the best results with less %AARD was obtained from Wong-Sandler mixing rule in the most of cases.
Research Square (Research Square), 2024
The COnductor-like Screening MOdels-Segment Aactivity Coefficient (COSMO-SAC) is a promising approach for computing activity coefficients in the liquid phase. Using Deep Eutectic Solvents (DESs) as green solvents to absorb greenhouse gases, particularly carbon dioxide (CO2), has attracted noticeable attention in research. Despite this, few modeling investigations have employed the COSMO-SAC model for estimating carbon dioxide solubility in choline chloride-based DESs. Our research aimed to overcome the obstacles with group contribution methods' parameters using the COSMO-SAC model which employs general parameters. In our study, we developed and validated the model using around 80% of the datasets, with the remaining 20% used for testing. The range of average relative deviation varied between 7.64% to 47.84. Furthermore, the calculation results indicated decreased average relative deviations at lower temperatures. The findings exhibited that the model is qualitatively successful in predicting carbon dioxide solubility in choline chloride-based DESs. However, adding more solvents and experimental data to enhance the model's accuracy would broaden the model's applicability to various DESs.
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 CO 2 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 CO 2 solubility of 0.6611, 0.6572 and 0.7017 mol CO 2 •(mole DES) −1 respectively. The results showed that CO 2 solubility in the DESs increased with increasing the molar ratio of hydrogen bond donor. In addition, the CO 2 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 CO 2 solubility. FTIR analysis confirms the DES synthesis since no new functional group was identified. The FTIR spectra also revealed the carbamate formation in DES-CO 2 mixtures. In addition, the densities and viscosities of the synthesized DESs were also measured. The CO 2 initial investigation of reported DESs shows that these can be potential alternative for conventional solvents in CO 2 capture processes.
Experimental Investigation of CO2 Solubility in New Amine-Based Deep Eutectic Solvents
Tikrit Journal of Engineering Sciences, 2024
The growing concern about global warming and climate has raised the research field dedicated to finding solutions. One area that has received considerable attention is the exponential increase of carbon dioxide emissions from the atmosphere from the petroleum and gas industries. So, to solve this problem, researchers investigated new ways to collect CO2 from the air depending on the fact that CO2 is soluble in water because using aqueous amine absorbents to collect CO2 has a lot of drawbacks, such as the need for tremendous energy to recycle the solvent and high operational costs. In this study, a specific type of deep eutectic solvent (DES), namely Choline chloride + monoethanolamine (ChCl-MEA), was used as a promising solvent in the CO2 capture process. Solubility measurements were conducted at 1:6 molar ratios. The amines chosen are typical of basic amines. Experiment absorption data were investigated at various parameters, including a concentration range of 0-3 mol/L, temperatures ranging from 25 to 45 °C, and absorption durations ranging from 60 to 120 minutes, to get the best conditions for high-loading CO2 uptake. The study found that amine-based DESs had a significantly greater absorption capacity than monoethanolamine-based and conventional DESs. The study examined what happened when water was added to a deep eutectic solvent made of choline chloride and monoethanolamine (ChCl-MEA DES). The most effective way to absorb CO2 was physical absorption, which can hold 276.13 mol CO2 per gram of DES at 1 bar and 29.025 °C when mixed with water. The deep eutectic was mixed with water to increase the absorption efficiency. 10 ml of aqueous solution (DESs + water) was taken. The combination of DES and water significantly increased CO2's low solubility. The modified Design-Expert model satisfactorily represents the experimental solubility of CO2 in the solvent. The average percent differences between experimental and projected values were 10.7% and 6.8% for binary and ternary systems, respectively. The optimal conditions for maximum absorption rate were 29.025°C, 2.233 mol/L, and 101 minutes, with an absorption ratio of 0.0734 mol/kg.min and efficiency of absorption of 85.3% for solution DESs and water.
Choline chloride + levulinic acid deep eutectic solvent is studied as a suitable material for CO 2 capturing purposes. The most relevant physicochemical properties of this solvent are reported together with the CO 2 solubility as a function of temperature. The corrosivity of this solvent is studied showing better performance than amine-based solvents. A theoretical study using both density functional theory and molecular dynamics approaches is carried out to analyze the properties of this fluid from the nanoscopic viewpoint, and their relationship with the macroscopic behavior of the system and its ability for CO 2 capturing. The behavior of the liquid-gas interface is also studied and its role on the CO 2 absorption mechanism is analyzed. The reported combined experimental and theoretical approach leads to a complete picture of the behavior of this new sorbent with regard to CO 2 , which together with its low cost, and the suitable environmental and toxicological properties of this solvent, lead to a promising candidate for CO 2 capturing technological applications.
Brazilian Journal of Chemical Engineering, 2024
In the present work, an amine-based deep eutectic solvent (DES) was prepared using ethanolamine hydrochloride (EAHC) as a hydrogen bond acceptor (HBA) and diethylenetriamine (DETA) as a hydrogen bond donor (HBD) with the molar ratio of 1:9. The synthesized DES was further diluted by adding 30 v% water in the prepared DES. The solubility of carbon dioxide was measured in the aqueous DES at various pressures and temperature ranging from 0.4 to 1.6 MPa and 303.15 to 333.15 K, respectively. The solubility tends to increase at higher pressures and showed a decreasing trend at the higher temperatures i.e. 333.15 K. The highest solubility of 3.770 mol/mol was recorded at 303.15 K and pressure of 1.6 MPa. In modelling the measured CO 2 solubility data in aqueous deep eutectic solvent, the system was deemed as a quasi-binary of CO 2 and a mixed solvent. It was further assumed that the gas phase is solely consisted of CO 2. Then, the gas phase was described by the Peng-Robinson equation of state while the unsymmetrical NRTL, 2-suffix Margules, and a modified Margules equation were utilized for the modelling of the liquid phase. Henry's law constants for the solubility of CO 2 in the aqueous deep eutectic solvent were estimated and reported. It was found that the NRTL equation described the aqueous solvent phase better than the 2-suffix Margules equation; however, inferior with respect to the modified Margules equation. The coupling of the Peng-Robinson equation of state with the modified Margules equation led to an average absolute relative deviation of 3.36%.
Effect of Hydrogen Bond Donors and Acceptors on CO2 Absorption by Deep Eutectic Solvents
2020
The effects of a hydrogen bond acceptor and hydrogen bond donor on carbon dioxide absorption via natural deep eutectic solvents were studied in this work. Naturally occurring non-toxic deep eutectic solvent constituents were considered; choline chloride, b-alanine, and betaine were selected as hydrogen bond acceptors; lactic acid, malic acid, and fructose were selected as hydrogen bond donors. Experimental gas absorption data were collected via experimental methods that uses gravimetric principles. Carbon dioxide capture data for an isolated hydrogen bond donor and hydrogen bond acceptor, as well as natural deep eutectic solvents, were collected. In addition to experimental data, a theoretical study using Density Functional Theory was carried out to analyze the properties of these fluids from the nanoscopic viewpoint and their relationship with the macroscopic behavior of the system, and its ability for carbon dioxide absorption. The combined experimental and theoretical reported ap...
Energy&Fuels, 2022
This study provides useful information on the existing interactions in an aqueous solution of deep eutectic solvents (DESs) by studying excess properties namely excess refractive index and excess logarithm viscosity at different concentrations and temperatures. In order to investigate the effects of DES mole fraction and temperature on the refractive index and viscosity of binary mixtures, the response surface methodology (RSM) was applied based on the mixed-level full factorial design. The analysis of variance (ANOVA) results revealed that although both DES mole fraction and temperature are significant, the DES mole fraction has more effect on these thermophysical properties. Results showed that as excess refractive index and excess logarithm viscosity values are positive over the whole composition range and maximum excess data were investigated at the water-reach region. Moreover, the effects of important factors influencing CO 2 solubilities such as pressure, temperature, water content, and molecular weight of DES were determined using the Taguchi L 18 method. A regression model was developed based on the Taguchi method for prediction of the prediction of CO 2 solubility. The results disclosed that the pressure is the most significant factor influencing the CO 2 fraction followed by the water content and molecular weight of DESs while the temperature had the lowest effect. The error evaluations indicated that the Taguchi model is an accurate model and had excellent performance in prediction of the CO 2 solubility.
CO2 capture with the help of Phosphonium-based deep eutectic solvents
Deep eutectic solvents (DESs) are derived from the concomitant reaction of two or more salts i.e. between hydrogen bond acceptor (HBA) and hydrogen bond donors (HBD) components. In this work, DESs were prepared namely allyltriphenyl phosphonium bromide-diethylene glycol (ATPPB-DEG) and allyltriphenyl phosphonium bromide-triethylene glycol (ATPPB-TEG) into three molar ratios 1:4, 1:10, and 1:16 salt to HBDs. The carbon dioxide solubility in DESs at temperature of 303.15 K and pressure up to 2 MPa were determined and reported in terms of mole fraction, CO 2 loading and Henry's law constants. Krichevsky–Kasarnovsky equation was used to correlate the solubility data and obtain Henry's law constants at 303.15 K. Finally, the effects of hydrogen bonding within DESs, molar ratio, molar volume, free volume, ether group and alkyl chain length were investigated based on CO 2 solubility in DESs. To the best of our knowledge, this is the first time CO 2 solubility in these DESs was studied.