Phase equilibria in ternary (carbon dioxide + tetrahydrofuran + water) system in hydrate-forming region: Effects of carbon dioxide concentration and the occurrence of pseudo-retrograde hydrate phenomenon

In the present work, the three- and four-phase hydrate equilibria of (carbon dioxide (CO₂) + tetrahydrofuran (THF) + water) system are measured by using Cailletet equipment in the temperature and pressure range of (272 to 292) K and (1.0 to 7.5) MPa, respectively, at different CO₂ concentration. Throughout the study, the concentration of THF is kept constant at 5 mol% in the aqueous solution. In addition, the fluid phase transitions of L_W–L_V–V → L_W–L_V (bubble point) and L_W–L_V–V → L_W–V (dew point) are determined when they are present in the ternary system. For comparison, the three-phase hydrate equilibria of binary (CO₂ + H₂O) are also measured. Experimental measurements show that the addition of THF as a hydrate promoter extends hydrate stability region by elevating the hydrate equilibrium temperature at a specified pressure. The three-phase equilibrium line H–L_W–V is found to be independent of the overall concentration of CO₂. Contradictory, at higher pressure, the phase equilibria of the systems are significantly influenced by the overall concentration of CO₂ in the systems. A liquid–liquid phase split is observed at overall concentration of CO₂ as low as 3 mol% at elevated pressure. The region is bounded by the bubble-points line (L_W–L_V–V → L_W–L_V), dew points line (L_W–L_V–V → L_W + V) and the four-phase equilibrium line (H + L_W + L_V + V). At higher overall concentration of CO₂ in the ternary system, experimental measurements show that pseudo-retrograde behaviour exists at pressure between (2.5 and 5) MPa at temperature of 290.8 K.     

Vapour–liquid equilibrium for β-myrcene and carbon dioxide and/or hydrogen and the volume expansion of β-myrcene or limonene in CO2 at 323.15 K

Vapour–liquid equilibrium measurements for binary and ternary (carbon dioxide + β-myrcene and carbon dioxide + β-myrcene + hydrogen) systems have been carried out at 323.15 K and pressures in the range from 7 MPa to the critical pressure of the binary mixture and at pressures from 10 to 14 MPa for the investigated ternary systems. Samples from the coexisting phases were taken, and compositions were determined experimentally. Results were correlated using the Peng–Robinson and the Soave–Redlich–Kwong equations of state with the Mathias–Klotz–Prausnitz mixing rule. The set of interaction parameters for the employed equations of state and applied mixing rule for the system of CO₂ + β-myrcene and of CO₂ + β-myrcene + H₂ were obtained. Additionally, the volume expansion of the liquid phase for the binary mixtures (carbon dioxide + β-myrcene and carbon dioxide + limonene) were measured at 323.15 K and at pressures from 4 MPa up to very close to the critical pressure of the mixture. The ratio of liquid phase total volumes at the given pressure and at 4 MPa was calculated.     

Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

In the present work, experimental data on the equilibrium conditions of mixed CO₂ and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl₂), magnesium chloride (MgCl₂), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO₂ and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L_W), liquid organic (L_V), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid–liquid phase split of (water + THF) mixture when pressurized with CO₂ and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl₂ < MgCl₂. Among the cations studied, the strength of hydrate inhibition increases in the following order: K⁺ < Na⁺ < Ca²⁺ < Mg²⁺. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br^? > Cl^? > F^?. Based on the results, it is suggested that the probability of formation and the strength of ionic–hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water network are the major factors that contribute to hydrate inhibition by electrolytes.     

Excess Gibbs energies and volumes of the ternary system chloroform + tetrahydrofuran + cyclohexane at 298.15 K

Vapour–liquid equilibria and densities for the ternary system chloroform + tetrahydrofuran + cyclohexane and for the binary mixtures containing chloroform have been determined at 298.15 K. Vapour–liquid equilibrium data have been collected by head-space gas-chromatographic analysis of the vapour phase directly withdrawn from an equilibration apparatus. Density measurements have been carried out by means of a vibrating tube densimeter. Molar excess Gibbs energies G^E and volumes V^E, as well as activity coefficients and apparent molar volumes of the components, have been obtained from the measured quantities and discussed. The binary chloroform + tetrahydrofuran displays negative deviations from ideality, while chloroform + cyclohexane positive deviations, for both volume and Gibbs energy. The G^E's and V^E's for the ternary system are positive in the region rich in cyclohexane while negative in the region rich in chloroform + tetrahydrofuran. This indicates that hydrogen bonding between chloroform and tetrahydrofuran molecules produces negative values of G^E and V^E and strongly influences the behaviour of the ternary system.     

CO2 and CH4 mole fraction measurements during hydrate growth in a semi-batch stirred tank reactor and its significance to kinetic modeling

A new experimental technique has been developed to measure the mole fraction of the gas hydrate former in the bulk liquid phase, at the onset of hydrate growth and thereafter, in a semi-batch stirred tank reactor. The mole fraction of carbon dioxide and methane in the bulk liquid phase was obtained for the first 11 and 13 min of the growth stage, for the carbon dioxide–water and methane–water systems respectively. Experiments were conducted at temperatures ranging from 275.3 K to 281.4 K and at pressures ranging from 2017 kPa to 4000 kPa for the carbon dioxide–water system, while temperatures ranging from 275.1 K to 279.1 K and pressures ranging from 3858 kPa to 6992 kPa were investigated for the methane–water system. The mole fraction of carbon dioxide in the bulk liquid phase was found to be constant during the growth period, varying on average by 0.6% and 0.3% at 275.4 K and 279.5 K. Similarly, the mole fraction of methane in the bulk liquid phase was found to remain constant during the growth stage, varying on average by 2.0%, 0.8% and 0.2% at 275.1 K, 277.1 K and 279.1 K respectively. The mole fraction of the gas hydrate former in the bulk liquid phase was also found to increase with pressure and decrease with temperature, while remaining greater than its hydrate-liquid water equilibrium value. As a result, an alternate formulation of a hydrate growth model is proposed.     

Volumetric study of (2-methoxyethanol + tetrahydrofuran + cyclohexane) at T=298.15 K

The excess molar volumes V_m^E at T=298.15 have been determined in the whole composition domain for (2-methoxyethanol + tetrahydrofuran + cyclohexane) and for the parent binary mixtures. Data on V_m^E are also reported for (2-ethoxyethanol + cyclohexane). All binaries showed positive V_m^E values, small for (methoxyethanol + tetrahydrofuran) and large for the other ones. The ternary V_m^E surface is always positive and exhibits a smooth trend with a maximum corresponding to the binary (2-methoxyethanol + cyclohexane). The capabilities of various models of either predicting or reproducing the ternary data have been compared. The behaviour of V_m^E and of the excess apparent molar volume of the components is discussed in both binary and ternary mixtures. The results suggest that hydrogen bonding decreases with alcohol dilution and increases with the tetrahydrofuran content in the ternary solutions.     

Experimental determination and prediction of methane hydrate stability in alcohols and electrolyte solutions

In petroleum exploration and production operations, gas hydrates pose serious flow assurance, economic and safety concerns. Thermodynamic inhibitors are widely used to reduce the risks associated with gas hydrate formation. In this communication, in order to establish the effects of salts and thermodynamic inhibitors on the locus of incipient hydrate–liquid water–vapour (H–L_W–V) curve, we report new experimental dissociation data for various quaternary systems, methane/water/thermodynamic inhibitor/salts for a pressure range of 6.89–29 MPa.     

High pressure vapor–liquid equilibria for carbon dioxide + tetrahydrofuran mixtures

Vapor–liquid equilibria and saturated density for carbon dioxide + tetrahydrofuran mixtures at high pressures were measured by the analytical method at the temperatures 298.15 and 313.15 K. The experimental apparatus equipped with three Anton Paar DMA 512S vibrating tube density meters was previously developed for measuring vapor–liquid–liquid equilibrium at high pressures. The equilibrium composition and saturated density of each phase were determined by gas chromatograph and vibrating tube density meters, respectively. The bubble point pressure at the temperature 313.15 K was further measured by the synthetic method. The experimental data were correlated with Soave–Redlich–Kwong (SRK) equation of state and the pseudocubic equation of state.     

Isothermal phase equilibria and structural phase transition in the carbon dioxide + cyclopropane mixed-gas hydrate system

The isothermal phase equilibria of the carbon dioxide + cyclopropane mixed-gas hydrate system were investigated by means of static temperature measurement and Raman spectroscopic analysis. Raman spectra indicated that the crystal structure of the carbon dioxide + cyclopropane mixed-gas hydrate changes from structure-I to structure-II and back to structure-I with an increase of the equilibrium carbon dioxide composition at 279.15 K, while each simple gas hydrate belongs to structure-I at the temperature. Whereas, unlike 279.15 K, no structural phase transition occurs along the isothermal stability boundary at 284.15 K.     

Liquid–liquid–solid equilibrium for the water + sodium chloride + potassium chloride + 1-butanol quaternary system at 25 °C

The methodology for the study of the liquid–liquid–solid equilibrium of quaternary systems including two inorganic salts, water and an organic solvent has been reviewed and applied to the water + sodium chloride + potassium chloride + 1-butanol quaternary system at 25 °C. The different equilibrium regions have been systematically studied.The experimental equilibrium data have been used to check the accuracy of the predictions using the electrolyte NRTL model (MNRTL) and the parameters obtained by correlation of ternary systems. The results obtained with the model are satisfactory.     

Equilibrium conditions for CO2 hydrate in porous medium

Experimental phase equilibrium conditions data for carbon dioxide (CO₂) hydrate in porous medium with the presence of sodium chloride (NaCl) solution were investigated in this study. The experimental data were generated using graphic-method in presence of solutions contained (0, 0.2, 0.4, 0.6, and 0.8) mol/L NaCl. The results indicated the increase of NaCl concentration caused the enhancement in the equilibrium pressure of CO₂ hydrate as the pore size and the temperature were kept the same. Effects of NaCl solutions on CO₂ hydrate equilibrium conditions could be neglected when the temperature is lower than ice point. An improved model was used to predict CO₂ hydrate equilibrium conditions, and the predictions showed good agreement with experimental measurements.     

Vapor–liquid equilibria and phase densities at saturation of carbon dioxide + 1-butanol and carbon dioxide + 2-butanol from 313 to 363 K

Experimental vapor–liquid equilibria for the systems carbon dioxide + 1-butanol and carbon dioxide + 2-butanol were obtained from 313 to 363 K via a static-analytic set-up. A vibrating U-tube densitometer was coupled to this apparatus to perform simultaneous measurements of both saturated densities of the vapor and liquid phases. The suitability of this apparatus was checked by comparing the experimental vapor–liquid equilibrium and saturated density results with the literature data. The experimental vapor–liquid equilibrium data were correlated using the Peng–Robinson equation of state coupled to the Wong–Sandler mixing rules with good agreement; however densities using the same model were not satisfactorily represented.     

Aqueous two-phase systems containing N-vinylpyrrolidone: Experimental results and correlation/prediction

Experimental results are presented for the liquid–liquid equilibrium of a ternary system (N-vinylpyrrolidone + sodium sulfate + water) and three quaternary systems composed of (N-vinylpyrrolidone + poly(vinylpyrrolidone) + sodium sulfate + water) at 25 °C. The quaternary systems differ in the number averaged molecular mass of the poly(vinylpyrrolidones). That molecular mass was between about 4 000 and 140 000. The experimental results are described with a semi-empirical model (VERS model) for the excess Gibbs energy.     

Pervaporation of dichloromethane from multicomponent aqueous systems containing n-butanol and sodium chloride

In this paper, pervaporation (PV) of dichloromethane (DCM) from binary and multicomponent systems at different feed concentrations and temperatures using a commercial hydrophobic membrane CMX-GF-010-D (CELFA AG, Switzerland) is reported. Coupling effects are studied by permeating DCM/n-butanol/water ternary mixtures. The effect of sodium chloride on the process performance is also evaluated by PV of ternary DCM/sodium chloride/water and quaternary DCM/n-butanol/sodium chloride/water mixtures. PV performance was evaluated by permeate flux and enrichment factor. Further, permeance was calculated for pure water, DCM/water and DCM/n-butanol/water systems at 40 °C.     

Solubility measurements for the CH4 + CO2 + H2O system under hydrate–liquid–vapor equilibrium

Phase equilibria for the CH₄ + CO₂ + H₂O system have been investigated in the past, but mole fraction of methane and carbon dioxide in the bulk liquid phase has not been measured under hydrate–liquid–vapor equilibrium. Equilibrium liquid composition is very important as it defines the driving force for hydrate growth. This study presents the solubility of methane and carbon dioxide under H–Lw–V equilibrium. Emphasis is made on the effect of pressure along the respective isotherms on the equilibrium mole fraction of the individual hydrate formers in the liquid.     

Parameters estimation and VLE calculation in asymmetric binary mixtures containing carbon dioxide + n-alkanols

In the present work, the estimation of the parameters for asymmetric binary mixtures of carbon dioxide + n-alkanols has been developed. The binary interaction parameter k₁₂ of the second virial coefficient and non-random two liquid model parameters τ₁₂ and τ₂₁ were obtained using Peng–Robinson equation of state coupled with the Wong–Sandler mixing rules. In all cases, Levenberg–Marquardt minimization algorithm was used for the parameters optimization employing an objective function based on the calculation of the distribution coefficients for each component. Vapor–liquid equilibrium for binary asymmetric mixtures (CO₂ + n-alkanol, from methanol to 1-decanol) was calculated using the obtained values of the mentioned parameters. The agreement between calculated and experimental values was satisfactory.     

The solubility of water in mixtures of dimethyl ether and carbon dioxide

This paper reports measurements of the solubility of water in liquid and supercritical fluid mixtures of dimethyl ether and carbon dioxide. The measurements were made by extracting water under saturation conditions using premixed liquid dimethyl ether–carbon dioxide mixtures. Results are reported for temperatures of 313.8 K and 333.3 K at 9.0 MPa and 15.0 MPa. Results are fitted to the Peng–Robinson cubic equation of state with mixing rules according to Wong and Sandler, using binary interaction parameters fitted to the literature data for the respective binary systems: dimethyl ether–water; dimethyl ether–carbon dioxide; and carbon dioxide–water. Liquid densities for dimethyl ether–carbon dioxide mixtures, measured using a coriolis flow instrument, are also reported.     

Three-liquid-phase equilibria of ternary and quaternary mixtures,water/n-decane/2-butyloxyethanol and water/n-octane/1-propanol/sodium chloride—experimental measurements and their correlation with the UNIQUAC model

Two- and three-phase liquid—liquid equilibrium data obtained for the ternary system water/n-decane/2-butyloxyethanol and the quaternary system water/n-octane/1-propanol/sodium chloride at 25±0.1°C are presented in this paper. The experimental results are correlated with the UNIQUAC model described by Abrams and Prausnitz using computational algorithms developed by Negahban to obtain the model parameters and to perform phase equilibria calculations.     

A phase diagram approach to determine the composition of vapor from a microemulsion base

The tangents to the evaporation path curves in the W/O microemulsion base of water, (W), pentanol, (P), and sodium dodecyl sulfate, (S), were extended to the W/P axis to establish the relative composition, (W_V, P_V), of the vapor leaving the liquid.The composition of the vapor, with which the microemulsion is in contact includes also the contribution from the relative humidity of the surrounding atmosphere. The difference between the composition of these gases is clarified using the algebraic expressions from the phase diagram, but the quantitative composition of the equilibrium vapor is not available without further numerical information. The limits of the vapor for evaporation direction under different relative humidities were clarified.     

Measurement of mineral solubilities in the ternary systems NaCl−ZnCl<Subscript>2</Subscript>−H<Subscript>2</Subscript>O and MgCl<Subscript>2</Subscript>−ZnCl<Subscript>2</Subscript>−H<Subscript>2</Subscript>O at 373 K

In this work, the solubilities of the salt minerals and the densities of solution in two ternary systems sodium chloride–zinc chloride–water and magnesium chloride–zinc chloride–water were measured at 373 K using an isothermal solution saturation method. Based on the determined equilibrium solubility data and the corresponding equilibrium solid phase, the phase diagrams and density diagrams of the two systems were plotted. The results show that the two ternary systems are complex and the eutectic points, the univariant solubility curves and the solid crystalline phase regions are shown and discussed. The phase diagram of the ternary system NaCl?ZnCl₂?H₂O at 373 K is constituted of two eutectic points, three univariant solubility curves and three solid crystalline phase regions corresponding to NaCl, ZnCl₂ and 2NaCl · ZnCl₂. And the phase diagram of the ternary system MgCl₂?ZnCl₂?H₂O at 373 K includes two eutectic points, three univariant solubility curves and three solid crystalline phase regions corresponding to MgCl₂ · 6H₂O, MgCl₂ · ZnCl₂ · 5H₂O and ZnCl₂. The experimental results were simply discussed.