Search Results (25)

The vapor–liquid equilibrium (VLE) data of the binary acetonitrile + water system and three ternary systems containing ionic liquids (ILs): acetonitrile + water + 1-butyl-3-methylimidazolium chloride ([C₄mim][Cl]), + 1-butyl-3-methylimidazolium tetrafluoroborate ([C₄mim][BF₄]), and + 1-hexyl-3-methylimidazolium chloride ([C₆mim][Cl]) were experimentally measured at low pressures. In addition, the literature VLE data for the binary systems acetonitrile + [C₄mim][Cl], acetonitrile + [C₄mim][BF₄], and acetonitrile + [C₆mim][Cl] were adopted for model correlation. The NRTL and e-NRTL models were employed to correlate the binary data. The experimental results demonstrate that the presence of ILs causes a pronounced salting-out effect on acetonitrile, significantly increasing its relative volatility with respect to water. The separation performance of the three ILs for the acetonitrile + water mixture decreases in the order: [C₄mim][Cl] > [C₆mim][Cl] > [C₄mim][BF₄]. Full article

2-Methyl-3-butenenitrile, a key intermediate in the industrial production of Nylon-66, is often accompanied by two other by-products, 2-methyl-2-butenenitrile and 2-pentenenitrile, which have been proven to affect the production yield and quality of Nylon-66. Pure 2-pentenenitrile is a commercial synthetic intermediate for many chemical products and bioactive substances. As important foundational data for designing large-scale separation and purification processes for these three compounds are lacking, the saturated vapor pressure of pure 2-pentenenitrile was measured over the temperature range 298.5 K to 401.4 K, and vapor–liquid equilibrium (VLE) data for the binary systems (2-methyl-3-butenenitrile + 2-pentenenitrile, 2-methyl-2-butenenitrile + 2-pentenenitrile) were determined at pressures of 50.0 kPa and 100.0 kPa. In order to better utilize these experimental data for the design of large-scale separation distillation processes, the experimental saturated vapor pressure data of pure 2-pentenenitrile were well correlated using the Antoine equation, yielding an average relative deviation of 0.92%. For all binary systems, the thermodynamic consistency of the VLE results was verified using both the point test and the direct test. The binary VLE data were correlated with the Wilson and NRTL activity coefficient models, and the corresponding model parameters were obtained by regression, which can help to obtain complete data in the whole mole fraction range for industrial separation design. Full article

Since H₂O and Ethylene Glycol Monomethyl Ether (EM) form a minimum-boiling azeotrope, 1-pentanol, 1-hexanol, and 1-heptanol are selected as entrainers to separate the azeotropic mixture (H₂O/EM) using azeotropic distillation. The binary vapor liquid equilibrium (VLE) data were determined at 101.3 kPa, including H₂O/EM, EM/1-pentanol, EM/1-hexanol, EM/1-heptanol, H₂O/1-pentanol, H₂O/1-hexanol and H₂O/1-heptanol. Meanwhile, the Herington area test was used to validate the thermodynamic consistency of the experimental binary data. The VLE data for the experimental binary system were analyzed using the NRTL, UNIQUAC, and Wilson activity coefficient models, showing excellent agreement between predictions and measurements. Finally, molecular simulations were employed to calculate interaction energies between components, providing insights into the VLE behavior. The azeotropic distillation process was simulated using Aspen Plus to evaluate the separation performance and determine the optimal operating parameters. Therefore, this study provides guidance and a foundational basis for the separation of H₂O/EM systems at 101.3 kPa. Full article

Isobaric vapor-liquid equilibrium (VLE) data for binary mixtures of biomass–derived ethyl levulinate and ethanol were measured using an apparatus comprising a modified Rose-Williams still and a condensation system. Measurements were taken at temperatures ranging from 329.58 K to 470.00 K and pressures of 40.0, 60.0 and 80.0 kPa. The thermodynamic consistency of the VLE data was evaluated using the Redlich-Kister area test, the Fredenslund test and the Van Ness point-to-point test. The data was correlated using three activity coefficient models: Wilson, NRTL and UNIQUAC. The Gibbs energy of mixing of the VLE data was analyzed to verify the suitability of the binary interaction parameters of these models. The activity coefficients and excess Gibbs free energy, calculated from the VLE experimental data and model correlation results, were analyzed to evaluate the models’ fit and the non–ideality of the binary system. The accuracy of the regression results was also assessed based on the root mean square deviation (RMSD) and average absolute deviation (AAD) for both temperature and the vapor phase mole fraction of ethyl levulinate. The results indicate that the NRTL model provided the best fit to the experimental data. Notably, the experimental data showed strong correlation with the predictions of all three models, suggesting their reliability for practical application. Full article

Vapor–liquid equilibrium (VLE) experimental data are reported for three binary systems: isobutanol + 1-butanol, isobutanol + 2-ethyl-1-hexanol, and 1-butanol + 2-ethyl-1-hexanol. Due to the limited and incomplete data available in the literature, we determined the p-T-x experimental VLE data for these binaries using an equilibrium apparatus, designed and built in our laboratory, which had been used extensively in various determinations. The temperature and pressure ranges for determining the VLE data are as follows: (305.15–388.15) K and (2.284–99.779) kPa for the isobutanol + 1-butanol system, (305.15–455.15) K and (2.284–99.779) kPa for the isobutanol + 2-ethyl-1-hexanol, and (320.15–455.15) K and (3.635–98.039) kPa for the 1-butanol + 2-ethyl-1-hexanol. The experimental VLE data for these binary systems were regressed using the nonrandom two-liquid (NRTL) model. The results indicate a reasonably good agreement between the model and the experimental data, with maximum deviations of 7% in the liquid-phase composition of the most volatile component from the binary and 4.5% in pressure. Full article

The vapor–liquid equilibrium (VLE) data of the ternary system methanol–methyl formate–methylal was measured at atmospheric pressure using a modified Rose equilibrium kettle with vapor–liquid double circulation method. The experiment data were correlated with the NRTL, UNIQUAC, and Wilson activity coefficient model equations. The results shown that the root mean square deviation (RMSD) between the calculated and simulated values of the three models followed the order: UNIQUAC ≈ NRTL < Wilson, and except for the RMSD (T) in the range of 0.4–0.5, the others are less than 0.01. In addition, the NRTL model was selected to link with Aspen Plus software to simulate the separation process of polyformaldehyde (POM) waste liquid. The simulation results show that the methyl formate in POM waste stream can be purified by simple distillation, while the methylal separated from the POM waste liquid, which was affected by factors like the azeotropic behavior of binary components, necessitates a complex distillation process. Under optimal operating conditions, the recovery yield of methyl formate through direct distillation can reach 99.7%, with an economic benefit of 6960.1 CNY per ton of waste liquid. Although the economic benefit of the multi-component distillation reach 7281.2 CNY, the increase in the number of equipment and the complexity of the process have negative impacts. Full article

In this study, vapor–liquid equilibrium (VLE) experimental data were measured for two binary solvents based on 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), which can be used as a new CO₂-binding organic liquids (CO₂-BOLs) solvent. No experimental data are available in the literature and are fundamental to determine whether the considered mixtures are suitable to be possible alternatives to traditional amine solutions for CO₂ removal. The bubble point data of 1,2-propanediol+1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and 1,4-butanediol+DBU mixtures were measured at 30 kPa. The experimental determination was carried out in an all-glass dynamic recirculation still at the Process Thermodynamics laboratory (PT lab) of Politecnico di Milano. The thermodynamic modeling of the VLE behavior of two DBU-based mixtures was performed considering the NRTL, the UNIQUAC, and the Wilson models, and binary interaction parameters of the NRTL activity coefficients model were regressed on the basis of the measured experimental data. Full article

CO₂ removal, especially the one applied to reduce the emissions of CO₂ to the atmosphere (carbon capture, utilization, and storage), is one of the main research topics nowadays because of its great contribution to the reduction in climate change and to making many industrial processes sustainable. In this regard, alternative solvents to the traditional ones are under study with the aim of employing a more sustainable solvent for the environment, health, and society, in comparison with the traditional amine aqueous solutions that are toxic and corrosive. The CO₂-binding organic liquids (CO₂-BOLs) are a class of components of interest. In this work, the vapor–liquid equilibrium (VLE) data for two newly selected binary mixtures based on CO₂-BOLs, 1,3-Propanediol+DBU and DBU+Sulfolane, have been experimentally determined at the Process Thermodynamics laboratory (PT lab) of Politecnico di Milano to evaluate the suitability of these mixtures for being a solvent for CO₂ removal. All the experiments have been carried out by using the Fischer^® Labodest^® VLLE 602 unit at a constant pressure of 30 kPa. The densities of the mixtures for all the considered compositions have been determined at atmospheric pressure with a density meter (Mettler Toledo Densito Density2Go). No data on the VLE of these mixtures can be found in the literature. This is the first work focusing on mixtures of these components that could be employed as solvents for CO₂ removal as alternative solvents to the monoethanolamine (MEA) aqueous solution in the process of chemical absorption. The collected experimental data have then been used for the definition of the thermodynamic model by considering different possible theories (NRTL, Wilson, and UNIQUAC) that could be employed for the representation of the two systems. Full article

The growing demand for more sustainable routes and processes in the mixture separation and purification industry has generated a need to search for innovations, with new solvent alternatives being a possible solution. In this context, a new class of green solvents, known as deep eutectic solvents (DESs), has been gaining prominence in recent years in both academic and industrial spheres. These solvents, when compared to ionic liquids (ILs), are more environmentally friendly, less toxic, low-cost, and easier to synthesize. In addition, they have significantly lower melting points than their precursors, offering a promising option for various applications in this industrial sector. Understanding and studying the thermodynamic behavior of systems composed of these substances in purification and separation processes, such as liquid–liquid extraction and azeotropic distillation, is extremely important. This work aimed to study the phase behavior of liquid–liquid equilibrium (LLE) and vapor–liquid equilibrium (VLE) of water + 1-butanol + DES (choline chloride + glycerol) systems with a molar ratio of 1:2. Experimental LLE data, obtained at 298.15 K and 101.3 kPa, and VLE data, obtained at 101.3 kPa and in the temperature range of 364.05 K–373.85 K, were submitted to the thermodynamic quality/consistency test, proposed by Marcilla et al. and Wisniak, and subsequently modeled using the gamma–gamma approach for the LLE and gamma–phi for the VLE. The non-random two-liquid (NRTL) model was used to calculate the activity coefficient. The results are presented for the VLE in a temperature–composition phase diagram (triangular prism) and triangular phase diagrams showing the binodal curve and tie lines (LLE). The separation and distribution coefficients of LLE were determined to evaluate the extractive potential of the DES. For the VLE, the values of the relative volatility of the system were calculated, considering the entrainer free-basis, to evaluate the presence or absence of azeotropes in the range of collected points. From these data, it was possible to compare DES with ILs as extracting agents, using data from previous studies carried out by the research group. Therefore, the results indicate that the NRTL model is efficient at correlating the fluid behavior of both equilibria. Thus, this study serves as a basis for future studies related to the understanding and design of separation processes. Full article

This study presents a critical review of the experimental vapor-liquid equilibrium (VLE) data for the quaternary acetic acid-ethanol-ethyl acetate-water system and its subsystems that are reported in the literature. The thermodynamic consistency of the VLE data were verified using two integral tests: the Redlich–Kister test and the direct integration of the Gibbs–Duhem equation. The VLE data were correlated using the NRTL equation for further integration. Additionally, the reliable value of the integral derived from the direct integration of the Gibbs–Duhem equation for multicomponent systems under isothermal-isobaric conditions was estimated. This integral can be used for testing the thermodynamic consistency of experimental VLE data. Full article

This study focuses on separating a mixture consisting of 1,2-ethanediol (1,2-ED), 1,3-propanediol (1,3-PD), and 1,4-butanediol (1,4-BD). Vapor–liquid equilibrium (VLE) data for 1,2-ED + 1,4-BD and 1,3-PD + 1,4-BD are determined at 101.3 kPa using a modified Rose equilibrium still. The consistency of the VLE data is checked with both Redlich–Kister and Fredenslund tests. The VLE data are fitted by the Wilson, NRTL, and UNIQUAC activity coefficient models. All three models can effectively correlate the VLE data. Then, the separation of the mixture is designed with the NRTL model and its correlated binary interaction parameters. A liquid-only transfer dividing wall column (LDWC) is investigated on the basis of a direct conventional distillation sequence (DCDS). For a fair comparison, both DCDS and LDWC are optimized to minimize total annual cost using sequential iterative optimization procedures. After optimization, LDWC exhibits a 16.87% reduction in total annual cost, while cooling and heating utility consumptions are reduced by 28.40% and 19.24% compared to DCDS. Full article

Dichloromethane (DCM) is recognized as a very harmful air pollutant because of its strong volatility and difficulty to degrade. Ionic liquids (ILs) are considered as potential solvents for absorbing DCM, while it is still a challenge to develop ILs with high absorption performances. In this study, four carboxyl-functionalized ILs—trioctylmethylammonium acetate [N₁₈₈₈][Ac], trioctylmethylammonium formate [N₁₈₈₈][FA], trioctylmethylammonium glycinate [N₁₈₈₈][Gly], and trihexyl(tetradecyl)phosphonium glycinate [P₆₆₆₁₄][Gly]—were synthesized for DCM capture. The absorption capacity follows the order of [P₆₆₆₁₄][Gly] > [N₁₈₈₈][Gly] > [N₁₈₈₈][FA] > [N₁₈₈₈][Ac], and [P₆₆₆₁₄][Gly] showed the best absorption capacity, 130 mg DCM/g IL at 313.15 K and a DCM concentration of 6.1%, which was two times higher than the reported ILs [Beim][EtSO₄] and [Emim][Ac]. Moreover, the vapor–liquid equilibrium (VLE) of the DCM + IL binary system was experimentally measured. The NRTL (non-random two-liquid) model was developed to predict the VLE data, and a relative root mean square deviation (rRMSD) of 0.8467 was obtained. The absorption mechanism was explored via FT-IR spectra, ¹H-NMR, and quantum chemistry calculations. It showed a nonpolar affinity between the cation and the DCM, while the interaction between the anion and the DCM was a hydrogen bond. Based on the results of the study of the interaction energy, it was found that the hydrogen bond between the anion and the DCM had the greatest influence on the absorption process. Full article

Vapor–liquid equilibrium (VLE) and density data for binary systems of branched alkanes + ethyl acetate are scarce in the literature. In this study, the binary mixtures 3-methylpentane + ethyl acetate and 2,3-dimethylbutane + ethyl acetate were investigated. Density measurements at atmospheric pressure were performed using a vibrating tube density meter at 293.15, 298.15 and 303.15 K. Large and positive excess molar volumes were calculated and correlated using a Redlich–Kister-type equation. Isobaric VLE data at 101.3 kPa were obtained using a Gillespie-type recirculation ebulliometer. Equilibrium compositions were determined indirectly from density measurements. The experimental data were checked for consistency by means of the Fredenslund test and the Wisniak (L-W) test and were then successfully correlated using the NRTL model. The newly studied binary systems display high deviations from ideality and minimum boiling azeotropes, the coordinates of which are reported in this work. Full article

An equation of state (EOS) of CH₄-N₂ fluid mixtures in terms of Helmholtz free energy has been developed by using four mixing parameters, which can reproduce the pressure-volume-temperature-composition (PVTx) and vapor-liquid equilibrium (VLE) properties of CH₄-N₂ fluid mixtures. The average absolute deviation of all the PVTx data available up to 673.15 K and 1380 bar from this EOS is 0.38%. Combining this EOS of CH₄-N₂ fluid mixtures and the EOS of CH₄-CO₂ and CO₂-N₂ fluid mixtures in our previous work, an EOS of CO₂-CH₄-N₂ fluid mixtures has been developed, which is named ZMS EOS. The ZMS EOS can calculate all thermodynamic properties of ternary CO₂-CH₄-N₂ fluid mixtures and the average absolute deviation of the PVTx data from the ZMS EOS is 0.40% for the CO₂-CH₄-N₂ system. The ZMS EOS can be applied to calculate excess enthalpies of CO₂-CH₄-N₂ fluid mixtures, predict the solubility of CO₂-CH₄-N₂ fluid mixtures in brine and water, and quantitatively estimate the impact of the impurities (CH₄ and N₂) on the CO₂ storage capacity in the CO₂ capture and storage (CCS) processes. The ZMS EOS can also be applied to calculate the isochores of CO₂-CH₄-N₂ system in the studies of fluid inclusions. All Fortran computer codes and Origin drawing projects in this paper can be obtained freely from the corresponding author. Full article

In this work, we propose the idea of considering ${\left(\frac{\partial p}{\partial x}\right)}_{T, x\to 0}$ as an infinite dilution thermodynamic function. Our research shows that ${\left(\frac{\partial p}{\partial x}\right)}_{T,x\to 0}$ as a thermodynamic function is closely related to temperature, with the relation being simply expressed as: $\ln {\left(\frac{\partial p}{\partial x}\right)}_{T, x\to 0}=\frac{A}{T}+B$. Then, we use this equation to correlate the isothermal vapor–liquid equilibrium (VLE) data for 40 systems. The result shows that the total average relative deviation is 0.15%, and the total average absolute deviation is 3.12%. It indicates that the model correlates well with the experimental data. Moreover, we start from the total pressure expression, and use the Gibbs–Duhem equation to re-derive the relationship between ${\left(\frac{\partial p}{\partial x}\right)}_{T,x\to 0}$ and the infinite dilution activity coefficient (${\gamma }^{\infty }$) at low pressure. Based on the definition of partial molar volume, an equation for ${\left(\frac{\partial p}{\partial x}\right)}_{T,x\to 0}$ and gas solubility at high pressure is proposed in our work. Then, we use this equation to correlate the literature data on the solubility of nitrogen, hydrogen, methane, and carbon dioxide in water. These systems are reported at temperatures ranging from 273.15 K to 398.15 K and pressures up to 101.325 MPa. The total average relative deviation of the predicted values with respect to the experimental data is 0.08%, and the total average absolute deviation is 2.68%. Compared with the Krichevsky–Kasarnovsky equation, the developed model provides more reliable results. Full article