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Study of The Effect of Operating Parameters On The Extractive Distillation of Isopropyl Alcohol-Water Mixture Using Dimethyl Sulphoxide As An Entrainer
Study of The Effect of Operating Parameters On The Extractive Distillation of Isopropyl Alcohol-Water Mixture Using Dimethyl Sulphoxide As An Entrainer
To cite this article: Pravin D. Ghuge, Nilesh A. Mali & Rajkumar S. Sirsam (2017): Study of
the Effect of Operating Parameters on the Extractive Distillation of Isopropyl Alcohol–Water
Mixture Using Dimethyl Sulphoxide as an Entrainer, Indian Chemical Engineer, DOI:
10.1080/00194506.2017.1322923
Download by: [The UC San Diego Library] Date: 09 May 2017, At: 21:11
INDIAN CHEMICAL ENGINEER © 2017 Indian Institute of Chemical Engineers
https://doi.org/10.1080/00194506.2017.1322923
Abstract: In this paper, the simulation analysis of separation of isopropyl alcohol (IPA)–water via
extractive distillation by using dimethyl sulphoxide as an entrainer is presented. The steady-state
simulation for this process was done using Aspen Plus simulator. The aim of this work is to study the
effect of various operating parameters such as number of stages, molar reflux ratio, binary feed stage
number, entrainer feed stage number, temperature of entrainer feed and entrainer to feed molar ratio
on the purity and energy consumption. The sensitivity of these parameters serves as a basis to choose
the optimum operating conditions to maximize the IPA purity and minimize the energy requirement.
In this analysis, among various operating parameters, those which directly affect the IPA purity and
the parameters which affect the reboiler duty, for the given separation task, are identified. Simulation
results with optimum operating conditions and their economic analysis are also presented.
1. Introduction
Distillation is one of the most useful separation technologies in chemical engineering. It is
based on relative volatility or boiling point difference of the components involved. However,
separation of components having a close boiling point or forming azeotrope is difficult by con-
ventional distillation. For such types of systems, advance distillation methods are used such as
pressure swing distillation (PSD), heterogeneous azeotropic distillation and extractive distilla-
tion [1].
2. Extractive Distillation
The term extractive distillation was introduced by Dunn et al. [13]. In extractive distillation, a
higher boiling separating agent (solvent or entrainer) is added, which alters the relative
g1 s
1,s P1 1 P1
s
a1
1,2 = 1 s = S12,s s ,
g2,s P2 P2
where,g1 1 s
i,s , S12,s and Pi are the activity coefficient, selectivity at infinite dilution and saturation
vapour pressure of component i, respectively. The activity coefficient of the component to be
separated should be altered by the entrainer to achieve relative volatility far from unity.
From the result presented in Table 2, it is clear that DMSO has the largest separation factor
as compared to other entrainers. So, it is better to use it for this separation task.
Residue curve map (RCM) is another useful tool to compare different separating agents in
azeotropic and extractive distillation. Isovolatility curve is the locus of point at which the rela-
tive volatility of the IPA and water is equal to one [16]. From the isovolatility curve in Fig. 2, it
was noticed that IPA comes out as distillate from the EDC because the isovolatility curve inter-
cepts the IPA–entrainer edge of triangle more closely to the pure IPA. Also, the RCM does not
exhibit any distillation boundary, which indicates that DMSO is a good entrainer.
A RCM for the IPA–water–DMSO system at different pressures was generated and it was
observed that there was not any significant effect on the RCM because there is no new
additional azeotrope formation or elimination with the pressure. Only the boiling temperature
of pure components and the azeotropic mixture changes with pressure. The azeotropic compo-
sition of the IPA–water mixture is not pressure sensitive. So, it will be better to run the column
at atmospheric pressure, which helps to use cheap cooling water in the condenser and medium
pressure steam in the reboiler as utility, since a high pressure column needs costly high pressure
steam and a low pressure column needs an expensive chilled cooling utility.
Table 2. Separation factors for various solvents for the IPA–water system
using the UNIFAC model [18]
Solvent Tb (K) α∞
1,2
Fig. 2. RCM and isovolatility curves for the IPA–water–DMSO system at 1 atm.
3.1 Effect of Number of Stages (NS) and Molar RR on Distillate IPA Mole Composition
(XD), Reboiler Duty (QR) and Condenser Duty (QC)
The specified purity for IPA was 99.999 mol% in distillate (XD), which could be achieved using
an RR value greater than 0.5. It was noticed that XD increases with an increase in NS. From
Fig. 4, it was observed that if NS is greater than 41, XD does not change significantly, so the
column should have 41 stages and can be operated at an RR between 0.5 and 0.7.
For a particular RR, QC and QR do not have compelling changes in different stage
numbers of the column (Fig. 5). The RR is an important operating parameter from the
Parameter Value
Feed flow rate (kmol/h) 100
Distillate flow rate (kmol/h) 50
Feed temperature (°C) 25
Mole fraction of binary feed:
IPA 0.5
Water 0.5
Pressure (atm) 1
Desired IPA purity in distillate (mol %) 99.999
energy consumption point of view because at a higher RR, QR and QC are higher. From Fig. 4
and Table 4, it was concluded that at an RR of 0.7, the energy consumption and XD require-
ments were satisfied. Further increase in the RR unnecessarily increases QR.
It was noticed from Fig. 6 that a maximum XD is obtained at a RR of 0.7 and beyond this
value, the increase in XD was negligible. Beyond a certain RR, XD shows a decreasing trend.
This happens because the vapour phase at the top of the column is IPA-rich, and when it is con-
densed and refluxed back to the column, it dilutes the liquid phase which should be solvent-
rich. This dilution makes the entrainer less effective, so XD decreases.
There is a very interesting effect of RR on the curves obtained in Fig. 6. This type of be-
haviour is not seen in regular distillation in which an increasing RR always increases
product purity. If too little reflux is used, more heavy solvent goes overhead and lowers
purity. If too much reflux is used, the IPA-rich reflux dilutes the concentration of DMSO
inside the column, which lets more water go to the distillate.
3.2 Effect of Binary Feed Stage Number (NBF) and Molar RR on XD, QC and QR
It can be seen from Fig. 7 that at RR greater than 0.5, a greater purity of the distillate was
obtained and XD reached a specified value, when the binary mixture is fed between stages 33
and 36. As NBF was moved from the bottom to the top of the column, XD goes through a
Table 4. IPA mole composition at RR = 0.5–1 (NBF = 33, NEF = 6, TEF = 75°C, E/F = 1)
Fig. 4. Effect of NS and RR on XD (NBF = 33, NEF = 6, TEF = 75°C, E/F = 1, RR = 0.3–1).
Fig. 5. Effect of NS and RR on (a) QR, (b) QC (NBF = 33, NEF = 6, TEF = 75°C, E/F = 1, RR = 0.5–1).
Fig. 6. Effect of RR on XD, QC and QR (NS = 41, NBF = 33, NEF = 6, TEF = 75°C, E/F = 1.0).
maximum. Increase in contact time between the binary feed mixture and entrainer leads to
increase in purity. However, if the feed stage is very close to the bottom, number of stages in
the stripping section would not be sufficient to strip IPA in the mixture, so the IPA concen-
tration in the bottom product will increase. Consequently, XD will also decrease.
From Fig. 8, as the RR is kept constant, QC and QR do not change significantly with the
change in NBF. Hence, an appropriate NBF is at 33 at which the highest XD was achieved. It
ensures sufficient contact time between the binary feed mixture and the entrainer. It was also
observed that the QR was greater than the QC. These increased energy consumption because
of the sub-cooled binary mixture.
3.3 Effect of Entrainer Feed Stage Number (NEF) and Molar RR on XD, QC and QR
It was noticed from Fig. 9 that XD was higher at a higher RR, but it must be optimum to reduce
energy consumption during the operation. At a RR of 0.7, XD reached the required compo-
sition. Further increase in the RR does not significantly increase XD, as shown in Fig. 9. There-
fore, RR of 0.7 was chosen as the optimum value. As NEF approaches the bottom from the top,
XD rises to maximum and then decreases. This is because, as the contact time between the
binary feed mixture and the entrainer decreases, XD decreases. However, when NEF is very
close to the top of the column, the up-going flow of vapour drags the entrainer into the distil-
late; this decreases XD.
INDIAN CHEMICAL ENGINEER 2017
Study of Effect of Operating Parameters on the Extractive Distillation of Isopropyl Alcohol–
Water Mixture 9
Fig. 7. Effect of NBF and RR on XD (NS = 41, NEF = 6, TEF = 75°C, E/F = 1, RR = 0.3–1.0).
The interaction between the entrainer and the binary feed mixture components occurs
mainly in the liquid phase. It may be assumed that the entrainer exists in the liquid phase
(as it is less volatile) at all stages below NEF. Thus, interaction between an entrainer and
mixture components occurs only when the entrainer is fed from the top stage of a column;
hence, NEF should be located near the top of the column to improve the purity of the distillate.
From the above results, stage 6 was found to be the optimum at which the highest XD was
obtained. From Fig. 10, when the RR was kept constant, QC and QR did not change much
with the change in NEF. Hence, NEF was taken at stage 6 at which the highest XD was obtained,
ensuring sufficient interaction between the entrainer and the binary feed mixture.
3.4 Effect of Entrainer to Feed Molar Ratio (E/F) and RR on XD, QC and QR
It was observed from Fig. 11 that at a higher value of RR and E/F, XD was greater. This is
because at a higher value of E/F, dilution of the entrainer caused by the reflux is less, which
increases the distillate purity. At an E/F of 1.0 or higher, the XD remained constant, as
shown in Fig. 10. For all evaluated E/F, QC did not change significantly, while QR changed sig-
nificantly, as shown in Fig. 12. At higher values of E/F, larger volumes of liquid are required to
vaporize in the reboiler, which leads to an increased QR. An optimal value could be 1.0 because
at this value, QR is minimum with a desired XD.
INDIAN CHEMICAL ENGINEER 2017
10 GHUGE ET AL.
Fig. 8. Effect NBF on XD, QC and QR (NS = 41, NEF = 6, TEF = 75°C, RR = 0.7, E/F = 1.0).
E/F has a direct impact on XD; with an increase in E/F, greater enhancement in XD was
achieved, without appreciably affecting QC. At a specified RR and E/F in the range of 0.6–
1.0, the energy consumption increased slightly, but XD increased significantly, as shown in
Fig. 12. An RR of 0.7 was found to be optimum to meet XD while maintaining the E/F constant
at 1. This indicates that the RR must have the lowest value so E/F can achieve the desired dis-
tillate composition to minimize energy consumption; a higher value of E/F would unnecessarily
increase the QR of the recovery column.
3.5 Effect of Temperature of Entrainer Feed (TEF) and RR on XD, QC and QR.
From Fig. 13, it was learnt that a higher temperature of the entrainer feed demands a higher
RR to reach the specified XD. This arises because at a higher TEF, part of the water available
at the stage vaporizes, and ultimately the content of water in the distillate increases and its
purity decreases. Thus, a higher value of RR is necessary to compensate this effect. But, it
should be recalled that a higher RR leads to a greater energy demand. From Fig. 14, it can
be observed that at a temperature below 70°C, the purity matches with a specified value but
requires a higher QR. Conversely, if the entrainer is fed at a higher temperature, XD decreases,
and the XD curve drops down suddenly after 80°C.
INDIAN CHEMICAL ENGINEER 2017
Study of Effect of Operating Parameters on the Extractive Distillation of Isopropyl Alcohol–
Water Mixture 11
Fig. 9. Effect of NEF and RR on XD (NS = 41, NBF = 33, TEF = 75°C, E/F = 1, RR = 0.5–1).
Conclusively, at low reflux, TEF should be between 70 and 80°C to keep XD at the desired
value with lower energy consumption; this was found to be consistent with the value rec-
ommended by other authors [2,17]. They recommended that TEF should be about 5–15°C
below the top temperature of the EDC.
At a specified RR, for variation in TEF, in the range of 20–100°C, there was no considerable
effect on XD and QC, as shown in Fig. 14. Nevertheless, QR was significantly affected by TEF.
QR increases with a decrease in TEF because if the entrainer is fed at lower temperatures, more
energy will be consumed to vaporize it. In the case of a higher TEF, the amount of IPA conden-
sing to the liquid phase reduces and the liquid flow rate to the bottom is lower as compared to
that of the entrainer feed at a lower temperature, which leads to a lower QR. Taking into
account overall effect, in this case TEF should be at 75°C at which a higher XD can be achieved
with reasonable energy consumption. Using the information obtained from the sensitivity
analysis results, the best operating conditions for the EDC are as listed in Table 5. These
results were used for the complete simulation of the extractive distillation process explained
in the next section.
Fig. 10. Effect of NEF on XD, QC and QR (NS = 41, NBF = 33, TEF = 75°C, RR = 0.7, E/F = 1).
4. Simulation Results
The SRDC design was initially performed by a shortcut column model of ASPEN simulator
known as DSTWU to generate initial guesses for a rigorous simulation model (RadFrac),
which was then optimized to establish the molar RR, feed stage, number of stages and distillate
molar flow (kmol/h). The operating parameters for the SRDC are listed in Table 6. Optimiz-
ation was carried out individually for both the columns to avoid convergence problem in simu-
lation. It was carried out iteratively as if both the columns were simulated simultaneously.
Parameter Value
Number of stages 41
Binary feed stage number 33
Entrainer feed stage 6
Molar RR 0.7
Entrainer to feed molar ratio 1
Temperature of entrainer feed (°C) 75
Fig. 11. Effect of E/F and RR on XD (NS = 41, NBF = 33, NEF = 6, TEF = 75°C, RR = 0.5–1).
In the case of the EDC, the solvent feed stream was assumed to have same parameters such
as recycle stream from the SRDC. Similarly, in the case of the SRDC, the column feed stream
was assumed to have same parameters like the bottom stream from the EDC. After optimizing
individual columns, the simulation was run with the recycle stream connected, in which stream
parameters of the recycle solvent stream and SRDC feed matched the assumed parameters
during individual column optimization. Hence, there is negligible possibility to miss the inter-
action among columns and operating parameters.
Fig. 15, Tables 7 and 8 show the inlet feed streams’ specifications and configuration for the
extractive and recovery columns, respectively. The simulation results indicate that the IPA mole
composition in the distillate of the EDC is 0.99999 (Table 9), where as the water mole compo-
sition in the distillate of the SRDC is 0.9999. The energy consumption in the extractive and
recovery columns is presented in Table 10.
5. Economical Analysis
The economics of the extractive distillation system was evaluated in terms of TAC. Table 11
summarizes the basis of economics and equipment sizing relationships used, which were
INDIAN CHEMICAL ENGINEER 2017
14 GHUGE ET AL.
Fig. 12. Effect of E/F on XD, QC and QR (NS = 41, NBF = 33, NEF = 6, TEF = 75°C, RR = 0.7).
proposed by Luyben [12]. Table 12 gives the TAC of the two-column extractive distillation
sequence. Total capital investment was estimated to be $0.6106 × 106. Annual energy cost
obtained is 0.6969 × 106 $/y, using medium pressure steam in the reboiler of the EDC and
high pressure steam in the reboiler of the SRDC.
6. Process Comparison
Arifin and Chien [19] reported an overall process design for IPA–water separation by using
cyclohexane as the entrainer. Since the feed rate, composition and columns used in the
Parameter Value
Number of stages 20
Distillate mole flow (kmol/h) 50
Feed stage 7
Reflux ratio 0.4
Bottom temperature (°C) 190
Distillate temperature (°C) 100
Fig. 13. Effect of TEF and RR on XD (NS = 41, NBF = 33, NEF = 6, E/F = 1, RR = 0.5–1)
present study are the same as that of their design, direct comparison was made in terms of
heating duty and TAC. From Table 13, it was found that even though the number of stages
required is more, the TAC is lower in the DMSO case due to lower operating cost as compared
to using cyclohexane. The TAC of the overall process with DMSO as an entrainer is 0.9004 ×
Fig. 14. Effect of TEF on XD, QC and QR (NS = 41, NBF = 33, NEF = 6, RR = 0.7, E/F = 1)
Fig. 15. Process flow diagram for extractive distillation of IPA–water using DMSO as solvent.
106 $/y and total reboiler duty is 2473.88 kW, while the TAC and reboiler duties of the overall
process using cyclohexane as an entrainer are 1.2796 × 106 $/y and 6586.21 kW, respectively. It
means the overall TAC and reboiler duty required in the DMSO case are 29.63% and 62.43%
less, respectively, as compared to the Arifin and Chien [19] design.
Number of stages 41 20
Feed stage 33 7
Entrainer feed stage 6 –
Molar RR 0.7 0.4
Condenser Total Total
Pressure (atm) 1 1
Distillate flow (kmol/h) 50 50
Table 9. Simulation results for extractive distillation of IPA–water using DMSO as solvent
EDC SRDC
QC (kW) −883.47 −829.97
QR (kW) 1412.80 1061.08
Qcooler (kW) −510.13
7. Conclusions
In this simulation work, optimum operating conditions for the separation of the IPA–water
mixture by extractive distillation using DMSO as an entrainer were worked out. RCM and iso-
volatility curves were used for designing the distillation sequence in the extractive distillation
process. Sensitivity analysis was executed for the EDC to understand the relationship
between various operating parameters. The effects of E/F, molar RR, binary feed stage, entrai-
ner feed stage and feed temperature of the entrainer feed were studied to obtain the best design
of extractive distillation with minimum energy requirement. The economic analysis of the
process was done in terms of TAC, which was found to be reasonable.
The TAC of the overall process obtained in this study is 0.9004 × 106 $/y and the total
reboiler duty is 2473.88 kW. The overall TAC and reboiler duty required in the DMSO case
are 29.63% and 62.43% less, respectively, as compared to the Arifin and Chien [19] design
for the separation of an equimolar IPA–water mixture.
EDC SRDC
NT 41 20
D (m) 0.76 0.81
H (m) 28.53 13.17
Qr (MW) 1.4129 1.0611
Ar (m2) 61.62 29.60
Qc (MW) 0.8835 0.8300
Ac (m2) 25.80 16.75
Qcooler (MW) 0.51 –
Acooler(m2) 7.77 –
Total H.E. cost (106 $) 0.1943 0.1116
Column shell cost (106 $) 0.1935 0.1114
Total capital (106 $) 0.3877 0.2229
Cost of energy ($/GJ) 8.22 9.88
Operating cost (106 $/y) 0.3663 0.3306
payback period (y) 3 3
TAC (106 $/y) 0.4955 0.4049
Total capital cost (106 $) 0.6106
Total operating cost (106 $/y) 0.6969
Total TAC (106 $/y) 0.9004
Among the various operating variables studied, the number of stages, binary feed stage
number and entrainer feed stage number were found to have a direct effect on the distillate
IPA mole fraction, as it varies the contact time between the entrainer and the binary feed
mixture. Molar RR, temperature of the entrainer feed and entrainer to feed molar ratio
were found to affect directly the energy consumption of the column significantly.
Nomenclature
IPA isopropyl alcohol
DMSO dimethyl sulphoxide
TAC total annual cost
NRTL non-random two liquids
RCM residue curve map
NS number of stages
RR reflux ratio
NBF binary feed stage number
NEF entrainer feed stage number
TEF temperature of entrainer feed
E/F entrainer to feed molar ratio
XD distillate IPA mole composition
QR reboiler duty
QC condenser duty
EDC extractive distillation column
SRDC solvent recovery distillation column
D column diameter
INDIAN CHEMICAL ENGINEER 2017
20 GHUGE ET AL.
H column height
Ac condenser area
Ar reboiler area
Uc condenser heat transfer coefficient
Ur reboiler heat transfer coefficient
g1
i,s activity coefficient at infinite dilution
1
S12,s selectivity at infinite dilution
Psi saturation vapour pressure of component i
Acknowledgements
The authors are thankful to the Council for Scientific and Industrial Research (CSIR), India, for support-
ing the present work.
Disclosure statement
No potential conflict of interest was reported by the authors.
ORCID
Nilesh A. Mali http://orcid.org/0000-0001-6832-9230
References
[1] Luyben, W.L. and Chien, I.L., Design and Control of Distillation Systems for Separating
Azeotropes, John Wiley & Sons, New York (2011).
[2] Doherty, M.F. and Malone, M.F., Conceptual Design of Distillation Systems, McGraw-Hill,
New York (2001).
[3] Chien, I.L., Zeng, K.L. and Chao, H.Y., “Design and Control of a Complete Heterogeneous
Azeotropic Distillation Column System”, Ind. Eng. Chem. Res., 43, pp. 2160–2174 (2004).
[4] Cho, J. and Jeon, J.K., “Optimization Study on the Azeotropic Distillation Process for Isopropyl
Alcohol Dehydration”, Korean J. Chem. Eng., 23, pp. 1–7 (2006).
[5] Widagdo, S. and Seider, W.D., “Journal Review. Azeotropic Distillation”, AIChE J, 42, pp. 96–130
(1996).
[6] Lei, Z., Li, C. and Chen, B., “Extractive Distillation: A Review”, Sep. Pur. Rev., 32, pp. 121–213
(2003).
[7] Sommer, S. and Melin, T., “Design and Optimization of Hybrid Separation Processes for the
Dehydration of 2-Propanol and Other Organics”, Ind. Eng. Chem. Res., 43, pp. 5248–5259 (2004).
[8] Luyben, W.L., “Plant Wide Control of an Isopropyl Alcohol Dehydration Process”, AIChE J., 52,
pp. 2290–2296 (2006).
[9] Yao, J.Y, Lin, S.Y. and Chien, I.L., “Operation and Control of Batch Extractive Distillation for the
Separation of Mixtures with Minimum-boiling Azeotrope”, J. Chin. Inst. Chem. Eng., 38, pp. 371–
383 (2007).
[10] Knapp, J.P. and Doherty, M.F., “Thermal Integration of Homogeneous Azeotropic Distillation
Sequences”, AIChE J., 36, pp. 969–984 (1990).