Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for Jatropha curcas biodiesel

Reported in this study are (liquid + liquid) equilibrium data for binary, ternary, and quaternary systems formed by fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) of Jatropha curcas oil, water, glycerol, methanol, and ethanol at temperatures of (303.15, 318.15, and 333.15) K. In general, all the systems investigated resulted in good agreement between phase compositions of crunodes of tie-lines, solubility curves (binodal curves) and overall compositions, hence indicating low deviations from mass balance. Experimental results were correlated with the UNIQUAC model, showing low deviations among experimental and calculated values.     

Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for soybean biodiesel

This work reports (liquid + liquid) equilibrium (LLE) data for the systems of interest in soybean biodiesel production. Numerical data for LLE were obtained for binary, ternary and quaternary systems comprising fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE) from soybean oil, water, glycerol, methanol, and ethanol at temperatures of (303.15, 318.15, and 333.15) K. Quantification of compounds in equilibrium in both phases was determined by analytical methods whereas solubility curves (binodal) were obtained by the cloud-point method. For all systems investigated, good alignments were obtained between phase compositions and the initial as well as overall compositions hence indicating low deviations from the mass balance. Experimental results were correlated using the UNIQUAC model with satisfactory agreement between experiment and theory.     

Measurement and correlation of phase equilibria in aqueous two-phase systems containing polyvinylpyrrolidone and di-potassium tartrate or di-potassium oxalate at different temperatures

Experimental (liquid + liquid) equilibrium (LLE) measurements and the phase diagram have been determined for aqueous two-phase systems containing polyvinylpyrrolidone (PVP) and di-potassium oxalate or di-potassium tartrate at T = (298.15, 308.15, and 318.15) K. Also, the effects of temperature on the binodal curve and tie-lines have been studied. The Merchuk equation was used to correlate the binodal curves of these systems. Furthermore, several suitable equations were used to fit the tie-line data points. The results show that at each temperature, the agreement between the correlated and the experimental values is good with all of these equations. Also, the effects of the type of salt on LLE are discussed.     

Thermophysical properties of biodiesel and related systems: Low-pressure vapour–liquid equilibrium of methyl/ethyl Jatropha curcas biodiesel

Biodiesel production from non-edible oils has been considered in recent years due to their economic, politics and environmental aspects. Vapour–liquid equilibrium data for the pseudo-binary and pseudo-ternary systems involving fatty acid methyl/ethyl esters from Jatropha curcas oil were determined over the pressure range from (6.7 to 66.7) kPa in an Othmer-type ebulliometer. All systems presented non-ideal behaviour and positive deviations from Raoult’s law. It was observed that the addition of up to 10 wt.% of alcohol (methanol or ethanol) promoted a significant decrease in the boiling point temperatures for the evaluated systems. The UNIQUAC model was used to correlate the experimental values, with good agreement between experiment and model results.     

Coupling transesterifications for no-glycerol biodiesel production catalyzed by calcium oxide

In this study, a method consisting in coupling transesterifications for no-glycerol biodiesel production catalyzed by CaO was put forward. The transesterification between rapeseed oil and methanol was greatly improved by integrating glycerol and dimethyl carbonate (DMC) transesterification. From this result, it was found that the high fatty acid methyl ester (FAME) yield of 92.6% (with ultra-traces of glycerol as a by-product) was obtained at 65 °C under normal pressure, which is as high as the previously reported supercritical DMC method for no-glycerol biodiesel production at a reaction temperature of 350 °C and under pressures up to 17.8 MPa. Moreover, this new method has high water tolerance, and a yield of over 82% of FAME is still achieved in the presence of 0.2% of water. The optimized reaction conditions, such as the molar ratio of DMC to methanol, the catalyst dosage and the reaction time, were investigated to produce high-quality biodiesel. The fuel properties determined and discussed in light of EN 14214 (European standards) demonstrate that the biodiesel produced using this new method has good flow properties with a cloud filter plugging point of –10 °C and a pour point of –9.4 °C. Furthermore, the amount of free glycerol was found to be as low as 0.018% in the biodiesel obtained directly from this new method without any further processing. The results of this study indicate the feasibility of producing quality biodiesel fuels without glycerol by coupling transesterifications.     

A thermodynamic study on solubility and liquid−liquid phase behaviour for 2,2,2-trifluoroethanol + cyclohexane + 1-butanol at three temperatures and pressure 101.3 kPa

This study demonstrates the course of solubility and (liquid + liquid) equilibrium (LLE) for the system (cyclohexane + 1-butanol + 2,2,2-trifluoroethanol) at temperatures of (288.15, 298.15, and 308.15) K and pressure 101.3 kPa. The titration method was used to assess solubility (binodal) curves, while a direct analytical method to acquire tie lines.The consistency of the binodal curves and phase diagrams data were well calculated by Hand and Othmer–Tobias empirical equations. The NRTL and UNIQUAC thermodynamic models gave accurate tie-line values for the systems. Plait-point, distribution coefficient, solvent selectivity, and NRTL and UNIQUAC binary interaction parameters were obtained.The immiscibility region of the system decreases significantly with increasing temperature. The results present an overview of the high efficiency of liquid extraction using 2,2,2-trifluoroethanol as solvent to yield pure cyclohexane from its 1-butanol azeotrope mixture at ambient temperatures.     

Liquid–liquid equilibria for ternary systems of (water + carboxylic acid + 1-octanol) at 293.15 K: modeling phase equilibria using a solvatochromic approach

Liquid–liquid equilibrium data of the solubility (binodal) curves and tie-line end compositions are presented for mixtures of [water (1) + formic acid or propanoic acid or levulinic (4-oxopentanoic) acid or valeric (pentanoic) acid or caproic (hexanoic) acid (2) + 1-octanol (3)] at 293.15 K and 101.3 ± 0.7 kPa. A log-basis approach SERLAS (solvation energy relation for liquid associated system) has been proposed to estimate the properties and liquid–liquid equilibria (LLE) of tertiary associated systems containing proton-donating and -accepting components capable of a physical interaction through hydrogen bonding. The model combines the solvatochromic parameters with the thermodynamic factors derived from the UNIFAC-Dortmund model. The reliability of the model has been analyzed against the LLE data with respect to the distribution ratio and separation factor. The tie-lines were also correlated using the UNIFAC-original model. The proposed model, reflecting the simultaneous impact of hydrogen bonding, solubility and thermodynamic factors, yields a mean error of 27.9% for all the systems considered.     

(Liquid + liquid) equilibria of (water + butyric acid + esters) ternary systems

(Liquid + liquid) equilibrium (LLE) data of the solubility (binodal) curves and tie-line end compositions were examined for mixtures of {water (1) + butyric acid (2) + ethyl propionate or dimethyl phthalate or dibutyl phthalate (3)} at T = 298.15 K and (101.3 ± 0.7) kPa. The relative mutual solubility of the butyric acid is higher in the layers of esters than in the aqueous layer. The reliability of the experimental tie-line data was confirmed by using the Othmer–Tobias correlation. The LLE data of the ternary systems were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.     

(Liquid + liquid) equilibria of (water + propionic acid + diethyl succinate or diethyl glutarate or diethyl adipate) ternary systems

(Liquid + liquid) equilibrium (LLE) data of the solubility (binodal) curves and tie-line end compositions were examined for {water (1) + propionic acid (2) + diethyl succinate or diethyl glutarate or diethyl adipate (3)} at T = 298.15 K and 101.3 ± 0.7 kPa. The relative mutual solubility of the propionic acid is higher in the dibasic esters layers than in the aqueous layers. The reliability of the experimental tie-line data was confirmed by using the Othmer–Tobias correlation. The LLE data of the ternary systems was predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.     

Quaternary (liquid + liquid) equilibria of aqueous two-phase poly (ethylene glycol), poly (DMAM–TBAM), and KH2PO4: Experimental and generalized Flory–Huggins theory

Quaternary (liquid + liquid) equilibrium (LLE) data of the aqueous two-phase poly (ethylene glycol), poly (N,N-dimethylacrylamide-t-butylacrylamide) with abbreviation name poly (DMAM–TBAM) as a hydrophobic association water-soluble copolymer and KH₂PO₄ has been determined experimentally at T = 338.15 K. Furthermore, the generalized Flory–Huggins theory with two electrostatic terms (the Debye–Hückel and Pitzer–Debye–Hückel) was used for correlation of the phase behavior of the quaternary system and the interaction parameters between all species were calculated.It was found that addition of poly (DMAM–TBAM) copolymer as well as changing the temperature can shift the binodal curves of aqueous two-phase systems containing polyethylene glycol (PEG) and salt. Also, the phase behavior of the DMAM–TBAM copolymer with some salts containing sodium chloride, ammonium hydrogen phosphate, potassium hydrogen phosphate, and sodium carbonate were studied experimentally at T = 338.15 K and the effect of the salt type on the their binodal curves was determined.     

(Liquid + liquid) equilibria of (water + butyric acid + dibasic esters) ternary systems

(Liquid + liquid) equilibrium (LLE) data of the solubility (binodal) curves and tie-line end compositions were examined for mixtures of {water (1) + butyric acid (2) + dimethyl succinate or dimethyl glutarate or dimethyl adipate (3)} at T = 298.15 K and p = (101.3 ± 0.7) kPa. The relative mutual solubility of the butyric acid is higher in the dibasic esters layers than in the aqueous layer. The reliability of the experimental tie-line data was confirmed by using the Othmer–Tobias correlation. The LLE data of the ternary systems were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.     

Binodal curve measurements for (water + propionic acid + dichloromethane) ternary system by cloud point method

The binodal (solubility) curves and tie line data for ternary systems of (water + propionic acid + dichloromethane) at 91.3 kPa and T = (277.15, 284.15, and 294.15) K are reported. The binodal curve results were determined by cloud point measurements method. A simple titration method has been used for determining of the concentration of propionic acid in the both liquid phases at equilibrium. The results obtained were successfully correlated with the UNIQUAC activity coefficient model. The deviations between experimental and calculated compositions in both phases for the ternary system using this model are reported. The partition coefficients of propionic acid and the selectivity factor of dichloromethane for extracting of propionic acid from water were calculated and are reported. The phase diagrams for the ternary system studied including both the experimental and correlated tie lines are presented.     

Influence of temperature on the (liquid + liquid) equilibria of {3-methyl pentane + cyclopentane + methanol} ternary system at T = (293.15, 297.15, and 299.15) K

In order to show the influence of temperature on the (liquid + liquid) equilibria (LLE) of the {3-methyl pentane (1) + cyclopentane (2) + methanol (3)} ternary system, equilibrium results at T = (293.15, 297.15, and 299.15) K are reported. The effect of the temperature on the (liquid + liquid) equilibrium is determined and discussed. Experimental results show that this ternary system is completely homogeneous beyond T = 300 K. All chemicals were quantified by gas chromatography using a thermal conductivity detector. The tie line results were satisfactorily correlated by the Othmer and Tobias method, and the plait point coordinates for the three temperatures were estimated. Experimental values for the ternary system are compared with values calculated by the NRTL and UNIQUAC equations, and predicted by means of the UNIFAC group contribution method. It is found that the UNIQUAC and NRTL models provide similar good correlations of the solubility curve at these three temperatures. Finally, the UNIFAC model predicts binodal band type curves in the range of temperatures studied here, similar to those observed for systems classified by Treybal as type 2, instead of type 1 as experimentally observed. Distribution coefficients were also analysed through distribution curves.     

(Liquid + liquid) equilibria of (water + lactic acid + alcohol) ternary systems

(Liquid + liquid) equilibrium (LLE) measurements of the solubility (binodal) curves and tie-line end compositions were carried out for {water (1) + lactic acid (2) + octanol, or nonanol, or decanol (3)} at T = 298.15 K and 101.3 ± 0.7 kPa. The relative mutual solubility of lactic acid is higher in the water layers than in the organic layers. The reliability of the experimental tie-line data was confirmed by using the Othmer–Tobias correlation. The LLE results for the ternary systems were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.     

(Surfactant + polymer) interaction parameter studied by (liquid + liquid) equilibrium data of quaternary aqueous solution containing surfactant,polymer, and salt

(Liquid + liquid) equilibrium (LLE) data of quaternary aqueous system containing polyoxyethylene (20) cetyl ether (with abbreviation name Brij 58, non-ionic surfactant), diammonium hydrogen phosphate, and poly ethylene glycol (PEG) with three molar masses {M_W = (1000, 6000, and 35,000) g · mol^?1} have been determined experimentally at T = 313.15 K.Furthermore, the Flory–Huggins theory with two electrostatic terms (Debye–Hückel and Pitzer–Debye–Hückel equations) have been used to calculate the phase behavior of the quaternary systems and (surfactant + polymer) interaction parameter as well as interaction parameters between other species. Temperature dependency of the parameters of the Flory–Huggins theory has been obtained.Also an effort have been done to show that addition of PEG as well as increasing the temperature can shift the binodal curves of the ternary aqueous system containing surfactant and salt to lower mole fraction of salt. Also the effect of polymer molar mass on the binodal diagram displacement has been discussed.     

Quaternary (liquid + liquid) equilibria of aqueous two-phase polyethylene glycol,poly-N-vinylcaprolactam,and KH2PO4: Experimental and the generalized Flory–Huggins theory

A quaternary (liquid + liquid) equilibrium study was performed to focus attention on the interaction parameters between poly-N-vinylcaprolactam (PVCL) and poly-ethylene glycol (PEG) as well as between other species. At first, the new experimental data of (liquid + liquid) equilibria for aqueous two-phase systems containing PEG, KH₂PO₄, and PVCL at T = 303.15 K have been determined. Then the Flory–Huggins theory with two electrostatic terms (the Debye–Huckel and the Pitzer–Debye–Huckel equations) has been generalized to correlate the phase behavior of the quaternary system. Good agreement has been found between experimental and calculated data from both models especially from the Pitzer–Debye–Huckel equation.Also an effort was done to compare the effect of temperature as well as addition of PVCL on the binodal curves of PEG, KH₂PO₄, and water. The effect of the type of salt on the binodals has been also studied, and the salting out power of the salts has been determined.     

Liquid–liquid equilibria of the ternary system water + acetic acid + dimethyl succinate

Liquid–liquid equilibrium (LLE) data of water + acetic acid + dimethyl succinate were measured at 298.2, 308.2, and 318.2 K. Complete phase diagrams were obtained by determining binodal curves and tie lines. The reliability of the experimental tie line data was confirmed by using the Othmer–Tobias correlation. The UNIFAC and modified UNIFAC model were used to predict the phase equilibrium data in the ternary system. Distribution coefficients and separation factors were evaluated for the immiscibility region.     

(Liquid + liquid) equilibrium of (imidazolium ionic liquids + organic salts) aqueous two-phase systems at T = 298.15 K and the influence of salts and ionic liquids on the phase separation

(Liquid + liquid) equilibrium for the {1-ethyl-3-methylimidazolium tetrafluoroborate ([C₂mim]BF₄)/1-propyl-3-methylimidazolium tetrafluoroborate ([C₃mim]BF₄) + organic salt + H₂O} aqueous two-phase systems (ATPSs) have been experimentally ascertained at T = 298.15 K. Three empirical equations were used to correlate the binodal data. On the basis of the empirical equation of the binodal curve with the highest accuracy and lever rule, the (liquid + liquid) equilibrium data were calculated by MATLAB. The reliability of the tie line compositions was proved by the empirical correlation equations given by the Othmer–Tobias and Bancroft equations. The effective excluded volume (EEV) values obtained from the binodal model for these systems were determined. The EEV and the binodal curves plotted in molality both indicate that the salting-out abilities of the four salts follow the order: Na₃C₆H₅O₇ > (NH₄)₃C₆H₅O₇ > Na₂C₄H₄O₄ ≈ Na₂C₄H₄O₆, while the phase-separation abilities of the investigated ILs are in the order of [C₃mim]BF₄ > [C₂mim]BF₄. In the systems investigated, the effect of salts on the phase-forming capability was also evaluated in the shape of the salting-out coefficient obtained from fitting the tie-line data to a Setschenow-type equation. The phase-forming ability increases with the increase of salting-out coefficient.     

High-pressure multiphase equilibria in the system glycerol + olive oil + propane + AOT

This work investigated the high-pressure phase behavior of systems containing glycerol, olive oil and propane in the presence of surfactant AOT. The static synthetic method, using a variable-volume view cell, was employed for obtaining the experimental data in the temperature range from 298 to 373 K, and pressures up to 30 MPa. First, the effect of addition of AOT on the vapor pressure of pure propane was investigated and then the effect of addition of AOT to mixtures of propane + glycerol. Measurements were afterwards accomplished for the system propane + AOT + glycerol + olive oil. For the ternary system liquid–liquid (LLE) and vapor–liquid–liquid (VLLE) equilibrium were observed. Besides VLE, LLE and VLLE, the quaternary system propane + AOT + glycerol + olive oil exhibited at higher concentrations of the glycerol/olive oil ratio a fascinating phase behavior, with the occurrence of three (LLL) and four (VLLL)—phases in equilibrium.     

Experimental (vapour + liquid) equilibrium data of (methanol + water), (water + glycerol) and (methanol + glycerol) systems at atmospheric and sub-atmospheric pressures

Experimental (vapour + liquid) equilibrium results for the binary systems, (methanol + water) at the local atmospheric pressure of 95.3 kPa and at sub-atmospheric pressures of (15.19, 29.38, 42.66, 56.03, and 67.38) kPa, (water + glycerol) system at pressures (14.19, 29.38, 41.54, 54.72, 63.84, and 95.3) kPa and the (methanol + glycerol) system at pressures (32.02 and 45.3) kPa were obtained over the entire composition range using a Sweitoslwasky-type ebulliometer. The relationship of the liquid composition (x₁) as a function of temperature (T) was found to be well represented by the Wilson model. Computed vapour phase mole fractions, activity coefficients and the measured values along with optimum Wilson parameters are presented.