Ternary Equilibrium Data Research Articles

Energy-efficient recovery of fermented butyric acid using octyl acetate extraction

BackgroundA butyric acid recovery process using octyl acetate is proposed, and the design details of the extraction and subsequent distillation processes were investigated. Ternary equilibrium data for the extractor design were derived from molecular simulations and experimental measurements.ResultsA new procedure for estimating the thermodynamic parameters was introduced to determine the effect of the parameters on extractor design by comparison with previously reported parameters. Using the proposed recovery process with the newly estimated thermodynamic model, 99.8% butyric acid was recovered from the fermentation broth at a recovery rate of 99%. The energy demand for the proposed process was found to be lower than the average demand for several reported butyric acid recovery processes.ConclusionsThe investment cost is projected to be lower than that of other butyric acid processes due to the high efficiency of extraction solvent. The recovery cost of butyric acid was comparable to its selling price.Supplementary InformationThe online version contains supplementary material available at 10.1186/s13068-022-02146-6.

Solid–Liquid–Liquid Equilibria of the System Water, Acetonitrile, and Ammonium Bicarbonate in Multiphase Reacting Systems

The salting out of acetonitrile from water in the presence of ammonium bicarbonate was studied at atmospheric pressure from 4 to 35 °C. The coexisting phases were analyzed independently with H1 nuclear magnetic resonance, ion chromatography, calorimetry, and titrations. The binodal region was described with semiempirical functions and with the UNIQUAC thermodynamic model. The critical composition at ambient temperature is given by 0.02 g/g of salt and 0.58 g/g of acetonitrile: at lower salt concentrations; this mixture is widely employed in liquid chromatography, thanks to the buffering properties of the bicarbonate. The separation of acetonitrile and water for extraction purposes, instead, is often obtained with other ammonium salts. These ternary equilibrium data can then be useful to develop extraction and analysis procedures at buffered, mildly alkaline pH. In addition, this mixture can be encountered during the acetonitrile synthesis proposed from bioethanol and bioethylene, so these multiphase equilibria govern the separation and purification of acetonitrile in specific reactors that allow the recovery of ammonium bicarbonate as a valuable byproduct. Furthermore, the solubility of this salt in alcohols and its decomposition were investigated to target its stability in multiphase reactors, extractors, and driers.

Vapor-liquid equilibria for binary and ternary systems composed of acetone, 1-butanol, and ethanol at atmospheric pressure

The experimental vapor-liquid equilibrium data for three binary systems of acetone + 1-butanol, ethanol + 1-butanol, acetone + ethanol and a ternary system of ethanol + acetone + 1-butanol at atmospheric pressure were measured using an ebulliometer. The binary experimental data were correlated using the Wilson, NRTL, and UNIQUAC models to obtain the binary interaction parameters of the models. These parameters were used to predict the ternary equilibrium data. The average absolute deviations of temperature (AAD T) between the experimental and correlation data of the three models are the same, 0.63, for the acetone + 1-butanol system, 0.72, 0.65, and 0.70, for the ethanol + 1-butanol system, and 0.15, 0.30, and 0.19, for the acetone + ethanol system, respectively. The AAD T values for the ternary system of ethanol + acetone + 1-butanol by comparing the experimental data with the data calculated using the three models were 0.28, 0.56, and 0.67, respectively.

Post combustion carbon capture with supported amine sorbents: From adsorbent characterization to process simulation and optimization

Supported amine sorbents are extensively studied in literature due to their moisture tolerating abilities. Most of the work with this group of adsorbents pertain to experimental studies on adsorption capacity, kinetics, and stability tests on powdered sorbents. Only a handful of published studies have carried out thermodynamic assessment and process modelling to evaluate the performance of supported amine sorbents in the context of pressure and temperature swing adsorption processes. In this work, we have evaluated a commercially available mesoporous silica (PERLKAT) adsorbent grafted with N-[3-(trimethoxysilyl)propyl] ethylenediamine for post-combustion carbon capture by vacuum swing adsorption process (VSA). Experiments were first carried out to obtain information on single component and ternary equilibrium data. The adsorbent has a total capacity of 0.95 mmol/g at 0.15 bar CO2 and 0.8 mmol/g at 0.05 bar CO2 respectively at 70 °C. Ternary experiments at low relative humidity shows that the CO2 capacity is not affected in the presence of moisture. These results were used as input to simulate and optimize a 6-step dual reflux vacuum swing adsorption (VSA) cycle. Detailed process optimization shows that it is possible to capture 90% of the CO2 at 95% purity using our adsorbent. The minimum specific energy is 1 MJ/kg CO2 captured on an electric basis when the VSA process is operated at 90 °C.

Measurement and correlation of ternary (liquid–liquid) equilibrium data for n-heptane + p-xylene + (furfural or dimethyl sulfoxide) system at 303.15 K and 323.15 K

Liquid-liquid equilibrium (LLE) data for {n-heptane + p-xylene (PX) + furfural/dimethyl sulfoxide (DMSO)} ternary systems were measured at 303.15 K and 323.15 K and atmospheric pressure. Extraction performance of furfural and DMSO were evaluated using distribution coefficient (D) and selectivity (S) according to the measured tie-line data. And the results showed that DMSO had better extraction performance than furfural for separation of n-heptane and PX. Both UNIQUAC and NRTL models were used to correlate the experimental LLE data, and relevant interaction parameters were obtained. Consistency between the measured LLE data and the calculated by these two models was well evaluated by RMSD and maximum absolute deviation. Moreover, reliability of binary interaction parameters was confirmed by topological analysis related to the Gibbs tangent plane test.

Identification of UNIQUAC binary interaction parameters in liquid-liquid equilibrium

An algorithm is presented for the estimation of the UNIQUAC interaction parameters for liquid-liquid equilibrium of ternary systems. The algorithm is based on two optimization levels. In the inner level the algorithm performs the minimization of an objective function based on the isoactivity conditions. The outer level aims to minimize the error between calculated and experimental compositions. The Common Tangent Plane condition is checked at the end to guarantee a thermodynamically consistent representation of the phase behavior of ternary liquid systems.The algorithm is challenged with a historical Type 1 ternary liquid-liquid equilibrium system from the seminal study of Anderson and Prausnitz in which the authors showed the limitations of the original UNIQUAC model and justified its amendment in the modified UNIQUAC model. The present algorithm makes available single temperature and temperature-dependent interaction parameters enabling accurate and thermodynamically correct description of the experimental data with the original UNIQUAC model, therefore without the need of any model modification. This outcome does not change when the interaction parameters from the binary partially miscible constituent pair are first regressed and kept constant during the estimation of the remaining parameters on ternary equilibrium data. This investigation confirms that a model cannot be judged if the correctness of the model parameters has not been proved first.

Ternary liquid-liquid equilibria for β-caryophyllene(1) + 1-propanol(2) + water(3) system at temperatures 303.15, 313.15, and 323.15 K

The experimental liquid–liquid equilibrium data of the system β–caryophyllene(1) + 1-propanol(2) + water(3) at temperatures 303.15, 313.15, and 323.15 K are presented. The mixtures of β–caryophyllene + 1-propanol + water were stirred for 4 hours and settled for at least 20 hours at constant temperature. The samples taken from both phases were analyzed by a gas chromatography (GC). The experimental equilibrium data were correlated by NRTL and UNIQUAC models. The compatibility of the models is based on the value of root mean square deviation (RMSD). The liquid-liquid phase diagram of the system shows type I phase behavior, where two binary subsystems are miscible and only one binary subsystem is partially miscible. The temperature effect of this system on immiscible zone is very small. Based on the experiment and the calculation results, the ternary equilibrium data have been successfully represented using both the NRTL and the UNIQUAC models.

LLE of Methanol-Methylcyclohexane-Isooctane-Benzene Quaternary System

A quaternary system {methanol + methylcyclohexane + isooctane + benzene} was studied at T = 303.15 K. Only after all ternary equilibria data were determined experimentally, the quaternary binodal surface could be characterized fully. For this purpose, tie line data of {methanol + methylcyclohexane + benzene} ternary systems were obtained at the same temperature, while data for {methanol + isooctane+ benzene}, and {methanol + + isooctane + methylcyclohexane} were taken from literature. Experimental results show that the binodal surface with four quaternary sectional planes P1,P2,P3,P4 with several methylcyclohexane/isooctane in the solid diagram is small and that the highest benzene mass fraction values beyond which only one phase is present for the methanol-rich phase and hydrocarbon-rich one, respectively, are: 0.046 and 0.053 for P1, 0.053 and 0.057 for P2, 0.055 and 0.049 for P3, 0.034 and 0.041 for P4. So, if this quaternary system contains the correct methanol and hydrocarbons concentrations, this blend can be used as a reformulated gasoline because no phase separation should be observed. The distribution of benzene between both phases was also analysed. Ternary experimental results were correlated with the UNIQUAC and NRTL equation.The UNIQUAC equation is more accurate than the NRTL equation for the ternary systems studied here. The equilibria data of the three ternary systems were used to determine interactions parameters for the UNIQUAC equation. The UNIQUAC equation fitted to the experimental data is more accurate than the UNIFAC method for this quaternary system. The main reason for this is that F is fit in the size of the quaternary binodal surface.

Incorrect Ternary Liquid–liquid Equilibria Description Versus Extractor Design Simulation

The presented study focuses on the separation of aromatics from aliphatic hydrocarbons by liquid-phase extraction using ionic liquids. The aim of this study was to show the impact of incorrect description of liquid–liquid equilibria of the separated system on the extractor design parameters.Extraction is usually applied for the separation or concentration of dilute solutions with the aim to achieve minimum concentration of the separated component in the final raffinate. Therefore, correct description of the liquid–liquid (L-L) equilibrium in this concentration region is very important for the industrial practice. For thermodynamic description of a ternary L-L equilibrium, excess Gibbs energy dependencies on the mixture composition are applied. Model parameters of the mentioned equations can be evaluated from different experimental equilibrium data. The most commonly used experimental data are ternary tie lines.Parameters of the GE equations evaluated from experimental tie lines usually provide good or evenexcellent description of the given ternary L-L area. Extrapolation of the L-L data beyond this region, however, can sometimes lead to incorrect L-L equilibrium description. This problem is shown on the real ternary system heptane – toluene – 3-methyl-N-butylpyridinium tetracyanoborate ([3-mebupy][B(CN)4)]). This study proves serious discrepancies in the extractor design parameters using the NRTL equation parameters evaluated from experimental ternary equilibrium data. Depending on the initial guess, the mathematical model of a continuous counter-current extraction column offered at least three different values of the extraction solvent consumption for the preset purity of the final raffinate and of the number of theoretical stages.

(Liquid + liquid) equilibria for mixtures of dodecane and ethanol with alkylsulfate-based ionic liquids

The ternary (liquid+liquid) equilibrium (LLE) data for mixtures of dodecane (C12H26) and ethanol with ionic liquids 1,3-dimethylimidazolium methylsulfate [Mmim][MeSO4], 1-ethyl-3-methylimidazolium methylsulfate, [Emim][MeSO4] and 1-butyl-3-methylimidazolium methylsulfate, [Bmim][MeSO4], were studied at T=298.15K and 0.101MPa. The selectivity and solute distribution coefficient ratios determined from the data were used to examine the possibility of using these ionic liquids for extraction of ethanol from dodecane. The temperature dependency was investigated by measuring the LLE data for {dodecane+ethanol+[Mmim][MeSO4]} at T=313.15K and 0.101MPa. The Othmer–Tobias and Hand equations were used to test the consistency of the tie-line data. The tie-line data were correlated with the Non-Random Two Liquid (NRTL) equation which provided a good model and representation for the experimental results.

Liquid–liquid phase equilibria for ternary systems of several polyethers with NaCl and H2O

Liquid–liquid extraction using polymers followed by induced phase separation is a potential energy reducing technology for water–salt separation. Ternary equilibrium data have been determined and reported for the (block co)poly ethers–sodium chloride–water systems at two different temperatures at 298.15K and 313.15K and atmospheric pressure. The experimental data were correlated with the NRTL model, and the obtained binary interaction parameters to describe the ternary liquid–liquid systems at different temperatures are presented. The model predictions are in good agreement with the experimental data.

Ternary (liquid–liquid) equilibrium data of furfuryl alcohol with organic solvents at T = 298.2 K: Experimental results and thermodynamic models

Basing on the importance of liquid–liquid equilibrium (LLE) data for the chemical industry, ternary LLE systems of water+furfuryl alcohol+(MIBK, ethyl acetate, furfural or n-butanol) were investigated at T=298.2K and atmospheric pressure. Solubility and tie-line data of these ternary LLE systems were determined by a direct measurement method. An uncertainty propagation calculation was used to validate the reliability of LLE results. Distribution coefficients (D) and separation factors (S) were calculated to evaluate the capability of selective organic solvents for separation of furfuryl alcohol from water. The correlations of experimental results with results obtained by using NRTL, UNIQUAC and UNIFAC models were presented and confirmed by rmsd values which were less than 5%.

Separation of thiophene from heptane with ionic liquids

Ionic liquids (ILs) are well known novel green solvents, which can be used for removing sulfur compounds from gasoline and diesel oils. Ternary (liquid+liquid) equilibrium data are presented for mixtures of {ionic liquid (1)+thiophene (2)+heptane (3)} at T=298.15K and ambient pressure to analyze the performance of the ionic liquid (IL) in the extraction of thiophene from the alkanes. Three pyrrolidinium-based ionic liquids have been studied: 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, ([BMPYR][FAP]), 1-butyl-1-methylpyrrolidinium tetracyanoborate, [BMPYR][TCB] and 1-butyl-1-methylpyrrolidinium tricyanomethanide, [BMPYR][TCM]. The results are discussed in terms of the selectivity and distribution ratio of separation of related systems. The immiscibility in the binary liquid systems of (thiophene+heptane) with all used ILs was observed. The [TCM]− anion in comparison with [TCB]− and [FAP]− anions shows much higher selectivity and slightly lower distribution ratio for extraction of thiophene. The non-random two liquid NRTL model was used successfully to correlate the experimental tie-lines and to calculate the phase composition error in mole fraction in the ternary systems. The average root mean square deviation (RMSD) of the phase composition was 0.047. The densities of [BMPYR][TCM] in temperature range from (298.15 to 348.15)K were measured. The data presented here show that the [BMPYR][TCM] ionic liquid can be used as an alternative solvent for the separation of thiophene from the hydrocarbon stream using solvent liquid–liquid extraction at ambient conditions.

Study of the ion exchange equilibrium of Cl−, $$ NO_3^{ - } $$ , and $$ SO_4^{{2 - }} $$ ions on the AMX membrane

Equilibrium between the ion exchange membrane and solutions of anions at various valences has been the subject of this investigation. Competitive ion exchange reactions were studied on a strong base anion exchange membrane AMX manufactured by Tokuyama, commercialized by Eurodia, involving Cl−, \( {\text NO}_3^{ - } \) and \( {\text SO}_4^{{2 - }} \) ions. Solution concentrations studied were 0.05 and 0.1 M for all the systems reported. Experiments were performed with sodium as the counter ion, and the temperature was kept constant (T = 298 K). Ionic exchange isotherms for the binary systems—\( {{\text Cl}^{ - }}/{\text NO}_3^{ - } \), \( {{\text Cl}^{ - }}/{\text SO}_4^{{2 - }} \), and \( {\text NO}_3^{ - }/{\text SO}_4^{{2 - }} \)—were established. The obtained results show that the sulfate was the most strongly sorbed, and the selectivity order is \( {\text SO}_4^{{2 - }} > {\text NO}_3^{ - } > {{\text Cl}^{ - }} \) at 0.05 M and \( {\text NO}_3^{ - } > {\text SO}_4^{{2 - }} > {{\text Cl}^{ - }} \) at 0.1 M under the experimental conditions. Selectivity coefficients \( K_{{{{{\text Cl} }^{ - }}}}^{{{\text NO}_3^{ - }}} \), \( K_{{2{{{\text Cl} }^{ - }}}}^{{{\text SO}_4^{{2 - }}}} \), and \( K_{{2{\text NO}_3^{ - }}}^{{{\text SO}_4^{{2 - }}}} \) for the three binary systems were determined. All the results given by this membrane were compared with those obtained, in the same conditions, with the RPA membrane (produced by RHONE POULENC). Ternary equilibrium data were taken for \( {{\text Cl}^{ - }}/{\text NO}_3^{ - }/{\text SO}_4^{{2 - }} \). The prediction of the ternary system based only on the binary data was consistent with the experimental data obtained for this system. The good agreement between the experimental and the predicted data showed that the proposed framework can be considered as an effective method to predict many ternary systems from binary systems.

Extraction of butan-1-ol from water with ionic liquids at T = 308.15 K

Ionic liquids (ILs) are novel green solvents that can be proposed for removing butan-1-ol from the aqueous fermentation media. Ternary (liquid+liquid) equilibrium data are presented for {ionic liquid (1)+butan-1-ol (2)+water (3)} at T=308.15K and ambient pressure to analyze the performance of the ionic liquid (IL) in the extraction of butan-1-ol from aqueous phase. The tetracyanoborate-based ILs have been studied: 1-hexyl-3-methylimidazolium tetracyanoborate, ([HMIM][TCB]), 1-decyl-3-methylimidazolium tetracyanoborate, ([DMIM][TCB]) and trihexyltetradecylphosphonium tetracyanoborate, ([P14,6,6,6][TCB]). The results are discussed in terms of the selectivity and distribution ratio of separation of related systems. The complete miscibility in the binary liquid systems of butan-1-ol with all used ILs was observed. The imidazolium cation in comparison with phosphonium cation shows lower selectivity and distribution ratio. The IL with the longer alkyl chain at the cation shows higher selectivity and distribution ratio in this process. The non-random two liquid NRTL model was used successfully to correlate the experimental tie-lines and to calculate the phase composition error in mole fraction in the ternary systems. The average root mean square deviation (RMSD) of the phase composition was 0.0027. The data presented here indicates the usefulness of [P14,6,6,6][TCB] as a solvent for the separation of butan-1-ol from water using solvent extraction. The density of [P14,6,6,6][TCB] was measured as a function of temperature.

(Liquid + liquid) equilibrium data of (water + phosphoric acid + solvents) systems at T = (308.2 and 318.2) K

Ternary equilibrium data for the mixtures of {water+phosphoric acid+organic solvent (cyclohexane, methylcyclohexane, and toluene)} were determined at T=(308.2 and 318.2)K and atmospheric pressure. Solubility data were determined by the cloud-point titration method. In order to obtain the tie-line data, the concentration of each phase was determined by acidimetric titration, the Karl–Fischer technique, and refractive index measurements. The experimental tie-line data were correlated using the UNIQUAC and NRTL models. The reliability of the experimental data was determined through the Othmer–Tobias and Hand plots. Distribution coefficients and separation factors were evaluated over the immiscibility regions. The Katritzky LSER model was applied to correlate distribution coefficients and separation factors in these ternary systems.

Ternary equilibrium data of mixtures consisting of 2-butanol, water, and heavy alcohols at T = 298.2 K

Experimental solubility curves and tie-line data for the (water+2-butanol+organic solvents) systems were obtained at T=298.2K and atmospheric pressure. The organic solvents were four heavy alcohols, i.e. 1-hexanol, 1-heptanol, 1-octanol, and 1-decanol. The consistency of the experimental tie-line data was determined through the Othmer–Tobias and Bachman equations. Distribution coefficients and separation factors were calculated to evaluate the extracting capability of the solvents. The experimental data were correlated using the NRTL (α=0.2) and UNIQUAC models, and binary interaction parameters were obtained. The average root mean square deviation values between the experimental and calculated data show the capability of these models, in particular NRTL model, in correlation of the phase behavior of the ternary systems.

Extractive distillation modeling of the ternary system 2-methoxy-2-methylpropane-methanol-butan-1-ol

AbstractInfluence of model complexity on the separation equipment performance was investigated. As an example, separation of azeotrope formed by 2-methoxy-2-methylpropane and methanol was considered using butan-1-ol as an extractive solvent. Non-equilibrium model of a column for extractive distillation accounting for the mass and heat transfer rates was composed according to the rigorous Maxwell-Stefan theory. An empirical AICHE correlation was adopted for the calculation of binary mass transfer coefficients at column trays. Results of the column steady-state operation were compared with those obtained assuming different equilibrium models. Effect of the quality of the vapor-liquid equilibrium (VLE) description on the results of the separation simulation considering real behavior of either liquid or both equilibrium phases was tested. Real behavior of the liquid phase was computed according to the NRTL equation taking into account binary and, in some cases, also ternary equilibrium data. In case of real behavior of the vapor phase, the equation of state in the form of virial expansion was employed. Qualitative agreement was found comparing the simulation results calculated by equilibrium and non-equilibrium models of the extractive distillation column while using the same description of ternary VLE.

LLE for the extraction of alcohol from aqueous solutions with diethyl ether and dichloromethane at 293.15 K, parameter estimation using a hybrid genetic based approach

Experimental liquid–liquid equilibrium (LLE) data for the extraction of methanol, ethanol and 1-propanol from water by diethyl ether and dichloromethane at 293.15 K and at ambient pressure were investigated. Data for the binodal curves have been determined by cloud-point titration method and conjugate points on tie-line were obtained by correlating the refractive index of the binodal curves as a function of composition. The experimental ternary (liquid + liquid) equilibrium data have been estimated using the NRTL and UNIQUAC activity coefficient models to obtain the binary interaction parameters of these components by a combination of Levenberg–Marquardt method and the genetic algorithm based method. The distribution coefficients and the selectivity factor of the solvent used were calculated and presented. From our experimental and calculated results, we conclude that for the extraction of alcohol from aqueous solutions with dichloromethane solvent has a higher selectivity factor than the diethyl ether solvent.

Binary and ternary (liquid + liquid) equilibrium for {methylcyclohexane (1) + toluene (2) + 1-hexyl-3-methylimidazolium tetracyanoborate (3)/1-butyl-3-methylimidazolium tetracyanoborate (3)}

This paper focuses on the study of the solubility behaviour of 1-hexyl-3-methylimidazolium tetracyanoborate [HMIM][TCB] and 1-butyl-3-methylimidazolium tetracyanoborate [BMIM][TCB] in combination with methylcyclohexane and toluene as representatives for non-aromatic and aromatic components. Binary and ternary (liquid+liquid) equilibrium data were collected at three different temperatures and at atmospheric pressure (0.1MPa). The experimental data were well-correlated with the NRTL and UNIQUAC thermodynamic models; however, the UNIQUAC model gave better predictions than the NRTL, with a root mean square error below 0.97%. The non-aromatic/aromatic selectivities of the ionic liquids make them suitable solvents to be used in extractive distillation processes.