Fluid Phase Equilibria最新文献_第2页

Thermodynamic modelling of dissociating Al2Br6 and Al2Cl6 used as reactive working fluids in thermodynamic cycles 解离Al2Br6和Al2Cl6在热力学循环中作为反应性工质的热力学建模

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-01-08 DOI: 10.1016/j.fluid.2026.114661

Julien Joliat , Konstantin Samukov , Rachid Hadjadj , Thijs J.H. Vlugt , Olivier Herbinet , Silvia Lasala

To enhance the efficiency of thermodynamic cycles in heat pumps and power plants, we explore a novel approach: replacing conventional inert pure fluids or mixtures with reactive fluids that undergo reversible chemical reactions. A key step towards the implementation of this concept is the development of a fully predictive framework for determining the thermodynamic properties of such reactive working fluids. In this context, the present work extends a semi-empirical methodology previously proposed by the authors, aiming to address the challenge introduced by newly developed reactive fluids for which experimental data are unavailable. The methodology presented in this work requires only the critical-point properties and acentric factor of the molecules participating in the chemical reaction. As in the earlier approach from the authors, it combines ab-initio quantum mechanics calculations to determine the ideal gas properties of each molecule, the a-thermal version of the “Peng-Robinson + EoS/

a_{r e s}^{E, γ}

mixing rules” equation of state and molecular Monte Carlo simulations to assess real fluid properties and enable cross-validation between methods. This work, however, applies a simplification to the force fields used in Monte Carlo simulations consisting in employing single-particle force fields instead of all-atom models. This strategy decreases the amount of experimental data required to parametrise the force field of each molecule contained in the reactive mixture, and allows the use of the same inputs in equation of state modelling and Monte Carlo simulations (i.e., molecular critical parameters). Indeed, this work proposes to calculate force field parameters using either the critical temperature and pressure, or the critical temperature and density of each molecule. The methodology is applied to two reactive systems, Al₂Br₆ ⇌ 2AlBr₃ and Al₂Cl₆ ⇌ 2AlCl₃. The results show that Monte Carlo predictions, although less accurate than those from the equation of state, remain acceptably close to experimental data, while the equation of state results demonstrate significantly higher accuracy.

为了提高热泵和发电厂的热力学循环效率，我们探索了一种新的方法：用经过可逆化学反应的反应性流体取代传统的惰性纯流体或混合物。实现这一概念的关键一步是开发一个完整的预测框架，以确定这种反应性工作流体的热力学性质。在此背景下，本工作扩展了作者先前提出的半经验方法，旨在解决新开发的反应性流体带来的挑战，这些流体无法获得实验数据。在这项工作中提出的方法只需要参与化学反应的分子的临界点性质和偏心因子。与作者先前的方法一样，该方法结合了从头算量子力学计算来确定每个分子的理想气体性质，结合了“Peng-Robinson + EoS/aresE，γ混合规则”状态方程的非热版本和分子蒙特卡罗模拟来评估真实流体性质，并实现方法之间的交叉验证。然而，这项工作对蒙特卡罗模拟中使用的力场进行了简化，包括使用单粒子力场而不是全原子模型。这种策略减少了将反应混合物中每个分子的力场参数化所需的实验数据量，并允许在状态方程建模和蒙特卡罗模拟中使用相同的输入（即分子临界参数）。事实上，这项工作建议使用临界温度和压力或每个分子的临界温度和密度来计算力场参数。该方法应用于Al2Br6 + 2AlBr3和Al2Cl6 + 2AlCl3两种反应体系。结果表明，蒙特卡罗预测虽然不如状态方程预测准确，但仍然可以接受地接近实验数据，而状态方程结果显示出更高的精度。

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引用次数: 0

Surface tension and viscosity of carbon dioxide near the critical point using molecular dynamics simulations and surface light scattering 用分子动力学模拟和表面光散射研究二氧化碳在临界点附近的表面张力和粘度

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-01-08 DOI: 10.1016/j.fluid.2026.114660

Neda Sanchouli , Chathura J. Kankanamge, Andreas P. Fröba, Thomas M. Koller

The present study investigates the surface tension and viscosity of carbon dioxide (CO₂) in the vicinity of the critical point using molecular dynamics (MD) simulations and surface light scattering (SLS). The latter technique was applied to simultaneously obtain the sum of the dynamic shear viscosities of the liquid phase, η_L, and vapor phase, η_V, as well as the surface tension σ at macroscopic thermodynamic equilibrium at temperatures T from (283.15 to 303.65) K, corresponding to reduced temperatures T_R from 0.931 to 0.998. The measurement results for (η_L + η_V) and σ with average expanded (k = 2) uncertainties of (2.4 and 2.6) % agree very well with the few data available in the literature. The T-dependent behavior of the SLS results for σ can be described by a van der Waals-type surface tension equation in accordance with scaling theory. The experimental results for σ of CO₂ served to evaluate the performance of equilibrium molecular dynamics (EMD) simulations in predicting its surface tension together with the phase behavior at T between (288.15 and 298.15) K. For this purpose, seven different force fields (FFs) employed from literature were applied, which provide all-atom or united-atom representations and involve rigid or flexible intramolecular potentials. It was found that a reliable representation of the vapor and liquid densities, vapor pressure, and σ near the critical point can only be realized using rigid FFs, all of which were not optimized against surface tension data.

本文利用分子动力学（MD）模拟和表面光散射（SLS）技术研究了临界点附近二氧化碳（CO2）的表面张力和粘度。采用后一种技术同时得到了液相动态剪切粘度ηL和气相动态剪切粘度ηV之和，以及宏观热力学平衡时的表面张力σ，温度T为（283.15 ~ 303.65）K，对应的还原温度TR为0.931 ~ 0.998。（ηL + ηV）和σ的平均扩展（k = 2）不确定度分别为（2.4和2.6）%，其测量结果与文献中为数不多的数据吻合得很好。σ对SLS结果的t依赖性可以用范德瓦尔斯型表面张力方程根据标度理论描述。CO2的σ的实验结果用于评估平衡分子动力学（EMD）模拟在预测其表面张力以及T (288.15 ~ 298.15) k之间的相行为方面的性能。为此，我们采用了来自文献的7种不同的力场（FFs），这些力场提供了全原子或联合原子的表示，并涉及刚性或柔性分子内势。研究发现，只有使用刚性FFs才能可靠地表示临界附近的汽液密度、蒸汽压和σ，而所有这些都没有针对表面张力数据进行优化。

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引用次数: 0

Separation of ethyl alcohol/water azeotropic mixture using triethylene glycol and triethylene glycol-based deep eutectic solvent: Vapor-liquid equilibria and molecular interactions 用三甘醇和三甘醇基深度共晶溶剂分离乙醇/水共沸混合物：汽液平衡和分子相互作用

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-01-07 DOI: 10.1016/j.fluid.2026.114659

Serli Dwi Rahayu , Onjira Sopakayang , Hong-Ming Ku , Ardila Hayu Tiwikrama

Ethyl alcohol and water form an azeotropic mixture that is widely used in industry. The present study reports a series of entrainers for triethylene glycol (TEG) and TEG-based deep eutectic solvents (DESs) for separation of ethyl alcohol and water. The choline chloride (ChCl):TEG with a molar ratio of 1:3 was selected as the DES-based system and was assumed as pseudo-pure component system. These two entrainers, TEG and ChCl:TEG (1:3), were investigated to separate the ethyl alcohol and water with the entrainer concentration was up to 30 wt%. The vapor-liquid equilibrium (VLE) data were measured using a modified Othmer-recirculation still ebuilliometer at 101.3 kPa. The VLE data were also validated using the L-W Wisniak and Van Ness consistency test. With an additional of entrainer, the ethyl alcohol + water azeotropic point was shifted for TEG (15 wt% and 30 wt%) and ChCl:TEG 1:3 (15 wt%). While the break point of azeotrope of ethyl alcohol + water was observed for ChCl:TEG 1:3 (30 wt%). Two thermodynamic models, the non-random two liquids (NRTL) and universal quasi-chemical (UNIQUAC) were well-correlated with VLE data. In addition, the sigma profile (σ) and the reduced density gradient (RDG) analysis were also performed the molecular interaction of ethyl alcohol, water, and entrainer with strong hydrogen bonding.

乙醇和水形成一种共沸混合物，广泛用于工业。本研究报道了一系列用于分离乙醇和水的三甘醇（TEG）和TEG基深共晶溶剂（DESs）的夹带剂。选择氯化胆碱：TEG摩尔比为1:3的体系作为des基体系，并假设其为伪纯组分体系。研究了两种夹带剂TEG和ChCl:TEG（1:3）对乙醇和水的分离效果，夹带剂浓度可达30%。汽液平衡（VLE）数据使用改进的other -再循环仍气量计在101.3 kPa下测量。VLE数据也使用L-W Wisniak和Van Ness一致性检验进行验证。添加夹带剂后，TEG （15 wt%和30 wt%）和ChCl:TEG 1:3 （15 wt%）的乙醇+水共沸点发生改变。当ChCl:TEG 1:3 （30% wt%）时，观察到乙醇+水共沸物的断点。非随机双液（NRTL）和通用准化学（UNIQUAC）两种热力学模型与VLE数据具有良好的相关性。此外，还对具有强氢键作用的乙醇、水和夹带剂的分子相互作用进行了sigma剖面（σ）和还原密度梯度（RDG）分析。

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引用次数: 0

Density measurements of homogeneous-phase fluid mixtures comprising CO2/limonene and CO2/linalool binary systems and correlation with the PC-SAFT equation of state 二氧化碳/柠檬烯和二氧化碳/芳樟醇二元体系均相流体混合物的密度测量及其与PC-SAFT状态方程的相关性

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-30 DOI: 10.1016/j.fluid.2025.114658

Hiroaki Matsukawa , Ken Kuwabara , Tomoya Tsuji , Katsuto Otake

Chemical process design relies on accurate knowledge of physical properties; however, it is unknown for a process to have both a single dominant property and broad range of well-documented properties. Supercritical extraction is one such case: while solubility data for essential-oil components in CO₂ are available, information on other physical properties remains limited. This study investigates the previously unreported density of homogeneous-phase fluid mixtures as an additional key property, using limonene and linalool as representative essential-oil components. Densities of the CO₂/limonene and CO₂/linalool binary systems are measured with a high-pressure oscillating density apparatus equipped with a circulating pump and variable-volume observation cell. The obtained data is correlated using the perturbed chain-statistical associating fluid theory equation of state, which requires pure-component parameters for each component. Pure-component parameters are often reported in sets obtained through different methods, and limonene and linalool likewise have multiple sets reported. In conventional physical property estimation, a single set is often selected ad hoc with little acknowledgment of the existence of alternative sets. This study examines the impact of pure-component parameter selection on density estimation by performing density correlation on mixtures using each available set of pure-component parameters. The accuracy of the mixture density correlation depends on the precision of the pure-component density estimation, although mixture-related parameters can partially compensate for such deviations. These findings demonstrate the importance of accurate pure-component parameters and complementary role of mixture parameters in improving the reliability of thermodynamic modeling for supercritical CO₂ systems.

化学工艺设计依赖于对物理性质的准确了解；然而，对于一个过程既具有单一的主导性质又具有广泛的记录良好的性质，这是未知的。超临界萃取就是这样一个例子：虽然精油成分在二氧化碳中的溶解度数据是可用的，但关于其他物理性质的信息仍然有限。本研究以柠檬烯和芳樟醇为代表的精油成分，研究了以前未报道的均相流体混合物的密度作为另一个关键特性。采用配有循环泵和变体积观测池的高压振荡密度仪测量CO2/柠檬烯和CO2/芳樟醇二元体系的密度。得到的数据用摄动链-统计关联流体理论状态方程进行关联，该方程要求每个组分的参数为纯组分。纯组分参数通常以不同方法获得的集合为单位报告，柠檬烯和芳樟醇同样有多个集合报告。在传统的物理性质估计中，一个单一的集合往往是临时选择的，很少承认替代集合的存在。本研究通过使用每组可用的纯成分参数对混合物进行密度相关，检验了纯成分参数选择对密度估计的影响。混合密度相关性的准确性取决于纯组分密度估计的精度，尽管混合相关参数可以部分补偿这种偏差。这些发现证明了准确的纯组分参数和混合参数在提高超临界CO2系统热力学建模可靠性方面的重要作用。

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引用次数: 0

Corrigendum to “A Review of Experimental Solubilities and a General Correlation between the Temperature-Dependent Solubility and Solute and Solvent Molar Masses for Binary n-Alkane Mixtures” [Fluid Phase Equilibria (2022) 113380] “对二元正构烷烃混合物的实验溶解度的回顾和温度依赖性溶质和溶剂摩尔质量之间的一般相关性”的更正[流体相平衡（2022）113380]

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-30 DOI: 10.1016/j.fluid.2025.114655

Sverre Gullikstad Johnsen

引用次数: 0

Liquid-liquid equilibrium of water + 2,3-butanediol + n-alcohols (1-heptanol, 1-octanol, 1-nonanol, 1-decanol) and water + acetoin + n-alcohols ternary systems at 298.2 K 298.2 K时水+ 2,3-丁二醇+正醇（1-庚醇、1-辛醇、1-壬醇、1-癸醇）和水+乙醇+正醇三元体系的液液平衡

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-24 DOI: 10.1016/j.fluid.2025.114657

Peter Förster , William Graf von Westarp , Janik Hense , Johannes von Campenhausen , Andreas Jupke

Liquid-liquid equilibrium (LLE) data were experimentally determined for ternary systems containing 2,3-butanediol (2,3-bdo) or acetoin as solutes, water and 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol as solvents, at 298.2 K and atmospheric pressure. Distribution coefficients increased with decreasing carbon-chain length of the solvents, ranging from 0.2610 (1-decanol) to 0.3827 (1-heptanol) for 2,3-bdo and from 0.2817 (1-decanol) to 0.4252 (1-heptanol) for acetoin. Acetoin exhibited higher maximum distribution coefficients (0.4252 in 1-heptanol) and selectivities (7.9429 in 1-decanol) compared to 2,3-bdo (0.3827 in 1-heptanol and 4.5745 in 1-heptanol, respectively). Trends are consistent with solute functionality and solvent polarity. Experimental LLE data were correlated using the NRTL activity coefficient model, and the binary interaction parameters were successfully regressed. A topological analysis confirmed the consistency of the model correlations at 298.2 K.

在298.2 K和常压下，以2,3-丁二醇（2,3-丁二醇）或乙托因为溶质，水和1-庚醇、1-辛醇、1-壬醇和1-癸醇为溶剂的三元体系的液-液平衡（LLE）数据进行了实验测定。分布系数随溶剂碳链长度的减小而增大，2,3-bdo的分布系数为0.2610（1-癸醇）~ 0.3827（1-庚醇），乙托因的分布系数为0.2817（1-癸醇）~ 0.4252（1-庚醇）。Acetoin的最大分布系数为0.4252（1-庚醇），选择性为7.9429（1-癸醇），2,3-bdo的最大分布系数为0.3827（1-庚醇），选择性为4.5745（1-庚醇）。趋势与溶质官能团和溶剂极性一致。利用NRTL活度系数模型对实验LLE数据进行关联，并成功地回归了二元相互作用参数。拓扑分析证实了298.2 K下模型相关性的一致性。

{"title":"Liquid-liquid equilibrium of water + 2,3-butanediol + n-alcohols (1-heptanol, 1-octanol, 1-nonanol, 1-decanol) and water + acetoin + n-alcohols ternary systems at 298.2 K","authors":"Peter Förster , William Graf von Westarp , Janik Hense , Johannes von Campenhausen , Andreas Jupke","doi":"10.1016/j.fluid.2025.114657","DOIUrl":"10.1016/j.fluid.2025.114657","url":null,"abstract":"<div><div>Liquid-liquid equilibrium (LLE) data were experimentally determined for ternary systems containing 2,3-butanediol (2,3-bdo) or acetoin as solutes, water and 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol as solvents, at 298.2 K and atmospheric pressure. Distribution coefficients increased with decreasing carbon-chain length of the solvents, ranging from 0.2610 (1-decanol) to 0.3827 (1-heptanol) for 2,3-bdo and from 0.2817 (1-decanol) to 0.4252 (1-heptanol) for acetoin. Acetoin exhibited higher maximum distribution coefficients (0.4252 in 1-heptanol) and selectivities (7.9429 in 1-decanol) compared to 2,3-bdo (0.3827 in 1-heptanol and 4.5745 in 1-heptanol, respectively). Trends are consistent with solute functionality and solvent polarity. Experimental LLE data were correlated using the NRTL activity coefficient model, and the binary interaction parameters were successfully regressed. A topological analysis confirmed the consistency of the model correlations at 298.2 K.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"604 ","pages":"Article 114657"},"PeriodicalIF":2.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881392","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}

引用次数: 0

A molecular simulation study on solubility of elemental sulfur in hydrogen sulfide confined in calcite nanopores 单质硫在方解石纳米孔硫化氢中溶解度的分子模拟研究

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-23 DOI: 10.1016/j.fluid.2025.114656

Yuan Wei , Xuan Li , Shuangli Yue , Xue Wu , Xiangyu Huo

Knowledge of the solubility evolution of elemental sulfur in natural gas is the theoretical basis for preventing sulfur deposition in high-sulfur carbonate gas reservoir developments. In addition to temperature, pressure and composition, confinement nanopore throats also affects the sulfur solubility. All-atom equilibrium molecular dynamic simulations are conducted to study the solubility of elemental sulfur in H₂S confined in calcite slit nanopores under reservoir conditions. The sulfur solubility in the calcite pore reduces with slit aperture, and it is dramatically larger than that in the unconfined bulk system. The molecular mechanism of the over-solubility of sulfur is identified as the adsorption-driven effect of solute molecules, which is revealed through analysis on the interaction between the solute/solvent and calcite surface, the particle structure distribution, as well as the evolution of the size and number of sulfur clusters in the simulations. The relevant conclusions indicate that confinement effect is in favor of the dissolution of elemental sulfur in H₂S. Our study is critical to construct the theoretical basis for sulfur dissolution or deposition in the development of high-sulfur carbonate gas reservoirs.

了解天然气中单质硫的溶解度演化是防止高硫碳酸盐岩气藏硫沉积的理论基础。除了温度、压力和组成外，限制纳米孔喉也影响硫的溶解度。采用全原子平衡分子动力学模拟研究了储层条件下方解石狭缝纳米孔中单质硫在H2S中的溶解度。硫在方解石孔隙中的溶解度随裂隙的增大而减小，且明显大于无约束体体系中的溶解度。通过分析模拟过程中溶质/溶剂与方解石表面的相互作用、颗粒结构分布以及硫簇大小和数量的演变，将硫的超溶解度的分子机制确定为溶质分子的吸附驱动效应。相关结论表明，约束效应有利于单质硫在H2S中的溶解。本研究对高含硫碳酸盐岩气藏开发中硫的溶解或沉积理论基础的构建具有重要意义。

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引用次数: 0

Weak salting-out of H2 gas from aqueous NaCl solutions confined in kaolinite nanopores 高岭石纳米孔中NaCl水溶液中H2气体的弱盐析

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-15 DOI: 10.1016/j.fluid.2025.114654

Khang Quang Bui, Gabriel D. Barbosa, Dimitrios V. Papavassiliou, Alberto Striolo

Towards implementing modern geo-energy applications such as geological hydrogen storage, it is imperative to quantify the behavior of aqueous electrolyte systems confined in narrow pores exposed to high pressure and temperature conditions. This study systematically compares the properties of aqueous NaCl solutions in kaolinite nanopores as predicted when three widely used NaCl forcefields are implemented, namely the Smith-Dang (SD), the Joung-Cheatham (JC), and the Horinek et al. (HR). Nanoconfinement is found to dictate fluid distribution and mobility within the pores. Significant differences due to the implemented forcefields emerge in ion pairing, local water structure, and hydrogen bond network. Vibrational spectra show pronounced forcefield sensitivity as well, both in bulk and in confinement; confinement amplifies these differences substantially. Consistent with experiments, all models predict salting-out effects in the bulk; the effects predicted in confinement are weaker, suggesting that increasing salt content may not be as effective at reducing H₂ solubility in confined water as it is in bulk systems. These results should be considered when geo-energy operations are being designed, for example geological hydrogen storage.

为了实现地质储氢等现代地能应用，必须量化高压和高温条件下狭窄孔隙中的水电解质体系的行为。在Smith-Dang （SD）、jung - cheatham （JC）和Horinek et al. （HR）三种常用的NaCl力场作用下，本研究系统地比较了高岭石纳米孔中NaCl水溶液的性质。发现纳米约束决定了孔隙内的流体分布和流动性。在离子对、局部水结构和氢键网络中，由于实施力场的不同而产生了显著的差异。振动谱也显示出明显的力场敏感性，无论是在块状还是在约束中；禁闭大大放大了这些差异。与实验结果一致，所有的模型都预测了整体的盐析效应；约束条件下预测的效应较弱，这表明增加盐含量在降低H2在约束水中的溶解度方面可能不如在散装体系中有效。在设计地能操作时，例如地质储氢，应该考虑这些结果。

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引用次数: 0

Phase behavior of CO2/Organic Solvent/Poly(ethylene glycol) ternary systems CO2/有机溶剂/聚乙二醇三元体系的相行为

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-13 DOI: 10.1016/j.fluid.2025.114652

Hiroaki Matsukawa , Ryota Suzuki , Katsuto Otake

Phase diagrams of CO₂/cosolvent/polymer systems are critical for polymer processing applications, yet most studies have focused on pressure–temperature diagrams, leaving pressure–composition (Px) diagrams less understood. In particular, the influence of cosolvent species on ternary Px phase behavior and its molecular-level origin has not been systematically investigated. This study examined the phase behavior of CO₂/ethanol (EtOH) or dimethyl sulfoxide (DMSO)/poly(ethylene glycol) (PEG) ternary systems to evaluate the effect of cosolvent species on the phase diagram. Measurements were performed using a synthetic method combined with laser displacement and turbidity detection. Bubble points (vapor–liquid (VL) phase separation) were determined from piston displacement changes, and cloud points (liquid–liquid (LL) phase separation) were identified from turbidity variations. Phase boundaries were obtained for CO₂ mass fractions of 0.148–0.680 while varying the cosolvent/PEG mass ratio. The polymer did not participate in VL phase separation, reflecting the affinity between CO₂ and the cosolvent. By contrast, LL phase separation required consideration of the mutual affinities among all three components. To support this interpretation, the free volume fraction difference (Δf) estimated from the Sanchez–Lacombe equation and the dipole and quadrupole moments obtained from quantum chemical calculations were analyzed. The Δf values explained the cosolvent-dependent shifts in the LL line, whereas the μ and Q values clarified the order of mutual solubility (EtOH > DMSO > Tol) in agreement with experimental observations. These findings provide a more comprehensive understanding of the CO₂/cosolvent/polymer phase behavior and facilitate the prediction of phase diagrams.

CO2/助溶剂/聚合物体系的相图对于聚合物加工应用至关重要，然而大多数研究都集中在压力-温度图上，而对压力-组成（Px）图的了解较少。特别是，共溶剂种类对三元Px相行为及其分子水平起源的影响尚未得到系统的研究。本研究考察了CO2/乙醇（EtOH）或二甲亚砜(DMSO)/聚乙二醇（PEG）三元体系的相行为，以评价共溶剂种类对相图的影响。测量采用激光位移和浊度检测相结合的综合方法进行。从活塞位移变化确定气泡点（气液相分离），从浊度变化确定云点（液液相分离）。在CO2质量分数0.148 ~ 0.680范围内，随着共溶剂/PEG质量比的变化，得到了相界。聚合物没有参与VL相分离，反映了CO2与共溶剂之间的亲和力。相比之下，LL相分离需要考虑所有三个组分之间的相互亲和力。为了支持这一解释，从Sanchez-Lacombe方程估计的自由体积分数差（Δf）和从量子化学计算得到的偶极矩和四极矩进行了分析。Δf值解释了LL线上的助溶剂依赖位移，而μ和Q值澄清了相互溶解度（EtOH > DMSO > Tol）的顺序，与实验观察结果一致。这些发现为CO2/共溶剂/聚合物的相行为提供了更全面的理解，并有助于相图的预测。

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引用次数: 0

New initialization procedures from phase stability testing in three-phase flash calculations for CO2-hydrocarbon mixtures co2 -烃混合物三相闪蒸计算中相稳定性测试的新初始化程序

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-12-13 DOI: 10.1016/j.fluid.2025.114653

Juan Heringer , Michiel Wapperom , Catinca Secuianu , Denis Voskov , Dan Vladimir Nichita

Phase equilibrium calculations play an important role in a wide variety of applications in chemical and petroleum engineering. In this work, we focus on CO₂-hydrocarbon mixtures, with applications ranging from enhanced oil recovery processes to CO₂ storage. In compositional reservoir simulation, both robustness and efficiency are of utmost importance. The conventional approach for multiphase equilibrium consists of a sequence of phase stability and flash calculations. At each level of the stepwise process, stability testing is performed starting from several initial guesses; therefore, reducing the number of stability calls and using judiciously the information from stability to initialize a phase split are key points in developing an efficient stability-flash algorithm. Two new initialization strategies for multiphase flash calculations are proposed. The first one (improved stepwise initialization) follows the conventional procedure, but uses additional initial guesses. In the second one (improved multiple initialization), a three-phase split is initiated if at least three minima of the tangent plane distance (TPD) function are detected by stability analysis of feed composition. Both proposed methods are using all information from phase stability testing at each stage. Unlike in previous formulations, compositions at all minima of the TPD function, including trivial and positive TPDs are used to generate initial equilibrium constants. Highly robust routines are used, based on successive substitution iterations (SSI) in early iteration stages, followed by Newton iterations with modified Cholesky factorization and line search, in both stability and flash calculations. The proposed methods are tested and compared with the conventional procedure for several benchmark mixtures from the literature, containing hydrocarbon components and CO₂. Phase diagrams are constructed in the P-Z plane, focusing on the number of stationary points of the TPD functions found in each step of the multiphase stability-flash algorithm and on how they must be efficiently used in initialization. For all the test mixtures, in the proposed stability-flash strategy, the number of calls of the stability and flash routines and the number of iterations in flash calculations are significantly reduced as compared to previous approaches, recommending the new approach as a useful tool in compositional simulation.

相平衡计算在化学和石油工程中有着广泛的应用。在这项工作中，我们专注于二氧化碳-碳氢化合物混合物，其应用范围从提高石油采收率到二氧化碳储存。在组成油藏模拟中，鲁棒性和效率是至关重要的。多相平衡的传统方法包括一系列相稳定性和闪速计算。在逐步过程的每个层次上，稳定性测试是从几个初始猜测开始进行的；因此，减少稳定性调用的次数和合理地利用来自稳定性的信息来初始化相位分裂是开发高效稳定闪存算法的关键。提出了两种新的多相闪光计算初始化策略。第一个（改进的逐步初始化）遵循常规过程，但使用了额外的初始猜测。在第二种（改进的多重初始化）中，如果通过进料组成的稳定性分析检测到至少三个切平面距离（TPD）函数的最小值，则启动三相分裂。这两种方法都使用了每个阶段相位稳定性测试的所有信息。与以前的公式不同，TPD函数的所有最小值的组合，包括平凡的和正的TPD，被用来生成初始平衡常数。在早期迭代阶段，采用基于连续替换迭代（SSI）的高度鲁棒例程，然后在稳定性和快速计算中使用带有改进的Cholesky分解和线搜索的牛顿迭代。本文对所提出的方法进行了测试，并与文献中几种含有碳氢化合物成分和二氧化碳的基准混合物的常规方法进行了比较。在P-Z平面上构造相图，重点关注多相稳定闪算法每一步中发现的TPD函数的驻点数量，以及如何有效地在初始化中使用它们。对于所有的测试混合物，在所提出的稳定性-闪光策略中，稳定性和闪光例程的调用次数以及闪光计算的迭代次数与之前的方法相比显着减少，推荐新方法作为组合模拟的有用工具。

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引用次数: 0