Fluid Phase Equilibria最新文献

{"title":"Multi-objective optimization of PC-SAFT parameters for ionic liquids from density and viscosity data using entropy scaling","authors":"Diego T. Melfi ,&nbsp;Aaron M. Scurto","doi":"10.1016/j.fluid.2025.114427","DOIUrl":"10.1016/j.fluid.2025.114427","url":null,"abstract":"<div><div>Equations of state using the Statistical Associating Fluid Theory (SAFT EoS) have found tremendous success in the thermodynamic modeling of ionic liquids (ILs) and mixtures. Traditionally, SAFT EoS parameters are fit to pure component pressure-volume-temperature (PVT) (density) data and vapor pressure data. We have recently combined the PC-SAFT EoS with entropy scaling theory to correlate and predict the viscosity of ILs and IL mixtures. We found that the PC-SAFT EoS parameters for ionic liquids regressed to PVT data can sometimes lead to relatively large deviations in the viscosity correlations, especially at high pressure. Here, we investigate the effect of including viscosity data along with PVT data for the PC-SAFT parameter regression of two series of 1-n-alkyl-3-methyl imidazolium ionic liquids ([C<em>_n</em>MIm][Tf₂N] and [C<em>_n</em>MIm][BF₄]). From analyzing the Pareto fronts, the inclusion of viscosity data to PVT data for PC-SAFT parameters resulted in only a small loss in accuracy for the density, but with much improved viscosity correlations through entropy scaling. We found that the parameter sets obtained from density and viscosity data regression are less prone to numerical pitfalls, i.e. fictitious SAFT critical points, than the parameter sets obtained from PVT data alone. In addition, the predicted (<em>k_ij</em>=0) phase equilibrium (VLE) of ionic liquids and mixtures with CO₂, CH₄, and water were equal to, if not better than the predictions using PVT data alone. Overall, the use of pure PVT and viscosity data in the parameterization of PC-SAFT yields a more widely applicable prediction method for both thermodynamic and transport properties.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114427"},"PeriodicalIF":2.8,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of CO2 hydrate capsules in partially water-saturated sediment as vessels for underground mechanical energy storage: Promoting effect of tetrahydrofuran and cyclopentane","authors":"Qian Ouyang ,&nbsp;Omer Lev-Yehudi ,&nbsp;Jyoti Shanker Pandey ,&nbsp;Andrea Franza ,&nbsp;Irene Rocchi ,&nbsp;Assaf Klar ,&nbsp;Nicolas von Solms","doi":"10.1016/j.fluid.2025.114428","DOIUrl":"10.1016/j.fluid.2025.114428","url":null,"abstract":"<div><div>The intermittency of renewable energy sources and the increase in renewable energy shares require energy storage capability to sustain the green transition. One promising solution for underground energy storage is the use of subsurface CO₂ hydrate capsules, which act as impermeable vessels that store compressed fluids and discharge them upon need. However, as part of the proof-of-concept study of this technology, the feasibility of constructing such vessels, e.g. CO₂ hydrate capsules, has yet to be demonstrated. This work employed CO₂ gas injection assisted by chemical solution into partially water-saturated sand sediments to synthesize CO₂ hydrate capsules. The concentrations of chemical solutions (THF, CP and DIOX) were screened out in the gas/liquid/sand system in terms of kinetic promotion, using a rocking cell. Separately, experiments were carried out with a new high-pressure chamber set-up that quantified the effects of water saturation and chemical promoters on the efficiencies of CO₂ hydrate synthesis in confined partially water-saturated sand. Results on the gas/liquid/sand system showed that 0.025 water/CP weight ratio CP solution and 1.3mol% THF solution induced the largest pressure drops of 18.4 ± 0.2 bar and 16.7 ± 0.1 bar, respectively, indicating the most promoted CO₂ hydrate formation kinetics. Results with the pressure chamber showed three stages during slow CO₂ gas injection: (1) initial pressure “build-up stage”; subsequent (2) CO₂ gas “uptake stage”; and (3) CO₂ injection “closing stage”. CO₂ hydrate formation kinetics of CO₂ hydrate retention percentage (S_CO2) and CO₂ hydrate density (ρ_CO2) were directly proportional to the initial water saturation (6.0–76.7%). Injection of THF or CP solutions increased S_CO2 by 16.5% or 18.5%, and ρ_CO2 by 74.5% or 128.3% compared to injection of water. The best performances were obtained at a fluid pressure of 27.0 bar, with a 0.025 water/CP solution-assisting CO₂ gas injection, in sediment with an initial water saturation of 32.6% and porosity of 44.6%, giving rise to S_CO2 of 67.2% and ρ_CO2 of 80.6%. These findings demonstrated that the injection of THF or CP solution with CO₂ gas facilitated the possibility of the formation and stabilization of subsurface CO₂ hydrate capsules.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114428"},"PeriodicalIF":2.8,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Predicting transport properties of simple fluids using an extended FMSA model and a Mode-Coupling Theory","authors":"Ignace N°II Yapi,&nbsp;Oriana Haddad,&nbsp;Mounir Ben Amar,&nbsp;Jean-Philippe Passarello","doi":"10.1016/j.fluid.2025.114426","DOIUrl":"10.1016/j.fluid.2025.114426","url":null,"abstract":"<div><div>A mode-coupling approach proposed by Egorov (J. Chem. Phys. 119 (2003) 4798‑4810 and J. Chem. Phys. 128 (2008) 144508) and combined with the first-order mean spherical approximation (FMSA) of Tang and Lu (J. Chem. Phys. 99 (1993) 9828‑9835) extended by an analytical SEXP approximation has been systematically tested for the prediction of transport properties (shear viscosity and self-diffusion coefficient) of simple fluids (interacting with various Mie n-6 potentials where n ranging from 9 to 24). Calculations were performed over a the full range of fluid density (<span><math><mrow><mn>0</mn><mo>&lt;</mo><msup><mrow><mi>ρ</mi></mrow><mo>*</mo></msup><mo>&lt;</mo><mn>1</mn></mrow></math></span>) and in a wide domain of temperature (<span><math><mrow><mn>1</mn><mo>&lt;</mo><msup><mrow><mi>T</mi></mrow><mo>*</mo></msup><mo>&lt;</mo><mn>4</mn></mrow></math></span>). As a conclusion of this work, this purely predictive model (no adjustable parameters) is favorably compared with the molecular dynamics data related to a large variety of simple spherical molecules and has successfully predicted the shear viscosity and self-diffusion coefficient of the real noble fluids Ne, Ar, Kr and Xe using <em>ab initio</em> pair potentials.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114426"},"PeriodicalIF":2.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A general Gibbs energy minimization algorithm for modelling solid-fluid equilibria in binary systems involving totally and partially miscible solids, pure solids, hydrates and co-crystals","authors":"Wen Hwa Siah,&nbsp;Marco Campestrini,&nbsp;Paolo Stringari","doi":"10.1016/j.fluid.2025.114425","DOIUrl":"10.1016/j.fluid.2025.114425","url":null,"abstract":"<div><div>At a fixed temperature and pressure, a mixture is at equilibrium if and only if the Gibbs energy of the system is at its global minimum. In other words, phase equilibrium calculations can be treated as optimization problems, as the minimization of the Gibbs energy represents the sufficient condition for thermodynamic equilibrium. However, the necessary condition of equilibrium resulting from the iso-fugacity criterion of each individual component in each guess equilibrium phase is more used. Despite being computationally simpler, this approach may lead to metastable solutions. On the whole, the minimization of Gibbs energy should be prioritized as it is the only approach that provides the true thermodynamic state of a given mixture since it considers the overall Gibbs energy of the system.</div><div>This work presents a general algorithm based on the Gibbs energy minimization approach for binary systems. Provided that suitable fluid-phase and solid-phase models are chosen, the algorithm is able to evaluate the most stable thermodynamic state of a system for a given global composition, temperature, and pressure without prior assumptions about the number, nature, or compositions of equilibrium phases.</div><div>To the authors’ knowledge, this is the first Gibbs energy minimization approach capable of handling solid-fluid phase equilibria involving diverse solid types: from totally miscible solids (e.g., N₂+Ar, CH₄+Kr systems), partially miscible solids (e.g., N₂+O₂, CH₄+Ar systems), pure solids (e.g., N₂+CO₂, CH₄+C₂H₆ systems), and hydrates (e.g., CH₄+H₂O system), to cocrystals with both congruent and incongruent melting (e.g., C₆H₆+C₂H₃N, CH₃OH+H₂O systems).</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114425"},"PeriodicalIF":2.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Density measurements of homogeneous phase fluid mixtures comprising CO2/propanol and CO2/butanol binary systems and correlation with PC-SAFT equation of state","authors":"Hiroaki Matsukawa ,&nbsp;Masamune Yomori ,&nbsp;Tomoya Tsuji ,&nbsp;Katsuto Otake","doi":"10.1016/j.fluid.2025.114424","DOIUrl":"10.1016/j.fluid.2025.114424","url":null,"abstract":"<div><div>Given that supercritical CO₂–alcohol mixtures are often encountered in natural gas, oil, and petroleum industries, the properties of binary CO₂/alcohol mixtures are essential for chemical process design, and their prediction is important. Equations of state (EoSs) are powerful tools for estimating physical properties and can be used to determine those of CO₂/alcohol binary mixtures if molecular association is considered, i.e., the examination of the CO₂–alcohol association from the EoS perspective improves property estimation. Herein, the densities of homogeneous phase fluid mixtures comprising CO₂/1-propanol, CO₂/2-propanol, and CO₂/1-butanol binary systems, which are greatly affected by mixing, were measured using a high-pressure vibration-type density meter equipped with a circulation pump and variable-volume viewing cell. Homogeneity was ensured by observing the fluid through the viewing window of the variable-volume cell. Measurements were carried out at temperatures of 313–353 K, CO₂ contents of 0–80 mol%, and pressures of up to 20 MPa, and the obtained data were correlated using the considering association between CO₂ and alcohol-perturbed chain-statistical associating fluid theory (CACA-PC-SAFT) EoS. The mixture density correlation was affected by the estimation accuracy of the pure-alcohol density. Therefore, the pure-alcohol density was correlated using the PC-SAFT EoS, and the pure-alcohol parameters were determined. The mixture density was effectively correlated using the CACA-PC-SAFT EoS based on these parameters. Furthermore, we determined the dependence of the obtained mixing parameters on temperature and alcohol species, revealing that mixing parameters could be predicted by combining experimental or quantum chemical information on alcohols or CO₂ and alcohols.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114424"},"PeriodicalIF":2.8,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A second-order Dry Glass Reference Perturbation Theory for modeling sorption in glassy polymers: applications to systems containing light gases, alcohols, and water vapor","authors":"Hasan Ismaeel ,&nbsp;Bennett D. Marshall ,&nbsp;Eleonora Ricci ,&nbsp;Maria Grazia De Angelis","doi":"10.1016/j.fluid.2025.114410","DOIUrl":"10.1016/j.fluid.2025.114410","url":null,"abstract":"<div><div>The solubility of gases and vapors plays a critical role in determining the overall performance of membrane-based separation processes. Through the use of advanced Equations of State (EoS), the Non-Equilibrium Thermodynamics for Glassy Polymers (NET-GP) theory rose into prominence as a powerful correlative and predictive tool for the sorption of guest species in glassy polymers. The recently proposed Dry Glass Reference Perturbation Theory (DGRPT) provided a method to account for the polymer swelling through the NET-GP framework. In this work, we introduce a second-order modification to the DGRPT that improves upon the model’s flexibility in representing different types of isotherms. We have also investigated different association and parameterization schemes for water and alcohol sorption using the PC-SAFT EoS in glassy polymers. For the non-self associating polymers investigated here, our results concluded that the sorption of alcohols can be represented adequately using the induced association assumptions formulated by Kleiner and Sadowski. On the contrary, the same assumptions often lead to poor water sorption results. We speculate that the Wolbach and Sandler combining rule may be incapable of representing the cross-association effects between water and the glassy polymer. As a result, we fitted the cross association volume of bonding (κ<span><math><msub><mrow></mrow><mrow><msub><mrow><mi>A</mi></mrow><mrow><mi>i</mi></mrow></msub><msub><mrow><mi>B</mi></mrow><mrow><mi>j</mi></mrow></msub></mrow></msub></math></span>) on the sorption data while fixing the cross association energetic parameter (ε<span><math><msub><mrow></mrow><mrow><msub><mrow><mi>A</mi></mrow><mrow><mi>i</mi></mrow></msub><msub><mrow><mi>B</mi></mrow><mrow><mi>j</mi></mrow></msub></mrow></msub></math></span>) to half of water’s parameter. The adjusted κ<span><math><msub><mrow></mrow><mrow><msub><mrow><mi>A</mi></mrow><mrow><mi>i</mi></mrow></msub><msub><mrow><mi>B</mi></mrow><mrow><mi>j</mi></mrow></msub></mrow></msub></math></span> can then be treated as a temperature-independent parameter, while the effects of temperature variation can be delegated to the binary interaction parameter (k<span><math><msub><mrow></mrow><mrow><mi>i</mi><mi>j</mi></mrow></msub></math></span>).</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114410"},"PeriodicalIF":2.8,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143644982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling heat capacity of liquid siloxanes using artificial intelligence methods","authors":"Wei Guo ,&nbsp;Baraa Mohammed Yaseen ,&nbsp;Hardik Doshi ,&nbsp;Anupam Yadav ,&nbsp;Asha Rajiv ,&nbsp;Aman Shankhyan ,&nbsp;Sachin Jaidka ,&nbsp;A.S. Madhusadan Acharyulu ,&nbsp;Rafid Jihad Albadr ,&nbsp;Waam mohammed taher ,&nbsp;Mariem Alwan ,&nbsp;Mahmood Jasem Jawad ,&nbsp;Hiba Mushtaq ,&nbsp;Mehrdad Mottaghi","doi":"10.1016/j.fluid.2025.114423","DOIUrl":"10.1016/j.fluid.2025.114423","url":null,"abstract":"<div><div>In organic Rankine cycle (ORC) technology, heat capacity is an extremely important thermophysical property as it has significant implications for heat exchangers design as well as the determination of cycle performance. Given its importance, it is crucial that the heat capacity values used in the aforementioned applications are highly accurate, to ensure optimal performance and efficiency of ORC systems. Thus, the goal of this research is to develop precise data-driven models based on Random Forest, Decision Tree, AdaBoost, K-Nearest Neighbors, Ensemble Learning, Multilayer Perceptron Artificial Neural Network, Convolutional Neural Network and Support Vector Machine learning algorithms to accurately predict liquid siloxanes’ heat capacity as a function of molar mass, boiling point, temperature, and pressure. The findings suggest that nearly all the collected experimental data are technically appropriate for building the model. The analysis of sensitivity indicates a positive effect of temperature and negative effect of pressure, siloxane boiling point, and molar mass on the heat capacities. The evaluation metrics and graphical analyses indicate that the CNN-based model is the most accurate for the prediction task of heat capacity. It achieves the highest R-squared value (0.975042) and the lowest mean square error (0.000554) on the test set, along with the lowest average absolute relative error percentage (0.632605). These results highlight the CNN's superior ability to capture complex patterns and deliver precise predictions specifically for the prediction task of heat capacity.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114423"},"PeriodicalIF":2.8,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solid–liquid equilibria of selected ternary systems containing diphenyl carbonate, alcohol, dialkyl carbonate, and phenol","authors":"Hiroyuki Matsuda ,&nbsp;Yuki Ohashi ,&nbsp;Tomoya Tsuji ,&nbsp;Ken Naito ,&nbsp;Yusuke Kakuta ,&nbsp;Kiyofumi Kurihara ,&nbsp;Katsumi Tochigi","doi":"10.1016/j.fluid.2025.114420","DOIUrl":"10.1016/j.fluid.2025.114420","url":null,"abstract":"<div><div>We studied the solid–liquid equilibria (SLE) of five ternary systems for application to the purification of diphenyl carbonate (DPC) during crystallization. These systems contained DPC, alcohol, dimethyl carbonate (DMC), diethyl carbonate (DEC), and phenol, i.e., ethanol + DEC + DPC, methanol + DMC + DPC, phenol + DMC + DPC, ethanol + phenol + DPC, and DEC + phenol + DPC. The SLE data of these ternary systems were experimentally determined at atmospheric pressure and temperatures of approximately 245 – 352 K. The SLE measurements of the ternary systems were made for pseudo-binary systems by varying the value of the mole fraction (on a DPC-free basis) of one component of the binary system. The melting points were experimentally determined using a synthetic, visual technique we designed in a previous study. The experimental SLE data of the ethanol + DEC + DPC and methanol + DMC + DPC systems were compared with the predictions of the nonrandom two-liquid model based on binary interaction parameters determined for the constituent binary systems. The predictions of the NIST modified UNIFAC group contribution method were also assessed.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114420"},"PeriodicalIF":2.8,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143644980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Parameter Estimation for Liquid-Liquid Equilibrium Using Homotopy Continuation as Stability Constraints","authors":"John O Bamikole ,&nbsp;Caleb Narasigadu ,&nbsp;Naadhira Seedat","doi":"10.1016/j.fluid.2025.114421","DOIUrl":"10.1016/j.fluid.2025.114421","url":null,"abstract":"<div><div>Parameter estimation for the activity models such as NRTL and UNIQUAC for liquid-liquid equilibrium (LLE) is a nontrivial task, and this is due to the complex nature of these models and the need to uniquely fit the binary interaction parameters that predict phase behaviour and compositions similar to the experimental ones while ensuring satisfaction of the stability criterion and other conditions. To achieve this task, there is a need for a robust formulation that will capture all the necessary constraints and a good algorithm that will proffer the right solution. This study formulated an LLE problem by introducing the homotopy continuation to create discretised points for tracking the tie-lines to ensure phase stability. Other constraints were also included in this formulation to avoid fictitious phase prediction. The algorithm was applied to several LLE problems, including binary, ternary, and quaternary, for isothermal and non-isothermal LLE systems. The algorithm tackled all the problems, and the estimated parameters predicted stable phases with existent behaviour and compositions with very small discrepancies from the measured compositions. Though the constraint may increase the computational effort, it was beneficial, and the formulation also avoids the back and forth of a posteriori check.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114421"},"PeriodicalIF":2.8,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682211","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling of ionic liquid solubility in supercritical carbon dioxide + co-solvent phase predicted by ε*-modified Sanchez-Lacombe equation of state","authors":"Yuya Hiraga ,&nbsp;Ikuo Ushiki","doi":"10.1016/j.fluid.2025.114417","DOIUrl":"10.1016/j.fluid.2025.114417","url":null,"abstract":"<div><div>Supercritical fluid deposition (SCFD) using supercritical carbon dioxide (CO₂) has environmental advantages and enables the uniform and precise impregnation of ionic liquids (ILs) into porous supports. In general, the solubility of ILs in CO₂ is extremely low, but it can be greatly increased by adding a co-solvent. However, due to the diversity of IL and co-solvent combinations, models for predicting IL solubility remain limited. This study employs the <em>ε</em>*-modified Sanchez-Lacombe equation of state (<em>ε</em>*-mod SL-EoS) to predict IL solubility in supercritical CO₂ + co-solvent systems. Compared to the Peng-Robinson equation of state (PR-EoS) previously used, <em>ε</em>*-mod SL-EoS, derived from lattice fluid theory, has superior predictive capabilities, particularly for systems involving heavy molecules like ILs. Pure component parameters for ILs, CO₂, and co-solvents were determined through high-pressure density and vapor pressure correlations. Binary interaction parameters for IL + CO₂, CO₂ + co-solvent, and IL + co-solvent systems were fitted using available phase equilibrium data. Ternary phase equilibrium predictions using <em>ε</em>*-mod SL-EoS showed improved accuracy, achieving an average logarithmic AARD of 11.0%, outperforming PR-EoS (13.8%). The results highlight the <em>ε</em>*-mod SL-EoS as a robust predictive tool for IL solubility in CO₂-rich phases, even under dilute conditions with co-solvents, offering valuable insights for optimizing the SCFD processes.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114417"},"PeriodicalIF":2.8,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143592342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}