Pub Date : 2024-10-29DOI: 10.1016/j.fluid.2024.114276
Ana Cristina Ramirez-Gallardo, I. Garcia-Cruz, C. Lira-Galeana
A method to predict the gas/oil (GOC) and oil/tar (OTC) fluid contacts of reservoir fluid columns containing heavy fractions and asphaltenes is presented. A new formulation and solution to the gravitational equilibrium equations in terms of the method of moments, and the use of an equation of state for semicontinuous mixtures are shown to provide a robust and consistent method to describe the variation of pressure, reservoir fluid composition and heavy-ends molecular weights with depth, as well as the location of the fluid contacts of a petroleum reservoir. Use of the new method is first illustrated by locating the GOC of a (continuous) ideal reservoir described by Raoult´s law, and by predicting the GOC and OTC of two reservoir systems where measured data are available. The good agreement of the new method with measured gradients shows the adequacy of the proposed approach.
{"title":"Predicting gas-cap and tar-mat formation conditions in hydrocarbon reservoirs. Application of Continuous Thermodynamics","authors":"Ana Cristina Ramirez-Gallardo, I. Garcia-Cruz, C. Lira-Galeana","doi":"10.1016/j.fluid.2024.114276","DOIUrl":"10.1016/j.fluid.2024.114276","url":null,"abstract":"<div><div>A method to predict the gas/oil (GOC) and oil/tar (OTC) fluid contacts of reservoir fluid columns containing heavy fractions and asphaltenes is presented. A new formulation and solution to the gravitational equilibrium equations in terms of the method of moments, and the use of an equation of state for semicontinuous mixtures are shown to provide a robust and consistent method to describe the variation of pressure, reservoir fluid composition and heavy-ends molecular weights with depth, as well as the location of the fluid contacts of a petroleum reservoir. Use of the new method is first illustrated by locating the GOC of a (continuous) ideal reservoir described by Raoult´s law, and by predicting the GOC and OTC of two reservoir systems where measured data are available. The good agreement of the new method with measured gradients shows the adequacy of the proposed approach.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114276"},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577985","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}
Pub Date : 2024-10-29DOI: 10.1016/j.fluid.2024.114277
Nikolaos Prinos, Epaminondas Voutsas
This work presents the development of a modified variant of the COSMO-SAC model, aiming to achieve reliable phase equilibrium predictions at both low and high pressures. Two major modifications of the previously published COSMO-SAC models are introduced. First, an improved combinatorial term is used to improve the results in nearly athermal and asymmetric mixtures. Second, a further separation of the hydrogen-bonding sigma profile has been introduced, differentiating the hydroxyl group belonging to water from hydroxyl groups belonging to other compounds, to improve the results in aqueous systems. The model's performance is studied for vapor-liquid equilibrium at low pressures and infinite dilution activity coefficient predictions, and it is benchmarked with respect to COSMO-SAC and COSMO-SAC 2010 models. Furthermore, the model is combined with the Peng Robinson equation of state via the Universal Mixing Rules (UMR) and applied for high pressure vapor-liquid equilibrium predictions. The results indicate that the modified COSMO-SAC model represents a reliable tool for phase-equilibria predictions for systems of various degrees of non-ideality and asymmetry.
{"title":"Phase equilibrium calculations at low and high pressures with a modified COSMO-SAC model","authors":"Nikolaos Prinos, Epaminondas Voutsas","doi":"10.1016/j.fluid.2024.114277","DOIUrl":"10.1016/j.fluid.2024.114277","url":null,"abstract":"<div><div>This work presents the development of a modified variant of the COSMO-SAC model, aiming to achieve reliable phase equilibrium predictions at both low and high pressures. Two major modifications of the previously published COSMO-SAC models are introduced. First, an improved combinatorial term is used to improve the results in nearly athermal and asymmetric mixtures. Second, a further separation of the hydrogen-bonding sigma profile has been introduced, differentiating the hydroxyl group belonging to water from hydroxyl groups belonging to other compounds, to improve the results in aqueous systems. The model's performance is studied for vapor-liquid equilibrium at low pressures and infinite dilution activity coefficient predictions, and it is benchmarked with respect to COSMO-SAC and COSMO-SAC 2010 models. Furthermore, the model is combined with the Peng Robinson equation of state via the Universal Mixing Rules (UMR) and applied for high pressure vapor-liquid equilibrium predictions. The results indicate that the modified COSMO-SAC model represents a reliable tool for phase-equilibria predictions for systems of various degrees of non-ideality and asymmetry.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114277"},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594153","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}
Pub Date : 2024-10-28DOI: 10.1016/j.fluid.2024.114275
Binqi Wang , Hongshuai Gao , Yuxing Wu , Huizheng Wu , Tiancheng Li , Xue Liu , Yi Nie
The utilization of ionic liquids (ILs) as solvents in the preparation of regenerated cellulose fibers (RCFs) has garnered considerable research attention. The physicochemical properties of the ILs mixtures with coagulants significantly impact the morphology and characteristics of RCFs. This study determines the density and viscosity of 1-ethyl-3- methylimidazolium diethylphosphate ([Emim][DEP]), 1-ethyl-3-methylimidazolium dimethylphosphate ([Emim][DMP]), and 1‑butyl‑3-methylimidazolium dimethylphosphate ([Bmim][DMP]) in mixtures with water and ethanol. The thermodynamic data such as excess molar volumes, viscosity deviation, and excess Gibbs energy of activation for viscous flow, were also calculated and analyzed. The density and viscosity of [Bmim][DMP] is 1.1579 g·cm−3 and 367.97 mPa·s at 303 K, and the order of the interaction between different ILs and coagulants was obtained. In the meantime, the water activity of the ILs-water mixtures was also tested, and the constant pressure boiling point of ILs with water and ethanol mixtures was measured. Furthermore, the polar action parameters of ILs were determined by Reichardt's dye. The experimental results obtained have mutually confirmed each other. The investigation of the interaction between ILs and coagulants furnishes foundational data and theoretical support for the controlled formation of RCFs prepared using ILs as solvents.
利用离子液体（ILs）作为溶剂制备再生纤维素纤维（RCFs）的研究备受关注。离子液体与凝固剂混合物的理化性质对再生纤维素纤维的形态和特性有重大影响。本研究测定了 1-乙基-3-甲基咪唑二乙基磷酸盐（[Emim][DEP]）、1-乙基-3-甲基咪唑二甲基磷酸盐（[Emim][DMP]）和 1-丁基-3-甲基咪唑二甲基磷酸盐（[Bmim][DMP]）与水和乙醇的混合物的密度和粘度。此外，还计算和分析了过量摩尔体积、粘度偏差和粘流活化过量吉布斯能等热力学数据。在 303 K 时，[Bmim][DMP] 的密度和粘度分别为 1.1579 g-cm-3 和 367.97 mPa-s，并得出了不同 IL 与凝固剂之间相互作用的顺序。同时，还测试了 ILs 与水混合物的水活性，并测量了 ILs 与水和乙醇混合物的恒压沸点。此外，还利用赖哈特染料测定了 ILs 的极性作用参数。实验结果相互印证。ILs 与混凝剂之间相互作用的研究为以 ILs 为溶剂制备 RCFs 的可控形成提供了基础数据和理论支持。
{"title":"Investigation of the physicochemical and thermodynamic characteristics of imidazole ionic liquids with water and ethanol mixtures","authors":"Binqi Wang , Hongshuai Gao , Yuxing Wu , Huizheng Wu , Tiancheng Li , Xue Liu , Yi Nie","doi":"10.1016/j.fluid.2024.114275","DOIUrl":"10.1016/j.fluid.2024.114275","url":null,"abstract":"<div><div>The utilization of ionic liquids (ILs) as solvents in the preparation of regenerated cellulose fibers (RCFs) has garnered considerable research attention. The physicochemical properties of the ILs mixtures with coagulants significantly impact the morphology and characteristics of RCFs. This study determines the density and viscosity of 1-ethyl-3- methylimidazolium diethylphosphate ([Emim][DEP]), 1-ethyl-3-methylimidazolium dimethylphosphate ([Emim][DMP]), and 1‑butyl‑3-methylimidazolium dimethylphosphate ([Bmim][DMP]) in mixtures with water and ethanol. The thermodynamic data such as excess molar volumes, viscosity deviation, and excess Gibbs energy of activation for viscous flow, were also calculated and analyzed. The density and viscosity of [Bmim][DMP] is 1.1579 g·cm<sup>−3</sup> and 367.97 mPa·s at 303 K, and the order of the interaction between different ILs and coagulants was obtained. In the meantime, the water activity of the ILs-water mixtures was also tested, and the constant pressure boiling point of ILs with water and ethanol mixtures was measured. Furthermore, the polar action parameters of ILs were determined by Reichardt's dye. The experimental results obtained have mutually confirmed each other. The investigation of the interaction between ILs and coagulants furnishes foundational data and theoretical support for the controlled formation of RCFs prepared using ILs as solvents.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114275"},"PeriodicalIF":2.8,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577988","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}
Pub Date : 2024-10-24DOI: 10.1016/j.fluid.2024.114270
Xurui Li , Jianxiang Tian
Based on our previous work [Fluid Phase Equilibria, 2023, 567, 113709], we here use the radial distribution function (RDF) to determine the state points (density and temperature) of a fluid under the Yukawa potential at equilibrium. The reduced density and reduced temperature are defined as and , respectively. Through the Molecular Dynamics (MD) simulations, we obtain equilibrium configurations and use these data for building models via two methods. The first method establishes two empirical correlations for each potential considered, one between the heights of the first peaks of the RDFs and state points, as well as the other between the displacements of the first peaks of the RDFs and state points. Through these empirical correlations, we can determine the state points of new Yukawa fluid systems with 100% accuracy. The second method utilizes artificial neural network models to predict state points from the heights and displacements of the first peaks of the RDFs, achieving 100% accuracy when the predicted results are rounded to one decimal place. The success of these methods again demonstrates the feasibility of determining state points solely based on equilibrium configurations, is an extension from the Lennard-Jones fluids to the Yukawa potential related fluids.
{"title":"Determining state points through the radial distribution function of Yukawa fluids at equilibrium","authors":"Xurui Li , Jianxiang Tian","doi":"10.1016/j.fluid.2024.114270","DOIUrl":"10.1016/j.fluid.2024.114270","url":null,"abstract":"<div><div>Based on our previous work [<strong><em>Fluid Phase Equilibria</em></strong>, 2023, <strong>567</strong>, 113709], we here use the radial distribution function (RDF) to determine the state points (density and temperature) of a fluid under the Yukawa potential at equilibrium. The reduced density and reduced temperature are defined as <span><math><mrow><msup><mrow><mi>ρ</mi></mrow><mo>*</mo></msup><mo>=</mo><mi>ρ</mi><msup><mrow><mi>σ</mi></mrow><mn>3</mn></msup></mrow></math></span> and <span><math><mrow><msup><mrow><mi>β</mi></mrow><mo>*</mo></msup><mo>=</mo><mn>1</mn><mo>/</mo><msup><mrow><mi>T</mi></mrow><mo>*</mo></msup><mo>=</mo><mi>ϵ</mi><mo>/</mo><msub><mi>k</mi><mi>B</mi></msub><mi>T</mi></mrow></math></span>, respectively. Through the Molecular Dynamics (MD) simulations, we obtain equilibrium configurations and use these data for building models via two methods. The first method establishes two empirical correlations for each potential considered, one between the heights of the first peaks of the RDFs and state points, as well as the other between the displacements of the first peaks of the RDFs and state points. Through these empirical correlations, we can determine the state points of new Yukawa fluid systems with 100% accuracy. The second method utilizes artificial neural network models to predict state points from the heights and displacements of the first peaks of the RDFs, achieving 100% accuracy when the predicted results are rounded to one decimal place. The success of these methods again demonstrates the feasibility of determining state points solely based on equilibrium configurations, is an extension from the Lennard-Jones fluids to the Yukawa potential related fluids.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114270"},"PeriodicalIF":2.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552758","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}
Pub Date : 2024-10-23DOI: 10.1016/j.fluid.2024.114259
Larissa F. Torres , Thales Barbalho , Iuri Segtovich , Cláudio Dariva , Frederico W. Tavares , Papa M. Ndiaye
The capability to accurately determine and predict the water content is essential to assess and plan potential flow assurance issues associated with water condensing from gas in pipelines and leading to hydrate formation. Various experimental techniques and devices have been evaluated/tested to determine water content and different equations of state are used to describe these data. Here, a critical review of experimental techniques and thermodynamic methods to determine water content is presented. Particular attention is paid to the experimental techniques using Chilled Mirror, Quartz Crystal Microbalance (QCM), and Tunable Diode Laser Spectroscopy (TDLAS). A literature review and an experimental data bank of water content in binary and ternary gas mixtures with methane and/or CO2 are also presented.
{"title":"A critical review of experimental methods, data, and predictions of water content","authors":"Larissa F. Torres , Thales Barbalho , Iuri Segtovich , Cláudio Dariva , Frederico W. Tavares , Papa M. Ndiaye","doi":"10.1016/j.fluid.2024.114259","DOIUrl":"10.1016/j.fluid.2024.114259","url":null,"abstract":"<div><div>The capability to accurately determine and predict the water content is essential to assess and plan potential flow assurance issues associated with water condensing from gas in pipelines and leading to hydrate formation. Various experimental techniques and devices have been evaluated/tested to determine water content and different equations of state are used to describe these data. Here, a critical review of experimental techniques and thermodynamic methods to determine water content is presented. Particular attention is paid to the experimental techniques using Chilled Mirror, Quartz Crystal Microbalance (QCM), and Tunable Diode Laser Spectroscopy (TDLAS). A literature review and an experimental data bank of water content in binary and ternary gas mixtures with methane and/or CO<sub>2</sub> are also presented.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114259"},"PeriodicalIF":2.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577987","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}
Pub Date : 2024-10-22DOI: 10.1016/j.fluid.2024.114262
Jibao Zhang , Yan Li , Yang Li , Mengqi Xiao , Yizhi Rao , Praveen Linga , Lijie Chen , Zhenyuan Yin
Hydrogen (H2) as the most abundant element offers a clean energy solution for a sustainable future. Thermodynamic hydrate promoters can enhance hydrate-based H2 storage under mild pressure conditions. 1,3-dioxolane (DIOX) as a low-toxicity promoter has attracted attention for its potential to improve H2 hydrate kinetics. However, the phase equilibria of H2-DIOX in the presence of DIOX and its thermodynamic promotion mechanism are not fully elaborated and warrant thorough investigation. In this study, the phase equilibria of H2-DIOX hydrates were measured for DIOX concentrations (CDIOX) ranging from 2.0 mol% to 5.56 mol%. The equilibrium temperature of H2-DIOX hydrates shifted rightward by 2.3 K at 15.0 MPa for 5.56 mol% DIOX compared to 2.0 mol% DIOX. The measured thermodynamic data were validated by fitting the H2-DIOX hydrate phase equilibira using the Clausius–Clapeyron equation. The cage occupancy of H2 and DIOX in H2-DIOX sII hydrates was revealed through Raman spectroscopy and DSC thermal analysis. Two types of hydrates (DIOX and H2-DIOX) were observed for all CDIOX. Single H2 molecules were enclathrated in the 512 cages of H2-DIOX hydrates and increasing CDIOX effectively enhanced DIOX molecules enclathration in the 51264 cages but had limited effect on the H2 molecules in the 512 cages. The findings of this study provide fundametnal thermodynamic data and cage occupancy charateristics for H2-DIOX sII hydrates below 15.0 MPa. The results provide guidance on the optimal thermodynamic promoter concentrations for future large-scale hydrate-based H2 storage application.
{"title":"Phase equilibria and guest gas occupancy characteristics of H2-DIOX sII hydrates based on calorimetric and Raman analysis","authors":"Jibao Zhang , Yan Li , Yang Li , Mengqi Xiao , Yizhi Rao , Praveen Linga , Lijie Chen , Zhenyuan Yin","doi":"10.1016/j.fluid.2024.114262","DOIUrl":"10.1016/j.fluid.2024.114262","url":null,"abstract":"<div><div>Hydrogen (H<sub>2</sub>) as the most abundant element offers a clean energy solution for a sustainable future. Thermodynamic hydrate promoters can enhance hydrate-based H<sub>2</sub> storage under mild pressure conditions. 1,3-dioxolane (DIOX) as a low-toxicity promoter has attracted attention for its potential to improve H<sub>2</sub> hydrate kinetics. However, the phase equilibria of H<sub>2</sub>-DIOX in the presence of DIOX and its thermodynamic promotion mechanism are not fully elaborated and warrant thorough investigation. In this study, the phase equilibria of H<sub>2</sub>-DIOX hydrates were measured for DIOX concentrations (<em>C<sub>DIOX</sub></em>) ranging from 2.0 mol% to 5.56 mol%. The equilibrium temperature of H<sub>2</sub>-DIOX hydrates shifted rightward by 2.3 K at 15.0 MPa for 5.56 mol% DIOX compared to 2.0 mol% DIOX. The measured thermodynamic data were validated by fitting the H<sub>2</sub>-DIOX hydrate phase equilibira using the Clausius–Clapeyron equation. The cage occupancy of H<sub>2</sub> and DIOX in H<sub>2</sub>-DIOX sII hydrates was revealed through Raman spectroscopy and DSC thermal analysis. Two types of hydrates (DIOX and H<sub>2</sub>-DIOX) were observed for all <em>C<sub>DIOX</sub></em>. Single H<sub>2</sub> molecules were enclathrated in the 5<sup>12</sup> cages of H<sub>2</sub>-DIOX hydrates and increasing <em>C<sub>DIOX</sub></em> effectively enhanced DIOX molecules enclathration in the 5<sup>1</sup><sup>2</sup>6<sup>4</sup> cages but had limited effect on the H<sub>2</sub> molecules in the 5<sup>12</sup> cages. The findings of this study provide fundametnal thermodynamic data and cage occupancy charateristics for H<sub>2</sub>-DIOX sII hydrates below 15.0 MPa. The results provide guidance on the optimal thermodynamic promoter concentrations for future large-scale hydrate-based H<sub>2</sub> storage application.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114262"},"PeriodicalIF":2.8,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552757","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}
This short paper investigates the applicability of our previously developed entropy scaling model to pure ionic liquids and concludes that it can be used without any modification and leads to very satisfactory results when coupled with the Peng-Robinson or Soave-Redlich-Kwong cubic equations of state. For the considered ionic liquids, the average deviations between calculated and experimental viscosities were found to be around 4.6 and 5.8% for the two cubic equations of state, respectively.
{"title":"Coupling cubic equations of state with the concept of entropy scaling to model the viscosity of ionic liquids","authors":"Aghilas Dehlouz , Romain Privat , Jean-Noël Jaubert","doi":"10.1016/j.fluid.2024.114261","DOIUrl":"10.1016/j.fluid.2024.114261","url":null,"abstract":"<div><div>This short paper investigates the applicability of our previously developed entropy scaling model to pure ionic liquids and concludes that it can be used without any modification and leads to very satisfactory results when coupled with the Peng-Robinson or Soave-Redlich-Kwong cubic equations of state. For the considered ionic liquids, the average deviations between calculated and experimental viscosities were found to be around 4.6 and 5.8% for the two cubic equations of state, respectively.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114261"},"PeriodicalIF":2.8,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528760","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}
Pub Date : 2024-10-20DOI: 10.1016/j.fluid.2024.114260
Rajamani Krishna, Jasper M. van Baten
Microporous crystalline adsorbents such as zeolites, and metal-organic frameworks (MOFs) have potential use in a wide variety of separations applications. In applications such as CO2 capture, the Ideal Adsorbed Solution Theory (IAST) often fails to provide a quantitative description of mixture adsorption equilibrium especially in cation-exchanged zeolites. The failure of the IAST is ascribable to non-compliance with one or more tenets mandated by the IAST such as (a) homogeneous distribution of adsorbates within the pore landscape, (b) no preferential location of guest species, and (c) absence of molecular clustering due to say hydrogen bonding. The focus of this article is on the reliability of the Real Adsorbed Solution Theory (RAST) models for quantitative estimation of adsorption equilibrium. Configurational-Bias Monte Carlo (CBMC) simulations are undertaken to determine the adsorption equilibrium for ternary CO2/CH4/N2, CO2/CH4/C3H8, CO2/CH4/H2, and water/methanol/ethanol mixtures in NaX, LTA-4A, CHA, DDR, and MFI zeolites. Additionally, CBMC simulations of the constituent binary pairs are used to determine the Wilson or NRTL parameters, taking due account of the dependence of the activity coefficients on the spreading pressure. Use of the binary pair Wilson or NRTL parameters allows the estimation of ternary mixture adsorption equilibrium, that is tested against the CBMC data on component loadings. In all investigated guest/host combinations, the RAST provides a good estimation of ternary mixture adsorption equilibrium.
{"title":"How reliable is the Real Adsorbed Solution Theory (RAST) for estimating ternary mixture equilibrium in microporous host materials?","authors":"Rajamani Krishna, Jasper M. van Baten","doi":"10.1016/j.fluid.2024.114260","DOIUrl":"10.1016/j.fluid.2024.114260","url":null,"abstract":"<div><div>Microporous crystalline adsorbents such as zeolites, and metal-organic frameworks (MOFs) have potential use in a wide variety of separations applications. In applications such as CO<sub>2</sub> capture, the Ideal Adsorbed Solution Theory (IAST) often fails to provide a quantitative description of mixture adsorption equilibrium especially in cation-exchanged zeolites. The failure of the IAST is ascribable to non-compliance with one or more tenets mandated by the IAST such as (a) homogeneous distribution of adsorbates within the pore landscape, (b) no preferential location of guest species, and (c) absence of molecular clustering due to say hydrogen bonding. The focus of this article is on the reliability of the Real Adsorbed Solution Theory (RAST) models for quantitative estimation of adsorption equilibrium. Configurational-Bias Monte Carlo (CBMC) simulations are undertaken to determine the adsorption equilibrium for ternary CO<sub>2</sub>/CH<sub>4</sub>/N<sub>2</sub>, CO<sub>2</sub>/CH<sub>4</sub>/C<sub>3</sub>H<sub>8</sub>, CO<sub>2</sub>/CH<sub>4</sub>/H<sub>2</sub>, and water/methanol/ethanol mixtures in NaX, LTA-4A, CHA, DDR, and MFI zeolites. Additionally, CBMC simulations of the constituent binary pairs are used to determine the Wilson or NRTL parameters, taking due account of the dependence of the activity coefficients on the spreading pressure. Use of the binary pair Wilson or NRTL parameters allows the estimation of ternary mixture adsorption equilibrium, that is tested against the CBMC data on component loadings. In all investigated guest/host combinations, the RAST provides a good estimation of ternary mixture adsorption equilibrium.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114260"},"PeriodicalIF":2.8,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528147","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}
Pub Date : 2024-10-18DOI: 10.1016/j.fluid.2024.114258
Gonçalo M.C. Silva, José Santos Pereira, Milton Ponte, Tiago M. Eusébio, Diogo Machacaz, Pedro Morgado, Eduardo J.M. Filipe
New thermodynamic data are reported for aqueous solutions of highly fluorinated alcohols of different chain lengths. The liquid-liquid equilibrium (LLE) T-x diagram of the binary mixture (1H,1H-perfluoropropanol + water) was determined, as well as the LLE phase diagram of the ternary mixture (1H,1H-perfluoropropanol + 1-propanol + water) at 298.15 K and atmospheric pressure. The mutual solubilities of water with several linear perfluorinated alcohols (CF3(CF2)nCH2OH, n = 1–5) and the tertiary alcohol perfluoro-t-butanol ((CF3)3COH) were also measured at 298.15 K. Finally, volumetric properties such as the excess molar volumes and partial molal volumes at infinite dilution of the different fluorinated alcohols in water were also determined and discussed comparing with equivalent data from the literature for the corresponding hydrogenated alcohols.
报告了不同链长的高氟化醇水溶液的新热力学数据。确定了二元混合物（1H,1H-全氟丙醇 + 水）的液液平衡（LLE）T-x 图，以及三元混合物（1H,1H-全氟丙醇 + 1-丙醇 + 水）在 298.15 K 和大气压力下的液液平衡相图。最后，还测定了水与几种线性全氟醇（CF3(CF2)nCH2OH，n = 1-5）和全氟叔丁醇（(CF3)3COH）在 298.15 K 下的互溶性。
{"title":"Phase equilibria and volumetric properties of mixtures of highly fluorinated alcohols and water","authors":"Gonçalo M.C. Silva, José Santos Pereira, Milton Ponte, Tiago M. Eusébio, Diogo Machacaz, Pedro Morgado, Eduardo J.M. Filipe","doi":"10.1016/j.fluid.2024.114258","DOIUrl":"10.1016/j.fluid.2024.114258","url":null,"abstract":"<div><div>New thermodynamic data are reported for aqueous solutions of highly fluorinated alcohols of different chain lengths. The liquid-liquid equilibrium (LLE) <em>T-x</em> diagram of the binary mixture (1H,1H-perfluoropropanol + water) was determined, as well as the LLE phase diagram of the ternary mixture (1H,1H-perfluoropropanol + 1-propanol + water) at 298.15 K and atmospheric pressure. The mutual solubilities of water with several linear perfluorinated alcohols (CF<sub>3</sub>(CF<sub>2</sub>)<sub>n</sub>CH<sub>2</sub>OH, <em>n</em> = 1–5) and the tertiary alcohol perfluoro-<em>t</em>-butanol ((CF<sub>3</sub>)<sub>3</sub>COH) were also measured at 298.15 K. Finally, volumetric properties such as the excess molar volumes and partial molal volumes at infinite dilution of the different fluorinated alcohols in water were also determined and discussed comparing with equivalent data from the literature for the corresponding hydrogenated alcohols.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114258"},"PeriodicalIF":2.8,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142537056","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}
Ionic liquids possess novel properties and can efficiently absorb harmful gases, potentially serving as a new type of absorbent. In this study, the binary system of ionic liquid N-octylpyridinium tetrafluoroborate [OPy][BF4] and sulfur dioxide (SO2) has been selected as the research object, and the structure and properties of the system have been studied by molecular dynamics simulation. The interaction between SO2 and ionic liquids is explored by using the radial distribution functions (RDFs), coordination numbers (CNs) and spatial distribution functions (SDFs). The results of microstructures show that due to the strong interaction with anions, SO2 is mostly orderly distributed around the anions of ionic liquids. However, the coordination ability of the polar region of the ionic liquid and SO2 is nearly equivalent to that of the non-polar region. At the same time, it is found that the addition of SO2 enhanced the order degree of the polar and the non-polar regions of ionic liquids, especially on non-polar regions. Through the discussion of the interaction between [OPy][BF4] and SO2, it can be concluded that the mechanism of SO2 absorption by [OPy][BF4] is the combined effect of anions and cations. This study aims to provide new insights for the potential applications of ionic liquids in industrial fields such as petroleum and flue gas desulfurization.
{"title":"Molecular dynamics simulation of the interaction between ionic liquid [OPy][BF4] and SO2","authors":"Guanglai Zhu , Siwen Zhou , Zhaopeng Ma , Jianqiang Xu","doi":"10.1016/j.fluid.2024.114257","DOIUrl":"10.1016/j.fluid.2024.114257","url":null,"abstract":"<div><div>Ionic liquids possess novel properties and can efficiently absorb harmful gases, potentially serving as a new type of absorbent. In this study, the binary system of ionic liquid N-octylpyridinium tetrafluoroborate [OPy][BF<sub>4</sub>] and sulfur dioxide (SO<sub>2</sub>) has been selected as the research object, and the structure and properties of the system have been studied by molecular dynamics simulation. The interaction between SO<sub>2</sub> and ionic liquids is explored by using the radial distribution functions (RDFs), coordination numbers (CNs) and spatial distribution functions (SDFs). The results of microstructures show that due to the strong interaction with anions, SO<sub>2</sub> is mostly orderly distributed around the anions of ionic liquids. However, the coordination ability of the polar region of the ionic liquid and SO<sub>2</sub> is nearly equivalent to that of the non-polar region. At the same time, it is found that the addition of SO<sub>2</sub> enhanced the order degree of the polar and the non-polar regions of ionic liquids, especially on non-polar regions. Through the discussion of the interaction between [OPy][BF<sub>4</sub>] and SO<sub>2</sub>, it can be concluded that the mechanism of SO<sub>2</sub> absorption by [OPy][BF<sub>4</sub>] is the combined effect of anions and cations. This study aims to provide new insights for the potential applications of ionic liquids in industrial fields such as petroleum and flue gas desulfurization.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114257"},"PeriodicalIF":2.8,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528149","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}
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