High-pressure phase equilibria of systems carbon dioxide + n-eicosane and propane + n-eicosane

In this work we investigated the phase equilibrium behavior of the binary asymmetric systems propane (C3) + n-eicosane (C20) and carbon dioxide (CO₂) + n-eicosane (C20). We used a variable-volume view cell for obtaining fluid–fluid equilibrium (FFE), solid–fluid equilibrium (SFE) and solid–fluid–fluid equilibrium (SFFE) experimental data. We modeled the phase equilibria of both systems using the Peng–Robinson Equation of State for describing the fluid phases and an expression for the fugacity of pure solid n-eicosane with parameters fit to reproduce the pure n-eicosane melting line. We performed the phase equilibrium calculations by implementing path-following methods for tracking entire solid–fluid (SF) and solid–fluid–fluid (SFF) equilibrium curves for binary asymmetric mixtures. This made it possible to obtain complete isoplethic lines or complete three-phase equilibrium lines in single runs. Although the model is relatively simple, it is able to grasp the complex observed behavior for the systems studied here.     

High-pressure phase equilibria of systems carbon dioxide + n-eicosane and propane + n-eicosane

In this work we investigated the phase equilibrium behavior of the binary asymmetric systems propane (C3) + n-eicosane (C20) and carbon dioxide (CO₂) + n-eicosane (C20). We used a variable-volume view cell for obtaining fluid–fluid equilibrium (FFE), solid–fluid equilibrium (SFE) and solid–fluid–fluid equilibrium (SFFE) experimental data. We modeled the phase equilibria of both systems using the Peng–Robinson Equation of State for describing the fluid phases and an expression for the fugacity of pure solid n-eicosane with parameters fit to reproduce the pure n-eicosane melting line. We performed the phase equilibrium calculations by implementing path-following methods for tracking entire solid–fluid (SF) and solid–fluid–fluid (SFF) equilibrium curves for binary asymmetric mixtures. This made it possible to obtain complete isoplethic lines or complete three-phase equilibrium lines in single runs. Although the model is relatively simple, it is able to grasp the complex observed behavior for the systems studied here.     

High-pressure phase equilibria for the binary system carbon dioxide + benzyl alcohol

The phase equilibria of the carbon dioxide + benzyl alcohol system were measured at 298.15, 306.35 and 313.15 K, under pressures from 1.03 to 16.15 MPa. An upper critical end point (UCEP) of the binary system was identified at 307.45 K and 7.77 MPa and three-phase equilibria were observed along the liquid-liquid-vapor (LLV) equilibrium line between 279.75 and 307.45 K. The experimental data were correlated well by the Peng-Robinson equation of state with two binary parameters. According to the experimental results, the phase behavior of the carbon dioxide + benzyl alcohol system appears to belong to Type-III according to the classification of van Konynenburg and Scott.     

High pressure phase behavior and density of the carbon dioxide + 1-methylimidazole binary system

The phase behavior of the carbon dioxide + 1-methylimidazole binary system has been investigated in a high-pressure variable-volume view cell using an analytical method. Phase equilibrium data for the system carbon dioxide + 1-methylimidazole was measured at 293.15, 309.75 and 323.15 K. The pressure under investigation was between 2.83 and 14.16 MPa. There coexisted three phases (LLV) of the binary system, which were found in a temperature range of 297.85–313.95 K. The densities of the binary mixture at phase transition points were also measured. The experimental data were correlated well by the Peng–Robinson equation of state with two binary parameters. According to the experimental results, the phase behavior of the binary system might be classified to Type-IV or Type-V according to the classification of six principal types of binary phase diagrams.     

High-pressure phase equilibrium data for the l-lactic acid + (propane + ethanol) and the l-lactic acid + (carbon dioxide + ethanol) systems

Biodegradable polymers have received increased attention due to their potential applications in the medicine and food industries; in particular, poly(l-lactic acid) (PLA) is of primary importance because of its biocompatibility and resorbable features. Recently, the synthesis of this biopolymer through the enzyme-catalyzed ring-opening polymerization of l-lactic acid in a compressed fluid has been considered promising. The aim of this work was to report the phase equilibrium data (cloud points) of the l-lactic acid + (propane + ethanol) and the l-lactic acid + (carbon dioxide + ethanol) systems. The phase equilibrium experiments were conducted in a variable-volume view cell employing the static synthetic method. These experiments were conducted in the temperature range of 323.15–353.15 K and at pressures up to 25 MPa; the mass ratio of ethanol to either CO₂ or propane was maintained at 1:9. The l-lactic acid + (propane + ethanol) system exhibited vapor–liquid, liquid–liquid and vapor–liquid–liquid transitions, whereas the l-lactic acid + (carbon dioxide + ethanol) system only exhibited liquid–liquid type transitions.     

Measurement and correlation of high pressure phase behavior of carbon dioxide + water system

A visual and variable volume view cell analyzer was installed and the phase behaviors of the carbon dioxide + water system were measured in the temperature and pressure ranges from 313.2 K to 343.2 K and from 4.33 MPa to 18.34 MPa, respectively. The measured data were correlated with the MF-NLF-HB equation of state to consider the effects of the hydrogen bonding of the saturated liquid and vapor mixture. The calculated data agree well with the measured data within an absolute average error deviation of 5%. The fraction of hydrogen bonding could be calculated by the MF-NLF-HB EOS for the carbon dioxide + water system with the obtained VLE data. The calculated hydrogen bonding fraction of the saturated liquid phase of the mixture decreased with increasing pressure in the isothermal calculations. The hydrogen bond strength was affected by the concentration of carbon dioxide and solubility of carbon dioxide was affected by pressure. The calculated hydrogen bonding fraction of the saturated vapor phase of the mixture had a minimum value near 10 MPa for the three isothermal calculations.     

High-pressure phase equilibria and densities of the binary system carbon dioxide/methyl laurate

The equilibrium compositions and densities in the gaseous and liquid phases of the binary system carbon dioxide/methyl laurate (dodecanoic acid methyl ester) have been measured at 40 °C, 50 °C and 60 °C, and at pressures up to 120 bar. Equilibrium was attained by recirculating both phases through a high-pressure view cell. A vibrating sensor tube was used to determine densities. Compositions were measured by taking samples from both phases by means of six-way valves.     

Antisolvent micronization of BSA using supercritical mixtures carbon dioxide + organic solvent

In this work, expanded liquid antisolvent (ELAS) process has been used to micronize bovine serum albumin (BSA) solubilized in water. Carbon dioxide mixtures with ethanol, acetone or isopropyl alcohol, at expanded liquid conditions, have been used as the antisolvent. The effect of process parameters, such as the kind of co-antisolvent and the organic co-antisolvent/water/carbon dioxide mole fraction on the morphology and dimensions of the precipitates, was studied. Changing co-antisolvent and operating conditions, we obtained nanoparticles (with a mean diameter of about 60 nm ± 10 nm), sub-microparticles (with a mean diameter of 470 nm ± 130 nm), microparticles (with a mean diameter of 0.93 μm ± 0.37 μm) and expanded microparticles with an empty core (with a mean diameter of about 9 μm ± 5 μm). Fourier transform infrared analysis on BSA powders revealed that, using acetone as co-antisolvent, no modifications of the protein secondary structure were induced by ELAS processing.     

Experimental and molecular modelling study of the three-phase behaviour of (propane + carbon dioxide + water) at reservoir conditions

Acquiring a comprehensive understanding of the phase behaviour of mixtures of crude-oil with carbon dioxide and water is a key input for reservoir engineering in processes of enhanced oil recovery and geological storage of carbon dioxide. To gain an insight, given the very complex nature of crude-oil mixtures, the study of simpler systems is of interest. In this work the system (propane + carbon dioxide + water) has been chosen as a model (light oil fraction + carbon dioxide + water) mixture. Phase equilibrium measurements have been carried out using a quasi-static-analytical high-pressure apparatus that was validated on the system (n-decane + carbon dioxide) in comparison with literature data, and used to study the system (n-decane + carbon dioxide + water) [E. Forte, A. Galindo, J. P.M. Trusler, The Journal of Physical Chemistry B 115 (49) (2011) 14591–14609]. In the present work, new experimental data have been measured for the system (propane + carbon dioxide + water) under conditions of three-phase equilibria. Compositions of the three coexisting phases have been obtained along four isotherms at temperatures from 311 to 353 K and at pressures up to the upper critical end points where the propane-rich and the carbon dioxide-rich phases become critical. The experimental data obtained for the ternary mixture have been compared to the predictions obtained with the statistical associating fluid theory for potentials of variable range (SAFT-VR). The phase behaviour of each pair of binary subsystems has been calculated using this theory and, where applicable, a modification of the Hudson and McCoubrey combining rules has been used to treat the systems predictively. Furthermore, a detailed analysis of the phase behaviour of the ternary mixture has been carried out based on comparison with available data for the constituent binary subsystems, as well as with the previous findings for the ternary (n-decane + carbon dioxide + water). Such comparison is useful to examine the effect that adding a third component has in the mutual solubility of each pair. Remarks relevant to reservoir processing are also highlighted.     

Measurement and modeling of the phase behavior of the (carbon dioxide + water) mixture at temperatures from 298.15 K to 448.15 K

An analytical apparatus has been designed to study the phase behavior of fluid mixtures of relevance to CO₂-enhanced oil recovery and carbon dioxide storage in deep aquifers or depleted oil fields. The fluid phases are circulated by means of a dual-channel magnetically-coupled pump and aliquots may be withdrawn from the re-circulation loops, by means of high-pressure sampling valves, for analysis by gas chromatography. The high-pressure cell is fitted with a special probe that may be rotated in order to draw liquid into the re-circulation loop from different heights within the cell, thereby permitting the study of three-phase vapor–liquid–liquid equilibria. The working temperature range of the apparatus is from (298 to 448) K and the maximum working pressure is 50 MPa.In this work, measurements have been made on the binary system (CO₂ + H₂O) at temperatures from (298.15 to 448.15) K and pressure from (1.5 to 18.0) MPa, and the results are compared with the available literature data. Vapor–liquid–liquid and liquid–liquid equilibrium points were also measured at T = 298.15 K. Standard uncertainties were 0.04 K for temperature, 0.04% of reading for pressure, and typically 3 × 10⁻⁴ and 8 × 10⁻⁴ for the mole fractions in liquid and vapor phases respectively. The results have been correlated by means of an asymmetric approach based on the Peng–Robinson equation of state, for the vapor phase, and an extended form of Henry's law incorporating the NRTL solution model, for the aqueous liquid-phase. The ability of the Krichevsky–Kasarnovsky (KK) approach to correlate the data has also been evaluated.     

High-pressure phase equilibria for the water/methane system

A semitheoretical method has been established for superimposing the residual thermodynamic properties of pure methane and of pure water over wide ranges of pressure (0.01 to 1,000 MPa) and temperature (triple point to twice the critical temperature). Using reasonable mixing rules with two binary parameters, this superposition also gives mixture properties, including high-pressure vapor-liquid equilibria.     

Phase equilibria of allyl sulfide + carbon dioxide binary mixtures: Experimental data and thermodynamic modeling

This contribution reports new experimental data on vapor–liquid equilibrium of the binary system diallyl sulfide + carbon dioxide, at temperatures between 275 and 370 K and pressures up to 12 MPa. These data are of interest to study the extraction of Allium oils from garlic and onion, using near-critical CO₂. The experimental data were modeled with a group-contribution equation of state. A (CH₂S) functional group has been defined to represent alkyl and allyl sulfides. Pure group and binary interaction parameters for this new functional group have been determined. Good correlation and prediction of phase equilibrium conditions were obtained.     

High pressure densities of carbon dioxide + dipentaerythritol hexaheptanoate: New experimental setup and volumetric behavior

To perform an appropriate selection of the lubricants in air conditioned systems working with carbon dioxide as refrigerant, the thermodynamic behavior of the CO₂ + lubricant systems must be well known. In this work we present a new setup to prepare compressed gas–liquid mixtures and to determine the high pressure density by using an automated densimeter HPM and two syringe pumps. To analyze the reliability of the procedure proposed, we have determined the densities and mixing volumes of four CO₂ + n-decane mixtures. We have found a good agreement with previous literature data. In addition new density values are reported for the binary system CO₂ + dipentaerythritol hexaheptanoate (DiPEC7) at several temperatures and pressures from 10 MPa to 120 MPa.     

Use of artificial neural networks for prediction of phase equilibria in the binary system containing carbon dioxide

Present work investigated the potential of artificial neural network (ANN) model to correlate the bubble and dew points pressures of binary systems containing carbon dioxide (CO₂) and hydrocarbon systems as functions of reduced temperature of non-CO₂ compounds, critical pressure, acentric factor of non-CO₂ compounds and CO₂ composition. In this regards, five binary systems at the temperature and pressure ranges of 263.15–393.15 K at 0.18–12.06 MPa were used to examine the feasibility of cascade-forward back-propagation ANN model. In this regard, the collected experimental data were divided in to two different subsets namely training and testing subsets. The training subset was selected in a way that covers all the ranges of the experimental data and operating conditions. Then, the accuracy of the proposed ANN model was evaluated through a test data set not used in the training stage. The optimal configuration of the proposed model was obtained based on the error analysis including minimum average absolute relative deviation percent (AARD %) and the appropriate (close to one) correlation coefficient (R²) of test data set. The obtained results show that the optimum neural network architecture was able to predict the phase envelope of binary system containing CO₂ with an acceptable level of accuracy of AARD % of 2.66 and R² of 0.9950 within their experimental uncertainty. In addition, comparisons were done between the Peng–Robinson (PR) equation of state (EOS) and ANN model for three different binary systems including CO₂ + 1-hexene, CO₂ + n-Hexane, and CO₂ + n-butane. Results show that developed optimal ANN model is more accurate compared to the PR EOS.     

Phase equilibria of (CO2 + H2O + NaCl) and (CO2 + H2O + KCl): Measurements and modeling

We report experimental measurements of the phase behavior of (CO₂ + H₂O + NaCl) and (CO₂ + H₂O + KCl) at temperatures from 323.15 K to 423.15 K, pressure up to 18.0 MPa, and molalities of 2.5 and 4.0 mol kg⁻¹. The present study was made using an analytical apparatus and is the first in which coexisting vapor- and liquid-phase composition data are provided. The new measurements are compared with the available literature data for the solubility of CO₂ in brines, many of which were measured with the synthetic method. Some literature data show large deviations from our results.The asymmetric (γ–φ) approach is used to model the phase behavior of the two systems, with the Peng–Robinson equation of state to describe the vapor phase, and the electrolyte NRTL solution model to describe the liquid phase. The model describes the mixtures in a way that preserves from our previous work on (CO₂ + H₂O) the values of the Henry's law constant and the partial molar volume of CO₂ at infinite dilution Hou et al. [22]. The activity coefficients of CO₂ in the aqueous phase are provided. Additionally, the correlation of Duan et al. [14] for the solubility of CO₂ in brines is tested against our liquid-phase data.     

Liquid–liquid equilibria and thermo physical properties for 1-methyl-2-pyrrolidinone + heterocyclic nitrogen compounds + hexadecane systems at 298.15 K

Liquid–liquid equilibrium data for {1-methyl-2-pyrrolidinone (NMP) + heterocyclic nitrogen compounds + hexadecane} systems were analytically determined at 298.15 K and atmospheric pressure using stirred and thermo-regulated cell. The experimental data were modeled with the NRTL and UNIQUAC equations. Besides, the Bachman–Brown correlation was used to ascertain the reliability of the experimental data. Additionally, excess molar volumes (V^E) and deviations in the molar refractivity (ΔR) data at 298.15 K were determined for the {NMP + heterocyclic nitrogen compounds} binary systems using a digital vibrating-tube densimeter and a precision digital refractometer. The V^E and ΔR data were modeled with the Redlich–Kister equation.     

Vapor–liquid phase equilibrium of carbon dioxide with mixed solvents of DMSO + ethanol and chloroform + methanol including near critical regions

A visual and volume-variable high-pressure phase equilibrium analyzer was used for measuring the vapor–liquid phase boundaries of the ternary systems containing carbon dioxide and mixed solvents of dimethyl sulfoxide (DMSO) + ethanol or chloroform + methanol at temperatures from 298.15 K to 348.15 K over wide composition ranges including near critical points. Four pseudo-binary systems of carbon dioxide plus mixed solvents with constant molar ratios of DMSO/ethanol = 3/7, 5/5, 7/3, and chloroform/methanol = 1/2, were studied in this work. The critical conditions at each investigated temperature were estimated from the experimental isothermal phase boundaries by interpolation. The Peng–Robinson equation of state with the two-parameter van der Waals mixing rules was applied to calculate the phase boundaries. The experimental values were compared with the predicted results from the Peng–Robinson equation using the binary interaction parameters determined from the vapor–liquid equilibrium data of the constituent binaries. The agreement is reasonably well for carbon dioxide + chloroform + methanol, but obvious overestimations are found near the critical regions of carbon dioxide + DMSO + ethanol, especially at higher temperatures.     

Liquid–liquid equilibria for ternary systems of dimethyl carbonate + C1–C4 alcohols + water at 298.15 K and atmospheric pressure

The ternary liquid–liquid equilibria (LLE) of the following systems were analytically determined at 298.15 K and atmospheric pressure using stirred and thermo-regulated cells: {dimethyl carbonate (DMC) + methanol + water}, {DMC + ethanol + water}, {DMC + 1-propanol + water}, {DMC + 2-propanol + water}, {DMC + 1-butanol + water} and {DMC + 2-butanol + water}. The experimental ternary LLE data were correlated with the non-random two liquid (NRTL) and UNIversal QUAsiChemical (UNIQUAC) activity coefficient models. In addition, the Bachman–Brown correlation was used to ascertain the reliability of the experimental data for each system.     

Phase equilibria of carbon dioxide + 1-nonanol system at high pressures

Vapor-liquid-equilibria (VLE) and vapor-liquid-liquid equilibria (VLLE) data for the carbon dioxide + 1-nonanol system were measured at 303.15, 308.15, 313.15, 333.15, and 353.15 K. Phase behavior measurements were made in a high-pressure visual cell with variable volume, based on the static-analytic method. The pressure range under investigation was between 1.15 and 103.3 bar. The Soave-Redlich-Kwong (SRK) equation of state (EOS) coupled with both classical van der Waals and a Gibbs excess energy (G^E) mixing rules was used in semi-predictive approaches, in order to represent the complex phase behavior (critical curve, liquid-liquid-vapor (LLV) line, isothermal VLE, LLE, and VLLE) of the system. The topology of phase behavior is correctly predicted.