Vapor Liquid Phase Equilibrium Research Articles

Vapor–liquid phase equilibrium prediction for mixtures of binary systems using graph neural networks

AbstractVapor–liquid phase equilibrium (VLE) plays a crucial role in chemical process design, process equipment control, and experimental process simulation. However, experimental acquisition of VLE data is a challenging and complex task. As an alternative to experimentation, VLE data prediction offers great convenience and utility. In this article, an artificial intelligence network is proposed to predict the temperature and the vapor phase composition of binary mixtures. We constructed a graph neural network (GNN) and designed an uncertainty‐aware learning and inference mechanism (UALF) in the prediction process. The model was tested on both a self‐constructed dataset and a publicly available dataset. The results demonstrate that the proposed method effectively reveals the phase equilibrium properties of the target data. This work presents a novel approach for predicting vapor–liquid phase equilibrium in binary systems and proposes innovative ideas for investigating phase equilibrium mechanisms and principles.

Vapor–Liquid Equilibrium Phase Behavior for Binary Mixtures Isopropyl Alcohol and Methyl Ethyl Ketone with Dimethyl Sulfoxide

Vapor–Liquid Equilibrium Phase Behavior for Binary Mixtures Isopropyl Alcohol and Methyl Ethyl Ketone with Dimethyl Sulfoxide

Phase equilibrium and separation process of byproduct vinyl acrylate in the ethylene vapor phase method producing vinyl acetate

Vinyl acrylate is one of the byproducts in the ethylene vapor phase method for the production of vinyl acetate (VAc), which not only has a toxic effect on the catalyst but also affects the purity of the product. Currently, phase equilibrium data for vinyl acrylate with water are missing, making the destination of vinyl acrylate in the distillation process uncertain. This has led to a lack of effective removal means, which restricts the optimization of the ethylene vapor phase method. This paper uses a method combining quantum chemistry and molecular dynamics simulation (MD) to investigate the existential form of the water molecule. And based on the ab initio calculation of the first principle, the force field parameters of the special water molecular structure are calculated, and the TIP4P-P force field that can describe the special water structure is established. Using the Gibbs Ensemble Monte Carlo (GEMC) method, the reliability of the improved water molecule force field for modeling the phase equilibrium of a binary system is first verified. Further, vapor–liquid phase equilibrium data for the vinyl acrylate-water binary system at 110 kPa and 150 kPa are calculated and the corresponding x-y and T-x-y phase diagrams are plotted. After performing the thermodynamic consistency test, the phase equilibrium data are fitted to obtain the binary interaction parameters of vinyl acrylate with water. The fitted parameters are applied to the process simulation of the VAc refining process to optimize the conditions and obtain an effective separation scheme for vinyl acrylate. The concentration distribution of vinyl acrylate in the distillation column is investigated, thus clarifying the destination of vinyl acrylate in the distillation process and facilitating the optimization of the ethylene vapor phase method.

Data-driven guided physics-informed segmented neural network for liquid–vapor flash calculation

Liquid–vapor phase equilibrium is ubiquitous in industrial and engineering field, which involves the flash calculation. The conventional flash calculation is solved with the numerical simulator, accompanying with large computational efforts. In this paper, we propose a data-driven guided physics-informed segmented neural network (DDG-PISNN) for the liquid–vapor pressure–temperature flash calculation. The training of DDG-PISNN is divided into two stages. First, a classifier for determining the stability of the system and a guiding network are built using data-driven methods. Subsequently, various control equations are employed to construct loss functions based on the results of classifier. In this way, DDG-PISNN fully leverages the advantages of data-driven approaches and physical equations. The accuracy and robustness of DDG-PISNN are calibrated by experiments under different conditions, and the performance is compared with that of DDG-PINN. In addition, a surrogate model for flash calculation is constructed based on DDG-PISNN. The accuracy of the surrogate model is also validated against a numerical case, and the computational efficiency is more than 800 times. Then, the surrogate model is embedded into the reservoir simulation technique to perform the flash calculation and form a surrogate-based compositional model. The surrogate-based model is employed to simulate the process of CO2 displacing crude oil. The results are in good agreement with the results of numerical solution.

Comparison of methods for calculating the enthalpy of vaporization of binary azeotropic mixtures

Objectives. To calculate the molar enthalpy of vaporization of binary homogeneous mixtures based on isothermal and isobaric vapor–liquid equilibrium data, and to compare the results of calculation of molar enthalpy of vaporization by different methods with experimental data.Methods. Simulation of the vapor–liquid equilibrium of binary systems according to the Non-Random Two Liquid “local compositions” equation and thermodynamic calculations of molar vaporization enthalpies of binary mixtures at different conditions of vapor–liquid equilibrium were used.Results. Arrays of calculated data were obtained with regard to molar enthalpies of vaporization for 25 compositions of binary azeotropes (isothermal, isobaric conditions of phase equilibrium), and the full range of compositions of the benzene–ethanol system at atmospheric pressure.Conclusions. The accuracy of thermodynamic methods for calculating the vaporization enthalpy of binary azeotropic mixtures according to vapor–liquid equilibrium data is higher in 85% of cases for isothermal, and in 75% of cases for isobaric conditions. By taking into account the influence of temperature on the activity coefficients of components in the liquid phase, the values of excess molar enthalpy both for azeotrope compositions and for the full concentration range of the benzene–ethanol system under isobaric conditions of liquid–vapor phase equilibrium can be accurately reproduced.

Efficient separation in n‐butyl ether production process from computational thermodynamics to process intensification

AbstractBiobutanol is a green solvent commonly used as gasoline additive. In this study, it is proposed the separation of azeotropic mixtures of butanol and n‐butyl ether (DBE) using ionic liquids (ILs). Suitable anions [AC]− and [H2PO4]− were screened by COSMO‐RS, and the effect of carbon chain length on the separation effect was investigated using quantum chemical calculations. It was found that the anion was primarily responsible for the separation effect, which grew as the carbon chain grew. Molecular dynamics simulations were used to verify the separation performance of the selected ILs. The separation effect of ILs was further verified using vapor–liquid phase equilibrium (VLE) experiments. The extractive distillation process with [PrMIM][AC] as the extractant was investigated to demonstrate the feasibility of ILs for the separation of butanol and DBE. This study analyzes the whole process from microscopic mechanism of action, which provides new ideas for the separation of alcohol‐ether systems.

UNIFAC PREDICTION OF VAPOR LIQUID EQUILIBRIA INVOLVING GAMMA-VALEROLACTONE DERIVATIVE SYSTEMS

Researchers have studied the hydrogenation of Gamma-Valerolactone (GVL) over Ru/C to produce 2-methyltetrahydrofuran (2-MTHF), a biomass-based platform chemical with potential as a biofuel and green solvent. Other byproducts of this reaction include 2-butanol (2-BuOH), 2-pentanol (2-PeOH), and 1,4-pentanediol (1,4-PDO). In this study, UNIFAC activity coefficient models were used to predict the vapor-liquid equilibrium of several systems included in the process to explain the phase behavior which is important in purification process. The accuracy of the UNIFAC model is tested by comparing the experimental boiling points for the binary system of 2-propanol + 1-butanol and the vapor-liquid equi-librium of the GVL + 2-MTHF system. From this comparison, the Root Mean Square Deviation (RMSD) values for the boiling point measurements are obtained to be 3.153%, and for the liquid and vapor phases in the vapor-liquid equilibrium measurements, the RMSD values are 1.934% and 0.298% respectively. These RMSD values indicate the level of accuracy of the UNIFAC model in representing the experimental data for both boiling point measurements and vapor-liquid equilibrium phase behavior. The prediction results of vapor-liquid equilibrium data for GVL derivative systems showed that the 2-BuOH + 2-MTHF system does form an azeotrope when the mol fraction of 2-BuOH is 0.0031 at 79.780C. The calculation was performed using ChemCAD commercial software for chemical process modeling and simulation

Application of ionic liquid extractant in enhanced separation of 2-propanol-n-hexane azeotrope system

2-Propanol and n-hexane are widely used (as) chemical reagents in electronic, pharmaceutical, and chemical industries. An efficient separation of the azeotropic system of 2-propanol-n-hexane is of profound practical significance. By using the conductor-like screening model for real solve (COSMO-RS) predictive model, ionic liquids as extractants for separating the azeotropic system of 2-propanol-n-hexane were evaluated with selectivity coefficients (S) and capacity (C) as the evaluation indexes. Based on the evaluation results, one high-performance extractants named hydroxylamine Cl (C8A19) was selected from 435 kinds of ionic liquids designed by combining 29 kinds of anions and 15 kinds of cations. Moreover, the reliability of the model in predicting the vapor–liquid phase equilibrium behavior of 2-propanol-n-hexane system was verified. Then, the effect of C8A19 on the vapor–liquid phase equilibrium of the 2-propanol-n-hexane system was investigated theoretically and experimentally. The results show that the azeotrope of the system can be broken when the molar fraction of C8A19 is 0.02, denoting that C8A19 can be used for enhanced separation of 2-propanol-n-hexane system. On the basis of the aforementioned study, the selectivity mechanism of the extractant was analyzed from the perspective of microscopic molecular interactions by using the descriptor (σ-profiles) of COSMO-RS. This study provides both theoretical and data support for further designing high-performance ionic liquid extractants and extraction process.

Study on separation of acetonitrile and methanol azeotropic system using tetraethylammonium chloride-based deep eutectic solvents

Large quantities of waste streams containing mixed acetonitrile (ACN) and methanol (MeOH) are generated during pharmaceutical and chemical production. The polarity of these two substances is extremely similar, resulting in the formation of an azeotrope at room temperature and atmospheric pressure. In this study, deep eutectic solvents (DESs) were selected as extractants for the separation of ACN-MeOH binary azeotrope. To obtain suitable DESs, the σ-profiles of ACN, MeOH, DESs were calculated using the COSMO-SAC model, and the results demonstrated that the DESs synthesized when tetraethylammonium chloride (TEAC) was chosen as the hydrogen bond acceptor (HBA) and acetamide as the hydrogen bond donor (HBD) could effectively break the azeotropy of ACN and MeOH. Therefore, four DESs were synthesized with molar ratios of TEAC: acetamide = 1: n (n = 1, 2, 3, 4) for subsequent ACN-MeOH-DESs ternary vapor–liquid phase equilibrium (VLE) experiments at 101.3 kPa to determine the optimal extractant. The measured VLE data revealed the higher separation of DES TEAC-2acetamide on the ACN-MeOH binary azeotrope compared with other DESs. Afterward, the NRTL model was adopted to calculate the binary interaction parameters between ACN/MeOH and DESs. The results of the fitting indicated agreement with the experimental data. Finally, the separation mechanism was further analyzed using the interaction energy analysis, improved independent gradient model (IGMH), and the theory of atoms in molecules (AIM). The results indicated that the strong interaction between DESs and MeOH is the primary factor in the ability of DESs to break the azeotrope of the system.

Effect of glucose–citric acid deep eutectic solvent on the vapor–liquid equilibrium of an aqueous ethanol solution

Objectives. To study the effect of a deep eutectic solvent (DES) based on glucose and citric acid on the vapor–liquid equilibrium of an aqueous solution of ethanol.Methods. A qualitative and quantitative analysis of the conditions of vapor–liquid equilibrium in an ethanol–water–DES ternary mixture was performed based on the open evaporation method and the measurement of TPxy data using a Świętosławski ebulliometer. Since the volatility of the DES is negligible in comparison with that of water and ethanol, the composition of the vapor phase was measured by means of Karl Fischer titration. The conditions of vapor–liquid phase equilibrium were modeled using the UNIFAC model.Results. The open evaporation method was used to determine the curves of residual concentrations for the ethanol–water–DES mixture at various DES concentrations and compositions (glucose–citric acid ratios). TPxy data was obtained for the mixture produced by adding 30 wt % DES to an aqueous solution of ethanol at atmospheric pressure. Studies show that DES based on glucose and citric acid has a significant effect on the relative volatility of ethanol in aqueous solution, leading to the disappearance of the azeotropic point. This effect is due to only the presence of glucose. Citric acid does not change the composition of the equilibrium phases, but rather increases the solubility of glucose in aqueous ethanol solutions. This is especially important at high ethanol concentrations, since glucose is poorly soluble in ethanol.Conclusions. Addition of DES based on glucose and citric acid to an aqueous solution of ethanol leads to the disappearance of the azeotropic point. DES can thus be considered as a promising entrainer for extracting ethanol from aqueous solutions using extractive distillation. Modeling of the conditions of vapor–liquid equilibrium in the ethanol–water–DES system using the UNIFAC model showed a satisfactory level of accuracy. The error in the calculated data increases with increasing the glucose concentration, while remaining acceptable for practical use.

The Vapor–Liquid Phase Equilibrium Line for Water within the Framework of the Renormalization Group Theory

The Vapor–Liquid Phase Equilibrium Line for Water within the Framework of the Renormalization Group Theory

Parameters of the UNIQUAC Model for Describing the Vapor–Liquid Phase Equilibrium of the Isotope Mixtures of Hydrogen H2–D2, H2–HD, HD–D2

Parameters of the UNIQUAC Model for Describing the Vapor–Liquid Phase Equilibrium of the Isotope Mixtures of Hydrogen H2–D2, H2–HD, HD–D2

Force Field for Calculation of the Vapor-Liquid Phase Equilibrium of trans-Decalin

Based on the TraPPE force field, previously unknown values of the parameters of the intermolecular interaction potential of trans-decalin were determined. Parametrization was carried out using experimental data on saturated vapor pressure and density at atmospheric pressure. The found parameters make it possible to adequately describe the boiling and condensation lines of trans-decalin and also predict the critical values of pressure, density, and temperature with satisfactory accuracy. Calculations of vapor-liquid phase equilibrium conditions for a binary CO2—trans-decalin mixture in supercritical conditions for CO2 were carried out. When quantitatively comparing the calculated values with experimental data, an underestimation of pressure at a temperature of 345.4 K by 30% is observed, which decreases to 5% for temperatures up to 525 K.

Vapor-liquid equilibrium data and performance analysis on binary mixture of R32 and R1216 for residential air condition system

In order to accurately evaluate the performance of R32 and unsaturated fluorinated olefins (HFOs) binary mixtures in residential air condition (RAC) system, the vapor-liquid phase equilibrium (VLE) data of R32 and R1216 binary mixture has been measured with a liquid phase circulation system in the temperature range from 285 to 315 K. The experimental data were correlated by Peng-Robinson (PR) equation of state with Huron-Vidal (HV) mixing rule and non-random two-liquid (NRTL) activity coefficient model. Maximum deviation of the pressure and the mole fraction was 1.38% and 0.013, respectively. The azeotropic behavior was observed for the R32 and R1216 binary mixture when the mole fraction of R32 was around 0.9. The RAC system with standard refrigeration, heating and variable evaporation temperature operating condition was simulated. The cycle performance of binary mixtures of R32 + R1216, R1234yf and R1234ze(E) at different concentrations was compared. The azeotrope R32/R1216 (molar ratio 0.9/0.1) has an extremely low GWP, the COP, refrigeration/heating capacity per unit volume and condensation pressure close to pure R32, and lower discharge temperature. At the same time, it also has well variable operating conditions performance and can be considered as a drop-in replacement for R32 and R410A in RAC systems.

Separation process and mechanism of cyclohexane/ethanol system using deep eutectic solvents based on betaine and choline chloride

The efficient separation of azeotropes is of great significance for the effective recovery and utilization of chemical raw materials and environmental protection. This study investigated the separation efficiency and mechanism of deep eutectic solvents (DESs) with different combinations and ratios of hydrogen bond acceptors (HBA) and hydrogen bond donors (HBD) for cyclohexane/ethanol azeotropic systems. Through vapor-liquid phase equilibrium experiments, the effects of different DESs and different HBD: HBA molar ratios as solvents on the phase behavior of cyclohexane/ethanol azeotropic system were studied, and different combinations and molar ratios of DESs with the best separation performance were obtained. The effective separation of azeotropes by DESs is primarily due to the stronger molecular surface electrostatic potential of ethanol compared to that of cyclohexane, which results in a stronger interaction between the DESs and ethanol. Finally, through process simulations, a cyclohexane/ethanol extractive distillation separation process using a DES as the main solvent was established. The results showed that the separation effect of DESs increased with the increase of the interaction force between DESs and ethanol, achieving efficient recovery of chemical raw materials. This study established a safe and efficient separation process using DESs, which is of great significance for environmental protection and the development of safety processes.

A study on the vapor–liquid equilibria of vinyl acrylate-acetic acid and vinyl acetate-acetic acid with GEMC method

Vinyl acetate (VAc) is one of the widely utilized industrial organic raw materials. In the acetoxylation of ethylene to vinyl acetate, there is a by-product vinyl acrylate. However, the vapor–liquid phase equilibrium data of this component with acetic acid and vinyl acetate have not been reported. Here, by Density Functional Theory calculations, we fitted the TraPPE-UA force field parameters of vinyl acrylate. The vapor–liquid phase equilibrium data of the vinyl acrylate-acetate and vinyl acrylate-vinyl acetate binary systems were calculated using the Gibbs Ensemble Monte Carlo (GEMC) method. The calculated phase equilibrium data were utilized to fit the binary interaction parameters of the NRTL equations for the binary systems which were used for the separation process simulation of the vinyl acrylate, acetic acid and vinyl acetate systems. It was verified that the TraPPE-UA force field parameters fitted in this paper have high accuracy. The results clarify the concentration distribution of vinyl acrylate gas–liquid phase components in the distillation column, which builds the foundation for the development of the separation process.

Vapor–Liquid Equilibrium Phase Behavior of Binary Systems of Carbon Dioxide with Eugenol or Guaiacol

Vapor–Liquid Equilibrium Phase Behavior of Binary Systems of Carbon Dioxide with Eugenol or Guaiacol

Preparation of high-purity copper through vacuum distillation

Copper is capable of maintaining strong competitiveness in the metal materials market for its prominent ductility, thermal conductivity, and electrical conductivity. As more rigorous purity requirements of industrial sputtering targets and aerospace have been raised, the clean and efficient production of high-purity copper turns out to be an urgent problem over the past few years. In this paper, the possibility of removing impurities from copper melt was investigated by integrating theoretical calculations and experiments, and the separation coefficient and vapor-liquid equilibrium phase diagram of copper and impurity elements were determined and plotted using the molecular interaction volume model (MIVM). Moreover, the effects of the distillation temperature, the holding time, and the system pressure on the experimental results were discussed. As indicated by the results, with the rise of the temperature and with the extension of the holding time, the purity of copper was first increased and then decreased, and the purity of residual copper reached 99.9993% at 1473 K temperature, 1.5 h holding time, and 5 Pa pressure, and the method effectively separated impurities from copper raw materials. Besides, no waste water or waste gas emission was generated in the experiment.

Separation of fuel additives based on mechanism analysis and thermodynamic phase behavior

tert-butanol and ethyl acetate, as fuel additives and oxygenated fuels, can improve fuels quality and reduce exhaust emissions. Therefore, the recovery of these compounds from azeotropic systems is of great significance. Ionic liquids (ILs) are promising green solvents for separating azeotropic systems. In this study, an efficient extraction strategy based on 1-butyl-3-methylimidazolium acetate ([Bmim][AC]) is proposed. The mechanism by which ILs enable the separation of binary alcohol-ester azeotropes was revealed by evaluating the lowest conformational energy through combining an independent gradient model based on the Hirshfeld partition (IGMH) and frontier molecular orbitals, to preliminarily screen the extractants. The range of extractants was further reduced by a vapor–liquid phase equilibrium (VLE) experiment, and a modeling method for separating the alcohol–ester system and recovering the solvent using [Bmim][AC] and 1-ethyl-3-methyl-3-imidazolium acetate ([Emim][AC]) is established. Under the optimal operating conditions, the use of [Bmim][AC] can reduce the total annual cost (TAC) per year by 17.78%, and the emissions of CO2, SO2, and NO can be reduced by 10.86%. In this study, a comprehensive method for screening extractants is proposed, and the simulation process is optimized in combination with the economic and environmental impact. The results have important guiding significance for realizing efficient, energy-saving, and green azeotropic separation systems in industry.

Holding water in a sieve—stable droplets without surface tension

Our understanding of supercritical fluids has seen exciting advances over the last decades, often in direct contradiction to established textbook knowledge. Rather than being structureless, we now know that distinct supercritical liquid and gaseous states can be distinguished and that a higher order phase transition - pseudo boiling - occurs between supercritical liquid and gaseous states across the Widom line. Observed droplets and sharp interfaces at supercritical pressures are interpreted as evidence of surface tension due to phase equilibria in mixtures, given the lack of a supercritical liquid-vapor phase equilibrium in pure fluids. However, here we introduce an alternative physical mechanism that unexpectedly causes a sharpening of interfacial density gradients in absence of surface tension: thermal gradient induced interfaces (TGIIF). We show from first principles and simulations that, unlike in gases or liquids, stable droplets, bubbles, and planar interfaces can exist without surface tension. These results challenge and generalize our understanding of what droplets and phase interfaces are, and uncover yet another unexpected behavior of supercritical fluids. TGIIF provide a new physical mechanism that could be used to tailor and optimize fuel injection or heat transfer processes in high-pressure power systems.