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Salts effect on isobaric vapor−liquid equilibrium for separation of the azeotropic mixture allyl alcohol + water
Accepted Manuscript Salts effect on isobaric vapor−liquid equilibrium for separation of the azeotropic mixture Allyl alcohol + water Li Xu, Dongmei Xu, Puyun Shi, Kai Zhang, Xiaolong Ma, Jun Gao, Yinglong Wang PII:
S0378-3812(17)30409-0
DOI:
10.1016/j.fluid.2017.10.025
Reference:
FLUID 11626
To appear in:
Fluid Phase Equilibria
Received Date: 25 July 2017 Revised Date:
25 October 2017
Accepted Date: 26 October 2017
Please cite this article as: L. Xu, D. Xu, P. Shi, K. Zhang, X. Ma, J. Gao, Y. Wang, Salts effect on isobaric vapor−liquid equilibrium for separation of the azeotropic mixture Allyl alcohol + water, Fluid Phase Equilibria (2017), doi: 10.1016/j.fluid.2017.10.025. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Salts Effect on Isobaric Vapor−Liquid Equilibrium for Separation of the Azeotropic Mixture Allyl Alcohol +Water Li Xu†,a , Dongmei Xu
, Puyun Shi a, Kai Zhang a, Xiaolong Ma a, Jun Gao *,a , Yinglong Wang b
College of Chemical and Environmental Engineering, Shandong University of Science and
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a
†,a
Technology, Qingdao 266590, China b
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao
266042, China
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*Corresponding author
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E-mail addresses: [email protected]
Abstract: Allyl alcohol and water can form an azeotrope with the minimum boiling point. To separate the azeotrope of allyl alcohol and water by salt distillation, three salts calcium chloride, calcium nitrate and magnesium nitrate were selected to break the azeotrope. The vapor-liquid
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equilibrium (VLE) data for the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate were measured at pressure of 101.3 kPa. The results indicated that the relative volatility of allyl alcohol to
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water increased by adding the salts at the molar fraction of allyl alcohol higher than 0.2. With increasing the concentrations of the salts, the azeotropic point of the system allyl alcohol + water
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moved. When the concentrations of calcium chloride and magnesium nitrate were 0.10, 0.15, respectively, the azeotropic point was broken. The effect of salts on the azeotropic point of the system allyl alcohol + water follows the order: calcium chloride > magnesium nitrate > calcium nitrate. Moreover, the experimental VLE data were correlated by the NRTL model. All the root-mean-square deviations for the temperature (T) and the mole fraction of the vapor phase (y1) between the measured and calculated data were less than 0.26 K and 0.005, respectively. Meanwhile, the binary interaction parameters of the NRTL model were regressed. Keywords: vapor-liquid equilibrium; allyl alcohol; water; azeotrope; salts 1
ACCEPTED MANUSCRIPT 1.Introduction Allyl alcohol is an important chemical intermediate. Due to its excellent physical and chemical properties, allyl alcohol is widely applied in the production of medicine, spices, and agricultural chemicals [1-4]. Generally, allyl acetate hydrolysis method is adopted to produce allyl alcohol in
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industry, from which the production mixture consisted of allyl alcohol, water and a small amount of allyl aldehyde and acetic acid can be obtained [5]. To separate allyl alcohol from the mixture, the distillation technology is needed. However, since allyl alcohol and water can form a minimum
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azeotrope, the special distillation is necessary.
Usually, for the separation of the azeotropic mixtures, special distillations are applied, such as
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extractive distillation, azeotropic distillation, salt distillation, pressure-swing distillation and reactive distillation [6]. Considering the salts effect on isobaric vapor-liquid equilibrium of the azeotropic mixtures, which can affect the relative volatility of the components in the mixtures [7-10], in this work, the salt distillation technology was adopted for its high-efficiency separation capacity for the
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azeotropic mixture of allyl alcohol and water.
In the previous works, some researchers reported the VLE for the system of allyl alcohol + water [11-15]. Grabner [11] and Zhang [12] determined the isobaric VLE data for the system allyl alcohol
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+ water at 101.3kPa. Aucejo [13] measured the isobaric VLE data for allyl alcohol + water at
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pressures of 30, 60 and 100 kPa. And the isobaric VLE data of allyl alcohol + water at 100.26 kPa were determined by Harper [14]. Meanwhile, Lesteva reported the isothermic VLE data for allyl alcohol + water at 313.14 K [15]. To separate azeotropic systems contain alcohols, calcium chloride, calcium nitrate and magnesium nitrate were selected as azeotrope destroyers [9, 16-19], which have a strong salting out effect and lead to the elimination of the azeotropic points. Since calcium chloride, calcium nitrate and magnesium nitrate are well dissolved in water and allyl alcohol, and the solubilities of the salts in allyl alcohol are different than water, the three salts were adopted in this work to break the azeotrope of allyl alcohol and water. According to the retrieve results from the 2
ACCEPTED MANUSCRIPT NIST, the salts (calcium chloride, calcium nitrate and magnesium nitrate) effect on isobaric VLE for the system of allyl alcohol + water has not been reported. In this work, the isobaric vapor-liquid equilibrium data for the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water
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+ magnesium nitrate were determined at 101.3 kPa. and the thermodynamic consistency of the measured VLE data were checked by the van Ness test [20, 21]. Meantime, the VLE data were correlated by the nonrandom two-liquid model (NRTL) [22, 23].
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2. Experimental 2.1. Chemicals
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Allyl alcohol was purchased from Shandong Xiya Chemical Co, Ltd with the mass fraction of 0.99. The purity of allyl alcohol was checked and confirmed by gas chromatography (SP6890, Shandong Rui Hong Chemical Co., Ltd). The salts, calcium nitrate, calcium chloride, and magnesium nitrate were provided by Chengdu Kelong Chemical Reagents Co., Ltd. The water content of the salts was
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checked by Karl Fisher titration. Allyl alcohol and calcium chloride were used without further purification. Calcium nitrate and magnesium nitrate were desiccated under a vacuum for at least 24 h. The deionized water (conductivity < 1.0 µs·cm-1) was made in our lab by the ultrapure water
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machine (Chengdu Down’s Corning Technology Development Co., Ltd.). Specifications of the
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chemicals are listed in Table 1.
2.2. Apparatus and procedures. The densimeter (Dahometer DH-120N, Beijing Yitenuo Electronic Technology Co., Ltd.) was used to measure density. Before analysis the density of a sample, the densimeter was calibrated with dried air. Then, the sample was added into the densimeter with a volume of 2.5 ml. The value of density was obtained with the uncertainty of 0.0003 g.cm−3. Meanwhile, the Abbe refractometer (2AWJ, Shanghai Experimental Instrument Co. Ltd.) was used to measure the refractive index, and the measurement range was 1.3000−1.7000. The reliability of the refractometer was confirmed by a 3
ACCEPTED MANUSCRIPT standard glass block (n = 1.51670) before testing the samples. After that, the sample with a volume of 0.05ml was added into the refractometer for analysis, and the value of refractive index was obtained with the uncertainty of 0.0001. The measured data of density and refractive index for allyl alcohol and water are listed in Table 2.
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For the isobaric VLE measurement, a modified Rose type recirculating equilibrium still was used, which was presented in detail in the previous literatures [26-28]. The pressure was maintained with a manometer (Nanjing Hengyuan Automatic Gauge Co., Ltd.) and the pressure fluctuation was
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controlled within 1 kPa with the two-step automatic control scheme. Meanwhile, a precise mercury thermometer was used to measure the equilibrium temperature with the accuracy of ± 0.1 K.
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In each experiment, the ternary mixture of allyl alcohol + water + salt was added into the equilibrium still, which was prepared by an electronic analytical balance (SL512N, Mettler Toledo Instrument Co., Ltd) with the accuracy of ± 0.0001 g. For the purpose of making contact sufficiently, the vapor and liquid phases were circulated continuously. When the vapor temperature was kept
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constant for 50 min, the equilibrium was established. The vapor and liquid phase samples were withdrawn by syringes with the volume about 0.5 mL at the same time immediately, and put into the vials for analysis. The compositions of the samples were determined by gas chromatography, and the
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salt mass fractions of the samples were determined by the gravimetric method after vacuum
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desiccation, where allyl alcohol and water were evaporated. 2.3. Analysis
The equilibrium compositions of allyl alcohol and water in the vapor and liquid phase were analyzed by GC (SP6890, Shandong Rui Hong Chemical Co., Ltd), which were equipped with a packed column (Porapak Q 3mm×2m, Dalian Sanjie Scientific Development Co., Ltd.) and a thermal conductivity detector TCD (Shandong Rui Hong Chemical Co., Ltd). The carrier gas was hydrogen with purity of 99.999%, and the flow rate was 50ml/min. The oven temperature was 423.15 K. The
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ACCEPTED MANUSCRIPT injection temperature was fixed at 443.15 K. And the temperature of TCD detector was held at 443.15 K. Before sample analysis, the peak areas of GC were calibrated by five different standard samples that covered the whole composition range. When analyzing the samples, each sample was analyzed
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at least three times. The mean value was adopted when the deviation of three times was not more than 0.001. The compositions of all samples were measured by GC with the workstation of N2000, which was developed by Zhejiang University. The uncertainty of mole fraction was 0.006.
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3. Results and discussion 3.1. Validation of the apparatus
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The isobaric VLE data for the binary system allyl alcohol and water at pressure of 101.3 kPa were determined to verify the reliability of the equilibrium still, which are listed in Table 3. For comparison, the references data reported by Grabner [11] and Zhang [12] are plotted in Fig. 1. As shown in Fig. 1, the measured VLE data agree well with literature data, which indicate that the
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apparatus is reliable. Moreover, the system of allyl alcohol and water formed an azeotrope at x1 ≈ 0.451 and pressure of 101.3 kPa as shown in Fig. 1. 3.2. Vapor-liquid equilibrium for salt containing ternary systems
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The isobaric VLE data for the systems allyl alcohol (1) + water (2) + calcium chloride (3), allyl
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alcohol (1) + water (2) + calcium nitrate (3) and allyl alcohol (1) + water (2) + magnesium nitrate (3) were determined at 101.3 kPa by keeping the mass fractions of salts nearly constant at 0.05, 0.1 and 0.15, respectively, which are listed in Tables 4-6, where w3 represents the mass fraction of the salts in the liquid phase, x1′ is the mole fraction of allyl alcohol in the liquid phase on the salts free basis, y1 is the mole fraction of allyl alcohol in the vapor phase, T is the equilibrium temperature, γi is the activity coefficient of the component, α12 is the relative volatility of allyl alcohol (1) to water (2), which is calculated by using the following equation:
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ACCEPTED MANUSCRIPT α12 =
y1 / x1 y 2 / x2
(1)
where x (salt-free) and y are mole fractions of component in the liquid phase and vapor phase, respectively. Meanwhile, the x-y diagrams of the isobaric VLE data for the systems are presented in
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Figs. 2-4. 3.3. Thermodynamic consistency test.
To confirm the quality of the VLE data obtained, the thermodynamic consistency for all the
follows: 1 N
N
∑
∆yi =
1 N
N
∑ 100
yi
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∆y =
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experimental data was checked with the van Ness test [16,17]. The van Ness test is presented as
i =1
where N is the number of the experimental data; yi
cal
in the vapor phase calculated by the NRTL model; yi
exp
i =1
cal
− yi
exp
(2)
stands for the mole fraction of component i stands for the experimental mole fraction
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of component i in the vapor phase. If △y is less than 1, the measured VLE data can be considered as thermodynamically consistent.
By the van Ness test, the values of ∆y are 0.298, 0.375 and 0.282 for the system of (allyl alcohol +
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water + calcium chloride), 0.318, 0.399 and 0.357 for the system of (allyl alcohol + water + calcium nitrate), 0.324, 0.395 and 0.313 for the system of (allyl alcohol + water + magnesium nitrate) at the
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salt concentration of 0.05, 0.1 and 0.15 (mass fraction), respectively. All the values of ∆y are less than 1, which indicate that the measured VLE data are thermodynamic consistency. 3.4. Salts effect on vapor-liquid equilibria To explore the salts effect on vapor-liquid equilibrium for the systems, the x-y and x-α diagrams for the ternary systems allyl alcohol + water + calcium chloride / calcium nitrate / magnesium nitrate are presented in Figs 2-4 and Figs 5-7, where x1ˊ is the mole fraction of allyl alcohol in the liquid phase on the salt free basis. 6
ACCEPTED MANUSCRIPT As shown in Figs. 2-4, the content of allyl alcohol increases in the vapor phase with increasing the concentration of salts, and the relative volatility of allyl alcohol to water increases with increasing the content of the salts as shown in Figs.5-7. The azeotropic point of the system moved and was eliminated with increasing the amount of salt, which is salting-out effect. For calcium chloride, the
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azeotropic point of the system was broken when its mass fraction was 0.10, while more content of calcium nitrate and magnesium nitrate were needed to break the azeotropic point of the system. Therefore, calcium chloride is more effective than calcium nitrate and magnesium nitrate to break the
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azeotropic point of the system.
As shown in Figures 5-6, in water rich region, when the mass fraction of calcium chloride and
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calcium nitrate is 0.05, the relative volatility of allyl alcohol decreased due to the strong interaction between the salts and allyl alcohol. However, in allyl alcohol rich region, the interactions between the salts and water were strong, so the activity of allyl alcohol increased, which led to the increase of the relative volatility of allyl alcohol. Figure 7 shows that in water rich region, when the mass
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fractions of magnesium nitrate are 0.05 and 0.10, the relative volatility of allyl alcohol decreased, and increased in allyl alcohol rich region.
To compare the salt effect of calcium chloride, magnesium nitrate and calcium nitrate, the relative
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volatility of allyl alcohol to water changed by the three salts at the salt concentration of 15 wt% is
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shown in Fig. 8. The salting-out effect of the three salts follow the order: calcium chloride > magnesium nitrate >calcium nitrate. As results, the salts could improve the separation effect of the azeotropic system, and calcium chloride can be selected as an appropriate salt for the separation of the azeotropic mixture allyl alcohol and water. 3.5. Correlation of the VLE data The vapor-liquid phase equilibrium can be expressed as follows:
(
Vi L P − Pi s yiϕˆ P = xiγ iϕ P exp RT v i
s s i i
7
)
(3)
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[
]
s where the Poynting factor exp Vi L (P − Pi s ) / RT , ϕˆiv and ϕi associated with nonideality were all
close to 1, since the pressure was low, xi and yi represent the mole fraction of component i in the s liquid phase and vapor phase, respectively, Pi is the saturation vapor pressure of pure component i,
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which was estimated by the extended Antoine expression [29]. Considering the non-ideality of the liquid phase, Equation (3) can be simplified as: y i P = xi γ i Pi s
(4)
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The saturation vapor pressure of pure component is calculated by the extended Antoine equation, which is given as:
C2i + C 4 iT + C5i ln T + C6 iT C7 i for C8i ≤ T ≤ C9i (5) T + C 3i
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ln( Pi s / kPa ) = C1i +
where C1i to C9i are the parameters for each component i, C8i and C9i are the limits of the temperature range, which were obtained directly from the Aspen databank [30] and are listed in Table 7. Since the NRTL model is frequently used to correlate the VLE data of the salt containing systems
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[31, 32], in this work, the NRTL model is adopted to correlate the VLE data of the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate. The binary interaction parameters for allyl alcohol and
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water were obtained from literature [12]. The other parameters are regressed from the VLE data by
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minimizing the following objective function N
{(
) (
F = ∑ γ 1cal − γ 1exp i + γ 2cal − γ 2exp i =1
2
)} 2
i
(6)
cal exp where γ i and γ i are the calculated and experimental activity coefficient of component i in salt
containing system. The regressed parameters for all the systems are listed in Table 8. The root-mean-square deviation (RMSD) for the temperature (T) and the mole fraction of the vapor phase (y1) are expressed as follows: N
RMSD (Ti ) = ( ∑ (Ti cal − Ti i =1
8
exp 2
) / N ) 0.5
(7)
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RMSD( yi ) = (∑ ( yi i =1
cal
− yi
exp 2
) / N ) 0.5
(8)
The values of RMSD (y1) and RMSD (T) are listed in Table 9, which are less than 0.005 and 0.26 K, respectively. According to the calculated values of RMSD (y1) and RMSD (T), the NRTL model is
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suitable for the VLE calculation for the systems of allyl alcohol + water + salts.
4. Conclusions
The isobaric vapor-liquid equilibrium data for the systems allyl alcohol + water, allyl alcohol +
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water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate were determined at pressure of 101.3 kPa. The consistency of the measured VLE
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data were checked by the van Ness test. With addition of the salts, the azeotropic point of the system allyl alcohol and water moved and was eliminated. The salting-out effect of the salts follow the order: calcium chloride > magnesium nitrate > calcium nitrate. Meanwhile, the NRTL model was adopted to correlate the VLE experimental data of the systems, and the interaction parameters of the NRTL
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model were also regressed. The correlated results were in agreement with the measured data.
Acknowledgement
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Financial support from the National Natural Science Foundation of China (Project 21306093) is gratefully acknowledged.
: Li Xu and Dongmei Xu contributed equally
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†
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ACCEPTED MANUSCRIPT List of symbols Binary energy parameter of NRTL model
xiˊ
Mole fraction of solvent i in the liquid phase
xi
Mole fraction of solvent i in the liquid phase including salt
yi
Mole fraction of solvent i in the vapor phase
T
Equilibrium temperature
P
Total pressure in the equilibrium system
pis
Saturated vapor pressure of component i
w3
Mass fraction of salts in the liquid phase
α12
Relative volatility of component 1 to component 2
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γi
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∆g ij
Activity coefficient of component i
Calculated the mole fractions of component i in the vapor phases
Ti cal
Temperature calculated by NRTL model
y exp i
Experimental the mole fractions of component i in the vapor phases
Ti exp
Experimental temperature
λcal i
Calculated activity coefficient of component i in salt containing system
λexp i
Experimental activity coefficient of component i in salt containing system
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y cal i
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ACCEPTED MANUSCRIPT Figure captions
Fig.1. Comparison of the isobaric VLE data for the binary system of allyl alcohol (1)
mole fraction; y, vapor phase mole fraction.
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+ water (2) at 101.3 kPa: (○) this work; (▲) Ref. [11]; (■) Ref [12], x, liquid phase
Fig.2. Isobaric y1-x1′ diagram for the system of allyl alcohol (1) + water (2) + calcium chloride (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid
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line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis); y, vapor phase mole fraction.
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Fig.3. Isobaric y1-x1′ diagram for the system of allyl alcohol (1) + water (2) + calcium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis); y, vapor phase mole fraction.
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Fig.4. Isobaric y1-x1′ diagram for the system of allyl alcohol (1) + water (2) + magnesium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts
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free basis); y, vapor phase mole fraction.
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Fig.5. Relative volatility α12 for the system of allyl alcohol (1) + water (2) + calcium chloride (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis).
Fig.6. Relative volatility α12 for the system of allyl alcohol (1) + water (2) + calcium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis).
Fig.7. Relative volatility α12 for the system of allyl alcohol (1) + water (2) + magnesium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w
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ACCEPTED MANUSCRIPT salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis).
Fig.8. Relative volatility α12 for the system of allyl alcohol (1) + water (2) with different salts at 15% w/w and 101.3 kPa: (○), salt free; (☆), calcium chloride; (▽),
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liquid phase mole fraction (salts free basis).
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magnesium nitrate; (□), calcium nitrate; solid line, correlated by the NRTL model, x′,
14
ACCEPTED MANUSCRIPT Table 1 Specifications of the chemicals
allyl alcohol
Shandong Xiya Chemical Co, Ltd calcium Chengdu kelong chloride Chemical Reagents factory. calcium Chengdu kelong nitrate Chemical Reagents factory. magnesium Chengdu kelong nitrate Chemical Reagents factory. a Gas choromatography
Purification method None
Final water mass fractiom -
Analysis method GC a
≥0.98
None
-
KF b
≥0.99
vacuum desiccation
≥0.99
vacuum desiccation
Karl Fisher titration
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b
Mass fraction purity 0.99
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Source
0.0007
KF b
0.0007
KF b
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Name
15
ACCEPTED MANUSCRIPT Table 2 Molecular weights (M), boiling temperatures (Tb), density (ρ), and refractive index (n) at 293.15 K under pressure P=101.3 kPa. a
Ref. [24], page 2315.
c
Determined at 15℃, Ref. [24], page 2289.
d
Ref. [24], page 2289.
e
Ref. [24], page 1206.
f
Ref. [25], page 89.
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b
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ρ /g.cm-3 n -1 component M/g.mol Tb /K exp lit exp lit b c Allyl alcohol 58.08 369.75 0.8550 0.8573 1.4129 1.4135 d water 18.02 373.15 e 0.9983 0.9982 f 1.3327 1.3330 f a Standard uncertainties u are u(ρ)=0.0003 g.cm-3, u(n)=0.0001, u(T)=0.1 K, u(P)=1 kPa.
16
ACCEPTED MANUSCRIPT Table 3 Isobaric vapor-liquid equilibrium data for temperature T, liquid phase mole fraction x, vapor phase mole fraction y and the activity coefficient γ for allyl alcohol (1) + water (2) at pressure 101.3 kPa. a γ2 0.980 0.980 0.978 0.984 0.994 0.989 1.005 1.032 1.163 1.352 1.590 1.771 1.912 2.078 2.105 2.147 2.320 2.405 2.451
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EP
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SC
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T (K) x1 y1 γ1 373.40 0.000 0.000 372.15 0.004 0.038 9.051 371.52 0.007 0.063 8.769 370.40 0.013 0.107 8.347 368.73 0.026 0.166 6.877 367.62 0.037 0.200 6.063 366.24 0.054 0.257 5.616 365.24 0.077 0.291 4.628 364.00 0.121 0.338 3.583 363.02 0.248 0.385 2.066 362.70 0.391 0.428 1.475 362.66 0.535 0.487 1.228 363.18 0.640 0.549 1.135 363.92 0.724 0.616 1.095 364.60 0.777 0.654 1.056 365.22 0.816 0.704 1.057 365.55 0.835 0.726 1.053 366.61 0.887 0.789 1.035 367.33 0.918 0.837 1.034 368.55 0.958 0.911 1.031 369.90 1.000 1.000 a Standard uncertainties u are u(x1)=u(y1)=0.006, u(T)=0.1 K, u(P)=1kPa.
17
ACCEPTED MANUSCRIPT Table 4 Isobaric ternary vapor-liquid equilibrium data for temperature T, liquid phase mass fraction w, liquid phase mole fraction (salts free basis) x′, vapor phase mole fraction y, activity coefficient γ, relative volatility α, and the absolute deviation between the experimental and calculated values of temperature, △T, vapor phase mole fractions, △y, results for allyl alcohol (1) + water (2) + calcium chloride (3) at pressure 101.3 kPa. a T (K)
x1ˊ
y1
γ1
γ2
α12
368.40 363.60 362.25 362.10 362.90 364.00 365.15 366.15 367.30 368.80
0.020 0.080 0.167 0.257 0.380 0.535 0.657 0.725 0.805 0.911
0.119 0.312 0.432 0.506 0.591 0.671 0.728 0.758 0.809 0.886
6.537 5.125 3.583 2.749 2.111 1.639 1.389 1.265 1.166 1.070
1.056 1.052 1.011 0.994 0.958 0.990 1.063 1.139 1.215 1.506
6.619 5.215 3.794 2.961 2.358 1.773 1.397 1.188 1.026 0.759
0.20 0.46 0.10 0.41 0.03 0.06 0.05 0.17 0.07 0.07
0.001 0.006 0.002 0.008 0.001 0.001 0.002 0.004 0.003 0.002
372.75 364.99 363.87 363.18 364.37 365.26 366.20 366.98 368.00 369.55
0.009 0.063 0.140 0.284 0.424 0.506 0.602 0.689 0.771 0.865
0.095 0.373 0.494 0.598 0.679 0.709 0.760 0.799 0.843 0.895
10.011 7.461 4.648 2.866 2.095 1.780 1.554 1.392 1.269 1.138
0.924 0.902 0.829 0.818 0.780 0.800 0.792 0.829 0.850 0.914
11.559 8.848 5.997 3.750 2.874 2.379 2.098 1.794 1.595 1.330
0.05 0.19 0.20 0.42 0.01 0.32 0.02 0.16 0.13 0.19
0.003 0.003 0.004 0.009 0.000 0.009 0.000 0.005 0.004 0.006
15.11 370.85 0.017 0.231 13.943 0.857 17.370 15.09 367.25 0.040 0.372 10.887 0.819 14.217 15.23 364.68 0.082 0.497 7.827 0.757 11.062 15.90 363.05 0.148 0.590 5.506 0.711 8.284 15.61 363.05 0.240 0.654 3.783 0.676 5.986 15.23 365.20 0.360 0.701 2.528 0.649 4.168 15.76 366.25 0.488 0.761 1.953 0.625 3.341 15.41 368.50 0.665 0.830 1.453 0.631 2.460 15.23 369.55 0.741 0.862 1.308 0.640 2.183 15.14 370.70 0.801 0.883 1.193 0.679 1.875 a Standard uncertainties u are u(x1ˊ)=u(y1)=0.006, u(T)=0.1 K, u(P)=1 kPa.
0.34 0.40 0.22 0.22 0.07 0.10 0.03 0.03 0.03 0.18
0.004 0.004 0.003 0.005 0.001 0.003 0.001 0.001 0.001 0.006
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About 15%
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10.10 10.34 10.00 10.35 10.26 10.31 10.17 10.26 10.35 10.20
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About 10%
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5.32 5.45 5.33 5.50 5.32 5.53 5.22 5.30 5.12 5.03
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About 5%
18
△T (K)
△y1
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w3 (%)
ACCEPTED MANUSCRIPT Table 5 Isobaric ternary vapor-liquid equilibrium data for temperature T, liquid phase mass fraction w, liquid phase mole fraction (salts free basis) x′, vapor phase mole fraction y, activity coefficient γ, relative volatility α, and the absolute deviation between the experimental and calculated values of temperature, △T, vapor phase mole fractions, △y, results for allyl alcohol (1) + water (2) + calcium nitrate (3) at pressure 101.3 kPa. a T (K)
x1ˊ
y1
γ1
γ2
α12
368.25 364.35 362.35 362.20 362.65 363.55 364.58 365.85 367.45 368.75
0.026 0.069 0.211 0.310 0.452 0.561 0.705 0.802 0.892 0.942
0.156 0.242 0.409 0.487 0.573 0.628 0.696 0.751 0.823 0.883
9.555 4.465 2.665 2.175 1.729 1.478 1.256 1.138 1.058 1.026
1.475 1.109 1.102 1.102 1.138 1.197 1.403 1.634 2.008 2.358
6.924 4.308 2.588 2.113 1.627 1.321 0.958 0.745 0.563 0.465
0.29 0.35 0.29 0.36 0.21 0.12 0.12 0.00 0.02 0.10
0.002 0.003 0.005 0.006 0.005 0.002 0.003 0.001 0.001 0.004
0.032 0.052 0.100 0.163 0.328 0.441 0.565 0.671 0.766 0.857
0.213 0.272 0.355 0.413 0.532 0.598 0.661 0.721 0.788 0.839
7.601 6.418 4.668 3.479 2.236 1.823 1.517 1.340 1.234 1.127
0.993 1.008 1.008 1.031 1.028 1.035 1.081 1.131 1.162 1.385
8.187 6.811 4.953 3.613 2.329 1.886 1.501 1.267 1.135 0.870
0.36 0.15 0.40 0.31 0.27 0.07 0.12 0.03 0.36 0.16
0.002 0.002 0.005 0.004 0.006 0.002 0.003 0.001 0.010 0.005
0.275 0.336 0.421 0.482 0.534 0.599 0.674 0.731 0.776 0.830
8.904 7.181 4.658 3.537 2.644 2.038 1.631 1.426 1.293 1.177
0.950 0.952 0.944 0.930 0.942 0.941 0.963 0.985 1.031 1.077
10.024 8.071 5.282 4.072 3.006 2.317 1.811 1.549 1.341 1.168
0.01 0.11 0.48 0.17 0.37 0.27 0.11 0.02 0.05 0.10
0.000 0.003 0.008 0.003 0.007 0.006 0.003 0.000 0.002 0.003
367.45 365.52 363.70 362.60 362.61 363.35 364.40 365.55 366.65 367.83
About 15%
366.75 365.00 363.48 363.05 363.10 363.89 364.95 366.05 367.05 368.50
0.036 0.059 0.121 0.186 0.276 0.392 0.533 0.637 0.721 0.807
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15.11 15.21 15.34 15.51 15.23 15.36 15.41 15.23 15.14 15.20
EP
10.32 10.40 10.33 10.26 10.30 10.17 10.16 10.35 10.20 10.14
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About 10%
a
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5.12 5.45 5.23 5.33 5.33 5.22 5.30 5.12 5.03 5.10
SC
About 5%
Standard uncertainties u are u(x1ˊ)=u(y1)=0.006, u(T)=0.1 K, u(P)=1 kPa.
19
△T (K)
△y1
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w3 (%)
ACCEPTED MANUSCRIPT Table 6 Isobaric ternary vapor-liquid equilibrium data for temperature T, liquid phase mass fraction w, liquid phase mole fraction (salts free basis) x′, vapor phase mole fraction y, activity coefficient γ, relative volatility α, and the absolute deviation between the experimental and calculated values of temperature, △T, vapor phase mole fractions, △y, results for allyl alcohol (1) + water (2) + magnesium nitrate (3) at pressure 101.3 kPa. a T (K)
x1ˊ
y1
γ1
γ2
α12
371.80 364.60 363.10 362.80 362.25 362.65 363.75 364.85 365.85 368.50
0.006 0.066 0.140 0.181 0.292 0.405 0.584 0.657 0.745 0.899
0.029 0.231 0.356 0.404 0.499 0.572 0.656 0.690 0.737 0.855
4.686 4.418 3.398 3.020 2.363 1.927 1.474 1.323 1.200 1.052
1.011 1.112 1.071 1.054 1.048 1.051 1.161 1.218 1.341 1.697
4.948 4.251 3.396 3.067 2.415 1.963 1.358 1.162 0.959 0.662
0.30 0.30 0.11 0.34 0.28 0.18 0.24 0.17 0.04 0.10
0.000 0.002 0.001 0.005 0.005 0.004 0.006 0.004 0.001 0.003
371.80 370.20 366.95 365.20 364.70 363.65 365.05 366.20 367.60 368.50
0.011 0.026 0.068 0.158 0.226 0.393 0.491 0.556 0.657 0.726
0.080 0.163 0.305 0.443 0.499 0.616 0.666 0.689 0.730 0.770
7.104 6.488 5.230 3.497 2.811 2.086 1.719 1.507 1.287 1.191
0.970 0.950 0.930 0.883 0.882 0.901 0.890 0.911 0.975 1.007
7.818 7.295 6.015 4.238 3.411 2.478 2.067 1.769 1.412 1.264
0.35 0.35 0.11 0.13 0.28 0.29 0.28 0.021 0.31 0.20
0.002 0.002 0.001 0.002 0.006 0.006 0.007 0.000 0.008 0.005
0.18 0.16 0.15 0.26 0.20 0.18 0.13 0.03 0.05
0.001 0.003 0.003 0.005 0.005 0.005 0.003 0.001 0.001
About 15%
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10.34 10.40 10.26 10.31 10.17 10.26 10.35 10.20 10.11 10.07
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About 10%
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5.22 5.50 5.32 5.53 5.22 5.30 5.12 5.03 5.01 5.21
SC
About 5%
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15.23 371.35 0.017 0.172 10.125 0.900 12.012 0.101 0.460 5.785 0.816 7.582 15.76 364.95 15.41 364.75 0.158 0.516 4.188 0.789 5.681 15.23 365.20 0.252 0.575 2.889 0.769 4.016 15.14 366.67 0.409 0.650 1.919 0.765 2.684 15.23 367.18 0.486 0.685 1.677 0.779 2.300 15.25 368.05 0.583 0.730 1.445 0.801 1.934 15.30 368.50 0.638 0.759 1.358 0.812 1.787 15.17 369.85 0.816 0.856 1.149 0.916 1.340 a Standard uncertainties u are u(x1ˊ)=u(y1)=0.006, u(T)=0.1 K, u(P)=1 kPa.
20
△T (K)
△y1
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w3 (%)
ACCEPTED MANUSCRIPT Table 7 Parameters of the extended Antoine equation a component
C1i
C2i
C3i
C4i
C5i
allyl alcohol
77.83
-8057.60
0
0
-8.71
water
66.74
-7258.20
0
0
-7.30
1.66×10
-11
4.17
C7i
C8i (K)
C9i (K)
6.00
144.15
545.10
2.00
273.16
647.10
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Taken from Aspen property databank
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a
C6i (×106)
21
ACCEPTED MANUSCRIPT Table 8 Nonrandom factors and binary energy parameters for NRTL model. NRTL parameters
∆g ji (J/mol) -479.85 a -32595.94 -8125.59
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0.3 a 0.06 0.94
-479.85 a -31315.01 -8184.91
0.3 a 0.08 0.92
-479.85 a -43078.23 -8634.15
0.3 a 0.035 0.875
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allyl alcohol (1) + water (2) + calcium chloride (3) 1-2 7155.62 a 1-3 91298.79 2-3 11602.28 allyl alcohol (1) + water (2) + calcium nitrate (3) 1-2 7155.62 a 1-3 76591.47 2-3 15267.18 allyl alcohol (1) + water (2) + magnesium nitrate (3) 1-2 7155.62 a 1-3 80340.18 2-3 8640.48 a From Ref. [12]. ∆gi, j = gi, j − gi,i , τ i , j = ( gi , j − gi,i ) / RT .
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∆g ij (J/mol)
α12
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i-j
ACCEPTED MANUSCRIPT Table 9 The root-mean-square deviation(RMSD) for the equilibrium temperature(T) and mole fractions of the vapor phase (y1) of the NRTL model
calcium chloride
calcium nitrate
5 10 15 5 10 15 5 10 15
RMSD y1 0.004 0.005 0.003 0.004 0.004 0.005 0.004 0.005 0.003
T (K) 0.22 0.21 0.21 0.23 0.26 0.22 0.23 0.26 0.17
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magnesium nitrate
w3 (%)
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salt
23
ACCEPTED MANUSCRIPT
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SC
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Figure 1.
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EP
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Figure 2.
24
ACCEPTED MANUSCRIPT
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SC
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Figure 3.
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EP
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Figure 4.
25
ACCEPTED MANUSCRIPT
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Figure 5.
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EP
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Figure 6.
26
ACCEPTED MANUSCRIPT
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Figure 7.
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Figure 8.
27
S0378-3812(17)30409-0
DOI:
10.1016/j.fluid.2017.10.025
Reference:
FLUID 11626
To appear in:
Fluid Phase Equilibria
Received Date: 25 July 2017 Revised Date:
25 October 2017
Accepted Date: 26 October 2017
Please cite this article as: L. Xu, D. Xu, P. Shi, K. Zhang, X. Ma, J. Gao, Y. Wang, Salts effect on isobaric vapor−liquid equilibrium for separation of the azeotropic mixture Allyl alcohol + water, Fluid Phase Equilibria (2017), doi: 10.1016/j.fluid.2017.10.025. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Salts Effect on Isobaric Vapor−Liquid Equilibrium for Separation of the Azeotropic Mixture Allyl Alcohol +Water Li Xu†,a , Dongmei Xu
, Puyun Shi a, Kai Zhang a, Xiaolong Ma a, Jun Gao *,a , Yinglong Wang b
College of Chemical and Environmental Engineering, Shandong University of Science and
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a
†,a
Technology, Qingdao 266590, China b
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao
266042, China
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*Corresponding author
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E-mail addresses: [email protected]
Abstract: Allyl alcohol and water can form an azeotrope with the minimum boiling point. To separate the azeotrope of allyl alcohol and water by salt distillation, three salts calcium chloride, calcium nitrate and magnesium nitrate were selected to break the azeotrope. The vapor-liquid
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equilibrium (VLE) data for the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate were measured at pressure of 101.3 kPa. The results indicated that the relative volatility of allyl alcohol to
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water increased by adding the salts at the molar fraction of allyl alcohol higher than 0.2. With increasing the concentrations of the salts, the azeotropic point of the system allyl alcohol + water
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moved. When the concentrations of calcium chloride and magnesium nitrate were 0.10, 0.15, respectively, the azeotropic point was broken. The effect of salts on the azeotropic point of the system allyl alcohol + water follows the order: calcium chloride > magnesium nitrate > calcium nitrate. Moreover, the experimental VLE data were correlated by the NRTL model. All the root-mean-square deviations for the temperature (T) and the mole fraction of the vapor phase (y1) between the measured and calculated data were less than 0.26 K and 0.005, respectively. Meanwhile, the binary interaction parameters of the NRTL model were regressed. Keywords: vapor-liquid equilibrium; allyl alcohol; water; azeotrope; salts 1
ACCEPTED MANUSCRIPT 1.Introduction Allyl alcohol is an important chemical intermediate. Due to its excellent physical and chemical properties, allyl alcohol is widely applied in the production of medicine, spices, and agricultural chemicals [1-4]. Generally, allyl acetate hydrolysis method is adopted to produce allyl alcohol in
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industry, from which the production mixture consisted of allyl alcohol, water and a small amount of allyl aldehyde and acetic acid can be obtained [5]. To separate allyl alcohol from the mixture, the distillation technology is needed. However, since allyl alcohol and water can form a minimum
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azeotrope, the special distillation is necessary.
Usually, for the separation of the azeotropic mixtures, special distillations are applied, such as
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extractive distillation, azeotropic distillation, salt distillation, pressure-swing distillation and reactive distillation [6]. Considering the salts effect on isobaric vapor-liquid equilibrium of the azeotropic mixtures, which can affect the relative volatility of the components in the mixtures [7-10], in this work, the salt distillation technology was adopted for its high-efficiency separation capacity for the
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azeotropic mixture of allyl alcohol and water.
In the previous works, some researchers reported the VLE for the system of allyl alcohol + water [11-15]. Grabner [11] and Zhang [12] determined the isobaric VLE data for the system allyl alcohol
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+ water at 101.3kPa. Aucejo [13] measured the isobaric VLE data for allyl alcohol + water at
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pressures of 30, 60 and 100 kPa. And the isobaric VLE data of allyl alcohol + water at 100.26 kPa were determined by Harper [14]. Meanwhile, Lesteva reported the isothermic VLE data for allyl alcohol + water at 313.14 K [15]. To separate azeotropic systems contain alcohols, calcium chloride, calcium nitrate and magnesium nitrate were selected as azeotrope destroyers [9, 16-19], which have a strong salting out effect and lead to the elimination of the azeotropic points. Since calcium chloride, calcium nitrate and magnesium nitrate are well dissolved in water and allyl alcohol, and the solubilities of the salts in allyl alcohol are different than water, the three salts were adopted in this work to break the azeotrope of allyl alcohol and water. According to the retrieve results from the 2
ACCEPTED MANUSCRIPT NIST, the salts (calcium chloride, calcium nitrate and magnesium nitrate) effect on isobaric VLE for the system of allyl alcohol + water has not been reported. In this work, the isobaric vapor-liquid equilibrium data for the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water
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+ magnesium nitrate were determined at 101.3 kPa. and the thermodynamic consistency of the measured VLE data were checked by the van Ness test [20, 21]. Meantime, the VLE data were correlated by the nonrandom two-liquid model (NRTL) [22, 23].
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2. Experimental 2.1. Chemicals
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Allyl alcohol was purchased from Shandong Xiya Chemical Co, Ltd with the mass fraction of 0.99. The purity of allyl alcohol was checked and confirmed by gas chromatography (SP6890, Shandong Rui Hong Chemical Co., Ltd). The salts, calcium nitrate, calcium chloride, and magnesium nitrate were provided by Chengdu Kelong Chemical Reagents Co., Ltd. The water content of the salts was
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checked by Karl Fisher titration. Allyl alcohol and calcium chloride were used without further purification. Calcium nitrate and magnesium nitrate were desiccated under a vacuum for at least 24 h. The deionized water (conductivity < 1.0 µs·cm-1) was made in our lab by the ultrapure water
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machine (Chengdu Down’s Corning Technology Development Co., Ltd.). Specifications of the
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chemicals are listed in Table 1.
2.2. Apparatus and procedures. The densimeter (Dahometer DH-120N, Beijing Yitenuo Electronic Technology Co., Ltd.) was used to measure density. Before analysis the density of a sample, the densimeter was calibrated with dried air. Then, the sample was added into the densimeter with a volume of 2.5 ml. The value of density was obtained with the uncertainty of 0.0003 g.cm−3. Meanwhile, the Abbe refractometer (2AWJ, Shanghai Experimental Instrument Co. Ltd.) was used to measure the refractive index, and the measurement range was 1.3000−1.7000. The reliability of the refractometer was confirmed by a 3
ACCEPTED MANUSCRIPT standard glass block (n = 1.51670) before testing the samples. After that, the sample with a volume of 0.05ml was added into the refractometer for analysis, and the value of refractive index was obtained with the uncertainty of 0.0001. The measured data of density and refractive index for allyl alcohol and water are listed in Table 2.
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For the isobaric VLE measurement, a modified Rose type recirculating equilibrium still was used, which was presented in detail in the previous literatures [26-28]. The pressure was maintained with a manometer (Nanjing Hengyuan Automatic Gauge Co., Ltd.) and the pressure fluctuation was
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controlled within 1 kPa with the two-step automatic control scheme. Meanwhile, a precise mercury thermometer was used to measure the equilibrium temperature with the accuracy of ± 0.1 K.
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In each experiment, the ternary mixture of allyl alcohol + water + salt was added into the equilibrium still, which was prepared by an electronic analytical balance (SL512N, Mettler Toledo Instrument Co., Ltd) with the accuracy of ± 0.0001 g. For the purpose of making contact sufficiently, the vapor and liquid phases were circulated continuously. When the vapor temperature was kept
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constant for 50 min, the equilibrium was established. The vapor and liquid phase samples were withdrawn by syringes with the volume about 0.5 mL at the same time immediately, and put into the vials for analysis. The compositions of the samples were determined by gas chromatography, and the
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salt mass fractions of the samples were determined by the gravimetric method after vacuum
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desiccation, where allyl alcohol and water were evaporated. 2.3. Analysis
The equilibrium compositions of allyl alcohol and water in the vapor and liquid phase were analyzed by GC (SP6890, Shandong Rui Hong Chemical Co., Ltd), which were equipped with a packed column (Porapak Q 3mm×2m, Dalian Sanjie Scientific Development Co., Ltd.) and a thermal conductivity detector TCD (Shandong Rui Hong Chemical Co., Ltd). The carrier gas was hydrogen with purity of 99.999%, and the flow rate was 50ml/min. The oven temperature was 423.15 K. The
4
ACCEPTED MANUSCRIPT injection temperature was fixed at 443.15 K. And the temperature of TCD detector was held at 443.15 K. Before sample analysis, the peak areas of GC were calibrated by five different standard samples that covered the whole composition range. When analyzing the samples, each sample was analyzed
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at least three times. The mean value was adopted when the deviation of three times was not more than 0.001. The compositions of all samples were measured by GC with the workstation of N2000, which was developed by Zhejiang University. The uncertainty of mole fraction was 0.006.
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3. Results and discussion 3.1. Validation of the apparatus
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The isobaric VLE data for the binary system allyl alcohol and water at pressure of 101.3 kPa were determined to verify the reliability of the equilibrium still, which are listed in Table 3. For comparison, the references data reported by Grabner [11] and Zhang [12] are plotted in Fig. 1. As shown in Fig. 1, the measured VLE data agree well with literature data, which indicate that the
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apparatus is reliable. Moreover, the system of allyl alcohol and water formed an azeotrope at x1 ≈ 0.451 and pressure of 101.3 kPa as shown in Fig. 1. 3.2. Vapor-liquid equilibrium for salt containing ternary systems
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The isobaric VLE data for the systems allyl alcohol (1) + water (2) + calcium chloride (3), allyl
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alcohol (1) + water (2) + calcium nitrate (3) and allyl alcohol (1) + water (2) + magnesium nitrate (3) were determined at 101.3 kPa by keeping the mass fractions of salts nearly constant at 0.05, 0.1 and 0.15, respectively, which are listed in Tables 4-6, where w3 represents the mass fraction of the salts in the liquid phase, x1′ is the mole fraction of allyl alcohol in the liquid phase on the salts free basis, y1 is the mole fraction of allyl alcohol in the vapor phase, T is the equilibrium temperature, γi is the activity coefficient of the component, α12 is the relative volatility of allyl alcohol (1) to water (2), which is calculated by using the following equation:
5
ACCEPTED MANUSCRIPT α12 =
y1 / x1 y 2 / x2
(1)
where x (salt-free) and y are mole fractions of component in the liquid phase and vapor phase, respectively. Meanwhile, the x-y diagrams of the isobaric VLE data for the systems are presented in
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Figs. 2-4. 3.3. Thermodynamic consistency test.
To confirm the quality of the VLE data obtained, the thermodynamic consistency for all the
follows: 1 N
N
∑
∆yi =
1 N
N
∑ 100
yi
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∆y =
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experimental data was checked with the van Ness test [16,17]. The van Ness test is presented as
i =1
where N is the number of the experimental data; yi
cal
in the vapor phase calculated by the NRTL model; yi
exp
i =1
cal
− yi
exp
(2)
stands for the mole fraction of component i stands for the experimental mole fraction
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of component i in the vapor phase. If △y is less than 1, the measured VLE data can be considered as thermodynamically consistent.
By the van Ness test, the values of ∆y are 0.298, 0.375 and 0.282 for the system of (allyl alcohol +
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water + calcium chloride), 0.318, 0.399 and 0.357 for the system of (allyl alcohol + water + calcium nitrate), 0.324, 0.395 and 0.313 for the system of (allyl alcohol + water + magnesium nitrate) at the
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salt concentration of 0.05, 0.1 and 0.15 (mass fraction), respectively. All the values of ∆y are less than 1, which indicate that the measured VLE data are thermodynamic consistency. 3.4. Salts effect on vapor-liquid equilibria To explore the salts effect on vapor-liquid equilibrium for the systems, the x-y and x-α diagrams for the ternary systems allyl alcohol + water + calcium chloride / calcium nitrate / magnesium nitrate are presented in Figs 2-4 and Figs 5-7, where x1ˊ is the mole fraction of allyl alcohol in the liquid phase on the salt free basis. 6
ACCEPTED MANUSCRIPT As shown in Figs. 2-4, the content of allyl alcohol increases in the vapor phase with increasing the concentration of salts, and the relative volatility of allyl alcohol to water increases with increasing the content of the salts as shown in Figs.5-7. The azeotropic point of the system moved and was eliminated with increasing the amount of salt, which is salting-out effect. For calcium chloride, the
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azeotropic point of the system was broken when its mass fraction was 0.10, while more content of calcium nitrate and magnesium nitrate were needed to break the azeotropic point of the system. Therefore, calcium chloride is more effective than calcium nitrate and magnesium nitrate to break the
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azeotropic point of the system.
As shown in Figures 5-6, in water rich region, when the mass fraction of calcium chloride and
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calcium nitrate is 0.05, the relative volatility of allyl alcohol decreased due to the strong interaction between the salts and allyl alcohol. However, in allyl alcohol rich region, the interactions between the salts and water were strong, so the activity of allyl alcohol increased, which led to the increase of the relative volatility of allyl alcohol. Figure 7 shows that in water rich region, when the mass
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fractions of magnesium nitrate are 0.05 and 0.10, the relative volatility of allyl alcohol decreased, and increased in allyl alcohol rich region.
To compare the salt effect of calcium chloride, magnesium nitrate and calcium nitrate, the relative
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volatility of allyl alcohol to water changed by the three salts at the salt concentration of 15 wt% is
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shown in Fig. 8. The salting-out effect of the three salts follow the order: calcium chloride > magnesium nitrate >calcium nitrate. As results, the salts could improve the separation effect of the azeotropic system, and calcium chloride can be selected as an appropriate salt for the separation of the azeotropic mixture allyl alcohol and water. 3.5. Correlation of the VLE data The vapor-liquid phase equilibrium can be expressed as follows:
(
Vi L P − Pi s yiϕˆ P = xiγ iϕ P exp RT v i
s s i i
7
)
(3)
ACCEPTED MANUSCRIPT
[
]
s where the Poynting factor exp Vi L (P − Pi s ) / RT , ϕˆiv and ϕi associated with nonideality were all
close to 1, since the pressure was low, xi and yi represent the mole fraction of component i in the s liquid phase and vapor phase, respectively, Pi is the saturation vapor pressure of pure component i,
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which was estimated by the extended Antoine expression [29]. Considering the non-ideality of the liquid phase, Equation (3) can be simplified as: y i P = xi γ i Pi s
(4)
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The saturation vapor pressure of pure component is calculated by the extended Antoine equation, which is given as:
C2i + C 4 iT + C5i ln T + C6 iT C7 i for C8i ≤ T ≤ C9i (5) T + C 3i
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ln( Pi s / kPa ) = C1i +
where C1i to C9i are the parameters for each component i, C8i and C9i are the limits of the temperature range, which were obtained directly from the Aspen databank [30] and are listed in Table 7. Since the NRTL model is frequently used to correlate the VLE data of the salt containing systems
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[31, 32], in this work, the NRTL model is adopted to correlate the VLE data of the systems allyl alcohol + water, allyl alcohol + water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate. The binary interaction parameters for allyl alcohol and
EP
water were obtained from literature [12]. The other parameters are regressed from the VLE data by
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minimizing the following objective function N
{(
) (
F = ∑ γ 1cal − γ 1exp i + γ 2cal − γ 2exp i =1
2
)} 2
i
(6)
cal exp where γ i and γ i are the calculated and experimental activity coefficient of component i in salt
containing system. The regressed parameters for all the systems are listed in Table 8. The root-mean-square deviation (RMSD) for the temperature (T) and the mole fraction of the vapor phase (y1) are expressed as follows: N
RMSD (Ti ) = ( ∑ (Ti cal − Ti i =1
8
exp 2
) / N ) 0.5
(7)
ACCEPTED MANUSCRIPT N
RMSD( yi ) = (∑ ( yi i =1
cal
− yi
exp 2
) / N ) 0.5
(8)
The values of RMSD (y1) and RMSD (T) are listed in Table 9, which are less than 0.005 and 0.26 K, respectively. According to the calculated values of RMSD (y1) and RMSD (T), the NRTL model is
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suitable for the VLE calculation for the systems of allyl alcohol + water + salts.
4. Conclusions
The isobaric vapor-liquid equilibrium data for the systems allyl alcohol + water, allyl alcohol +
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water + calcium nitrate, allyl alcohol + water + calcium chloride and allyl alcohol + water + magnesium nitrate were determined at pressure of 101.3 kPa. The consistency of the measured VLE
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data were checked by the van Ness test. With addition of the salts, the azeotropic point of the system allyl alcohol and water moved and was eliminated. The salting-out effect of the salts follow the order: calcium chloride > magnesium nitrate > calcium nitrate. Meanwhile, the NRTL model was adopted to correlate the VLE experimental data of the systems, and the interaction parameters of the NRTL
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model were also regressed. The correlated results were in agreement with the measured data.
Acknowledgement
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Financial support from the National Natural Science Foundation of China (Project 21306093) is gratefully acknowledged.
: Li Xu and Dongmei Xu contributed equally
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†
9
ACCEPTED MANUSCRIPT List of symbols Binary energy parameter of NRTL model
xiˊ
Mole fraction of solvent i in the liquid phase
xi
Mole fraction of solvent i in the liquid phase including salt
yi
Mole fraction of solvent i in the vapor phase
T
Equilibrium temperature
P
Total pressure in the equilibrium system
pis
Saturated vapor pressure of component i
w3
Mass fraction of salts in the liquid phase
α12
Relative volatility of component 1 to component 2
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γi
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∆g ij
Activity coefficient of component i
Calculated the mole fractions of component i in the vapor phases
Ti cal
Temperature calculated by NRTL model
y exp i
Experimental the mole fractions of component i in the vapor phases
Ti exp
Experimental temperature
λcal i
Calculated activity coefficient of component i in salt containing system
λexp i
Experimental activity coefficient of component i in salt containing system
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y cal i
10
ACCEPTED MANUSCRIPT References [1] O. Eric, M. John, A new stereoselective method for the preparation of allylic alcohols, Journal of the American Chemical Society. 119 (1997) 9065-9066. [2] M. Bandini, M. Tragni, π-Activated alcohols: an emerging class of alkylating agents for catalytic Friedel–Crafts reactions, Org. Biomol. Chem. 7 (2009) 1501-1507. [3] Y. K. Wu, H. J. Liu, J. L. Zhu, An Efficient Procedure for the 1,3-Transposition of Allylic
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Alcohols Based on Lithium Naphthalenide Induced Reductive Elimination of Epoxy Mesylates, Synlett. 2008 (2008) 621-623.
[4] X. L. Wang, X. D. Li, J. J. Xue, Y. L. Zhao, Y. M. Zhang, A novel and efficient procedure for the preparation of allylic alcohols from α,β-unsaturated carboxylic esters using LiAlH4/BnCl, Tetrahedron Letters. 50 (2009) 413-415.
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[5] K. E. Atkins, W. E. Walker, R. M. Manyik, Palladium catalyzed transfer of allylic groups. Tetrahedron Letters. 43(1970) 3821-3824.
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[6] Z. Lei, B. Chen, Z. Ding, Special Distillation Processes. Elsevier. Amsterdam. 2005. [7] E. Vercher, A. V. Orchillés, M. I. Vázquez, A. Martı́nez-Andreu, Isobaric vapor–liquid equilibria for 1-propanol + water + lithium chloride at 100kPa, Fluid Phase Equilibria. 216 (2004) 47-52.
[8] E. Vercher, M. I. Vázquez, A. Martínez-Andreu. Isobaric vapor–liquid equilibria for 1-propanol + water + lithium nitrate at 100kPa, Fluid Phase Equilibria. 202 (2002) 121–132. [9] J. Dhanalakshmi, P. S. T. Sai, A. R. Balakrishnan, Effect of bivalent cation inorganic salts on
(2014) 112-119.
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isobaric vapor–liquid equilibrium of methyl acetate–methanol system, Fluid Phase Equilibria. 379
[10] W. F. Furter, Extractive distillation by salt effect, Chem. Eng. Commun. 116 (1991) 35-40. [11] R. W. Grabner, C. W. Clump, Liquid-Vapor equilibrium and heats of vaporization of allyl
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alcohol-water mixtures, J. Chem. Eng. Date. 10 (1965) 13-16. [12] L. Z. Zhang, Y. C. Gao, D. M. Xu, Z. S. Zhang, J. Gao, D. Pratik, Isobaric vapor–liquid equilibrium for binary systems of allyl alcohol with water, methanol, and ethanol at 101.3kPa, J.
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Chem. Eng. Data. 61 (2016) 2071-2077. [13] A. Aucejo, S. Loras, J. B. Monton, Isobaric vapor-liquid equilibria of prop-2-en-1-ol (allyl alcohol) + water system at 30, 60, and 100kPa. ELDATA: The International Electronic Journal of Physico-Chemical Data. 2 (1996) 1−4. [14] B. G. Harper, J. C. Moore, Vapor-liquid equilibrium new still and method for determining vapor-liquid equilibrium, Ind. Eng. Chem. 49 (1957) 411−414. [15] T. M. Lesteva, E. I. Khrapkova, Duhen - margules equation used to check isothermic data on liquid-vapor equilibrium in binary and ternary system, Zh. Fiz. Khim. 46 (1972) 612−616. [16] F. Banat , S. Al-Asheh, J. Simandl, Effect of dissolved inorganic salts on the isothermal vapor liquid equilibrium of the propionic acid-water mixture, Chem. Eng. Process. 41 (2002) 793-798. [17] E. Vercher, A. Martıń ez-Andreu, Isobaric Vapor-Liquid equilibria for 1-propanol + water +
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ACCEPTED MANUSCRIPT calcium nitrate, J. Chem. Eng. Data. 44 (1999) 1216-1221. [18] J. Dhanalakshmi, P. S. T. Sai, A. R. Balakrishnan, Effect of inorganic salts on the isobaric vapor-liquid equilibrium of the ethyl acetate–ethanol system, J. Chem. Eng. Data. 58 (2013) 560-569. [19] K. Takakura, I. Sumoge, S. Araki, H. Yamamoto, Salt effects on vapor liquid equilibrium of acetic acid-water system, Netsu Bussei. 28 (2014) 166-174.
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[20] H. C. van Ness, S. M. Byer, R. E. Gibbs, Vapor-Liquid equilibrium: Part I. An appraisal of data reduction methods, AIChE J. 19 (1973) 238−244.
[21] A. Fredenslund, J.Gmehling, P. Rasmussen, Vapor-Liquid equilibria using UNIFAC: A group-contribution method; Elsevier:Amsterdam, The Netherlands. 1977.
[22] H. Renon, J. M. Prausnitz, Local compositions in thermodynamic excess functions for liquid
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mixtures, AIChE J. 14 (1968) 135−144.
[23] K. Iwakabe, H. Kosuge, A correlation method for isobaric vapor−liquid and vapor-liquid-liquid equilibria data of binary systems, Fluid Phase Equilibria. 266 (2008) 202−210.
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[24] G. S. James, Lange’s Chemistry Handbook, Version 16; McGraw-Hill: New York. 2005. [25] Z. X. Huang, L. Li, M. M. Zhou, H. M. Jiang, T. Qiu, Isobaric vapor-liquid equilibrium of trifluoroacetic acid + water, trifluoroacetic acid + ethyl trifluoroacetate and ethyl trifluoroacetate + ethanol binary mixtures, Fluid Phase Equilib. 408 (2016) 88−93.
[26] Z. Y. Zhu, Y. X. Ma, J. Gao, Isobaric vapor-liquid equilibria for binary systems of acetic acid + benzene, chloroacetic acid + benzene, and dichloroacetic acid + benzene at 101.33kPa, J. Chem.
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Eng. Data. 55 (2010) 3387−3390.
[27] J. Gao, H. Li, D. M. Xu, L. Z. Zhang, Isobaric vapor−liquid equilibrium for binary systems of thioglycolic acid with water, butyl Acetate, butyl formate, and isobutyl acetate at 101.3kPa, J. Chem. Eng. Data. 62 (2017) 355–361.
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[28] J. Gao, K. Zhang, D. M. Xu, L. Z. Zhang, N. N. Chen, C. L. Li, Isobaric vapor−liquid equilibrium for binary systems of cyclohexanone + benzene, cyclohexanone + toluene, and cyclohexanone + p-Xylene at 101.3 kPa, J. Chem. Eng. Data. 62 (2017) 1948-1954.
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[29] J. Gao, L. W. Zhao, L. Z. Zhang, D. M. Xu, Z. S. Zhang, Isobaric vapor–liquid equilibrium for binary systems of 2,2,3,3-Tetrafluoro-1-propanol + 2,2,3,3,4,4,5,5-Octafluoro -1 – pentanol at 53.3, 66.7, 80.0kPa, J. Chem. Eng. Data. 61 (2016) 3371-3376. [30] Aspen Plus software, Version 7.3; Aspen Technology, Inc.: Burlington, MA, 2001. [31] Q. S. Liu, H. Zeng, X. Q. Lan, Q. Y. Wang, H. Song, Isobaric vapor-liquid equilibria for 2-methyl-butan-1-ol + 3-methyl-butan-1-ol + CuCl2, ZnCl2, and FeCl3 systems at 101.3kPa, J. Chem. Eng. Data. 55 (2010) 2653–2657. [32] J. Bao, Y. M. Zhang, X. Jin. Vapor-liquid equilibria for the isopropanol + water + mixed solvent containing salt systems, Journal of chemical engineering in universities (Chinese). 19 (2005) 258-262.
12
ACCEPTED MANUSCRIPT Figure captions
Fig.1. Comparison of the isobaric VLE data for the binary system of allyl alcohol (1)
mole fraction; y, vapor phase mole fraction.
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+ water (2) at 101.3 kPa: (○) this work; (▲) Ref. [11]; (■) Ref [12], x, liquid phase
Fig.2. Isobaric y1-x1′ diagram for the system of allyl alcohol (1) + water (2) + calcium chloride (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid
SC
line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis); y, vapor phase mole fraction.
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Fig.3. Isobaric y1-x1′ diagram for the system of allyl alcohol (1) + water (2) + calcium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis); y, vapor phase mole fraction.
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Fig.4. Isobaric y1-x1′ diagram for the system of allyl alcohol (1) + water (2) + magnesium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts
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free basis); y, vapor phase mole fraction.
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Fig.5. Relative volatility α12 for the system of allyl alcohol (1) + water (2) + calcium chloride (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis).
Fig.6. Relative volatility α12 for the system of allyl alcohol (1) + water (2) + calcium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis).
Fig.7. Relative volatility α12 for the system of allyl alcohol (1) + water (2) + magnesium nitrate (3) at 101.3 kPa: (○) salt free, (●) 5%, (■) 10%, and (▲) 15% w/w
13
ACCEPTED MANUSCRIPT salt; solid line, correlated by the NRTL model, x′, liquid phase mole fraction (salts free basis).
Fig.8. Relative volatility α12 for the system of allyl alcohol (1) + water (2) with different salts at 15% w/w and 101.3 kPa: (○), salt free; (☆), calcium chloride; (▽),
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EP
TE D
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SC
liquid phase mole fraction (salts free basis).
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magnesium nitrate; (□), calcium nitrate; solid line, correlated by the NRTL model, x′,
14
ACCEPTED MANUSCRIPT Table 1 Specifications of the chemicals
allyl alcohol
Shandong Xiya Chemical Co, Ltd calcium Chengdu kelong chloride Chemical Reagents factory. calcium Chengdu kelong nitrate Chemical Reagents factory. magnesium Chengdu kelong nitrate Chemical Reagents factory. a Gas choromatography
Purification method None
Final water mass fractiom -
Analysis method GC a
≥0.98
None
-
KF b
≥0.99
vacuum desiccation
≥0.99
vacuum desiccation
Karl Fisher titration
AC C
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b
Mass fraction purity 0.99
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Source
0.0007
KF b
0.0007
KF b
SC
Name
15
ACCEPTED MANUSCRIPT Table 2 Molecular weights (M), boiling temperatures (Tb), density (ρ), and refractive index (n) at 293.15 K under pressure P=101.3 kPa. a
Ref. [24], page 2315.
c
Determined at 15℃, Ref. [24], page 2289.
d
Ref. [24], page 2289.
e
Ref. [24], page 1206.
f
Ref. [25], page 89.
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EP
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M AN U
SC
b
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ρ /g.cm-3 n -1 component M/g.mol Tb /K exp lit exp lit b c Allyl alcohol 58.08 369.75 0.8550 0.8573 1.4129 1.4135 d water 18.02 373.15 e 0.9983 0.9982 f 1.3327 1.3330 f a Standard uncertainties u are u(ρ)=0.0003 g.cm-3, u(n)=0.0001, u(T)=0.1 K, u(P)=1 kPa.
16
ACCEPTED MANUSCRIPT Table 3 Isobaric vapor-liquid equilibrium data for temperature T, liquid phase mole fraction x, vapor phase mole fraction y and the activity coefficient γ for allyl alcohol (1) + water (2) at pressure 101.3 kPa. a γ2 0.980 0.980 0.978 0.984 0.994 0.989 1.005 1.032 1.163 1.352 1.590 1.771 1.912 2.078 2.105 2.147 2.320 2.405 2.451
AC C
EP
TE D
M AN U
SC
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T (K) x1 y1 γ1 373.40 0.000 0.000 372.15 0.004 0.038 9.051 371.52 0.007 0.063 8.769 370.40 0.013 0.107 8.347 368.73 0.026 0.166 6.877 367.62 0.037 0.200 6.063 366.24 0.054 0.257 5.616 365.24 0.077 0.291 4.628 364.00 0.121 0.338 3.583 363.02 0.248 0.385 2.066 362.70 0.391 0.428 1.475 362.66 0.535 0.487 1.228 363.18 0.640 0.549 1.135 363.92 0.724 0.616 1.095 364.60 0.777 0.654 1.056 365.22 0.816 0.704 1.057 365.55 0.835 0.726 1.053 366.61 0.887 0.789 1.035 367.33 0.918 0.837 1.034 368.55 0.958 0.911 1.031 369.90 1.000 1.000 a Standard uncertainties u are u(x1)=u(y1)=0.006, u(T)=0.1 K, u(P)=1kPa.
17
ACCEPTED MANUSCRIPT Table 4 Isobaric ternary vapor-liquid equilibrium data for temperature T, liquid phase mass fraction w, liquid phase mole fraction (salts free basis) x′, vapor phase mole fraction y, activity coefficient γ, relative volatility α, and the absolute deviation between the experimental and calculated values of temperature, △T, vapor phase mole fractions, △y, results for allyl alcohol (1) + water (2) + calcium chloride (3) at pressure 101.3 kPa. a T (K)
x1ˊ
y1
γ1
γ2
α12
368.40 363.60 362.25 362.10 362.90 364.00 365.15 366.15 367.30 368.80
0.020 0.080 0.167 0.257 0.380 0.535 0.657 0.725 0.805 0.911
0.119 0.312 0.432 0.506 0.591 0.671 0.728 0.758 0.809 0.886
6.537 5.125 3.583 2.749 2.111 1.639 1.389 1.265 1.166 1.070
1.056 1.052 1.011 0.994 0.958 0.990 1.063 1.139 1.215 1.506
6.619 5.215 3.794 2.961 2.358 1.773 1.397 1.188 1.026 0.759
0.20 0.46 0.10 0.41 0.03 0.06 0.05 0.17 0.07 0.07
0.001 0.006 0.002 0.008 0.001 0.001 0.002 0.004 0.003 0.002
372.75 364.99 363.87 363.18 364.37 365.26 366.20 366.98 368.00 369.55
0.009 0.063 0.140 0.284 0.424 0.506 0.602 0.689 0.771 0.865
0.095 0.373 0.494 0.598 0.679 0.709 0.760 0.799 0.843 0.895
10.011 7.461 4.648 2.866 2.095 1.780 1.554 1.392 1.269 1.138
0.924 0.902 0.829 0.818 0.780 0.800 0.792 0.829 0.850 0.914
11.559 8.848 5.997 3.750 2.874 2.379 2.098 1.794 1.595 1.330
0.05 0.19 0.20 0.42 0.01 0.32 0.02 0.16 0.13 0.19
0.003 0.003 0.004 0.009 0.000 0.009 0.000 0.005 0.004 0.006
15.11 370.85 0.017 0.231 13.943 0.857 17.370 15.09 367.25 0.040 0.372 10.887 0.819 14.217 15.23 364.68 0.082 0.497 7.827 0.757 11.062 15.90 363.05 0.148 0.590 5.506 0.711 8.284 15.61 363.05 0.240 0.654 3.783 0.676 5.986 15.23 365.20 0.360 0.701 2.528 0.649 4.168 15.76 366.25 0.488 0.761 1.953 0.625 3.341 15.41 368.50 0.665 0.830 1.453 0.631 2.460 15.23 369.55 0.741 0.862 1.308 0.640 2.183 15.14 370.70 0.801 0.883 1.193 0.679 1.875 a Standard uncertainties u are u(x1ˊ)=u(y1)=0.006, u(T)=0.1 K, u(P)=1 kPa.
0.34 0.40 0.22 0.22 0.07 0.10 0.03 0.03 0.03 0.18
0.004 0.004 0.003 0.005 0.001 0.003 0.001 0.001 0.001 0.006
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About 15%
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10.10 10.34 10.00 10.35 10.26 10.31 10.17 10.26 10.35 10.20
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About 10%
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5.32 5.45 5.33 5.50 5.32 5.53 5.22 5.30 5.12 5.03
SC
About 5%
18
△T (K)
△y1
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w3 (%)
ACCEPTED MANUSCRIPT Table 5 Isobaric ternary vapor-liquid equilibrium data for temperature T, liquid phase mass fraction w, liquid phase mole fraction (salts free basis) x′, vapor phase mole fraction y, activity coefficient γ, relative volatility α, and the absolute deviation between the experimental and calculated values of temperature, △T, vapor phase mole fractions, △y, results for allyl alcohol (1) + water (2) + calcium nitrate (3) at pressure 101.3 kPa. a T (K)
x1ˊ
y1
γ1
γ2
α12
368.25 364.35 362.35 362.20 362.65 363.55 364.58 365.85 367.45 368.75
0.026 0.069 0.211 0.310 0.452 0.561 0.705 0.802 0.892 0.942
0.156 0.242 0.409 0.487 0.573 0.628 0.696 0.751 0.823 0.883
9.555 4.465 2.665 2.175 1.729 1.478 1.256 1.138 1.058 1.026
1.475 1.109 1.102 1.102 1.138 1.197 1.403 1.634 2.008 2.358
6.924 4.308 2.588 2.113 1.627 1.321 0.958 0.745 0.563 0.465
0.29 0.35 0.29 0.36 0.21 0.12 0.12 0.00 0.02 0.10
0.002 0.003 0.005 0.006 0.005 0.002 0.003 0.001 0.001 0.004
0.032 0.052 0.100 0.163 0.328 0.441 0.565 0.671 0.766 0.857
0.213 0.272 0.355 0.413 0.532 0.598 0.661 0.721 0.788 0.839
7.601 6.418 4.668 3.479 2.236 1.823 1.517 1.340 1.234 1.127
0.993 1.008 1.008 1.031 1.028 1.035 1.081 1.131 1.162 1.385
8.187 6.811 4.953 3.613 2.329 1.886 1.501 1.267 1.135 0.870
0.36 0.15 0.40 0.31 0.27 0.07 0.12 0.03 0.36 0.16
0.002 0.002 0.005 0.004 0.006 0.002 0.003 0.001 0.010 0.005
0.275 0.336 0.421 0.482 0.534 0.599 0.674 0.731 0.776 0.830
8.904 7.181 4.658 3.537 2.644 2.038 1.631 1.426 1.293 1.177
0.950 0.952 0.944 0.930 0.942 0.941 0.963 0.985 1.031 1.077
10.024 8.071 5.282 4.072 3.006 2.317 1.811 1.549 1.341 1.168
0.01 0.11 0.48 0.17 0.37 0.27 0.11 0.02 0.05 0.10
0.000 0.003 0.008 0.003 0.007 0.006 0.003 0.000 0.002 0.003
367.45 365.52 363.70 362.60 362.61 363.35 364.40 365.55 366.65 367.83
About 15%
366.75 365.00 363.48 363.05 363.10 363.89 364.95 366.05 367.05 368.50
0.036 0.059 0.121 0.186 0.276 0.392 0.533 0.637 0.721 0.807
AC C
15.11 15.21 15.34 15.51 15.23 15.36 15.41 15.23 15.14 15.20
EP
10.32 10.40 10.33 10.26 10.30 10.17 10.16 10.35 10.20 10.14
TE D
About 10%
a
M AN U
5.12 5.45 5.23 5.33 5.33 5.22 5.30 5.12 5.03 5.10
SC
About 5%
Standard uncertainties u are u(x1ˊ)=u(y1)=0.006, u(T)=0.1 K, u(P)=1 kPa.
19
△T (K)
△y1
RI PT
w3 (%)
ACCEPTED MANUSCRIPT Table 6 Isobaric ternary vapor-liquid equilibrium data for temperature T, liquid phase mass fraction w, liquid phase mole fraction (salts free basis) x′, vapor phase mole fraction y, activity coefficient γ, relative volatility α, and the absolute deviation between the experimental and calculated values of temperature, △T, vapor phase mole fractions, △y, results for allyl alcohol (1) + water (2) + magnesium nitrate (3) at pressure 101.3 kPa. a T (K)
x1ˊ
y1
γ1
γ2
α12
371.80 364.60 363.10 362.80 362.25 362.65 363.75 364.85 365.85 368.50
0.006 0.066 0.140 0.181 0.292 0.405 0.584 0.657 0.745 0.899
0.029 0.231 0.356 0.404 0.499 0.572 0.656 0.690 0.737 0.855
4.686 4.418 3.398 3.020 2.363 1.927 1.474 1.323 1.200 1.052
1.011 1.112 1.071 1.054 1.048 1.051 1.161 1.218 1.341 1.697
4.948 4.251 3.396 3.067 2.415 1.963 1.358 1.162 0.959 0.662
0.30 0.30 0.11 0.34 0.28 0.18 0.24 0.17 0.04 0.10
0.000 0.002 0.001 0.005 0.005 0.004 0.006 0.004 0.001 0.003
371.80 370.20 366.95 365.20 364.70 363.65 365.05 366.20 367.60 368.50
0.011 0.026 0.068 0.158 0.226 0.393 0.491 0.556 0.657 0.726
0.080 0.163 0.305 0.443 0.499 0.616 0.666 0.689 0.730 0.770
7.104 6.488 5.230 3.497 2.811 2.086 1.719 1.507 1.287 1.191
0.970 0.950 0.930 0.883 0.882 0.901 0.890 0.911 0.975 1.007
7.818 7.295 6.015 4.238 3.411 2.478 2.067 1.769 1.412 1.264
0.35 0.35 0.11 0.13 0.28 0.29 0.28 0.021 0.31 0.20
0.002 0.002 0.001 0.002 0.006 0.006 0.007 0.000 0.008 0.005
0.18 0.16 0.15 0.26 0.20 0.18 0.13 0.03 0.05
0.001 0.003 0.003 0.005 0.005 0.005 0.003 0.001 0.001
About 15%
EP
10.34 10.40 10.26 10.31 10.17 10.26 10.35 10.20 10.11 10.07
TE D
About 10%
M AN U
5.22 5.50 5.32 5.53 5.22 5.30 5.12 5.03 5.01 5.21
SC
About 5%
AC C
15.23 371.35 0.017 0.172 10.125 0.900 12.012 0.101 0.460 5.785 0.816 7.582 15.76 364.95 15.41 364.75 0.158 0.516 4.188 0.789 5.681 15.23 365.20 0.252 0.575 2.889 0.769 4.016 15.14 366.67 0.409 0.650 1.919 0.765 2.684 15.23 367.18 0.486 0.685 1.677 0.779 2.300 15.25 368.05 0.583 0.730 1.445 0.801 1.934 15.30 368.50 0.638 0.759 1.358 0.812 1.787 15.17 369.85 0.816 0.856 1.149 0.916 1.340 a Standard uncertainties u are u(x1ˊ)=u(y1)=0.006, u(T)=0.1 K, u(P)=1 kPa.
20
△T (K)
△y1
RI PT
w3 (%)
ACCEPTED MANUSCRIPT Table 7 Parameters of the extended Antoine equation a component
C1i
C2i
C3i
C4i
C5i
allyl alcohol
77.83
-8057.60
0
0
-8.71
water
66.74
-7258.20
0
0
-7.30
1.66×10
-11
4.17
C7i
C8i (K)
C9i (K)
6.00
144.15
545.10
2.00
273.16
647.10
EP
TE D
M AN U
SC
RI PT
Taken from Aspen property databank
AC C
a
C6i (×106)
21
ACCEPTED MANUSCRIPT Table 8 Nonrandom factors and binary energy parameters for NRTL model. NRTL parameters
∆g ji (J/mol) -479.85 a -32595.94 -8125.59
TE D EP AC C 22
0.3 a 0.06 0.94
-479.85 a -31315.01 -8184.91
0.3 a 0.08 0.92
-479.85 a -43078.23 -8634.15
0.3 a 0.035 0.875
M AN U
allyl alcohol (1) + water (2) + calcium chloride (3) 1-2 7155.62 a 1-3 91298.79 2-3 11602.28 allyl alcohol (1) + water (2) + calcium nitrate (3) 1-2 7155.62 a 1-3 76591.47 2-3 15267.18 allyl alcohol (1) + water (2) + magnesium nitrate (3) 1-2 7155.62 a 1-3 80340.18 2-3 8640.48 a From Ref. [12]. ∆gi, j = gi, j − gi,i , τ i , j = ( gi , j − gi,i ) / RT .
RI PT
∆g ij (J/mol)
α12
SC
i-j
ACCEPTED MANUSCRIPT Table 9 The root-mean-square deviation(RMSD) for the equilibrium temperature(T) and mole fractions of the vapor phase (y1) of the NRTL model
calcium chloride
calcium nitrate
5 10 15 5 10 15 5 10 15
RMSD y1 0.004 0.005 0.003 0.004 0.004 0.005 0.004 0.005 0.003
T (K) 0.22 0.21 0.21 0.23 0.26 0.22 0.23 0.26 0.17
AC C
EP
TE D
M AN U
SC
magnesium nitrate
w3 (%)
RI PT
salt
23
ACCEPTED MANUSCRIPT
M AN U
SC
RI PT
Figure 1.
AC C
EP
TE D
Figure 2.
24
ACCEPTED MANUSCRIPT
M AN U
SC
RI PT
Figure 3.
AC C
EP
TE D
Figure 4.
25
ACCEPTED MANUSCRIPT
M AN U
SC
RI PT
Figure 5.
AC C
EP
TE D
Figure 6.
26
ACCEPTED MANUSCRIPT
M AN U
SC
RI PT
Figure 7.
AC C
EP
TE D
Figure 8.
27