Accepted Manuscript

Title: Study on the Separation of Binary Azeotropic Mixtures

by Continuous Extractive Distillation

Author: Shenfeng Yuan Cancan Zou Hong Yin Zhirong Chen

Wendong Yang

PII: S0263-8762(14)00215-9
DOI: http://dx.doi.org/doi:10.1016/j.cherd.2014.05.005
Reference: CHERD 1583

To appear in:

Received date: 17-9-2013

Revised date: 13-4-2014
Accepted date: 7-5-2014

Please cite this article as: Yuan, S., Zou, C., Yin, H., Chen, Z., Yang,
W.,Study on the Separation of Binary Azeotropic Mixtures by Continuous
Extractive Distillation, Chemical Engineering Research and Design (2014),
http://dx.doi.org/10.1016/j.cherd.2014.05.005

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 1 Study on the Separation of Binary Azeotropic Mixtures by Continuous

2 Extractive Distillation

3 Shenfeng Yuan, Cancan Zou, Hong Yin, Zhirong Chen, Wendong Yang

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4 Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

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5 Abstract:

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6 For azeotropic mixtures or close-boiling mixtures which is often observed in the pharmaceutical

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7 and specialty chemicals industries, conventional distillation has been shown to be unable to reach

8 the separation desired. In this paper, continuous extractive distillation (CED) was used to separate

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9 acetonetetrahydrofuran, n-hexane-tetrahydrofuran, n-hexane-ethyl acetate and ethyl acetate-

10 ethanol that form azeotropic mixtures. The characters of the CED were simulated with Aspen Plus
M
11 and experiments also showed the feasibility of the technology in separating the azeotropic

12 mixtures. The mass fraction of the light component in the separation of acetonetetrahydrofuran,
d
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13 n-hexane-tetrahydrofuran, n-hexane-ethyl acetate and ethyl acetate-ethanol reached 99.02%,

14 99.00%, 99.15% and 98.80% respectively. These azeotropic mixtures were separated successfully
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15 through solvent selection based on polarity principle and pseudo-binary vapor-liquid equilibrium,
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16 simulation via Aspen Plus and experimental verification. This algorithm may become a generally
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17 applicable method for solvent selection in developing new extractive distillation processes.

18 Keywords: extractive distillation; azeotropic mixtures; simulation; separation

19 1. Introduction

Correspondence:Dr.HYin(yinh@zju.edu.cn)
DepartmentofChemicalandBiologicalEngineering,
ZhejiangUniversity,Hangzhou,310027,P.R.China.
1

Page 1 of 21
 1 In the specialty chemicals industry, distillation is one of the oldest and most widely used

2 separation processes. The separation is based on the difference in boiling temperature of the

3 components. By vaporising and condensing the mixtures, the lower boiling component is enriched

4 in the vapor phase while the higher boiling component is enriched in the liquid phase[1]. But not

t
5 all liquid mixtures can be separated by conventional distillation, when the components to be

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6 separated constitute azeotropic mixtures which are often observed in the pharmaceutical and

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7 specialty chemicals industries, conventional distillation has been shown to be unable to reach the

separation desired. The extractive distillation can be used to solve the problem[2].

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8

9 Extractive distillation has a history of about seventy years, during the Second World War,

an
10 because of the great demand of the butadiene and high purity of toluene. The extractive distillation

11 technology has been widely used and become an important industrial process. Extractive
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12 distillation can be divided into two categories according to the mode of operation: continuous

13 extractive distillation (CED) and batch extractive distillation[3,4].

d

14 In extractive distillation, usually a feasible solvent is fed to the column to break the azeotropes.
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15 When the solvent is fed continuously in the top section of the column, the process is called CED.

16 For separation of all constituents two columns are needed, one column for extractive separation
p

17 and a second column for solvent regeneration. The mixture and the solvent are fed to the first
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18 column, where the low boiling component is separated from the less volatile component plus

19 solvent. The less volatile component and the solvent collect in the bottoms and the light
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20 component collects on top of the column. The bottom product is fed to the second column in

21 which the solvent is recovered and recycled to the first column[5]. Aspen model of extractive

22 distillation process is presented in Fig. 1.

23 In the pharmaceutical and specialty chemicals industries batch extractive distillation is often

24 used for recovery of the organic solvents[6-8]. However, for higher throughput economics of CED

25 is better.

Page 2 of 21
 1 Identification of suitable solvents and optimum operating conditions are the crucial steps in the

2 design of extractive distillation processes. Solvent selection [9-14], optimization via computer

3 simulation with commercial process simulators [14-18] and experimental validation of extractive

4 distillation processes[19-21] have been investigated intensively. However, there are few papers

t
5 that study the universal applicability of the algorithm.

ip
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6 Fig. 2 showsthevapor-liquid equilibrium of acetone-tetrahydrofuran, n-hexane-tetrahydrofuran,

7 n-hexane- ethyl acetate and ethyl acetate - ethanol at 1atm predicted by UNIQUAC model. All of

us
8 these binary systems form azeotropic mixtures. They are often observed in the pharmaceutical and

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9 specialty chemicals industries. Separation of these binary systems by CED has not yet been

10 reported. Therefore, the separation of these four azeotropic mixtures was investigated applying a
M
11 procedure including solvent selection based on polarity principle, pseudo-binary vapor-liquid

12 equilibrium, simulation and optimization via Aspen Plus and experimental verification. The
d

13 purpose of this study is to establish a simple, convenient and generally applicable method in
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14 developing new extractive distillation processes.

p

15 2. Solvent selection
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16 2.1 Qualitative judgment

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17 The solvent must have special characteristics to achieve the desired separation as follows:

18 thermal stability, low toxicity, higher boiling point, simple recoverability and selectivity[21].

19 Thereamong selectivity is the key characteristic. In this paper, the solvents were chosen based on

20 polarity principle on the condition that the above basic requirements were satisfied. The polarity of

21 the solvent is close to the polarity of the heavy component, inducing interaction of the heavy

22 component and the solvent, and the relative volatility of the original components of the mixture is

Page 3 of 21
 1 modified. The dielectric constant serves as a proper scale of polarity. Therefore, the difference of

2 dielectric constant between the selected solvent and the heavy component should be less than that

3 between the selected solvent and the light component. For large difference of the boiling points of

components of the azeotropic mixture, the low boiling component is chosen as the light

t
4

ip
5 component. For close-boiling mixture, owing to strong molecular interaction between molecules

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6 with high polarity, the component whose dielectric constant is smaller is chosen as the light

us
7 component. Table 1[22] presents the dielectric constant and boiling point of each component and

8 potential solvents.

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9 For acetonetetrahydrofuran, the boiling point of acetone is lower than that of tetrahydrofuran.

10 Acetone is the light component which is collected in the top of the column. Butyl ether, xylene,
M
11 1,3,5-trimethylbenzene and diethylbenzene whose dielectric constant is lower than that of

12 tetrahydrofuran are chosen as the potential solvents.

d
te

13 For n-hexane-tetrahydrofuran, the boiling point of n-hexane is close to that of tetrahydrofuran.

14 The dielectric constant of tetrahydrofuran is higher than that of n-hexane. n-Hexane is the light
p

15 component which is collected in the top of the column. N,N-Dimethylformamide (DMF),

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16 N-methyl-2-pyrrolidone (NMP), 2-methylpyridine and 3-methylpyridine whose dielectric constant

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17 is higher than that of tetrahydrofuran are chosen as the potential solvents.

18 For n-hexane-ethyl acetate, the boiling point of n-hexane is lower than that of ethyl acetate.

19 n-Hexane is the light component which is collected in the top of the column. NMP, pyrrole,

20 2-methylpyridine and 3-methylpyridine whose dielectric constant is higher than that of ethyl

21 acetate are chosen as the potential solvents.

22 For ethyl acetate-ethanol, the boiling point of ethyl acetate is close to that of ethanol, the

Page 4 of 21
 1 dielectric constant of ethanol is higher than that of ethyl acetate. Ethyl acetate is the light

2 component which is collected in the top of the column. DMF, NMP, and dimethyl sulfoxide

3 (DMSO) whose dielectric constant is higher than that of ethanol are chosen as the potential

solvents.

t
4

ip
5 2.2 Vapor-liquid equilibrium

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6 In order to determine the final solvent, the pseudo-binary vapor-liquid equilibrium data of the

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7 four azeotropic mixtures were predicted by UNIQUAC model. The solvent that gives the largest

8 relative volatility of the original components of the mixture was chosen as the final solvent.

an
9 Fig. 3 shows the pseudo-binary vapor-liquid equilibrium of acetone-tetrahydrofuran with a

10 solvent to feed volume ratio 3. From Fig. 3 it could be seen that the relative volatility with the
M
11 solvent butyl ether is larger than that with xylene, 1,3,5-trimethylbenzene or diethylbenzene as

12 solvent. So butyl ether was chosen as the solvent to separate acetone and tetrahydrofuran.
d
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13 Fig. 4 shows the pseudo-binary vapor-liquid equilibrium of n-hexane-tetrahydrofuran with a

14 solvent to feed volume ratio 3. From Fig. 4 it could be seen that the relative volatility with the
p

15 solvent NMP is larger than that with DMF, 2-methylpyridine or 3-methylpyridine as solvent. So
ce

16 NMP was chosen as the solvent to separate n-hexane and tetrahydrofuran.

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17 Fig. 5 shows the pseudo-binary vapor-liquid equilibrium of n-hexane-ethyl acetate with a

18 solvent to feed volume ratio 3. From Fig. 5 it could be seen that the relative volatility with the

19 solvent NMP is larger than that with pyrrole, 2-methylpyridine or 3-methylpyridine as solvent. So

20 NMP was chosen as the solvent to separate n-hexane and ethyl acetate.

21 Fig. 6 shows the pseudo-binary vapor-liquid equilibrium of ethyl acetate-ethanol witha solvent

22 to feed volume ratio 3. From Fig. 6 it could be seen that the relative volatility with the solvent

Page 5 of 21
 1 DMSO is larger than that with NMP or DMF as solvent. So DMSO was chosen as the solvent to

2 separate ethyl acetate and ethanol.

3 3. Simulation

Extractive distillation was simulated with RadFrac routine of Aspen Plus. Sensitivity analysis

t
4

ip
5 was used to establish the operating conditions for the extractive distillation column. UNIQUAC

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6 model was selected for the prediction of physical properties in the simulation. The parameters

us
7 analyzed were as follows: number of stage (NS), reflux mass ratio (R), mixture feed stage (FS),

8 solvent feed stage (SFS) and solvent to feed volume ratio (S/F). The optimum parameters obtained

an
9 was shown in Table 2, and Table 3 shows the corresponding simulation results. From Table 3 it

10 could be seen that the mass fraction of the light component in the separation of
M
11 acetonetetrahydrofuran, n-hexane-tetrahydrofuran, n-hexane-ethyl acetate and ethyl acetate-

12 ethanol reached 99.00%, 99.10%, 99.00% and 99.10% respectively.

d
te

13 4. Experiment

14 Table 4 shows the parameters of the experiment and Fig. 7 shows the drawing of the
p

15 experimental equipment. The extractive distillation column has a total height of 3.0 m and an
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16 internal diameter of 0.05 m. It was packed with glass spring packing of 3 mm 10 mm. The
Ac

17 bottom is a flask of 3000 ml. The flow rate and reflux ratio is controlled by constant flow pump

18 and solenoid valve respectively. The solvent recovery column has a total height of 1.8 m and an

19 internal diameter of 0.05 m. It was packed with glass spring packing of 3 mm 10 mm. The

20 bottom is a flask of 3000 ml.

21 4.1 Experimental procedure

22 1. 500 ml binary mixture was charged into the flask of the extractive distillation column. It

Page 6 of 21
 1 was heated and kept under total reflux for 60 min.

2 2. Solvent was charged into the extractive distillation column according to the data in Table 4

3 and binary mixture was charged into the extractive distillation column at 3ml/min, then the

extractive distillation column was kept under total reflux until the mass fraction of the light

t
4

ip
5 component in distillate reached a stable state.

cr
6 3. The distillate was taken out at the constant reflux ratio, the flow rate of binary mixture was

us
7 gradually increased till the value in Table 4. The bottom product was pumped to the solvent

8 recovery column to keep the extractive distillation column under an equilibrium state. In the

an
9 solvent recovery column, the heavy component was taken out and the solvent was pumped to the

10 storage tank of the solvent to keep the solvent recovery column under an equilibrium state.
M
11 4.2 Results and discussions
d

12 Table 5 shows the experimental results. From Table 5 it could be seen that the light component
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13 and the heavy component of acetonetetrahydrofuran, n-hexane-tetrahydrofuran, n-hexane-ethyl

acetate and ethyl acetate-ethanol reached high purity respectively. The experimental data and
p

14
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15 simulation results compare well (within a standard deviation of 0.8%). No major discrepancy is

16 noticed, even though the simulation is based on numerous assumptions such as constant molar
Ac

17 hold-up in the column, omission of fluid-dynamics, no heat losses over the column and no

18 sub-cooling at the condenser[23].

19 5. Conclusions

20 Acetone-tetrahydrofuran, n-hexane-tetrahydrofuran, n-hexane -ethyl acetate and ethyl acetate-

21 ethanol were separated successfully through solvent selection based on polarity principle and

22 pseudo-binary vapor-liquid equilibrium, simulation via Aspen Plus and experimental verification.
7

Page 7 of 21
 1 The simulation results were experimentally verified. The proposed algorithm may become a

2 simple, convenient and generally applicable method for solvent selection in developing new

3 extractive distillation processes. It may greatly reduce the workload and save time. The work for

the validation of the algorithm in other low boiling azeotropic mixtures is in progress.

t
4

ip
5 Acknowledgments

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6 This work is supported by the Program for Zhejiang Leading Team of S&T Innovation

us
7 (2011R50007).

8 Abbreviations

an
NS number of stage

R reflux mass ratio

M
FS mixture feed stage

SFS solvent feed stage

d
te

S/F solvent to feed volume ratio

Ds the distillation mass fraction of the simulation

p

Ws the bottom mass fraction of the simulation

ce

DE the distillation mass fraction of the experiment

Ac

WE the bottom mass fraction of the experiment

9 References:

10 [1] Emhamed AM, Czuczai B, Rev E, Lelkes Z. Analysis of Extractive Distillation with

11 Mathematical Programming. Ind Eng Chem Res 47(2008) 9983-9995.

12 [2] Luyben W L, Chien I L, Design and Control of Distillation Systems for Separating Azeotropes.

13 New York. Wiley-VCH. 2010.

Page 8 of 21
 1 [3] Benedict M RR. Extractive and Azeotropic Distillation.Trans Inst Chem Eng 41(1945)

2 353-370.

3 [4] Yatim H, Moszkowicz P, Otterbein M, Lang P. Dynamic Simulation of a Batch Extractive

Distillation Process, Comput. Chem. Eng 17(1993) S57-62.

t
4

ip
5 [5] Gil ID, Botia DC, Ortiz P, Sanchez OF.Extractive Distillation of Acetone/Methanol Mixture

cr
6 Using Water as Entrainer. Ind Eng Chem Res 48(2009)4858-4865.

us
7 [6] Van Kaam R, Rodriguez-Donis I, Gerbaud V. Heterogeneous extractive batch distillation of

8 chloroform-methanol-water: Feasibility and experiments. Chem Eng Sci 63(2008)78-94.

an
9 [7]Lang P, Kovacs G, Kotai B, Gaal-Szilagyi J, Modla G. Industrial application of a new batch

10 extractive distillation operational policy. IChemE Symposium Series 152 (2006) 830-839,.
M
11 [8]Lang P, Hegely L, Kovacs G, Gaal-Szilagyi J, Kotai B. Solvent Recovery From A

12 Multicomponent Mixture By Batch Extractive Distillation And Hybrid Process, Distillation&

d
te

13 Absorption 2010, Eindhoven, 11 -15 Sept., 295-300.

14 [9] Van DB, Nieuwoudt I. Design of solvents for extractive distillation. Ind Eng Chem Res
p

15 39(2000) 1423-1429.
ce

16 [10] Kossack S, Kraemer K, Gani R, Marquardt W. A systematic synthesis framework for

Ac

17 extractive distillation processes. Chem Eng Res Des 86(2008) 781-792.

18 [11] Venkatasubramanian V, Chan K, Caruthers JM. Computer-aided molecular design using

19 genetic algorithms. Comput Chem Eng 18: 833-844(1994).

20 [12] Krummen M, Gruber D, Gmehling J. Measurement of activity coefficients at infinite dilution

21 in solvent mixtures using the dilutor technique. Ind Eng Chem Res 39(2000) 2114-2123.

22 [13] Ewell RH HJBL. Rapid screening of extractive distillation solvents. Ind Eng Chem Res

Page 9 of 21
 1 871(1994).

2 [14] Lek-utaiwan P, Suphanit B, Douglas PL, Mongkolsiri N. Design of extractive distillation for

3 the separation of close-boiling mixtures: Solvent selection and column optimization. Comput

Chem Eng 35(2011)1088-1100.

t
4

ip
5 [15] Langston P, Hilal N, Shingfield S, Webb S. Simulation and optimisation of extractive

cr
6 distillation with water as solvent. Chem Eng Process 44(2005)345-351.

us
7 [16] Gil ID, Uyazan AM, Aguilar JL, Rodriguez G, Caicedo LA. Separation of ethanol and water

8 by extractive distillation with salt and solvent as entrainer: Process simulation. Braz J Chem Eng

an
9 25(2008)207-215.

10 [17] Lladosa E, Monton JB, Burguet M. Separation of di-n-propyl ether and n-propyl alcohol by
M
11 extractive distillation and pressure-swing distillation: Computer simulation and economic

12 optimization. Chem Eng Process 50(2011)1266-1274.

d
te

13 [18] de Figueiredo MF, Guedes BP, de Araujo J, Vasconcelos L, Brito RP.Optimal design of

14 extractive distillation columns-A systematic procedure using a process simulator. Chem Eng Res
p

15 Des 89(2011) 341-346.

ce

16 [19] Xu SL, Wang HY.A new entrainer for separation of tetrahydrofuran-water azeotropic mixture
Ac

17 by extractive distillation. Chem Eng Process 45(2006) 954-958.

18 [20] Resa JM, Gonzalez C, Ruiz A. Experiments of extractive distillation at laboratory scale for

19 the rupture of the azeotropic mixture acetone plus isopropyl ether. Sep Purif Technol

20 18(2000)103-110.

21 [21] Lladosa E, Monton JB, Burguet MC, Munoz R. Phase equilibria involved in extractive

22 distillation of dipropyl ether+1-propyl alcohol using 2-ethoxyethanol as entrainer. Fluid Phase

10

Page 10 of 21
1 Equilib 255(2007) 62-69.

2 [22] Cheng NL. Solvent Handbook. BeiJing. Chem Ind Press. 2008.

3 [23] Xu S, Wang H. Separation of tetrahydrofuran-water azeotropic mixture by batch extractive

distillation process. Chem Eng Res Des 84(2006)478-482.

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4

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5

cr
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an
M
d
p te
ce
Ac

11

Page 11 of 21
 1 Table Captions

2 Table1 The dielectric constant and boiling point of each component and potential solvents

3 Table 2 The optimum parameters obtained from sensitivity analysis

Table 3 Results of the simulation

t
4

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5 Table 4 Parameters of the experiment

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6 Table 5 The experimental results

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7

an
9

10
M
11

12
d
te

13

14
p

15
ce

16
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17

18

19

20

21

22 Table 1 The dielectric constant and boiling point of each component and potential solvents

12

Page 12 of 21
 material dielectric constant boiling point()

DMSO 48.9 189

DMF 36.71 153
NMP 32 204
ethanol 25.7 78.3
acetone 20.7 56.3

t
3-methylpyridine 10.71 143.8

ip
2-methylpyridine 9.46 129.4
pyrrole 8 130

cr
tetrahydrofuran 7.58 65.4
ethyl acetate 6.02 77
butyl ether 3.06 142

us
diethylbenzene 2.369 181.102
1,3,5-trimethylbenzene 2.279 164.716
xylene 2.266 144.4

an
n-hexane 1.89 68.7
1
2 Table 2 The optimum parameters obtained from sensitivity analysis
M
3
column parameters acetone- n-hexane- n-hexane- ethyl acetate-
tetrahydrofuran tetrahydrofuran ethyl acetate ethanol
Feed temperature 30 30 30 30
d

Solvent flow (m3/hr) 0.9 0.75 0.9 0.9

Mixture flow (m3/hr) 0.3 0.3 0.3 0.3
te

NS 53 37 40 38
EDC SFS 7 3 3 5
p

FS 24 20 18 17
R 3 2 2.5 3
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Pressure (atm) 1 1 1 1
Pressure (atm) drop of column 0.1 0.1 0.1 01.
Mass fraction of binary feed 0.62/0.38 0.43/0.57 0.61/0.39 0.32/0.68
Ac

NS 17 12 11 18
FS 10 5 5 10
SRDC R 3.5 2 1.5 2
Pressure (atm) 1 1 1 1
Pressure (atm) drop of tower 0.1 01. 0.1 0.1

6 Table 3 Results of the simulation

Mass fraction extractive distillation column solvent regeneration column

13

Page 13 of 21
 Ds Ws Ds Ws
acetone 99.00 0 0 0
tetrahydrofuran 1.00 11.90 100 0.0044
butyl ether 0.0037 88.10 0.0463 100
n-hexane 99.10 0 0 0
tetrahydrofuran 0.90 15.40 100 0

t
NMP 0.0911 84.60 0.0103 100

ip
n-hexane 99.00 0 0 0.0011
ethyl acetate 0.90 7.8 100 0

cr
NMP 0.0973 92.2 0.0213 100
ethyl acetate 99.10 0 0 0

us
ethanol 0.90 11.10 100 0
DMSO 0.0017 88.90 0.0018 100
1

an
2 Table 4 Parameters of the experiment
3
column parameters acetone- n-hexane- n-hexane- ethyl acetate-
M
tetrahydrofuran tetrahydrofuran ethylacetate ethanol
Distillate flow (ml/min) 3.2 2.3 3.2 3.3
Solvent flow (ml/min) 15 20 15 15
Mixture flow (ml/min) 5 5 5 5
d

NS 53 37 40 38
te

EDC SFS 7 3 3 5
FS 24 20 18 17
R 3 2 2.5 3
p

mass fraction of binary feed 0.62/0.38 0.4309/0.5691 0.61/0.39 0.6771/0.3229

NS 17 12 11 18
ce

FS 10 5 5 10
SRDC R 3.5 2 1.5 2
Distillate flow (ml/min) 1.8 2.7 1.8 1.7
Ac

8 Table 5 The experimental results

Time extractive distillation column solvent regeneration column

14

Page 14 of 21
 hr DE(acetone) WE(acetone) DE(tetrahydrofuran) WE(tetrahydrofuran)
(wt%) (wt%) (wt%) (wt%)
1.0 99.020 0.017 99.20 0.45
2.0 99.050 0.020 99.17 0.53
3.0 99.040 0.017 99.22 0.51
4.0 99.035 0.019 99.19 0.48

t
extractive distillation column solvent regeneration column
Time

ip
DE(n-hexane) WE(n-hexane) DE(tetrahydrofuran) WE(tetrahydrofuran)
hr
(wt%) wt% wt% wt%

cr
1.0 99.02 0. 03 99.41 0.35
2.0 99.03 0.04 99.31 0.38
3.0 99.01 0.03 99.29 0.49

us
4.0 99.00 0.05 99.34 0.36
extractive distillation column solvent regeneration column
Time

an
DE(n-hexane) WE(n-hexane) DE(ethyl acetate) WE(ethyl acetate)
hr
wt% wt% wt% wt%
1.0 99.17 0.06 99.28 0.43
2.0 99.15 0.05 99.32 0.41
M
3.0 99.15 0.06 99.29 0.40
4.0 99.16 0.07 99.27 0.44
d

extractive distillation column solvent regeneration column

Time
DE(ethyl acetate) WE(ethyl acetate) DE(ethanol) WE(ethanol)
hr
te

wt% wt% wt% wt%

1.0 98.81 0.19 99.32 0.27
p

2.0 98.80 0.20 99.33 0.29

3.0 98.82 0.20 99.29 0.28
ce

4.0 98.81 0.19 99.29 0.27

1
Ac

15

Page 15 of 21
 1 Figure Captions

2 Fig.1 Aspen model of extractive distillation process

3 Fig.2. Vapor-liquid equilibrium of azeotropic mixtures

Fig.3 Pseudo-binary x-y plot for acetone-tetrahydrofuran with a solvent to feed volume ratio 3

t
4

ip
5 Fig.4 a.Pseudo-binary x-y plot for n-hexane-tetrahydrofuran with a solvent to feed volume ratio 3

cr
6 Fig.5 Pseudo-binary x-y plot for n-hexane-ethyl acetate with a solvent to feed volume ratio 3

us
7 Fig.6 Pseudo-binary x-y plot for ethyl acetate-ethanol with a solvent to feed volume ratio 3

an
8 Fig.7 The scheme of the experimental equipment
9
M
10

11
d

12
te

13

14
p

15
ce

EDC SRDC
Ac

MIXER
S D-LIGHT D-HEAVY
S+

W
COOLER

SR

16

17 Fig.1

16

Page 16 of 21
 1.0

0.9
acetone-tetrahydrofuran

0.8 n-hexane-tetrahydrofuran

0.7 n-hexane-ethyl acetate

0.6 ethyl acetate-ethanol

t
ip
0.5
y

0.4

cr
0.3

0.2

us
0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x

an
1

2 Fig.2
M
3

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0 1.0
d
Butyl ether
0.9 Xylene 0.9
te

0.8 1,3,5-trimethylbenzene 0.8

0.7 --1,4-diethylbenzene 0.7

yacetone

0.6 0.6

0.5 0.5
ce

0.4 0.4

0.3 0.3

0.2 0.2
Ac

0.1 0.1

0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

xacetone
4

5 Fig.3

17

Page 17 of 21
 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0 1.0

0.9 NMP 0.9

DMF
0.8 0.8
2-methylpyridine
0.7 3-methylpyridine 0.7

y(n-hexane
0.6 0.6

t
0.5 0.5

ip
0.4 0.4

0.3 0.3

cr
0.2 0.2

0.1 0.1

us
0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x(n-hexane
1

an
2 Fig.4

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0 1.0
M
NMP
0.9 0.9
2-methylpyridine
0.8 3-methylpyridine 0.8
pyrrole
0.7 0.7
d
y(n-hexane

0.6 0.6
te

0.5 0.5

0.4 0.4
p

0.3 0.3

0.2 0.2
ce

0.1 0.1

0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

x(n-hexane
Ac

4 Fig.5

18

Page 18 of 21
 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0 1.0
DMSO
0.9 0.9
DMF
0.8 0.8

y(ethyl acetate
NMP
0.7 0.7

0.6 0.6

t
0.5 0.5

ip
0.4 0.4

0.3 0.3

cr
0.2 0.2

0.1 0.1

us
0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

x(ethyl acetate
1

an
2 Fig.6
M
d
p te
ce
Ac

1-thermometer; 2-the exit of cooling water; 3-condenser; 4-the entrance of cooling

water;5-controller of reflux ratio; 6-valve; 7-light key component sample collection; 8-light key

19

Page 19 of 21
 component receiver; 9-storage tank of solvent; 10-constant flow pump; 11-storage tank of

mixture;12- sample of heavy key component and solvent collection; 13- solvent sample collection;

14-flask;15-heating jacket; 16-extractive distillation column; 17- heavy key component receiver;

18- heavy key component sample collection; 19-solvent recovery distillation column

t
ip
1 Fig.7

cr
2

us
4
5

an
M
d
p te
ce
Ac

20

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1 Highlights

2 1. Four azeotropic mixtures were separated successfully by extractive distillation.

3 2. Solvent selection was based on polarity principle and Aspen Plus simulation.

3. Simulation results were experimentally verified.

t
4

ip
5 4. An algorithm in developing new extractive distillation processes was proposed.

cr
6

us
an
M
d
p te
ce
Ac

21

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