Article

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Solubilities of Adipic Acid in Acetic Acid + Water Mixtures and

Acetic Acid + Cyclohexane Mixtures
Binwei Shen, Qinbo Wang,*, Yufang Wang, Xiang Ye, Fuqiong Lei, and Xing Gong

Department of Chemical Engineering, Hunan University, Changsha, 410082 Hunan, P. R. China

Department of Mathematics and Physics, Jingchu University of Technology, Jingmen, 448000 Hubei, P. R. China

Zhejiang Shuyang Chemical Co. Ltd., Quzhou, 31000 Zhejiang, P. R. China

ABSTRACT: The solubilities of adipic acid in acetic acid +

water mixtures at (303.2 to 333.2) K and acetic acid +
cyclohexane mixtures at (303.2 to 343.2) K are measured. The
measured solubility of adipic acid in acetic acid + cyclohexane
mixtures with the mass fraction of acetic acid in the solvent
mixtures at (0.1 to 1.0) decreases with increasing mass fraction
of cyclohexane at constant temperature. However, for the
solubility of adipic acid in acetic acid + water with the mass
fraction of acetic acid in the solvent mixtures at (0 to 1.0),
acetic acid with a mass fraction of 50 % has the best dissolving
capacity for adipic acid at constant temperature. The experimental data was correlated by the nonrandom two-liquid (NRTL)
activity coecient model, and the values of the solubilities calculated using the model showed good agreement with the
experimental observations.

1. INTRODUCTION solvent mixtures. The solubility of AA was investigated by Mao

Currently, adipic acid (AA) is the main feedstocks for product
nylon-66, which plays an important role in our modern life.1 At
present, it is commercially manufactured by the two-step
oxidation of cyclohexane. The rst step involves oxidation of
cyclohexane to cyclohexanone and cyclohexanol at around
433 K and (1 to 2) MPa pressure using either a soluble cobalt
catalyst or no catalyst, in the liquid phase, in which the total
cyclohexane conversion is less than 4 %. Under such low
conversion the selectivity toward cyclohexanol and cyclo-
hexanone (KA oil) can be optimized at (70 to 85) % without
much overoxidation of the products. The second step involves
oxidation of the KA oil to adipic acid via the use of nitric acid as
a mild oxidant. The side product produced from this step
includes nitrous oxide (N2O), which shows a global warming
eect of 300 times higher than carbon dioxide.
Finding a one-step method for manufacturing adipic acid
from cyclohexane without producing NOx is the most urgent
issue from the viewpoint of green chemistry. Usually in the one-
step method, after being oxidized by air in an oxidation reactor,
cyclohexane is conversed into adipic acid, which is called crude
adipic acid. During the oxidization process, usually the solvent is
acetic acid (HOAc). Water (H2O) and AA are the main products.
Sequentially, crude adipic acid must be puried to produce pure
adipic acid. Usually, crystallization is used to obtain products with
a high purity.2 Solubilities of AA in acetic acid + water solvent
mixtures and acetic acid + cyclohexane solvent mixtures become a
crucial factor in designing separation equipment, as well as in
controlling relevant operation conditions.
Although it is useful for the aforementioned reasons, very few
data are available on the solubility of AA in the aforementioned
in six pure solvents.3 Fan measured the solubilites of AA in the
mixtures of cyclohexanone and cyclohexanol.1,4 In this work,
the solubilities of AA in acetic acid + water mixtures and acetic
acid + cyclohexane mixtures are measured at (293.15 to
333.15) K. The experimental solubility data are correlated by
the nonrandom two liquid (NRTL) activity coecient model.5
2. EXPERIMENTAL SECTION
2.1. Materials. Adipic acid, pimelic acid, acetic acid, and
cyclohexane were obtained with mass fraction >0.990 from
Aladdin Chemistry Co. and had a declared purity of 99.0 wt %.
Methanol and acetonitrile were obtained from USA Tedia
Company and had a declared purity of 99.9 wt %. Puried
water manufactured by Hangzhou Wahaha Group Co. was
obtained from the supermarket (596 mL each bottle). All of the
other chemicals used were of analytical purity and obtained
from Sinopharm Chemical Reagent Co., Ltd.
2.2. Solubility Measurements. The experimental appara-
tus and sampling methods used in this work were described in
detail by Wang et al.6 Briey, in each experiment, an excess
amount of solute AA was added to 80 5 mL of solvent in a
100 mL glass bottle, and then the bottle was heated to the
desired temperature within 0.1 K by putting it in a
thermostatic water bath. The bottle was sealed by a rubber
stopper to prevent the evaporation of solvent. The mixture was
stirred to accelerate the dissolution of solute AA. About 3 h
Received: November 9, 2012
Accepted: March 14, 2013
Published: March 25, 2013

2013 American Chemical Society 938 dx.doi.org/10.1021/je301202v | J. Chem. Eng. Data 2013, 58, 938942
Journal of Chemical & Engineering Data
later the stirring was stopped, and the mixture would be left
undisturbed in the following several hours. Fifteen min later,
two phases would appear in the bottle, i.e., the liquid phase in
the upper and the solid phase in the bottle bottom. To verify
the attainment of solidliquid equilibrium, the clear upper
liquid phase would be sampled once an hour, and the
concentration of AA would be determined. It was found that
2 h after stopping stirring was enough for solute AA in solvent
to reach equilibrium, because repetitive measurements during
the following several hours indicated the results were
reproducible with 3 %. For assurance, after stopping stirring
at each temperature, the solution was kept isothermal and
undisturbed for at least 12 h to ensure that the solution had
been saturated. In each measurement, 2 mL of the saturated
solution was sampled and then analyzed using the method
introduced in Section 2.3. Some of the solubility experiments
were conducted two or three times to check the repeatability.
The uncertainty in temperature was 0.1 K. To verify the
reliability of the experimental apparatus and method, the
solubility of AA in water and acetic acid was measured and
compared with literature data.1,3 As shown in Figures 1 and 2,
our results agreed well with the data in literature, with an
average deviation of 2 %.
Figure 1. Determined solubilities and literature data of AA in acetic
acid (2): , experimental data (w2 = 1.0); , literature data (w2 = 1.0)
from Fan;1,4 , solubility curve calculated from NRTL model eqs 1 to 4.
Figure 2. Determined solubilities and literature data of AA in water
(2): , experimental data (w2 = 1.0); , literature data (w2 = 1.0) from
Mao;3 , solubility curve calculated from NRTL model eqs 1 to 4.
2.3. Concentration Determination Method. The concen-
tration of AA in the solution was determined using a Shimadzu-
15C high-performance liquid chromatograph (HPLC) with an
Inertsil ODS-3 (250 mm 4.6 mm, 5 m) chromatographic
column. The column temperature is set to 40 C. The mobile
939
Article
phase constituted of two eluents (i.e., acetonitrile + water), and
the following two-component elution program was adopted:
from (0 to 10) min, 16 mass % acetonitrile and 84 mass %
water. The internal standard method was used to determination
the concentration of AA in the solution, and pimelic acid was
used as the internal standard. Similar as the method described
in the work of Wang et al,6 the instrument constant for AA is
determined to be 1.0920 by linear regression, and the linearity
was 0.9999.
To verify the reliability and reproducibility of the analysis
method, ve AA solutions of known concentration were
analyzed. The ve solutions were measured at least ve times,
and the repeatability was evaluated with a mean relative
deviation of less than 1 %. The estimated associated uncertainty
of the measured solubility values based on error analysis and
repeated observations was within 4 %.
3. RESULTS AND DISCUSSION
3.1. Solubility Data. Solubility of AA in Acetic Acid +
Water Mixtures. The measured solubility of AA in acetic acid +
water mixtures are summarized in Table 1, where w2 was dened
as the mass fraction of acetic acid in binary acetic acid + water
solvent mixtures. To verify the reliability of the experimental
apparatus, the measured solubility of AA in water and acetic acid
were compared with the literature reported data in Figures 1 and 2.
From Figures 1 and 2, it can be seen that the solubility data of AA
in acetic acid and water reported in this work are in agreement with
the data from the literature. The averaged relative deviation cal-
culated between the solubility of the literature and the measured
solubility in this work is less than 2 %. It indicates that the measured
solubility in this work is reliable.
By comparison of all of the solubilities of AA in aqueous
acetic acid, an interesting result comes up as shown in Figure 3. At
each measured temperature, acetic acid with mass fraction of 50 %
has the best dissolving capacity for AA. It indicates that the higher
or the lower the mass fraction of water, the less the solubility. In
other words, within this mass fraction of water range, there is a
slope presenting the change of solubility inuenced by solvent
concentrations at each measured temperature. This maximum-
solubility eect has also been noticed by Chen and Ma for the
solubility of terephthalic acid in the mixture of acetic acid and
water7 and Wang et al. for the solubility of phthalic acid in the
mixture of acetic acid and water.6
Solubility of AA in Acetic Acid + Cyclohexane Mixtures.
The measured solubilities of AA in acetic acid + cylcohexane
are summarized in Table 2, where w2 was dened as the mass
fraction of acetic acid in binary acetic acid + cyclohexane
solvent mixtures. From Table 2, it can be seen that, within the
temperature range of the measurements, the solubility of AA in
all of the mixtures shows an increasing trend as the temperature
increases. The solubility of AA in pure acetic acid shows the
highest, and it decreases with an increasing concentration of
cyclohexane in the mixed acetic acid + cyclohexane system at
constant temperature.
3.2. Correlation of Experimental Data. Generally, solid
liquid equilibrium can be approximated by eq 1 that involves
such properties of pure solute as enthalpy of fusion, melting
point, and so forth.68
fusH 1 1 trsH 1 1
ln(1x1) =
R T Tfus R T Ttrs
(1)
dx.doi.org/10.1021/je301202v | J. Chem. Eng. Data 2013, 58, 938942
Journal of Chemical & Engineering Data Article

Table 1. Solubilities S of AA (cr, 1) in Acetic

Acid (2) + Water (3) Solvent Mixtures at Temperatures
(303.2 to 333.2) K and Pressure p = 101.3 kPaa
T/K S/(g(100g)1) Sc/(g(100g)1) RD/%
w2 = 1.0
303.2 5.80 5.45 6.10
313.2 8.41 8.18 2.72
323.2 11.89 12.06 1.42
333.2 17.10 17.47 2.13
w2 = 0.9
303.2 6.58 6.16 6.47
313.2 9.48 9.31 1.76
323.2 13.29 13.80 3.79 Figure 3. Solubilities of AA (1) in acetic acid (2) + water (3) mixtures:
333.2 19.48 20.09 3.13 , T = 303.15 K; , T = 313.15 K; , T = 323.15 K; , T = 333.15 K; ,
w2 = 0.8 solubility curve calculated from NRTL model eqs 1 to 4.
303.2 7.06 6.80 3.67
313.2 10.64 10.28 3.39
323.2 15.09 15.23 0.88 occur, and the last term in eq 1 can be neglected. Therefore,
333.2 21.28 22.22 4.42 eq 1 becomes
w2 = 0.7
fusH 1 1
303.2 7.95 7.34 7.61 ln(1x1) =
313.2 11.76 11.05 6.02 R T Tfus (2)
323.2 16.71 16.33 2.26
In eqs 1 and 2, fusH is the molar fusion enthalpy of solute,
333.2 23.11 23.82 3.05
Tfus is the fusion temperature, trsH is the molar enthalpy of
w2 = 0.6
solidsolid phase transition, Ttrs is the transition temperature,
303.2 8.19 7.78 4.94
T is the absolute temperature, R is the universal gas constant, 1
313.2 12.10 11.62 3.93
is the activity coecient of solute, and x1 is the real mole fraction
323.2 17.46 17.06 2.29
of solute in solution. Because the activity coecient 1 depends on
333.2 24.00 24.81 3.35
the solution composition and temperature, eq 2 must be solved
w2 = 0.5
iteratively. For the denition of the activity coecient, the NRTL
303.2 8.62 8.06 6.57
activity coecient model was used as
313.2 12.49 11.91 4.68
323.2 18.70 17.40 6.93
3
j = 1 jiGjixj 3 xjGij x G
3
ln i = + ij k = 1 k kj kj
k = 1 Gkjxk k = 1 Gkjxk
333.2 24.86 25.23 1.48 3 3 3
w2 = 0.4 k = 1 Gkixk j=1
303.2 8.10 8.15 0.55 (3)
313.2 11.72 11.81 0.80 In eq 3, ij and Gij are NRTL model parameters that need to
323.2 17.55 17.06 2.80 be experimentally determined by
333.2 24.43 24.79 1.48
w2 = 0.3 bij
303.2 6.99 7.90 13.08
Gij = exp( ijij), ij = aij + , ij = ji ,
T
313.2 10.58 11.13 5.25
323.2 16.50 16.01 2.97 ij ji , ii = 0 (4)
333.2 23.58 23.56 0.09
To calculate the solubility, the fusion temperature (Tfus) and
w2 = 0.2
molar enthalpy of fusion of solute (fusH) are required. Tfus and
303.2 5.78 7.02 21.55
fusH used in the calculation are 426.15 K and 34 850 Jmol1,
313.2 8.73 9.47 8.44
which can be obtained from the literature.9
323.2 14.05 13.61 3.10
Using model eqs 1 to 4, the solubilities were correlated, and the
333.2 21.21 20.88 1.53
model parameters were optimized. In the optimization process, as
w2 = 0.1
303.2 4.39 4.90 11.55
Renon and Prausnitz proposed, ij was chosen as 0.3.5 Table 3
313.2 7.09 6.53 7.86
shows the optimized NRTL model parameters in eq 4. The
323.2 11.99 10.41 13.19
optimum algorithm applied in the parameter estimation program
333.2 18.64 17.75 4.78 was the NelderMead Simplex approach,10 which had been
w2 = 0.0 introduced in detail in the work of Wang et al.6 Function
303.2 3.25 3.08 5.19 fminsearch in the optimization toolbox of Matlab (Mathwork,
313.2 5.33 5.10 4.22 MA) uses the NelderMead Simplex approach and can be
323.2 7.98 7.52 5.76 employed for the minimization of the objective function, which is
333.2 13.80 15.46 12.04 the averaged relative deviation (ARD) between the experimental
a
Standard uncertainties u are u(T) = 0.1 K, ur(p) = 0.05, ur(S) = 0.04.
and the calculated solubility dened by
n
1 Sci Si
For the system of AA + acetic acid + water and AA + acetic ARD = abs(RDi), RDi = 100
n Si (6)
acid + cyclohexane, the solidsolid phase transition does not i=1

940 dx.doi.org/10.1021/je301202v | J. Chem. Eng. Data 2013, 58, 938942

Journal of Chemical & Engineering Data Article

Table 2. Solubilities S of AA (cr, 1) in Acetic Acid (2) + Cyclohexane (3) Solvent Mixtures at Temperatures (303.2 to 343.2) K
and Pressure p = 101.3 kPaa
T/K S/(g(100g)1) Sc/(g(100g)1) RD/% T/K S/(g(100g)1) Sc/(g(100g)1) RD/%
w2 = 1.0 w2 = 0.5
303. 2 5.80 5.81 0.14 303. 2 2.36 2.55 8.21
313. 2 8.41 8.36 0.67 313. 2 3.64 3.73 2.50
323. 2 11.89 11.77 1.01 323. 2 5.14 5.33 3.81
333. 2 17.10 16.25 5.00 333. 2 7.26 7.48 3.02
343. 2 23.01 22.17 3.64 343. 2 9.96 10.32 3.66
w2 = 0.9 w2 = 0.4
303. 2 5.38 5.23 2.79 303. 2 1.84 1.82 1.15
313. 2 7.40 7.56 2.05 313. 2 2.62 2.67 2.04
323. 2 10.96 10.64 2.92 323. 2 3.79 3.84 1.33
333. 2 14.92 14.76 1.05 333. 2 5.25 5.42 3.25
343. 2 20.11 20.18 0.33 343. 2 7.27 7.51 3.29
w2 = 0.8 w2 = 0.3
303. 2 4.86 4.62 4.94 303. 2 1.05 1.13 7.11
313. 2 6.98 6.67 4.39 313. 2 1.81 1.67 7.82
323. 2 9.80 9.44 3.67 323. 2 2.34 2.41 3.13
333. 2 13.29 13.12 1.28 333. 2 3.36 3.42 1.87
343. 2 18.09 17.95 0.79 343. 2 4.74 4.77 0.75
w2 = 0.7 w2 = 0.2
303. 2 4.03 3.97 1.68 303. 2 0.57 0.56 2.08
313. 2 5.60 5.76 2.86 313. 2 0.95 0.84 11.48
323. 2 8.28 8.16 1.44 323. 2 1.18 1.22 2.89
333. 2 11.49 11.36 1.09 333. 2 1.86 1.74 6.77
343. 2 15.36 15.59 1.45 343. 2 2.60 2.43 6.67
w2 = 0.6 w2 = 0.1
303. 2 3.23 3.27 1.29 303. 2 0.23 0.25 8.95
313. 2 4.83 4.76 1.31 313. 2 0.41 0.37 10.41
323. 2 6.61 6.79 2.71 323. 2 0.53 0.52 1.97
333. 2 9.45 9.48 0.23 333. 2 0.75 0.74 1.16
343. 2 12.91 13.03 0.94 343. 2 0.95 1.02 7.54
a
Standard uncertainties u are u(T) = 0.1 K, ur(p) = 0.05, ur(S) = 0.04.

Table 3. NRTL Model Parameters in eq 4 for AA + HOAc + Water and AA + HOAc + Cyclohexane
i j aij aji bij bji ij = ji
AA HOAc 1.1210102 2.5976 2.0094103 9.4977102 0.3
AA water 6.0867 41.006 2.0349103 1.9303104
AA cyclohexane 10.801 1.4474 8.9421102 8.6436103
HOAc water 1.9763 3.3293 6.0989102 7.2389102
HOAc cyclohexane 12.149 24.418 1.3236102 7.4150105
ARD/% 3.91

where Sci is the solubility calculated by eqs 1 to 4, and n is the Notes

number of experimental points. The model parameters and the The authors declare no competing nancial interest.

averaged relative deviation (ARD) between the experimental and
the correlated values of AA are also given in Table 3. These results
show that the NRTL activity coecient model equations can be
used to correlate the solubility of AA. The experimental solubility
and correlation equations in this work can be used as essential data
and models for the synthetic and purication process of AA.
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AUTHOR INFORMATION (3) Mao, Z. B.; Sun, X. B.; Luan, X. H. Measurement and Correlation
of Solubilities of Adipic Acid in Different Solvents. Chin. J. Chem. Eng.
Corresponding Author
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942 dx.doi.org/10.1021/je301202v | J. Chem. Eng. Data 2013, 58, 938942