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Article history: The liquid-liquid equilibrium of the water þ propargyl alcohol þ n-propyl acetate ternary system was
Received 6 July 2016 experimentally investigated in the temperature range (279.15e321.15) K under atmospheric pressure.
Received in revised form Five profiles of isothermal liquid-liquid equilibrium data measured through gas chromatography were
18 October 2016
provided. The extraction efficiency was evaluated using the distribution coefficient and selectivity factor.
Accepted 20 October 2016
Binary interaction parameters were obtained by correlating the equilibrium data with the UNIQUAC and
Available online 22 October 2016
NRTL models. The mutual solubility of both phases increased with rising temperature. Both models can
accurately describe the liquid-liquid equilibrium behavior of this system.
Keywords:
Liquid-liquid equilibrium
© 2016 Elsevier B.V. All rights reserved.
Propargyl alcohol
n-propyl acetate
UNIQUAC
NRTL
http://dx.doi.org/10.1016/j.fluid.2016.10.023
0378-3812/© 2016 Elsevier B.V. All rights reserved.
86 C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89
Table 1
Sources and purities of chemicals.
Chemical name Source Initial mass fraction puritya Final mass fraction purityb
w2
w
The tubes in the thermostatic oven were initially heated for 0.50
30 min to reach the expected and invariant temperature. Subse-
quently, they were oscillated for 50 min to achieve intensive mix-
ing. After oscillation, the tubes were allowed to set for 75 min, in 0.75
0.25
order to facilitate the separation of the resultant liquid into two
phases.
1.00
2.3. Analysis 0.00
0.00 0.25 0.50 0.75 1.00
w1
Samples from both phases were carefully extracted using
microsyringe and then injected into a GC apparatus (GC 1690T,
Fig. 1. Tie-lines and solution curves of water (1) þ PA (2) þ NPA (3) at (C) 279.15 K
Kexiao Science Apparatus Co., Ltd., China) with a and ( ) 321.15 K. Black dashed line, solution curve at 279.15 K; red dashed line, so-
ø2 mm 2000 mm column (packed with Porapak Q, 80/100 Mesh, lution curve at 321.15 K. (For interpretation of the references to colour in this figure
USA). legend, the reader is referred to the web version of this article.)
The temperatures of the TCD, column and injection port of the
GC apparatus were fixed at 453.15 K. The bridge current of the TCD
was 150 mA. The pre-column pressure of hydrogen as carrier gas splitting phases then merge into a single phase. This phenomenon
was 0.18 MPa. is also observed as the temperature rises to 321.15 K.
In Fig. 1, the co-existing region of the liquid-liquid phases
enveloped by the solution curves shrinks as temperature rises from
3. Experimental data 279.15 K to 321.15 K. This finding is different from that observed
from the LLE studies of ternary systems water þ PA þ DIPE [6] and
The mass fractions of the components in each phase at a water þ PA þ BA [7]. The authors of these two articles reported a
particular temperature are shown in Table 3. Each composition is an similar finding in which an approximately single solution curve
average value of three experimental replications. To evaluate the could describe the phase compositions of the respective systems
capacity of NPA to separate PA from water, the distribution coeffi- within the investigated temperature ranges. Temperature exerts a
cient (D) and selectivity (S) are calculated as follows: larger influence on the LLE data of the water þ PA þ NPA system
than on that of the water þ PA þ DIPE and water þ PA þ BA systems.
wI2 Meanwhile, the shrinking co-existing region from 279.15 K to
D¼ (1)
wII2 321.15 K demonstrates that the mutual solubility of both phases
increases when the temperature increases.
As presented in Table 3, the distribution coefficients of PA
wI2 wI1
S¼ (2) generally tend to increase when the PA content increases. The
wII2 wII1
distribution coefficient is relevant to the solubility of the solute (PA
in this study) in both co-existing phases, thus, it reflects the slope of
where wI1 and wI2 are the mass fractions of water and PA in the
the tie-line [13]. The distribution coefficients are not large enough,
organic phase, respectively, and wII1 and wII2 are the mass fractions of
which agrees with the slope of the tie-lines, as shown in Fig. 1. The
water and PA in the aqueous phase, respectively. Values of the
effectiveness of an extractant can be described by the selectivity.
distribution coefficient and selectivity of PA at five temperatures
Fig. 2 plots the selectivity of PA against the mass fraction in the
are listed in Table 3.
organic phase at the investigated temperature range. The selec-
Fig. 1 shows the tie-lines and the corresponding solution curves
tivity of PA decreases slightly with rising temperature, indicating
at 279.15 and 321.15 K. At 279.15 K, the tie-lines are approximately
that the extraction capacity of NPA decreases as the temperature
plain until the content of PA in the total compositions approaches
increases. The selectivity values of PA (values varying between 2
about 20%. As the PA concentration continues to increase in the
and 68) are greater than one, indicating the possibility of PA
ternary mixture, the increase in PA concentration becomes faster in
extraction using NPA.
the organic phase than in the conjugated aqueous phase. The
C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89 87
Table 3
70 Experimental liquid-liquid phase equilibrium data for the water (1) þ PA (2) þ NPA
(3) ternary system (mass fraction).a
60 Organic phase Aqueous phase D S
w1 w2 w3 w1 w2 w3
50
T ¼ 279.15 K
0.0141 0.0464 0.9395 0.9283 0.0454 0.0263 1.02 67.24
40 0.0251 0.0992 0.8757 0.8789 0.0928 0.0283 1.07 37.45
0.0465 0.1925 0.7610 0.8131 0.1578 0.0291 1.22 21.34
S
Fig. 3. Ternary phase diagram for the water (1) þ PA (2) þ NPA (3) system with tie-lines of the experimental and calculated data at (a) 279.15 K, (b) 291.15 K, (c) 301.15 K, (d) 311.15 K
and (e) 321.15 K. (C) experimental data; ( ) data calculated by the UNIQUAC model; ( ) data calculated by the NRTL model; blue dashed lines, solution curves predicted by the
UNIQUAC model; red dashed lines, solution curves predicted by the NRTL model. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
lines, respectively. The superscripts exp and cal denote the experi- Superscripts
mental data and the data calculated by the models, respectively. In I organic phase identifier
the correlation, sT and sx were set to 0.01 K and 0.001, respectively. II aqueous phase identifier
The data were correlated by using the commercial software ASPEN Exp experimental
Properties. Cal calculated
To quantify the deviation between the calculated and experi-
mental compositions, the root-mean-square deviation (RMSD) was
calculated by Eq. (5). Subscripts
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
I component index
u
u N 2 3 xexp xcal 2 J phase index
uX X X ijk
RMSD ¼ t
ijk
(5) K tie-line data index
j¼1 i¼3
6N
k¼1