Solubilities of Essential Oil Components of Orange in Supercritical Carbon Dioxide

The solubilities of pure limonene and linalool in compressed carbon dioxide have been measured using a flow apparatus at 318.2 K and 328.2 K and pressures ranging from 69 bar to 111 bar. The solubilities were successfully modeled using equations of state (Peng−Robinson, Soave−Redlich−Kwong, 3P1T, Dohrn and Prausnitz nopolar) and a semiempirical equation (Chrastill model). The generalized parameters for the Peng−Robinson EOS were obtained for each system. These parameters were independent of temperature, and they reproduce successfully all data available in the literature. The results show that the solubility of limonene in supercritical carbon dioxide was bigger than the solubility of linal…

Vapor−Liquid Equilibria for the Binary Systems Isobutanol with m-Xylene, o-Xylene and p-Xylene at 101.3 kPa

Vapor−liquid equilibria were measured for binary systems of isobutanol with m-xylene, o-xylene, and p-xylene at 101.3 kPa using a recirculating still. The accuracy of experimental measurements was ±0.1 K in temperature, ±0.01 kPa in pressure, and ±0.001 in mole fraction. The results were determined to be thermodynamically consistent according to the point-to-point consistency and Wisniak tests. All the systems show moderate positive deviations from ideality. The data were correlated with five liquid-phase activity coefficient models (Margules, Van Laar, Wilson, NRTL, UNIQUAC).

Approach to the 1-propanol dehydration using an extractive distillation process with ethylene glycol

Abstract The extractive distillation process exploits the capacity of some chemicals to alter the relative volatility between the components of a mixture. In this way, a third component (called entrainer) may be added to an azeotropic binary mixture to break the azeotrope. This paper discusses the potential use of ethylene glycol as entrainer in a 1-propanol dehydration process by extractive distillation. First, the present work focuses on the acquisition of isobaric vapor–liquid equilibrium data of the ternary system 1-propanol + water + ethylene glycol system and the binaries systems 1-propanol + ethylene glycol and water + ethylene glycol. All measurements were done at 101.3 kPa. The exp…

Measurements and correlation of liquid–liquid equilibria of 4-methyl-2-pentanone+ethanol+water and 4-methyl-2-pentanone+n-butanol+water ternary systems between 283.2 and 323.2K

Abstract In this work, experimental liquid–liquid equilibria data of the systems 4-methyl-2-pentanone + ethanol + water and 4-methyl-2-pentanone + n-butanol + water are presented. The liquid–liquid equilibria of both systems have been measured between 283.2 and 323.2 K. The NRTL and UNIQUAC models were applied to fit the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. The binodal lines were compared to the values predicted by the UNIFAC-LLE and UNIFAC models. Moreover, the solvent capability of 4-methyl-2-pentanone was checked in order to separate these azeotropic mixtures alcohol + water.

Phase equilibria for the ternary systems ethanol, water+ethylene glycol or+glycerol at 101.3kPa

Abstract Two solvents, ethylene glycol and glycerol, are proposed as possible entrainers for the extractive distillation of the binary azeotropic mixture formed by ethanol and water. In this way, consistent isobaric vapour–liquid equilibrium data at 101.3 kPa were measured for the ternary systems ethanol + water + ethylene glycol and ethanol + water + glycerol. The data were correlated by local compositions models Wilson, NRTL and UNIQUAC. Parameters of these models were later employed to evaluate ability of the candidates to break the original azeotrope. The obtained results led to consider the ethylene glycol and the glycerol as valid entrainers for the extractive distillation process of …

Vapor-liquid equilibria for the binary systems of methylcyclohexane with 1-propanol, 2-propanol, 1-butanol, and 2-butanol at 101.3 kPa

Isobaric vapor−liquid equilibrium measurements at 101.3 kPa are reported for the binary systems methylcyclohexane + 1-propanol, + 2-propanol, + 1-butanol, and + 2-butanol. The systems show a strong positive deviation from ideality and present a minimum temperature azeotrope. The activity coefficients were found to be thermodynamically consistent by the methods of Van Ness−Byer−Gibbs and Wisniak. The date were correlated with five liquid-phase activity coefficient models (Margules, Van Laar, Wilson, NRTL, and UNIQUAC). According to the average deviations in temperature and in vapor composition the best model for the systems is NRTL.

On the Mechanism of Xylene Isomerization and its Limitations as Reaction Test for Solid Acid Catalysts

The kinetics of the gas-phase isomerization of m-xylene, over a series of ultraestable Y zeolites, has been studied in a fixed-bed flow reactor under initial conditions. Using deuterated p-xylene as reactant it has been seen that more than 20% of the m- and o-xylene obtained, are formed via a bimolecular mechanism. The relative proportion of uni- to bimolecular mechanism depends on the zeolite composition. The relation between the turnover number, calculated from the kinetic rate constant for the unimolecular mechanism, and the framework Al content of the zeolite, was coincident with the topological zeolite model. Besides, the values of the adsorption constants indicate that dealumination h…

Cracking of n-heptane on a hzsm-5 zeolite. The influence of acidity and pore structure

Abstract The crackino of n-heptane on a HZSM-5 zeolite has been studied in a continuous qlass flow reactor, at atmospheric pressure, up to 470°C. The initial selectivities to the different reaction products, kinetic rate constants, activation energies and decay parameters have been calculated and compared with those obtained using a large pore zeolite (HYUS). A different product distribution is obtained with the two zeolites. In that way, and considering initial selectivities, different C 6 /C 1 , C 5 /C 2 , C 4 /C3, i-C 4 /n-C 4 , ethylene/ethane, propylene/propane ratios have been found on the two zeolite catalysts. The results have been quantitatively explained by considerinq a direct cr…

Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of Diisopropyl Ether, 2-Propyl Alcohol, and 3-Methyl-1-Butanol

Consistent vapor−liquid equilibrium data for the binary and ternary systems diisopropyl ether (1) + 2-propyl alcohol (2) + 3-methyl-1-butanol (3) are reported at 101.3 kPa. The diisopropyl ether (1) + 3-methyl-1-butanol (3) system shows positive deviations from ideal behavior, and the 2-propyl alcohol (2) + 3-methyl-1-butanol (3) system exhibits slight deviations from ideal behavior. The activity coefficients and the boiling points were correlated with their compositions by the Wilson, NRTL, UNIQUAC, and Wisniak−Tamir equations. It is shown that these models allow a very good prediction of the phase equilibria of the ternary system using the pertinent parameters of the binary systems. 3-Met…

Corrigendum to “Phase equilibria for the ternary systems ethanol, water + ethylene glycol or + glycerol at 101.3 kPa” [Fluid Phase Equilib. 341 (2013) 54–60]

Phase equilibria in the ternary system isobutyl alcohol+isobutyl acetate+1-hexanol and the binary systems isobutyl alcohol+1-hexanol, isobutyl acetate+1-hexanol at 101.3kPa

Abstract Consistent vapor–liquid equilibrium (VLE) data at 101.3 kPa have been determined for the ternary system isobutyl alcohol (IBA) + isobutyl acetate (IBAc) + 1-hexanol and two constituent binary systems: IBA + 1-hexanol and IBAc + 1-hexanol. The IBA + 1-hexanol system exhibits no deviation from ideal behaviour and IBAc + 1-hexanol system show lightly positive deviation from Raoult's law. The activity coefficients of the solutions were correlated with its composition by the Wilson, NRTL, UNIQUAC models. The ternary system is well predicted from binary interaction parameters. 1-Hexanol eliminates the IBA–IBAc binary azeotrope. However, the change of phase equilibria behaviour is small t…

Isobaric vapor-liquid equilibria for binary and ternary systems composed of water, 1-propanol, and 2-propanol at 100 kPa

Isobaric vapor−liquid equilibria data were obtained for the 2-propanol + 1-propanol binary system and the water + 1-propanol + 2-propanol ternary system at 100 kPa. The data were found to be thermodynamically consistent according to the Van Ness−Byer−Gibbs method for the binary system and according to the McDermott−Ellis method for the ternary one. The binary system is well represented by assuming ideal behavior. The binary interaction parameters obtained from this and our previous work are used to predict the vapor−liquid equilibrium for the ternary system using the UNIQUAC, NRTL, and Wilson models. The ternary system is well predicted from binary data.

Proposal of Isobutyl Alcohol as Entrainer To Separate Mixtures Formed by Ethanol and Water and 1-Propanol and Water

Isobutyl alcohol (IBA) has been proposed as a solvent to carry out the dehydration of ethanol and 1-propanol by means of a nonconventional distillation process. In this way, isobaric vapor–liquid equilibrium (VLE) and vapor–liquid–liquid equilibrium (VLLE) data at atmospheric pressure have been obtained for the ternary systems ethanol (1a) + water (2) + IBA (3) and 1-propanol (1b) + water (2) + IBA (3). Then, these data have been correlated to obtain a set of parameters capable of estimating VLE and VLLE. According to the results achieved, distillation sequences to separate water and ethanol or 1-propanol have been proposed. Finally, a study about the minimum amount of entrainer required to…

Isobaric vapour–liquid equilibria for the binary systems 4-methyl-2-pentanone+1-butanol and+2-butanol at 20 and 101.3kPa

Abstract Isobaric vapour–liquid equilibrium (VLE) measurements for the binary systems 4-methyl-2-pentanone + 1-butanol and 4-methyl-2-pentanone + 2-butanol are reported at 20 and 101.3 kPa. The system 4-methyl-2-pentanone + 1-butanol presents a minimum boiling point azeotrope at both pressures (20 and 101.3 kPa) and the system 4-methyl-2-pentanone + 2-butanol presents only a minimum boiling azeotrope at 20 kPa. In both systems, which deviate positively from ideal behaviour, the azeotropic composition is strongly dependent on pressure. The activity coefficients and boiling points of the solutions were correlated with its composition by the Wilson, UNIQUAC, and NRTL models for which the param…

Azeotropic distillation for 1-propanol dehydration with diisopropyl ether as entrainer: Equilibrium data and process simulation

Abstract Azeotropic distillation process is widely used to separate non-ideal binary mixtures into their constituent pure components. 1-Propanol dehydration was used as case study and diisopropyl ether was analysed as possible entrainer in an azeotropic distillation. The separation of some alcohols from their aqueous solution is a challenging task because these aqueous mixture forms minimum boiling azeotrope. In this way, isobaric vapor-liquid and vapour-liquid-liquid equilibrium data were measured for the 1-propanol+ water + diisopropyl ether ternary mixture at 101.3 kPa. The data were correlated by NRTL and UNIQUAC models. A separation sequence (a decanter and a single-feed distillation c…

Isobaric vapour–liquid equilibria for binary systems of 2-butanone with ethanol, 1-propanol, and 2-propanol at 20 and 101.3kPa

Abstract Consistent isobaric vapour–liquid equilibrium data have been measured for 2-butanone + ethanol, 2-butanone + 1-propanol, and 2-butanone + 2-propanol at 20 and 101.3 kPa. The binary systems 2-butanone + ethanol and 2-butanone + 2-propanol present a minimum boiling azeotrope at both pressures, and show that the azeotropic compositions is strongly dependent on pressure. The equilibrium data were correlated using the Wilson, NRTL, and UNIQUAC models for which the parameters are reported.

Isobaric Vapor−Liquid Equilibria for the Binary System 3-Methylpentane + Ethanol and for the Ternary System 2-Methyl-2-propanol + Ethanol + 3-Methylpentane at 101.3 kPa

Isobaric vapor-liquid equilibria data were measured for the 3-methylpentane + ethanol binary system and 2-methyl-2-propanol + ethanol + 3-methylpentane ternary system at 101.3 kPa in a temperature range from 329 to 356 K. The data were found to be thermodynamically consistent according to the Van Ness-Byer-Gibbs method for the binary system and according to the McDermott-Ellis method for the ternary one. The binary system shows a minimum boiling azeotrope that boils at 327.9 K and contains 71.4 mol % 3-methylpentane. The binary interaction parameters obtained from this work and literature data are used to predict the vapor-liquid equilibrium for the ternary system using the UNIQUAC, NRTL, a…

Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of Ethanol and 2-Propanol with 2-Butanone and Butyl Propionate at 101.3 kPa

This paper presents vapor−liquid equilibrium (VLE) data at 101.3 kPa for the ternary systems ethanol + 2-butanone + butyl propionate and 2-propanol + 2-butanone + butyl propionate and some of their...

Thermodynamic Analysis and Process Simulation of Ethanol Dehydration via Heterogeneous Azeotropic Distillation

The heterogeneous azeotropic distillation process is widely used to separate nonideal binary mixtures into their constituent pure components. This method uses the addition of a third component, called an entrainer, to cause liquid–liquid phase separation over a broad range of compositions in the ternary phase diagram. Ethanol dehydration was used as a case study and diisopropyl ether and isobutyl alcohol were analyzed as possible entrainers in a heterogeneous azeotropic distillation. In this way, isobaric vapor–liquid–liquid equilibrium was measured for the ethanol + water + diisopropyl ether or + isobutyl alcohol ternary mixtures at 101.3 kPa. The data were correlated by the NRTL and UNIQU…

Vapor–liquid equilibria in the ternary system dipropyl ether+1-propanol+1-pentanol and the binary systems dipropyl ether+1-pentanol, 1-propanol+1-pentanol at 101.3kPa

Abstract Consistent vapor–liquid equilibrium (VLE) data at 101.3 kPa have been determined for the ternary system dipropyl ether (DPE) + 1-propanol (PA) + 1-pentanol and two constituent binary systems: DPE + 1-pentanol and PA + 1-pentanol. The DPE + 1-pentanol system shows positive deviations from ideal behaviour and PA + 1-pentanol system exhibits no deviation from ideal behaviour. The activity coefficients and the boiling points were correlated with their compositions by the Wilson, NRTL, UNIQUAC and Wisniak–Tamir equations. It is shown that the models allow a very good prediction of the phase equilibria of the ternary system using the pertinent parameters of the binary systems. 1-Pentanol…

Isobaric Vapor–Liquid–Liquid Equilibria for the Ternary Systems Ethanol + Water + Propyl Acetate and 1-Propanol + Water + Propyl acetate

In order to break azeotropes appearing in mixtures of water and either ethanol or 1-propanol, an azeotropic distillation process is proposed using propyl acetate as entrainer. Therefore, isobaric vapor–liquid–liquid equilibrium (VLLE) data at atmospheric pressure have been obtained for the ternary systems ethanol + water + propyl acetate and 1-propanol + water + propyl acetate. Data correlation has been carried out in four different ways and a comparison between the results obtained in each correlation has been done. The set of parameters obtained from the best correlation has been used in the VLLE estimation. Effects of using propyl acetate as entrainer in the azeotropic distillation have …

Densities, Refractive Indices, and Derived Excess Properties of the Binary Systems Toluene + Isooctane and Methylcyclohexane + Isooctane and the Ternary Systems tert-Butyl Alcohol + Toluene + Isooctane and tert-Butyl Alcohol + Methylcyclohexane + Isooctane at 298.15 K

This paper reports mesurements of the densities and refractive indices of the binary systems toluene + isooctane and methylcyclohexane + isooctane and the ternary systems tert-butyl alcohol (TBA) + toluene + isooctane and tert-butyl alcohol (TBA) + methylcyclohexane + isooctane over the entire range of composition at 298.15 K. Excess molar volumes and changes of refractive indices were evaluated from the experimental data obtained. These derived properties were fitted to variable-degree polynomials. The experimental values of physical properties were compared with the values estimated by different methods.

Densities, refractive indices, and derived excess properties of the binary systems tert-butyl alcohol+toluene, +methylcyclohexane, and +isooctane and toluene+methylcyclohexane, and the ternary system tert-butyl alcohol+toluene+methylcyclohexane at 298.15 K

Abstract This paper reports experimental densities and refractive indices of the binary systems tert -butyl alcohol (TBA)+toluene, +isooctane, and +methylcyclohexane, and toluene+methylcyclohexane, and the ternary system TBA+toluene+methylcyclohexane, over the entire range of composition at 298.15 K. Excess molar volumes and changes of refractive indices were evaluated from the experimental data obtained. These derived properties were fitted to variable-degree polynomials. The experimental values of physical properties were compared with the values estimated by different methods of prediction.

Measurements and correlation at different temperatures of liquid–liquid equilibria of 2-butanol or 2-methyl-2-butanol+1,2,3-propanetriol+water ternary systems

Abstract In this work, the experimental liquid–liquid equilibria (LLE) data of 2-methyl-2-butanol + 1,2,3-propanetriol (glycerol) + water and 2-butanol + 1,2,3-propanetriol (glycerol) + water systems at different temperatures are presented. The LLE of the systems has been measured between 283 and 323 K. The NRTL and UNIQUAC models were applied to the ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. The experimental tie lines were compared to the values predicted by the UNIFAC method. Finally, the solvent capability of both alcohols was checked in order to separate the mixture formed by glycerol and water.

Nonazeotropy in the System Methyl Ethanoate + 1,2-Epoxybutane

New vapor−liquid equilibrium data for the binary system methyl ethanoate + 1,2-epoxybutane are reported at 35 and 101.3 kPa and at 298.15 K. It is shown that no azeotropes are present in the system, in disagreement with data reported by others who claim that two azeotropes are present at 298.15 K. We claim that previously reported data are in error because of impurities in the reagents and experimental errors. According to our results, the system methyl ethanoate + 1,2-epoxybutane behaves like a regular solution and its vapor phase can be considered practically ideal so that it cannot fulfill the necessary conditions for multiple azeotropy. The data were satisfactorily correlated using the …

Vapor–liquid equilibria in the ternary system isobutyl alcohol+isobutyl acetate+butyl propionate and the binary systems isobutyl alcohol+butyl propionate, isobutyl acetate+butyl propionate at 101.3kPa

Abstract Consistent vapor–liquid equilibrium (VLE) data at 101.3 kPa have been determined for the ternary system isobutyl alcohol (IBA) + isobutyl acetate (IBAc) + butyl propionate (BUP) and two constituent binary systems: IBA + BUP and IBAc + BUP. The IBA + BUP system show lightly positive deviation from Raoult's law and IBAc + BUP system exhibits no deviation from ideal behaviour. The activity coefficients of the solutions were correlated with its composition by the Wilson, NRTL, UNIQUAC models. The ternary system is very well predicted from binary interaction parameters. BUP eliminates the IBA–IBAc binary azeotrope. The change of phase equilibria behaviour is significant therefore this s…

Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of Dipropyl Ether, 1-Propyl Alcohol, and Butyl Propionate

Consistent vapor−liquid equilibrium (VLE) data at 101.3 kPa have been determined for the ternary system dipropyl ether + 1-propyl alcohol + butyl propionate and two constituent binary systems:  dipropyl ether + butyl propionate and 1-propyl alcohol + butyl propionate. The dipropyl ether + butyl propionate system exhibits ideal behavior, and the 1-propyl alcohol + butyl propionate system shows positive deviations from Raoult's law. No additional azeotropes are present. The activity coefficients of the solutions were correlated with its composition by the Wilson, NRTL, and UNIQUAC models. The ternary system is well-predicted from binary interaction parameters. Butyl propionate breaks the dipr…

Isobaric vapor–liquid equilibria for the binary systems isobutyl alcohol+isobutyl acetate and tert-butyl alcohol+tert-butyl acetate at 20 and 101.3kPa

Abstract New consistent vapor–liquid equilibrium data for the binary systems isobutyl alcohol (IBA) + isobutyl acetate (IBAc) and tert-butyl alcohol (TBA) + tert-butyl acetate (TBAc) are reported at 20 and 101.3 kPa. The IBA + IBAc system, which deviates positively from ideal behavior, can be described as symmetric solution and presents azeotrope at both pressures. The TBA + TBAc system shows positive deviations from ideal behavior and presents azeotrope only at 20 kPa. The activity coefficients and boiling points of the solutions were correlated with their composition by the Wilson, UNIQUAC, NRTL and Wisniak–Tamir equations.

Study of liquid–liquid extraction of ethanol + water azeotropic mixtures using two imidazolium-based ionic liquids

Abstract The present work was focused on the study of two imidazolium-based ionic liquids (ILs) as solvents in liquid–liquid extraction of ethanol from aqueous mixtures. With this aim, the experimental liquid–liquid equilibria (LLE) data of water (1) + ethanol (2) + 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) (3) and water (1) + ethanol (2) + 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N]) (4) systems were obtained at different temperatures: 283.2, 303.2, and 323.2 K, in order to check the influence of temperature. The results were correlated by non-random two-liquid (NRTL) and universal quasichemical (UNIQUAC) models with good c…

Densities, Viscosities, and Refractive Indices of the Binary Systems Methyl tert-Butyl Ether + 2-Methylpentane, + 3-Methylpentane, + 2,3-Dimethylpentane, and + 2,2,4-Trimethylpentane at 298.15 K

This paper reports experimental densities, viscosities, and refractive indices of the binary systems methyl tert-butyl ether (MTBE) + 2-methylpentane, + 3-methylpentane, + 2,3-dimethylpentane, and + 2,2,4-trimethylpentane over the entire range of composition, at 298.15 K and atmospheric pressure. Excess molar volumes and viscosity deviations were evaluated from the experimental data. These excess or derived properties were fitted to the Redlich−Kister equation to estimate the binary interaction parameters. The experimental values of viscosity have been compared to values predicted by means of the GC−UNIMOD model.

Study of separation of water + 2-propanol mixture using different ionic liquids: 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide

Abstract The liquid–liquid equilibria data of water (1) + 2-propanol (2) + [bmim][Tf2N] (3) and water (1) + 2-propanol (2) + [bmp][Tf2N] (3) at 283.2, 303.2 and 323.2 K and atmospheric pressure were measured with the objective of understanding the behavior of these two systems and to try to improve the extraction of 2-propanol from water from economical and environmental points of view. The thermodynamic parameters were determined using the non-random two-liquid (NRTL) and universal quasichemical (UNIQUAC) models, and excellent results were achieved in both cases (the maximum root-mean-square deviation was 0.433%). Lastly, the capability of the two ionic liquids to separate 2-propanol from …

High Pressure Solubility Data of the System Limonene + Linalool + CO2

The feasibility of deterpenating orange peel oil with supercritical CO2 depends on relevant vapor−liquid equilibrium data because the selectivity of this solvent for limonene and linalool (the two key components of the oil) is of crucial importance. In this work the solubility data for the CO2 + limonene + linalool ternary system were measured at (318.2 and 328.2) K. The range of pressures covered was from (70 to 110) bar. Two different mixtures of limonene + linalool were used:  a 40 mass % limonene + 60 mass % linalool mixture and a 60 mass % limonene + 40 mass % linalool mixture. To correlate the obtained results, two equations of state were successfully used (Peng−Robinson (PR) and Soav…

Influence of the process variables on the product distribution and catalyst decay during cracking of paraffins

Abstract The influence of the partial pressure of the hydrocarbon, reaction temperature, time on stream and the presence of olefins on the product distribution and the kinetics and decay during the cracking of n-heptane on an REHY zeolite were studied. It was found that the isomerization to cracking ratio depends on the hydrocarbon partial pressure. The active sites for cracking and isomerization are not the same and those for cracking decay faster, the selectivity changing with the degree of decay of the zeolite. The protolytic to β-cracking ratio, and therefore the paraffin to olefin ratio, are a function of the partial pressure of n-heptane. Both reactants and products have a marked infl…

High-pressure solubility data of system ethanol (1)+catechin (2)+CO2 (3)

Abstract Supercritical fluid extraction posses several advantages over traditional liquid–solvent-based extraction methods including improved selectivity, expeditiousness, automation and environmental safety. Fluid phase equilibrium data is essential for study the viability of supercritical extraction and the design of the extraction columns often used for this type of separations. During the past few years it has been demonstrated that phenolic compounds, such catechins and procyanidins from seeds, contribute to both the flavour properties and the pharmacological effects of wine. The extraction of catechin using supercritical CO2 is not possible, it only extracts traces of product, probabl…

Phase Equilibria Involved in Extractive Distillation of Dipropyl Ether + 1-Propyl Alcohol Using N,N-Dimethylformamide as Entrainer

Consistent vapor−liquid equilibrium data for the binary and ternary systems dipropyl ether (1) + 1-propyl alcohol (2) + N,N-dimethylformamide (3) are reported at 101.3 kPa. The results indicate that dipropyl ether (1) + N,N-dimethylformamide (3) system exhibits a positive deviation from ideal behavior and that 1-propyl alcohol (2) + N,N-dimethylformamide (3) system deviates negatively from ideality. The activity coefficients of the solutions were correlated by the Wilson, NRTL, and UNIQUAC models. It is shown that these models allow a very good prediction of the phase equilibrium of the ternary system using the pertinent parameters of the binary systems. In addition, the Wisniak−Tamir relat…

Density, Viscosity, and Sound Speed of Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids + 1-Propanol Mixtures

The density, viscosity, and speed of sound of three mixtures formed by 1-propanol and an ionic liquid were measured in a temperature range of 278.15–338.15 K. All measurements were made at atmospheric pressure and covered the entire range of miscible compositions. The three ionic liquids have the same anion but differ in the cation: 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [emim][NTf2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][NTf2], and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [hmim][NTf2]. The experimental data allowed calculate the molar volume and isentropic compressibility of the mixture and their respective exces…

Liquid–liquid equilibria of the systems dipropyl ether+n-propanol+water and dipropyl ether+n-propanol+ethylene glycol at different temperatures

Abstract In this work, experimental liquid–liquid equilibria (LLE) data of the dipropyl ether + n-propanol + water and dipropyl ether + n-propanol + ethylene glycol systems are presented. The LLE of both systems have been measured at 283.15 and 323.15 K. The equilibrium data presented are correlated using NRTL and UNIQUAC equations. The reliability of these models is tested by comparison with experimental results. Moreover, the solvent capabilities of water and ethylene glycol were compared, concluding that ethylene glycol is the best solvent to extract n-propanol.

Phase equilibrium for the systems diisopropyl ether, isopropyl alcohol+2,2,4-trimethylpentane and +n-heptane at 101.3kPa

Abstract Consistent vapour–liquid equilibrium data for the ternary systems diisopropyl ether + isopropyl alcohol + 2,2,4-trimethylpentane and diisopropyl ether + isopropyl alcohol + n-heptane are reported at 101.3 kPa. The vapour–liquid equilibrium data have been correlated by Wilson, NRTL and UNIQUAC equations. The ternary systems do not present ternary azeotropes.

Isobaric Vapor−Liquid Equilibrium in the Systems 2,3-Dimethylpentane + Methyl 1,1-Dimethylethyl Ether, + Diisopropyl Ether and + Methyl 1,1-Dimethylpropyl Ether

New, consistent vapor−liquid equilibrium data for the binary systems 2,3-dimethylpentane + methyl 1,1-dimethylethyl ether, + diisopropyl ether, and + methyl 1,1-dimethylpropyl ether are reported at 101.3 kPa. The measured systems deviate slightly from ideal behavior, and only the system methyl 1,1-dimethylpropyl ether + 2,3-dimethylpentane presents an azeotrope. The activity coefficients for the solutions were correlated with their compositions by the Wilson, UNIQUAC, and NRTL models. Wisniak−Tamir equations were used to correlate the boiling points of the solutions with their compositions.

Isobaric vapor–liquid equilibria for the binary systems 1-propyl alcohol+dipropyl ether and 1-butyl alcohol+dibutyl ether at 20 and 101.3kPa

Abstract Isobaric vapor–liquid equilibrium measurements for the binary systems 1-propyl alcohol + dipropyl ether and 1-butyl alcohol + dibutyl ether are reported at 20 and 101.3 kPa. Both systems, which deviate positively from ideal behavior present a minimum boiling point azeotrope at both pressures, showing the azeotropic compositions a strong dependency on pressure. The activity coefficients and boiling points of the solutions were correlated with its composition by the Wilson, UNIQUAC, NRTL, and Wisniak–Tamir equations.

Liquid–liquid equilibria of 4-methyl-2-pentanone+1-propanol or 2-propanol+water ternary systems: Measurements and correlation at different temperatures

Abstract In this work, experimental liquid–liquid equilibria data of the systems 4-methyl-2-pentanone + 1-propanol + water and 4-methyl-2-pentanone + 2-propanol + water are presented. The liquid–liquid equilibria of both systems have been measured at 283.2 and 323.2 K. The NRTL and UNIQUAC models were successfully applied to fit the data for both ternary systems. The binodal lines were compared to the values predicted by the UNIFAC-LLE and UNIFAC models. Moreover, the solvent capability of 4-methyl-2-pentanone was checked in order to separate the azeotropic mixtures formed by propanol's and water.

Liquid–liquid equilibria of the systems isobutyl acetate+isobutyl alcohol+water and isobutyl acetate+isobutyl alcohol+glycerol at different temperatures

Abstract In this work, experimental liquid–liquid equilibria (LLE) data of the isobutyl acetate + isobutyl alcohol + water and isobutyl acetate + isobutyl alcohol + glycerol systems are presented. The LLE of both systems have been measured at 283.15 and 323.15 K. The NRTL and UNIQUAC models were applied to both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. The experimental tie lines were compared to the values predicted by the UNIFAC method. Moreover, the solvent capabilities of water and glycerol were compared.

Answer to the Letter to the Editor by Dr. Sanjay Pralhad Shirsat concerning the article “Separation of isobutyl alcohol and isobutyl acetate by extractive distillation and pressure-swing distillation: Simulation and optimization”

Measurement and correlation of liquid-liquid equilibria at different temperatures in water + 1-propanol + 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ternary systems

Abstract In order to reduce the environmental impact and the economical costs of the separation of 1-propanol from aqueous mixtures, which enables the recycling of the alcohol, the experimental liquid-liquid equilibria (LLE) data of water (1) + 1-propanol (2) + 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) (3) and water (1) + 1-propanol (2) + 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N]) (3) systems were measured in this work at different temperatures: 283.2, 303.2 and 323.2 K at atmospheric pressure. The results were correlated by non-random two-liquid (NRTL) and universal quasichemical (UNIQUAC) models with good results in both…

High-pressure solubility data of the system resveratrol (3)+ethanol (2)+CO2 (1)

Abstract Supercritical fluid extraction possesses several advantages over traditional liquid-solvent-based extraction methods, including improved selectivity, expeditiousness, automation and environmental safety. Fluid-phase equilibrium data are essential for studying the viability of supercritical extraction and the design of the extraction columns often used for this type of separation. Resveratrol has been correlated with serum lipid reduction and inhibition of platelet aggregation, and its cancer chemopreventive activity has recently been reported. The extraction of resveratrol using supercritical CO 2 is not possible; it only extracts traces of product, probably due to its polar nature…

Isobaric (vapour+liquid+liquid) equilibrium data for (di-n-propyl ether+n-propyl alcohol+water) and (diisopropyl ether+isopropyl alcohol+water) systems at 100kPa

Abstract Isobaric (vapour + liquid + liquid) equilibria were measured for the (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) system at 100 kPa. The apparatus used for the determination of (vapour + liquid + liquid) equilibrium data was an all-glass dynamic recirculating still with an ultrasonic homogenizer couple to the boiling flask. The experimental data demonstrated the existence of a heterogeneous ternary azeotrope for both ternary systems. The (vapour + liquid + liquid) equilibria data were found to be thermodynamically consistent for both systems. The experimental data were compared with the estimation using UNIQUAC and NRTL models a…

Vapor−Liquid Equilibria for the Binary Systems tert-Butyl Alcohol + Toluene, + Isooctane, and + Methylcyclohexane at 101.3 kPa

Vapor-liquid equilibria were measured for binary systems of tert-butyl alcohol with toluene, isooctane, and methylcyclohexane at 101.3 kPa using a recirculating still. Experimental values of the vapor pressure of non-oxygenated pure components have been obtained. The accuracy of experimental measurements was ±0.01 K in temperature, ±0.01 kPa in pressure, and ±0.001 in mole fractions. The results are thermodynamically consistent according to the point-to-point consistency test. The data were correlated with five liquid-phase activity coefficients models (Margules, Van Laar, Wilson, NRTL, UNIQUAC).

Separation of isobutyl alcohol and isobutyl acetate by extractive distillation and pressure-swing distillation: Simulation and optimization

Abstract We have studied, simulated and evaluated economically two separation alternatives of a mixture made up of 52 mole% of isobutyl alcohol and 48 mole% of isobutyl acetate by means of a practical case of a plant to treat 12,000 Tm/year of the original mixture. The simulation has been carried out satisfactorily by means of a package of commercial software (Aspen HYSYS ® ) using the thermodynamic model UNIQUAC with binary parameters obtained experimentally by us. The two processes evaluated (extractive distillation using n -butyl propionate as a solvent and pressure-swing distillation) have been optimized independently from each other and the best configurations have been evaluated econo…

Measurements and correlation of vapour–liquid equilibria of 2-butanone and hydrocarbons binary systems at two different pressures

Abstract Consistent isobaric vapour–liquid equilibrium data have been measured for 2-butanone + n-hexane, 2-butanone + n-heptane, and 2-butanone + 2,2,4-trimethylpentane at two different pressures. All binary systems present a minimum boiling azeotrope at both pressures, and show that the azeotropic compositions are weakly dependent on pressure. The equilibrium data were correlated using the Wilson, NRTL, and UNIQUAC models for which the parameters are reported.

Effect of pressure and the capability of 2-methoxyethanol as a solvent in the behaviour of a diisopropyl ether–isopropyl alcohol azeotropic mixture

Abstract Consistent vapour–liquid equilibrium data for the binary and ternary systems of diisopropyl ether + isopropyl alcohol at 30 and 101.3 kPa and diisopropyl ether + 2-methoxyethanol, isopropyl alcohol + 2-methoxyethanol and diisopropyl ether + isopropyl alcohol + 2-methoxyethanol at 101.3 kPa are reported. The activity coefficients of the solutions were correlated with its composition using the Wilson, NRTL and UNIQUAC models. It is shown that the models allow a very good prediction of the phase equilibrium of the ternary system using the pertinent parameters of the binary systems. Moreover, the effect of pressure and the entrainer capability of 2-methoxyethanol were studied.

Separation of di-n-propyl ether and n-propyl alcohol by extractive distillation and pressure-swing distillation: Computer simulation and economic optimization

Abstract Azeotropic mixtures are impossible to separate by ordinary distillation. Two of the most common methods for separating a binary homogeneous azeotrope are pressure-swing distillation (PSD) and extractive distillation (ED). The PSD process is effective if the azeotropic composition changes significantly with pressure. The ED process is effective if a suitable solvent can be found. This paper compares these two alternatives to separate a mixture made up of 50 mol% of di-n-propyl ether and 50 mol% of n-propyl alcohol by means of a practical case of a plant to treat 12,000 Tm/year of this mixture. The simulation has been carried out satisfactorily by mean of a package of commercial soft…

Phase Equilibrium for the Esterification Reaction of Acetic Acid + Butan-1-ol at 101.3 kPa

In this work, the thermodynamic behavior of catalytic esterification reaction equilibrium and vapor–liquid equilibria (VLE) for the quaternary reactive system acetic acid + butan-1-ol + butyl acetate + water and constituent binary systems acetic acid + butyl acetate, butan-1-ol + butyl acetate, and butan-1-ol + water have been determined at 101.3 kPa, and liquid–liquid equilibria (LLE) of the binary system butan-1-ol + water have also been determined. The esterification reaction rate of the acetic acid and butan-1-ol mixture is very slow. So, in this study, p-toluenesulfonic acid was selected as the catalyst to accelerate the chemical reaction. The measured VLE data were correlated by the N…

Evaluation of the 2-Methoxyethanol as Entrainer in Ethanol–Water and 1-Propanol–Water Mixtures

In this paper, 2-methoxyethanol (commercially known as methyl cellosolve) is proposed as a potential entrainer for extractive distillation processes involving water–alcohol mixtures. The two alcohols studied in this work are ethanol and 1-propanol. Thereby, isobaric vapor–liquid equilibrium (VLE) data at atmospheric pressure have been measured for the ternary systems ethanol + water + 2-methoxyethanol and 1-propanol + water + 2-methoxyethanol. Moreover, data of the binary systems formed by the 2-methoxyethanol and each of the other chemicals used (ethanol, water, 1-propanol) have been obtained. The well-known local composition models Wilson, UNIQUAC, and NRTL have been used to correlate bin…

Phase equilibria involved in extractive distillation of dipropyl ether+1-propyl alcohol using 2-ethoxyethanol as entrainer

Abstract Consistent vapour–liquid equilibrium data at 101.3 kPa have been determined for the ternary system dipropyl ether + 1-propyl alcohol + 2-ethoxyethanol and two constituent binary systems: dipropyl ether + 2-ethoxyethanol and 1-propyl alcohol + 2-ethoxyethanol. The dipropyl ether + 2-ethoxyethanol system shows positive deviations from ideal behaviour and 1-propyl alcohol + 2-ethoxyethanol system exhibits no deviation from ideal behaviour. The activity coefficients and the boiling points were correlated with their compositions by the Wilson, NRTL and UNIQUAC equations. It is shown that the models allow a very good prediction of the phase equilibria of the ternary system using the pert…

Liquid−Liquid Equilibria for the System 1-Methyl Propyl Ethanoate (1) + Acetic Acid (2) + Water (3) at (283.15 and 323.15) K

Liquid−liquid equilibrium (LLE) data for the system 1-methyl propyl ethanoate + acetic acid + water were measured at temperatures of (283.15 and 323.15) K. The temperature influence on the LLE data is very small in the temperature range studied. The NRTL and UNIQUAC models were used to correlate the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions.

Phase equilibria in the systems isobutyl alcohol+N,N-dimethylformamide, isobutyl acetate+N,N-dimethylformamide and isobutyl alcohol+isobutyl acetate+N,N-dimethylformamide at 101.3kPa

Abstract Consistent vapor–liquid equilibria (VLE) were determined for the ternary system isobutyl alcohol (IBA) + isobutyl acetate (IBAc) + N,N-dimethylformamide (DMF) and two constituent binary systems at 101.3 kPa. The IBA + DMF system exhibits negative deviation from ideal behaviour and IBAc + DMF system deviates positively from ideal behaviour. The activity coefficients of the solutions were correlated with its composition by the Wilson, NRTL and UNIQUAC models. The ternary system is well predicted from binary interaction parameters.

Density, Speed of Sound, Viscosity, and Excess Properties of Binary Mixtures Formed by Ethanol and Bis(trifluorosulfonyl)imide-Based Ionic Liquids

In this work, viscosities, densities, and speeds of sound of three binary mixtures containing the ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [emim][NTf2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][NTf2], and 1-hexyl-3-methylimidazo-lium bis(trifluoromethylsulfonyl)imide, [hmim][NTf2], mixed with ethanol were measured at atmospheric pressure in the range of (278.15 to 338.15) K, covering the entire range of compositions. From these experimental data, the excess isentropic compressibility and molar isentropic compressibility of pure components and mixtures have been calculated. Additionally, excess properties, such as viscosity dev…

Comparison of the activity, selectivity and decay properties of lay and hyultrastable zeolites during the cracking of alkanes

Abstract The cracking of n-heptane on LaY ultrastable zeolite has been studied in a continuous glass flow reactor, at atmospheric pressure, up to 470°C. The initial selectivity to cracking, isomerization and disproportionation, kinetic rate constants, activation energies and decay parameters have been calculated and compared with those obtained using a HY ultrastable zeolite as a catalyst. It has been found that the HY ultrastable zeolite is about 7 times more active for cracking, and about 10 times more active for isomerization and disproportionation than the LaY ultrastable zeolite. The protolytic to β-cracking ratio is higher for the HY ultrastable zeolite. The deactivation takes place b…

Experimental Determination and Correlation of Liquid–Liquid Equilibria Data for a System of Water + Ethanol + 1-Butyl-3-methylimidazolium Hexafluorophosphate at Different Temperatures

Over the past few years, interest has increased regarding the application of ionic liquids (ILs) as extraction solvents for separating azeotropic mixtures. Following this trend, this work presents the experimental data of liquid–liquid equilibria (LLE) of the system envolving water, ethanol, and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) at different temperatures. The LLE data of the system was measured between 283.2 and 323.2 K to determine the temperature influence on the system. In the literature, reports of systems involving ILs that present type II behavior are scarce compared with those that present type I behavior; the system presented here also displays two immisc…

Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of Diisopropyl Ether, 2-Propyl Alcohol, and n-Butyl Propionate at 101.3 kPa

Consistent vapor−liquid equilibrium data at 101.3 kPa have been determined for the ternary system diisopropyl ether (1) + 2-propyl alcohol (2) + n-butyl propionate (3) and two constituent binary systems: diisopropyl ether (1) + n-butyl propionate (3) and 2-propyl alcohol (2) + n-butyl propionate (3). The diisopropyl ether (1) + n-butyl propionate (3) system does not present deviation from ideal behavior, and the 2-propyl alcohol (2) + n-butyl propionate (3) system shows light positive deviation from Raoult’s law. The activity coefficients of the solutions were correlated with their compositions by the Wilson, NRTL, and UNIQUAC models. Wisniak−Tamir equations were used to correlate the boili…