Article pubs.acs.org/jced
Liquid Phase Equilibria of the Water + Acetic Acid + Dimethyl Carbonate Ternary System at Several Temperatures Erol Iṅ ce,*,† Melisa Lalikoglu,† and Dana Constantinescu‡ †
Engineering Faculty, Chemical Engineering Department, Istanbul University, 34320, Avcilar/Istanbul, Turkey DDBST GmbH, Marie-Curie-Str. 10, D-26129 Oldenburg, Germany
‡
ABSTRACT: Liquid−liquid equilibria (LLE) of water + acetic acid + dimethyl carbonate were experimentally specified at (298.2, 308.2, and 318.2) K. Each diagram was obtained through specifying binodal curves and tie-lines. The reliability of the experimental tie-line data was calculated by the Othmer− Tobias correlation. The nonrandom two-liquid (NRTL) and unified quasichemical activity coefficient (UNIQUAC) models were used to obtain the binary interaction parameters of the experimental tie-line data. However, universal functional (UNIFAC) and modified UNIFAC methods were used as well to predict the phase equilibrium in the system specified from experimental data using the interaction parameters between CH3, OCOO, COOH, and H2O functional groups. Distribution coefficients and separation factors were assessed for the immiscibility region.
1. INTRODUCTION
equilibria of different ternary systems about dimethyl carbonate lately. Dimethyl carbonate is often considered to be a green reagent and environmentally friendly. It is a solvent which is supposed to replace chlorocarbons or aromatic hydrocarbons and is exempt from classification as volatile organic compounds which have excellent properties for industrial applications. Its main benefit over other methylating reagents such as iodomethane and dimethyl sulfate is that it has much lower toxicity and biodegradability. Dimethyl carbonate is growing in popularity and applications as a replacement for methyl ethyl ketone, tert-butyl acetate, and parachlorobenzotrifluoride. Dimethyl carbonate has an ester or alcohol like odor, more favorable to users than most hydrocarbon solvents it replaces.19−22 The goal of this study is to regain acetic acid from aqueous solutions with the help of an environmentally friendly solvent that has a low boiling point. In this study, LLE results have been reported for the water + acetic acid + dimethyl carbonate ternary system, and no such data have been published previously about that. Additionally, some calculations are performed via nonrandom two-liquid (NRTL), universal quasichemical activity coefficient (UNIQUAC), universal functional activity coefficient (UNIFAC), and modified UNIFAC, in order to describe their experimental thermodynamic behavior.
Acetic acid is a carboxylic acid which is used widely. It is used in quite a lot of reactions, such as synthesizing acetic esters, and it can also be used as a solvent, for example, to produce various acetate esters or prepare pharmaceuticals. It can also be used as a fungicide.1 Acetic acid is produced through a synthetic method or fermentation process. Both of these methods make dilute aqueous solutions. Therefore, separating acetic acid from dilute aqueous solutions is important in terms of industry.2−4 Separating acetic acid and water through distillation is very difficult, and it necessitates a column with many stages and a great reflux ratio, thus entailing high running costs. Liquid− liquid extraction is an alternative to distillation, as a result of the lower energy cost of extraction process. Besides, liquid−liquid extraction is a well-known technique which is used to separate the acetic acid from aqueous solutions, and in this respect, many solvents have been tried to improve recovery efficiency.5−10 In the field of investigating more benign solvents as potential replacements for chlorocarbons or aromatic hydrocarbons and as new solvents for separations, a lot of studies have been done on the dibasic esters, which have excellent properties for industrial applications. One of them is dimethyl carbonate. It is environmentally friendly and has low cost, low toxicity, better stability, and high boiling temperatures; however, viscosity and density that it has is close to those of water. The dibasic esters are also used as novel solvents in separation techniques.11 First, Uusi-Penttilä et al.12 studied liquid−liquid equilibria of different ternary systems. After, Iṅ ce and Kırbaşlar13−16 have studied liquid−liquid equilibria of various ternary systems. Then Iṅ ce and Aşcı̧ 17 have studied liquid−liquid equilibria of different ternary systems. Iṅ ce et al.18 have also studied liquid−liquid © 2014 American Chemical Society
2. EXPERIMENTAL SECTION 2.1. Materials. Acetic acid and dimethyl carbonate were bought from Merck Company, and they were received with a quoted purity of 0.998 and greater than 0.99 mass fraction, Received: April 10, 2014 Accepted: October 3, 2014 Published: October 15, 2014 3353
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Table 1. Densities ρ, Refractive Indices nD, and Boiling Temperatures (Tb) of the Pure Componentsa and Literature Values23 at 101.325 kPa ρ(298.2 K)/(kg·m−3)
a
compound
source
water acetic acid dimethyl carbonate
distilled Merck Merck
nD (298.2 K)
Tb/K
purity
exp.
lit.
exp.
lit.
exp.
lit.
99.8% >99%
998.21 1049.42 1061.90
997.04 1049.2 1063.01
1.3324 1.3713 1.3685
1.3325 1.3715 1.368b
373.2 391.2 363.23
373.25 391.26 363.15
Standard uncertainties u are u(ρ )= 0.01 kg·m−3, u(nD) = 0.00001, u(Tb) = 0.1 K, and u(p) = 0.5 kPa. bAt 293.2 K.
Table 2. Experimental Binodal Curve Data (as Mass Fraction) of the Water (1) + Acetic Acid (2) + Dimethyl Carbonate (3) at Each Temperaturea and Atmospheric Pressure T = 298.2 K
a
T = 308.2 K
T = 318.2 K
w1
w2
w3
w1
w2
w3
w1
w2
w3
0.0332 0.1005 0.1917 0.2877 0.3980 0.5339 0.6085 0.7167 0.8619
0.0000 0.0942 0.1349 0.1518 0.1617 0.1556 0.1306 0.0869 0.0000
0.9668 0.8053 0.6734 0.5605 0.4403 0.3105 0.2609 0.1964 0.1381
0.0402 0.1109 0.2015 0.2615 0.4086 0.5547 0.6635 0.7833 0.8449
0.0000 0.0854 0.1312 0.1409 0.1573 0.1525 0.1282 0.0509 0.0000
0.9598 0.8037 0.6673 0.5976 0.4341 0.2928 0.2083 0.1658 0.1551
0.0516 0.1089 0.1719 0.3117 0.4141 0.5193 0.6421 0.7972 0.8453
0.0000 0.0655 0.1097 0.1292 0.1273 0.1220 0.1062 0.0378 0.0000
0.9484 0.8256 0.7184 0.5591 0.4586 0.3587 0.2517 0.1650 0.1547
Standard uncertainties u are u(w) = 0.0001 and u(T) = 0.1 K.
lying within the two phase region and after stirring vigorously for at least 2 h jacked cells14 and then left to stand for at least 3 h (the period which is necessary to attain equilibrium was established in preliminary experiments). After separating the phases completely, samples were carefully taken from phases and analyzed to get the tie-lines. 2.3. Analysis. The liquid samples were analyzed by a gas chromatograph (Hewlett-Packard GC, model 6890 series), equipped with a thermal conductivity detector (TCD) for the quantitative determination of water, acetic acid, and dimethyl carbonate. A 15 m long HP-Plot Q column (320 μm diameter with a 20 μm film thickness) was used with a temperatureprogrammed analysis. The temperature of the oven was set at 503 K. The detector temperature was kept 503 K, while the injection-port temperature was held at 453 K. The flow rate of carrier gas, nitrogen, was kept at 4 cm3/min. Samples with known compositions were used to calibrate the instrument in the composition range of interest.
respectively. To check the substance purities, gas chromatography was used, and the compounds were used with no further purification. Water content was measured with a Mettler Toledo DL38 Karl Fischer titrator as 2·10−3 and 2·10−4 mass fraction, respectively. Distilled water was used throughout all experiments. Refractive indexes were measured with Anton Paar model RXA 170; its accuracy is ± 1·10−5. Densities were measured using an Anton Paar model DMA 4500 density meter. Boiling temperature measurements were obtained by using a Fischer boiling temperature instruments. The estimated uncertainties in the density and boiling point measurements were ± 1·10−5 g·cm−3 and ± 0.1 K, respectively. The measured physical properties are listed in Table 1, along with some values from the literature.23 2.2. Apparatus and Procedure. The binodal curve for the water + acetic acid + dimethyl carbonate ternary system was specified by a cloud-point method.13 Binary mixtures of known compositions were agitated in a glass stoppered cell equipped with a magnetic stirrer and jacketed for circulating water from a constant temperature bath at 298.2 ± 0.1 K, 308.2 ± 0.1 K, and 318.2 ± 0.1 K. The third component was gradually added to the mixture until the transition point was obtained. The end point was determined by viewing the transition from a homogeneous to a heterogeneous mixture. The mutual solubilities of the water + dimethyl carbonate system were also determined by using the cloud-point method. A certain amount of a component was put in the cell; then the other component was added until a permanent heterogenity was obtained. Temperature control was provided by using water from a thermostat, and the water temperature was measured with a thermometer with a precision of ± 0.1 K. Each mixture was prepared, weighed, and with a Mettler scale accurate within ±1·10−4 g. The solvent was added by a microburet (Metrohm) with an accuracy of ± 3·10−3 cm3. Tie-line data were obtained by preparing water + acetic acid + dimethyl carbonate ternary mixtures of known overall compositions
3. RESULTS AND DISCUSSION The experimental binodal curve data of the water + acetic acid + dimethyl carbonate ternary system at (298.2, 308.2, and 318.2) K, and tie-line data are illustrated in Tables 2 and 3, respectively. The experimental and predicted binodal curve and tie-lines at each temperature are illustrated in Figures 1 to 3. As can be seen in Figures 1 to 3, it has been found that dimethyl carbonate was slightly soluble in water, but miscible with acetic acid. Distribution coefficients, Di, for water (i = 1) and acetic acid (i = 2) and separation factors, S, were determined as follows:24 Di = wi3/wi1
(1)
S = (w23/w13)solvent‐rich phase /(w21/w11)water‐rich phase
(2)
The distribution coefficients and separation factors for the each temperature are given in Table 3. The extraction power of the 3354
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Table 3. Experimental Tie-Line Data (as Mass Fraction) for the Water (1) + Acetic Acid (2) + Dimethyl Carbonate (3) Ternary System at Each Temperaturea and Atmospheric Pressure with Distribution Coefficients and Separation Factors water-rich phase
a
water
acetic acid
0.7883 0.7025 0.6189
0.0482 0.0936 0.1317
0.7880 0.7135 0.6314
0.0491 0.0950 0.1347
0.7771 0.6785 0.5016
0.0493 0.0932 0.1193
solvent-rich phase water
acetic acid
T = 298.2 K 0.0393 0.0299 0.0670 0.0674 0.1306 0.1105 T = 308.2 K 0.0612 0.0314 0.0976 0.0695 0.1425 0.1140 T = 318.2 K 0.0812 0.0313 0.1086 0.0689 0.2087 0.1072
D2
S
0.6203 0.7201 0.8390
12.43 7.55 3.98
0.6395 0.7316 0.8463
8.23 5.35 3.75
0.6349 0.7393 0.8986
6.08 4.62 2.16
Figure 2. Ternary diagram for LLE of water (1) + acetic acid (2) + dimethyl carbonate (3) at 308.2 K. −+− experimental binodal curve; −O− experimental tie-line data; green −∗−, NRTL; red --□--, UNIFAC; purple ··△··, modified UNIFAC; blue −◇−, UNIQUAC tie-line data.
Standard uncertainties u are u(x) = 0.0002 and u(T) = 0.1 K.
Figure 1. Ternary diagram for LLE of water (1) + acetic acid (2) + dimethyl carbonate (3) at 298.2 K. −+− experimental binodal curve; −○− experimental tie-line data; green −∗−, NRTL; red --□--, UNIFAC; purple ··△··, modified UNIFAC; blue −◇−, UNIQUAC tie-line data.
Figure 3. Ternary diagram for LLE of water (1) + acetic acid (2) + dimethyl carbonate (3) at 318.2 K. −+− experimental binodal curve; green −∗−, NRTL; red --□--, UNIFAC; purple ··△··, modified UNIFAC; blue −◇−, UNIQUAC tie-line data.
parameters.26−28 The real behavior of fluid mixtures can be calculated with the help of activity coefficients. The correct description of the dependence on temperature, pressure, and composition in multicomponent systems requires reliable thermodynamic models, allowing the calculation of these properties from available experimental data.29 The UNIFAC method was developed by Fredenslund et al.30−32 The UNIFAC method for the calculation and prediction of activity coefficients is based on the group contribution method concept. As in every group contribution method, it is assumed that the mixture does not consist of molecules, but of structural groups.33 It has the advantage of forming a very large number of probable molecules from a relatively small set of structural groups. For the calculation of LLE the so-called isoactivity criterion must be fulfilled, where xEi and xRi are the mole fractions of LLE phases:
solvent at each temperature, plots of D2 vs w21 are shown in Figure 4. The reliability of experimentally measured tie-line data can be ascertained by applying the Othmer−Tobias correlation equation which is the following:25 ln[(1 − w33)/w33] = a + b ln[(1 − w11)/w11]
(3)
where w11 is the weight fraction of water (1) in the water-rich phase; w33 is the weight fraction of dimethyl carbonate (3) in the solvent-rich phase; a and b are the constant and slope of eq 3, respectively. The linearity of the plot indicates the degree of consistency of the data. Othmer−Tobias plots are shown in Figure 5 for all temperatures. The parameters of the Othmer−Tobias correlation are illustrated in Table 4. The proximity of the correlation factor (r2) to 1 shows the degree of consistency of related data. The experimental tie-line data were correlated using NRTL and UNIQUAC models in order to obtain the binary interaction
(γixi)E = (γixi)R 3355
(4)
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Table 5. UNIQUAC r and q Values38,39 compound
ri
qi
dimethyl carbonate acetic acid water
3.0613 2.2024 0.9200
2.8160 2.0720 1.3990
Table 6. Correlated Results from the NRTL (α = 0.2) and the UNIQUAC Models and the Corresponding Binary Interaction Parameters (aij and aji)/K for the Ternary Systemsa,44 components T/K
i−j
298.2
1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3 components
308.2
318.2
Figure 4. Distribution coefficient, D2, of acetic acid as a function of the mass fraction w21 of acetic acid in the water-rich phase.
NRTL parameters/K aij
aji
−735.50 −100.10 870.79 353.63 −877.24 773.17 −485.07 205.34 1030.8 157.87 −641.64 784.03 −353.55 −599.82 1060.6 116.68 −944.03 314.80 UNIQUAC parameters/K
RMSD 0.2663
0.1152
0.3992
T/K
i−j
aij
aji
RMSD
298.2
1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3
16.062 73.359 −128.76 46.469 106.24 −137.52 −255.11 98.363 −410.51
−350.14 514.74 −336.71 −328.24 361.53 −238.25 −337.59 362.04 68.508
0.3006
308.2
318.2
0.2165
0.4066
a The NRTL and UNIQUAC model parameters (aij, aji) are defined as aij = (gij − gjj)/R and aij = (uij − ujj)/R, respectively.
and form of molecules (entropic contribution), and the residual part considers the enthalpic contribution. To reduce the weaknesses of UNIFAC, the modified UNIFAC (Dortmund) method was proposed after several years. It presents various advantages when compared with the group contribution methods, UNIFAC or ASOG. These advantages were reached by using as an empirically modified combinatorial part, temperaturedependent group interaction parameters, and additional main groups. For fitting the temperature-group interaction parameters, besides VLE a larger database including activity coefficients at infinite dilution, excess enthalpy, excess heat capacity, LLE, SLE of simple eutectic systems, and azeotropic data are used.34−37 The UNIFAC and modified UNIFAC method depend on the interaction parameters between each pair of main groups present in the system, but the UNIQUAC and NRTL models depend on interaction parameters between the compounds in the system. The experimental tie-line data for the each ternary system were correlated using the NRTL and the UNIQUAC models. For the investigated system, the literature values were used for the UNIQUAC structural parameters38−41 in Table 5, and UNIQUAC and the NRTL corresponding binary interaction parameters42 for the ternary system are given in Table 6. The NRTL and UNIQUAC binary interaction parameters were determined using the experimental tie-line data and minimizing a composition-based objective function.43,44
Figure 5. Othmer−Tobias plot of the water (1) + acetic acid (2) + dimethyl carbonate (3) ternary system at T = green −□−, 298.2 K; blue −○−, 308.2 K; red −△−, 318.2 K.
Table 4. Constants of the Othmer−Tobias Equation for the Water + Acetic Acid + Dimethyl Carbonate Ternary System T/K
a
b
r2
298.2 308.2 318.2
0.1823 0.1259 0.7343
0.5716 0.6342 0.9619
0.9977 0.9981 0.9999
where E is the extract (solvent) phase, R is the raffinate (aqueous) phase, and γ is the activity coefficient of the component i. The UNIFAC equation for the liquid phase activity coefficient is represented as follows: ln γi = ln γi c + ln γi r
(5)
The activity coefficients are calculated from combinatorial and residual part in the same way as in UNIQUAC. The temperatureindependent combinatorial part takes into consideration the size 3356
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decreased by the increase of acetic acid concentration, and they can be viewed in Table 3. It was found that UNIFAC and modified UNIFAC prediction methods were not fitted satisfactorily to the experimental data for the ternary system, but the NRTL and UNIQUAC were more suitable than the rest. Besides, the UNIQUAC model was also more convenient than the NRTL model. Finally, it has been concluded that the dimethyl carbonate is a convenient separating agent for dilute aqueous acetic acid as a result of being environmentally friendly solvent and having low cost.
Table 7. RMSD Values of UNIFAC and Modified UNIFAC Methods RMSD T/K
UNIFAC
modified UNIFAC
298.2 308.2 318.2
0.1606 0.1413 0.2848
0.1790 0.1669 0.2868
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected] (E.I.̇ ). Tel.: +90-212-473 70 70. Fax: +90-212-473 71 80. Notes
The authors declare no competing financial interest. Author e-mail:
[email protected] (M.L.) and dana.
[email protected] (D.C.).
■
a b Di E I J K i
nD r2 R S T Tb wi w11 w21 w31
Figure 6. Separation factor diagram with experimental and theoretical values at each temperature.
The root-mean-square deviations (RMSD) are calculated from the difference between the experimental data and the predictions of NRTL, UNIQUAC, UNIFAC, and modified UNIFAC methods at each temperature, according to the following equation: RMSD = [∑ (∑ ∑ (X i,exp − X i,calcd)2 )/6N ]1/2 K
J
I
(6)
where I is water or acetic acid, J is the solvent-rich or water-rich phase, and K = 1, 2, 3, ...N (tie-line number). Root-mean-square deviation values of the NRTL and UNIQUAC models are given in Table 6; UNIFAC and modified UNIFAC methods are given in Table 7. Separation factors were obtained for all temperatures in Figure 6 with experimental and theoretical values. The effect of temperature change on the experimental values of separation factor was found to be insignificant. With respect to the separation factor, the result was obtained using the UNIFAC method fitted experimental data rather than that of modified UNIFAC method.
w13 w23 w33 x
LIST OF SYMBOLS constant, eq 3 slope, eq 3 distribution coefficient of the ith component, eq 1 extract (solvent) phase water or acetic acid solvent-rich or water-rich phase tie-line number component number of water (1), acetic acid (2), and dimethyl carbonate (3) refractive index regression coefficient raffinate (aqueous) phase separation factor, eq 2 temperature, K boiling point, K weight fraction of the ith component weight fraction of water (1) in the water-rich phase weight fraction of acetic acid (2) in the water-rich phase weight fraction of dimethyl carbonate (3) in the water-rich phase weight fraction of water (1) in the solvent-rich phase weight fraction of acetic acid (2) in the solvent-rich phase weight fraction of dimethyl carbonate (3) in the solvent-rich phase mole fraction of the component
Greek Letters
γ activity coefficient of the component i ρ density (kg·m−3) Subscripts
exp calcd i 1 2 3
4. CONCLUSION Liquid−liquid equilibrium data of the water + acetic acid + dimethyl carbonate ternary system were determined experimentally at each temperature. It has been found out that the temperature has no practical effect on the size of immiscibility region at the temperatures considered. The tie-lines in Figures 1 to 3 illustrate that acetic acid is equally soluble in both the waterrich phase and the solvent-rich phase. Separation factors are
experimental calculated the component water acetic acid dimethyl carbonate
Superscripts
E R c r 3357
extract (solvent) phase raffinate (aqueous) phase combinatorial part residual part dx.doi.org/10.1021/je500332k | J. Chem. Eng. Data 2014, 59, 3353−3358
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