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Fluid Phase Equilibria 432 (2017) 85e89

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Fluid Phase Equilibria


j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Liquid-liquid equilibrium of the ternary system water þ propargyl


alcohol þ n-propyl acetate
Chong Sun, Wei Cao, Jia Wu, Xiaoping Hu*
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, PR China

a r t i c l e i n f o a b s t r a c t

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

1. Introduction investigate the possibility of isolating PA from water. However, both


studies did not achieve the desired extraction efficiency for PA
Propargyl alcohol (PA) plays a significant role as an intermediate separation. Thus, the search of a suitable solvent is still continuous.
in the synthesis of pharmaceuticals [1,2]. As a typical acetylenic In general, esters are commonly used as solvents to separate
compound, PA is extensively used as an additive in various appli- water-alcohol systems [8e10]. In the present work, the extraction
cations, such as acidizing oil wells, chemical cleaning, acid pickling efficiency for n-propyl acetate (NPA) separation was experimentally
of heat-transfer equipment and removal of scales in metallurgy [3]. investigated by measuring the LLE data for the water þ PA þ NPA
In the anticorrosion protection of metals in acidic media, PA is an ternary system in the temperature range (279.15e321.15) K under
efficient inhibitor, especially for iron and steel alloys [3e5]. atmospheric pressure. The distribution coefficient and the selec-
Industrially, PA is a side product of 2-butyne-1,4-diol production tivity factor were calculated to assess the separation efficiency. The
which is difficult to separate and purify, resulting in the large gap UNIQUAC [11] and NRTL models [12] were used to correlate the LLE
between supply and demand. The azeotrope formed between PA data.
and water complicates the separation of PA. Thus, purifying PA
through direct distillation is not advisable. A suitable extractant is 2. Experimental methods
highly necessary to separate PA from water and to subsequently
develop a novel extraction process for PA. This development inev- 2.1. Materials
itably requires fundamental research on the liquid-liquid equilib-
rium (LLE) behavior of a water-PA system. The source and purity of each chemical used in this work are
Limited LLE data of the water þ PA þ extractant system are listed in Table 1. The purity of each material was determined
available in open literature. K. Ye et al. [6] investigated the LLE of through gas chromatography (GC). These chemicals were used
diisopropyl ether (DIPE) as a solvent to extract PA from water. G. without further purification. Deionized water was used throughout
Yuan et al. [7] applied butyl acetate (BA) as a substitute to all experiments.

2.2. Experimental apparatus and procedures


* Corresponding author.
E-mail address: huxp@zju.edu.cn (X. Hu). The measurements were performed in the temperature range

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

Water Hangzhou Wahaha Group Co., Ltd. >99.73%


PAc Northeast Pharmaceutical Factory Fushun Branch, China >99.50% >96.68%
NPAd Sinopharm Chemical Reagent Co., Ltd. 98.50% >99.90%
a
The purity labelled by the supplier.
b
The purity detected by GC.
c
IUPAC chemical name: 2-propyn-1-ol.
d
IUPAC chemical name: 1-propyl acetate.

(279.15e321.15) K under atmospheric pressure. An electronic bal- 0.00


1.00
ance (BS224S, accuracy ± 0.0001 g, Sartorious AG, Germany) was
used to weigh the required quantities of water, PA and NPA. The
weighed components were then mixed in a series of test tubes
according to the desired compositions of ternary mixtures. The 0.25
0.75
tubes were sealed with silicon rubber stops, and fixed vertically
onto an oscillator which was installed in a thermostatic oven (with
a PID temperature controller of accuracy ± 0.1 K).
0.50

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

30 0.0622 0.2621 0.6757 0.7737 0.1947 0.0316 1.35 16.76


0.0853 0.3264 0.5883 0.7333 0.2296 0.0371 1.42 12.23
0.1131 0.3738 0.5131 0.6763 0.2730 0.0507 1.37 8.18
20 0.1464 0.4152 0.4384 0.6289 0.3111 0.0600 1.33 5.74
T ¼ 291.15 K
10 0.0161 0.0527 0.9312 0.9176 0.0592 0.0232 0.89 50.62
0.0302 0.1036 0.8662 0.8606 0.1068 0.0326 0.97 27.62
0.0524 0.1904 0.7572 0.7993 0.1692 0.0315 1.12 17.15
0
0.0754 0.2608 0.6638 0.7496 0.2172 0.0332 1.20 11.95
0.0 0.1 0.2 0.3 0.4
0.1045 0.3214 0.5741 0.6954 0.2633 0.0413 1.22 8.13
wI2 0.1398 0.3663 0.4939 0.6444 0.3022 0.0534 1.21 5.59
0.1812 0.4024 0.4164 0.5979 0.3294 0.0727 1.22 4.03
T ¼ 301.15 K
Fig. 2. Selectivity of PA plotted against the mass fraction of PA in the organic phase at
0.0233 0.0515 0.9252 0.9251 0.0537 0.0212 0.96 37.99
(C) 279.15 K, ( ) 291.15 K, ( ) 301.15 K, ( ) 311.15 K and ( ) 321.15 K.
0.0280 0.1002 0.8718 0.8627 0.1130 0.0243 0.89 27.35
0.0558 0.1875 0.7567 0.7982 0.1699 0.0319 1.10 15.78
0.0825 0.2574 0.6601 0.7404 0.2225 0.0371 1.16 10.38
Table 2 0.1201 0.3148 0.5651 0.6961 0.2593 0.0446 1.21 7.04
CAS number (CAS), molecular weights (M), boiling points (Tb), densities (r) and 0.1507 0.3629 0.4864 0.6386 0.3022 0.0592 1.20 5.09
refractive indices (nD) at 298.15 K under atmosphere pressure. 0.2101 0.3923 0.3976 0.5614 0.3499 0.0887 1.12 2.99
T ¼ 311.15 K
Chemical name CAS M (g mol1) Tb (K)a r (g cm3)a nDb
0.0272 0.0523 0.9205 0.9211 0.0595 0.0194 0.88 29.72
Water 7732-18-5 18.02 373.15 0.9971 1.3330 0.0346 0.0992 0.8662 0.8750 0.1006 0.0244 0.99 24.89
PA 107-19-7 56.06 386.65 0.9450 1.4302 0.0589 0.1870 0.7541 0.8004 0.1690 0.0306 1.11 15.04
NPA 109-60-4 102.13 374.65 0.8823 1.3816 0.0899 0.2528 0.6573 0.7306 0.2352 0.0342 1.07 8.74
a 0.1149 0.3242 0.5609 0.6926 0.2632 0.0442 1.23 7.42
Obtained from ASPEN Properties Databank.
b 0.1592 0.3719 0.4689 0.6260 0.3061 0.0679 1.22 4.78
Obtained from DECHEMA.
0.2288 0.4078 0.3634 0.5344 0.3584 0.1072 1.14 2.66
T ¼ 321.15 K
0.0313 0.0542 0.9145 0.9208 0.0573 0.0219 0.95 27.79
4. Thermodynamic modelling 0.0403 0.1007 0.8590 0.8707 0.1058 0.0235 0.95 20.53
0.0658 0.1854 0.7488 0.7973 0.1707 0.0320 1.09 13.17
4.1. Selection of thermodynamic models 0.0927 0.2550 0.6523 0.7335 0.2277 0.0388 1.12 8.86
0.1211 0.3165 0.5624 0.6798 0.2680 0.0522 1.18 6.63
0.1618 0.3621 0.4761 0.6136 0.3069 0.0795 1.18 4.48
In terms of LLE modelling, the NRTL, UNIQUAC and UNIFAC a
Standard uncertainties u are u(T) ¼ 0.1 K, u(w) ¼ 0.004.
models are frequently used to correlate equilibrium systems.
Previous studies on the water þ PA þ DIPE and water þ PA þ BA
systems have shown that the UNIFAC group contribution method
cannot describe the LLE behavior of these systems [6,7], but the
UNIQUAC model predicts the latter fairly well [7]. The UNIQUAC Table 4
model, which considers the effects of molecular size and shape [11], UNIQUAC structural parameters of the three pure components.
has successfully correlated many LLE systems, including mixtures
Component r q
containing ketones [14], alcohols [13,15,16] and esters [15,17].
Considering the differences in molecular sizes and shapes of the Water 0.920 1.400
PA 2.471 2.154
three investigated compounds, we selected the UNIQUAC model to NPA 4.153 3.656
correlate this system.
Meanwhile, the NRTL model can represent well many LLE
mixtures through the proper selection of the nonrandomness
parameter aij [12]. PA is a multifunctional molecule, with the
acetylenic carbons and the acidic hydrogen on the carbon serving
as a proton acceptor and donor sites, respectively [18]. Meanwhile, Table 5
water is a typical compound which is easily involved in the Temperature-dependent coefficients of the binary interaction parameters of the
UNIQUAC and NRTL models for the water (1) þ PA (2) þ NPA (3) ternary system.
hydrogen bonding network. To test the predictability of the system,
we also applied the NRTL model to correlate the experimental data. iej UNIQUAC NRTL

Aij Bij aij bij aij


1e2 1.38 236.68 5.06 169.03 0.14
2e1 1.88 482.33 3.81 546.22 0.14
4.2. Data correlation 1e3 1.86 420.44 9.03 1282.70 0.23
3e1 3.47 1533.42 3.67 1539.69 0.23
Before the data correlation, the experimental mass composi- 2e3 2.08 525.52 3.08 1094.92 0.47
tions (wi) were converted to mole compositions (xi) using the 3e2 3.06 690.12 2.36 656.07 0.47
RMSD 0.0139 0.0124
equation
88 C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89

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.)

was included in the NRTL model. The commonly recommended aji


w =M values for different mixtures are between 0.1 and 0.47.
xi ¼ P i  i (3) The UNIQUAC structural parameters for the pure components
wj Mj
j were obtained from the ASPEN Properties Databank and are listed
in Table 4. The coordination number zi was set to 10. The binary
where Mi is the molecular weight of component i, with values of the interaction parameters for both models were obtained by mini-
three compounds listed in Table 2. mizing the objective function Q [19]:
The values of temperature-dependent parameters (Appendices
2 !2 !2 3
A and B, and Eqs. (A.5) and (B.3)) for the UNIQUAC and NRTL X
N X
2 X exp xexp  xcal
3 Tk  Tkcal
models can be determined through the correlation of the experi- Q¼ 4 þ
ijk ijk 5 (4)
mental data. To simplify the data correlation, we considered only k¼1 j¼1 i¼1
sT sx
four nonzero coefficients: Aji and Bji for the UNIQUAC model, and aji
and bji for the NRTL model. In addition to the temperature- where N is the number of the tie-lines, and x is the mole fraction.
dependent binary parameters, another adjustable parameter, aji, The subscripts i, j and k refer to the components, phases and tie-
C. Sun et al. / Fluid Phase Equilibria 432 (2017) 85e89 89

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

The temperature-dependent coefficients of the binary interac-


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