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Article history: The aim of this work is to analyze the possibility of separating isopropyl acetate and 2-propanol, an
Received 12 September 2015 azeotropic system, by using glycerol. Thus, liquideliquid equilibrium (LLE) data for the ternary system of
Received in revised form isopropyl acetate þ 2-propanol þ glycerin have been determined at various temperatures T ¼ (298.15,
25 December 2015
308.15, 318.15) K under atmospheric pressure. The consistency of the experimental data was verified by
Accepted 28 December 2015
Available online 30 December 2015
the mass balance. The extraction capacity was evaluated throughout the distribution coefficient and
selectivity parameters. Phase diagrams have been obtained at each temperature. To facilitate the
manipulation of the obtained data for industrial applications, the NRTL and the UNIQUAC models have
Keywords:
Liquid-liquid equilibrium
been applied to correlate the experimental data and low deviations were obtained.
Phase diagram © 2015 Elsevier B.V. All rights reserved.
Selectivity
Glycerol
NRTL
UNIQUAC
http://dx.doi.org/10.1016/j.fluid.2015.12.050
0378-3812/© 2015 Elsevier B.V. All rights reserved.
200 Y.-X. Li et al. / Fluid Phase Equilibria 412 (2016) 199e204
Additionally, the capacity of glycerol as an extractive solvent was (2) þ glycerol (3) system at various temperatures T ¼ (298.15,
analyzed by the solute distribution coefficient and the selectivity. 308.15, and 318.15) K under atmospheric pressure are listed in
Table 2. Triangular phase diagrams with tie-lines are shown in
2. Experimental Fig. 1. The experimental data show that the ternary system is a type-
I system. The large two-phase region in Fig. 1 enables a large
2.1. Materials operation range for the extraction process. The mutual solubility of
isopropyl acetate and glycerol increases with the addition of 2-
In this work, isopropyl acetate, 2-propanol and glycerol were propanol. The increasing temperature from 298.15 K to 318.15 K
used. The source, CASRN, mass fraction purity and analysis method does not show obvious effect on the equilibrium of the ternary
of all chemicals are listed in Table 1. Purities of the materials were system. But it is worthy of mention that increasing temperature will
determined by a gas chromatography (GC) equipped with a flame decrease the viscosity of glycerol significantly. According to the
ionization detector. In addition, the water contents were measured research of Secur et al. [16], the viscosity of glycerol decreases from
by Karl Fischer titration and no appreciable water was detected. All 1005 mPa s to 550 mPa s as the temperature increasing from
the materials were used without further purification. 293.15 K to 323.15 K, which provides convenience for operation.
The consistency of the LLE data was verified by the method
2.2. Apparatus and procedure proposed by Marcilla et al. [17]. According to the mass balance
between the initial mixture and the two conjugated phases (extract
The LLE experiment was carried out in a 30 mL glass cell with a phase and raffinate phase), three independent mass balance
magnetic stirrer in it. The experimental method was described in equations can be written as follows:
literature [13e15]. In this study it was specified as follows: The 0 0
temperature of the system was controlled by a refrigerated heating M ðx1 Þ ¼ MI ðx1 ÞI þ MII ðx1 ÞII (1)
circulator (Julabo FP45-HF, German, temperature stability ±0.01 K)
and measured by a platinum resistance thermometer Pt-100 0 0
M ðx2 Þ ¼ MI ðx2 ÞI þ MII ðx2 ÞII (2)
(calibrated with an accuracy of 0.01 K). In each measurement of
the LLE data, 10 ml mixture of isopropyl acetate and 2-propanol 0 0
plus 10 ml glycerol were added into the glass cell and then stir- M ðx3 Þ ¼ MI ðx3 ÞI þ MII ðx3 ÞII (3)
red vigorously by the magnetic stirrer. Through a series of
comparative tests, the stirring time was chosen to be 2 h to get a where M0 is the mole of initial mixture, MI and MII are the mole of
sufficient mixing for the extraction equilibrium. The mixture was the isopropyl acetate-rich phase and the glycerol-rich phase
settled for 5 h to ensure a complete separation of the two phases. respectively. (xi)’ is the mole fraction of component i in the initial
Then the samples of the upper and lower phase (isopropyl acetate- mixture, while (xi)I and (xi)II are the mole fraction of component i in
rich and glycerol-rich phase) were carefully collected by syringes at the isopropyl acetate-rich phase and the glycerol-rich phase
least three times for the composition analysis. respectively, i ¼ 1, 2, 3.
The values of MI and MII were calculated by solving these
2.3. Sample analysis overdetermined linear equations with least-squares method. The
relative error RE of the mass balance was determined by the
The collected samples were analyzed by gas chromatography following equation:
(Agilent Technologies 6890N). The gas chromatography was 0
equipped with a flame ionization detector and a HP-5 capillary MI þ MII M
RE ¼ 0 (4)
column (30 m 0.32 mm 0.25 mm). The carrier gas was nitrogen M
with the purity of 0.99999 provided by Liufang industrial gases co., The maximal RE is less than 1%. From Fig. 1, one can also
LTD, Tianjin. The operation condition was as follows: The injector conclude that the experimental data is reliable because the points
temperature and detector temperature were 573 K and 583 K, of the overall compositions agree the tie line with great accuracy.
respectively. The column temperature was programmed at 310 K
for 3 min firstly, then increased to 563 K at a rate of 45 K min1 and
held for 1 min. The calibration factor was obtained to correct the 3.2. Evaluation of the extractive solvent
measured values. The accuracy of the analytical method was tested
by known samples of mixtures and the maximum relative error of The distribution coefficient (b) and the selectivity (S) are used to
the mass fraction did not exceed 0.003. evaluate the extraction capacity of glycerol. These parameters are
defined as follows:
3. Results and discussion
xІІ
2
3.1. Experimental data b¼ (5)
xІ2
Table 1
Experimental chemicals.
Table 2
The experimental LLE data of isopropyl acetate (1) þ 2-propanol (2) þ glycerol (3), together with the distribution coefficient b and selectivity S.a
x1 x2 x3 x1 x2 x3 x1 x2 x3
T ¼ 298.15 K
0.388 0.000 0.612 0.995 0.000 0.005 0.010 0.000 0.990
0.342 0.057 0.601 0.850 0.130 0.020 0.012 0.049 0.939 0.373 26.784
0.298 0.113 0.589 0.782 0.198 0.020 0.013 0.071 0.916 0.359 21.650
0.256 0.165 0.579 0.633 0.324 0.043 0.020 0.121 0.859 0.374 11.785
0.216 0.216 0.568 0.545 0.390 0.065 0.021 0.129 0.850 0.332 8.586
0.196 0.241 0.563 0.508 0.418 0.074 0.024 0.153 0.823 0.365 7.649
0.177 0.265 0.558 0.447 0.447 0.106 0.029 0.173 0.798 0.388 6.044
0.157 0.290 0.553 0.372 0.483 0.145 0.037 0.209 0.754 0.434 4.336
0.138 0.313 0.549 0.319 0.493 0.188 0.047 0.225 0.728 0.457 3.116
0.120 0.337 0.543 0.265 0.500 0.235 0.045 0.246 0.709 0.491 2.854
T ¼ 308.15 K
0.388 0.000 0.612 0.994 0.000 0.006 0.011 0.000 0.989
0.342 0.057 0.601 0.857 0.114 0.029 0.013 0.043 0.944 0.378 24.517
0.298 0.113 0.589 0.785 0.192 0.023 0.014 0.063 0.923 0.328 18.111
0.256 0.166 0.578 0.634 0.316 0.050 0.022 0.115 0.863 0.364 10.784
0.216 0.216 0.568 0.564 0.372 0.064 0.024 0.129 0.847 0.348 8.205
0.196 0.241 0.563 0.491 0.414 0.095 0.025 0.155 0.820 0.373 7.265
0.177 0.265 0.558 0.420 0.457 0.123 0.027 0.165 0.808 0.360 5.680
0.157 0.290 0.553 0.361 0.480 0.159 0.036 0.221 0.743 0.459 4.570
0.132 0.320 0.548 0.305 0.490 0.205 0.039 0.249 0.712 0.507 3.928
0.120 0.336 0.544 0.260 0.499 0.241 0.040 0.275 0.685 0.552 3.581
T ¼ 318.15 K
0.388 0.000 0.612 0.989 0.000 0.011 0.012 0.000 0.988
0.342 0.057 0.601 0.840 0.132 0.028 0.013 0.043 0.944 0.327 21.747
0.298 0.113 0.589 0.795 0.180 0.025 0.016 0.065 0.919 0.360 17.515
0.256 0.165 0.579 0.649 0.296 0.055 0.023 0.097 0.880 0.326 9.301
0.216 0.216 0.568 0.566 0.362 0.072 0.026 0.133 0.841 0.367 7.982
0.196 0.241 0.563 0.495 0.415 0.090 0.032 0.158 0.810 0.380 5.824
0.177 0.265 0.558 0.421 0.450 0.129 0.033 0.181 0.786 0.402 5.061
0.157 0.290 0.553 0.358 0.468 0.174 0.045 0.216 0.739 0.462 3.649
0.120 0.336 0.544 0.292 0.483 0.225 0.051 0.259 0.690 0.537 3.089
0.111 0.349 0.540 0.217 0.490 0.293 0.055 0.301 0.644 0.614 2.412
a
All compositions are expressed as mole fraction, the standard uncertainties u are u(T) ¼ 0.01 K, u(x1) ¼ u(x2) ¼ u(x3) ¼ 0.001.
The equation has been used to correlate the variation of selec- Andreatta et al. summarized thermodynamic models describing
tivity with a good degree of accuracy in the published studies the ternary system alkyl ester þ alcohols þ glycerol [21]. Several
[18e20]. The parameters e, f, g in Eq. (7) and the standard de- models have been previously tested to correlate these kinds of
viations d are listed in Table 3. mixtures: NRTL model, UNIQUAC model, traditional UNIFAC and its
As demonstrated in Fig. 2, the selectivity decreases with the versions, Wilson activity coefficient model, GCPPCSAFT model
increase of the 2-propanol content in the isopropyl acetate-rich CPA EoS model and GCAEoS model.
phase, and slightly decreases with temperature. It should be Except Andreatta, many other researchers also spent much
noted in Fig. 2 that the values of S are much higher than the unity, effort on the LLE of alkyl ester þ alcohols þ glycerol system. For
especially at low content of 2-propanol. instance, Basso et al. [22] published the LLE data of
As a potential solvent, glycerol has many attractive features glycerol þ ethanol þ distilled fatty acid ethyl esters from crambe oil
including good chemical stability, non-toxicity, non-corrosivity, in the range of 298.2Ke338.2 K. The data were correlated with the
and relatively low price, besides its high selectivity. Moreover, NRTL and the UNIFAC models, and the NRTL model gave a better
compared to isopropyl acetate, its higher density improves the result. Mesquita et al. [23] measured the LLE data of
separation efficiency of the two phases in the extraction process. glycerol þ ethanol þ coconut biodiesel system. The NRTL and the
(The densities of glycerol and isopropyl acetate are 1.261 g/cm3, UNIQUAC models were used to correlate the LLE data and satis-
0.888 g/m3, respectively [3].) Its boiling point is higher than that of factory results were obtained. De Azevedo Rocha et al. [24] studied
202 Y.-X. Li et al. / Fluid Phase Equilibria 412 (2016) 199e204
2 !2 !2 3
X
N X2 X 3 exp
Tk Tkcal xexp xcal
OF ¼ 4 þ
ijk ijk 5 (8)
j¼1 i¼1
sT sx
k¼1
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
u
u N 2 3 xexp xcal 2
uX X X ijk
RMSD ¼ t
ijk
(9)
6N
k¼1 j¼1 i¼1
The values of the NRTL and the UNIQUAC model parameters are
shown in Table 5. The calculated data from these parameters are
plotted together with the experimental data in Fig. 1. Through Fig. 1
one can note that both models are in good agreement with the
experimental results, and the NRTL model makes a better correc-
tion. From the correlated results in Table 5, it can also be inferred
that the phase equilibria of the studied system can be accurately
described by the two models, and the NRTL model has a smaller
RMSD than the UNIQUAC model does.
Some authors correlated the LLE data of the system of alkyl
ester þ alcohols þ glycerol with other thermodynamic models.
Oliveira et al. [34] correlated the experimental data of this system
with the CPA-EoS model. The average deviations between the
experimental data and modeling results exceeded 2%. Andreatta
[21] applied the GCA-EoS and the A-UNIFAC model in this kind of
system. The standard deviations in the prediction of methanol
distribution coefficients were 9.5% and 3.93% for the two models,
respectively. Kuramochi et al. [35] applied different versions of the
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204 Y.-X. Li et al. / Fluid Phase Equilibria 412 (2016) 199e204