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Research Article

Received: 29 March 2014 Revised: 29 May 2014 Accepted article published: 5 June 2014 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.4452

Extractive distillation and pressure-swing


distillation for THF/ethanol separation
Yinglong Wang,* Peizhe Cui, Yuhong Ma and Zhen Zhang

Abstract
BACKGROUND: During the synthesis of a liquid crystal monomer, an effluent including tetrahydrofuran(THF) and ethanol is
produced. Since THF and ethanol are both important solvents used in the chemical industry, it is necessary to separate the
mixture of THF and ethanol for reuse. However, it is hard to effectively separate the mixture via simple distillation because a
minimum azeotrope is formed in the binary system.

RESULT: Extractive distillation and pressure-swing distillation are adopted to separate the mixture and carefully optimized to
achieve minimization of the total annual cost (TAC). A comparison between the two processes is carried out. Pressure-swing
distillation is used to separate mixtures of THF and ethanol with various compositions.

CONCLUSION: The results indicate that pressure-swing distillation performs better than extractive distillation from the
standpoint of both economic considerations and product purity. The feasible sequence of high and low pressure of two columns
in a pressure-swing distillation is related to the feed composition.
© 2014 Society of Chemical Industry

Keywords: THF; ethanol; extractive distillation; pressure-swing distillation; economic analysis

NOTATION to the formation of a minimum-boiling azeotrope in the binary


A heat transfer area of heat exchanger (m2 ) system, making it hard to separate the mixture. To date, many tech-
B bottom stream flow rate (kmol h−1) niques have been used for separating azeotropics, such as simple
D distillate flow rate (kmol h−1 ) distillation, pervaporation, extractive distillation, pressure-swing
ID diameter of the column (m) distillation, etc.1 All of them have advantages and disadvantages.
K heat transfer coefficient (kW/(K · m2 )) Simple distillation based on the difference in the volatility of each
L length of the vessel (m) component is unable to accomplish effective separation. The per-
NT number of stages vaporation technique usually uses a membrane for azeotrope
Q heat duty of the condenser (kW) separation, which has the advantage of low energy consump-
RR reflux ratio tion compared with conventional distillation technology.2 – 5 How-
S/F solvent-to-feed ratio ever, the technique requires a balance between permeability and
TAC total annual cost ($/y; 106 $/y) selectivity of solvent molecules, which limits the wide application
xD composition of the distillate of membrane technology. To our knowledge, the pervaporation
xB composition of the bottom stream membrane has not been reported as being used in an industrial
application for THF–ethanol separation until now. So only extrac-
tive distillation and pressure-swing distillation is studied in this
Index present work.
1, 2 column index Extractive distillation was first proposed in the 1930s,6 and
co cooler has been widely used in industrial processes during recent
C condenser decades.7 – 17 Recently, using ionic liquids or hyperbranched poly-
R reboiler mers as entrainers has become a cutting-edge topic18 – 22 and
dividing wall column systems have been implemented for extrac-
tive distillation.23 – 26 Generally, the solvent with highest boiling
INTRODUCTION point is added into the first extraction column near the top, aiming
During the synthesis of a liquid crystal monomer, an effluent
that contains THF and ethanol is produced. It is well known that
∗ Correspondence to: Y. Wang, College of Chemical Engineering, Qing-
THF and ethanol are widely used as organic solvents in chemical
and pharmaceutical industries. Therefore, it is necessary to sepa- dao University of Science and Technology, Qingdao 266042, China.
E-mail: yinglongw@126.com
rate and reuse THF and ethanol, which is also beneficial for envi-
ronmental protection and resource conservation. However, the College of Chemical Engineering, Qingdao University of Science and Techno-
mutual exclusion between THF and ethanol molecules can lead logy, Qingdao 266042, China

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www.soci.org Y Wang et al.

first extraction column. It should be pointed out that one of the


most disadvantageous features of extractive distillation is that in
addition to binary feed components, another solvent component
is introduced as an impurity in the bottom products. Taking green
chemistry principles into account, additional solvents should be
avoided as much as possible in chemical distillation processes. It is
noted that pressure-swing distillation seems to be more attractive
than extractive distillation because additional solvent is avoided.
Efficient separation is achieved by two columns operating at two
different pressures, which are determined by the variation in
composition of the azeotrope at different pressures.27 – 33 For the
minimum azeotrope, the distillate strean from the first column
enters the second column, while high-purity product streams are
obtained from the bottom of the columns.
It is realized that for separating azeotropic mixtures, extrac-
tive distillation and pressure-swing distillation are comparable
Figure 1. Effect of pressure on azeotrope composition and temperature. to some extent, and are widely applicable in many chemical
processes.34 – 41 For example, Luyben investigated the sepa-
ration of acetone–methanol36,38 and acetone–chloroform41
mixtures via extractive distillation and pressure-swing distillation,
where acetone–methanol is the minimum azeotrope, whereas
acetone–chloroform is the maximum azeotrope. Muñoz et al.
studied the separation of isobutyl alcohol and isobutyl acetate
through extractive distillation and pressure-swing distillation.35
Lladosa et al.37 found that pressure-swing distillation was more
attractive than extractive distillation for the separation of
di-n-propyl ether and n-propyl alcohol. Wang et al. designed and
controlled a distillation system for methylal/methanol separation
using extractive distillation and pressure-swing distillation.39,40
Through these studies, many improvements have been made in
extractive distillation and pressure-swing distillation, which will
contribute to achieving high efficiency and low cost. To date, the
separation of THF and ethanol via extractive distillation has only
been investigated by Huang,42 but the corresponding flowsheet
was not optimized, and pressure-swing distillation is also not
available in the literature. Separation of THF/ethanol azeotrope is
investigated via extractive distillation and pressure-swing distil-
lation, in which operating parameters are carefully optimized to
achieve minimization of the total annual cost (TAC).
Figure 1 shows the effect of pressure on azeotrope composition
and temperature, and Figs 2 and 3 display the Txy and xy diagrams
of THF–ethanol azeotrope at different pressures. It can be seen

Figure 2. Txy diagram of THF/ethanol azeotrope at 1 atm and 10 atm.

at altering the relative volatility of the binary components. One


component traveling overhead becomes a distillate stream with
high purity, while the other component, along with the solvent
leaving from the bottom of the extraction column, goes to the sec-
ond recovery column as the feed stream. In the recovery column,
a high-purity stream is produced at the top, and the bottom prod-
uct contains the high-purity solvent which is recycled back to the Figure 3. xy diagram of THF/ethanol azeotrope at 1 atm and 10 atm.

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Table 1. UNIQUAC parameters

UNIQUAC parameter

Ethanol Aij Bij Cij Dij Tlower (K) Eij


(i) 1.6 −442.92 0.0 0.0 301.55 0.0
THF Aji Bji Cji Dji Tupper Eji
(j) −1.8 381.99 0.0 0.0 351.55 0.0

that at 1 atm, the content of THF in the azeotrope is 85.82 mol%


THF, while it becomes 25.67 mol% THF at 10 atm, suggesting that
pressure-swing distillation is economically feasible in the binary
system.
Aspen Plus was adopted as the process simulator for the flow
sheets based on the UNIQUAC physical property. The UNIQUAC
parameters used are shown in Table 1. The economics analyses
were evaluated in terms of TAC, which was defined as the sum of
the operating cost and the capital investment. For the former, it Figure 4. Effect of RR1 and S/F ratio on ethanol content in distillate product
in extraction column.
represents the annual energy cost, while the latter is the annual
capital cost that is equal to the total capital investment divided by
a 3-year payback period.41
The major devices in a distillation system are the column vessel
and the two heat exchangers (i.e. reboiler and condenser). In the
design process, the height of a column is 20% larger than the
height required for the trays. Therefore, the formula to calculate
the length of the vessel (L) is L = 1.2 × 0.61 × (NT − 2), where 1.2
represents an additional 20% larger in height, 0.61 stands for the
typical distance between the trays with units of meter, NT − 2 is

Table 2. Basis of economics and equipment sizing

Column diameter: aspen tray sizing

Length: L = 1.2 × 0.61 × (NT − 2)


Vessel (diameter and length in meters)
Capital cost = 17 640 (ID)1.066 (L)0.802
Condensers (area in m2 )
Heat-transfer coefficient (KC ) = 0.852 kW/(K · m2 )
Differential temperature (ΔT C ) = reflux-drum temperature – 310 K Figure 5. Effect of solvent flow rate on energy consumption.
QC
AC = K ×ΔT
C C
Capital cost = 7296 (AC )0.65
Reboilers (area in m2 )
Heat-transfer coefficient (KR ) = 0.568 kW/(K · m2 )
Differential temperature (ΔT R ) = steam temperature – base
temperature
QR
AR = K ×ΔT
R R
Capital cost = 7296 (AR )0.65
Solvent cooler (area in m2 )
Heat-transfer coefficient (Kco ) = 0.852 kW/(K · m2 )
Log-mean differential temperature (ΔT co )
=process temperatures at inlet and outlet of cooler – 310 K
Qco
Aco = K ×ΔT
co co
Capital cost = 7296 (Aco )0.65
Energy cost
LP steam (433 K) = $7.72 per GJ
MP steam (457 K) = $8.22per GJ
HP steam (537 K) = $9.88 per GJ
TAC = total capital cos t
payback period
+ anual energy cos t
Figure 6. Economics for different NT in extraction column.
Payback period = 3 years

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Figure 7. Flowsheet of extractive distillation.

the number of trays (in Aspen Plus, the first and the last stages
Table 3. Impact of pressure on the boiling point of the pure
are the reflux drum and reboiler, respectively). The diameter of a component
column is determined by the ‘Tray Sizing’ function in Aspen Plus,
and ‘sieve tray’ was used. The cost of the pump is not included Boiling point (K)
in the capital cost because it is much smaller than the main Pressure (atm) THF Ethanol
distillation equipment cost. The basis of the economics, the sizing
relationships and parameters are listed in Table 2. The operating 1 339.12 351.46
time of the distillation system is set at 8000 h per year. 8 421.46 415.87
9 427.55 420.35
10 433.12 424.53
EXTRACTIVE DISTILLATION 12 443.16 435.28
For the extractive distillation system, there are two significant 13 447.72 428.37
design optimization variables, i.e. the solvent-to-feed ratio and
the reflux ratio (RR) after the solvent is selected. The extractive
distillation was investigated in the following order. In the extraction column, the distillate product is THF with a purity
of 99.9 mol %, and the bottom stream mainly contains ethanol
and ethylene glycol with a THF concentration ≤ 0.1 mol %. In the
Selection of solvent recovery column, the efficient separation of ethanol and ethylene
The separation of THF and ethanol was studied via extractive glycol is achieved and ethanol as the distillate product with a
distillation by Huang.42 In his study, the effect of different organic content of 99.9 mol % leaves the column from the top and the
solvents, such as ethylene glycol, dimethylformamide (DMF), bottom stream consists of almost pure ethylene glycol with a trace
dimethyl sulfoxide (DMSO) and N-methyl pyrrolidone, on the rel- amount of ethanol and THF.
ative volatility of THF and ethanol was investigated in detail. The
results showed that ethylene glycol is a suitable solvent for sepa-
Optimization of solvent flow rate
rating THF and ethanol. However, the flowsheet he provided was
Separation depends on the solvent flow rate in the extraction
not optimized to minimize the TAC of the process. In this work, the
column. It can be seen from Fig. 4 that with the same RR, the purity
extractive distillation process is optimized when ethylene glycol is
of the distillate product (THF) increases with an increasing amount
used as the solvent.
of solvent. For different solvent flow rates, the impurity content
displayed a trend of first declining and then rising with increasing
Design requirements RR, indicating that a lowest impurity content of the product can be
The flow rate of the mixture is 100 kmol h−1 , with content of 50 mol obtained. To achieve the desired distillate purity of 99.9 mol % THF,
% THF and 50 mol % ethanol. The initial stage numbers in the the minimum solvent-to-feed ratio is 2.09, and the corresponding
extraction and recovery columns are set at 55 and 10, respectively. solvent flow rate is 209 kmol h−1 .

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Figure 8. Effect of flow rate D2 (kmol h−1 ) and RRs on TAC.

Energy costs accounted for a large proportion of TAC. In this


work, the relationship between the reboiler heat duties and
the solvent flow rate has been studied in order to minimize
the energy cost (Fig. 5). The reboiler heat duty of the extrac-
tion column first decreases and then levels off as the solvent
flow rate is increased, whereas the recovery column continuously
increases. The optimum results indicate that when the solvent
flow rate is set at 225 kmol h−1 the total energy consumption is
minimized.

Optimization of NT in extraction column


It is clear that economical optimization should be focused on
the extraction column because separation in the solvent recovery
column is very easy. Adding more trays to the recovery column
can slightly reduce the energy consumption but increases the
capital cost, which is not effective for minimizing TAC. However,
the appropriate addition of trays in the extraction column can
achieve an obvious reduction in the energy cost, thus leading to
Figure 9. Effect of different NT s in two columns on TAC.
a minimum TAC. Herein, various column configurations (45, 55, 65,
70, 75, 80, 85 stages in the extraction column and 10 stages in the
recovery column) have been studied according to the procedures columns. The TAC calculated for the extractive distillation is $1 142
mentioned above, and the corresponding TAC values have also 600 which is much smaller than that reported by Huang.42
been calculated to explore the optimized conditions for achieving
the most economical extractive distillation. The annual capital
cost increases with the addition of trays in the extraction column, PRESSURE-SWING DISTILLATION
but the annual energy cost is gradually decreased, leading to a In comparison with extractive distillation, pressure-swing distilla-
non-monotonic effect of NT on TAC (Fig. 6). Among the different tion is adopted for separating the mixture of THF and ethanol with
stages in the extraction column, it was found that using 75 stages the same composition. The purity of the THF product stream is set
achieved the minimum TAC. at 99.9 mol %, which is equal to that of extractive distillation. Ini-
tially, using 35 stages is selected in both columns. The feed mixture
is added into the low-pressure column. The high-purity ethanol
Optimized process flowsheet product leaves the column from the bottom, while the distillate
Figure 7 shows the flowsheet and stream information of the opti- stream enters into the high-pressure column where the bottom
mized extractive distillation. Low-pressure steam is used in the stream is high-purity THF and the distillate stream recycles back to
extraction column, and high-pressure steam is used in the recov- the low-pressure column. The feed streams enter into the columns
ery column because of the temperatures of the reboilers in the two at the stage of which its composition is close to feed composition.

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Table 4. Effect of different NT1 –NT2 -stage column configurations

Item Unit 35-25-stage 35-35-stage 35-45-stage 35-55-stage

QC1 kW 2079 2002 2070 1996


QR1 kW 2053 1945 2012 1949
QC2 kW 1636 1004 900 963
QR2 kW 1951 1350 1246 1298
AC1 m2 85 82 85 82
AR1 m2 44 42 43 42
AC2 m2 17 10 9 10
AR2 m2 144 99 92 96
ID1 m 1.27 1.24 1.22 1.20
ID2 m 0.98 0.82 0.75 0.77
RR1 2.21 1.8 1.9 1.88
RR2 7.7 3.16 2.75 3.3
D2 kmol h−1 25 32.5 32.5 30
Total capital 106 $ 0.9062 0.8570 0.8718 0.9095
Energy cost 106 $ y−1 0.9219 0.7555 0.7425 0.7441
TAC 106 $ y−1 1.224 1.041 1.033 1.047
Item Unit 25-45-stage 35-45-stage 45-45-stage 55-45-stage
QC1 kW 2078 2002 1921 1905
QR1 kW 2022 1945 1873 1848
QC2 kW 1062 1004 878 909
QR2 kW 1407 1350 1214 1255
AC1 m2 85 82 79 78
AR1 m2 44 42 40 40
AC2 m2 11 10 9 9
AR2 m2 103 99 89 92
ID1 M 1.26 1.24 1.22 1.21
ID2 M 0.83 0.82 0.78 0.79
RR1 1.9 1.8 1.78 1.67
RR2 3.37 3.16 2.96 2.79
D2 kmol h−1 22.5 32.5 30.0 32.5
Total capital 106 $ 0.8480 0.8570 0.9310 0.9976
Energy cost 106 $ y−1 0.7860 0.7555 0.7040 0.7112
TAC 106 $ y−1 1.069 1.041 1.014 1.043

Selection of pressure design distillate composition x D1 is set as 83.82 mol % THF, while
The composition of the azeotrope changes significantly with the azeotrope contains 25.67 mol % THF at 10 atm and the design
pressure. The larger the composition changes, the smaller the distillate composition x D2 is set as 27.67 mol % THF. The desired
recycle flow rate and the energy consumption in the two reboilers compositions of the two product streams are x B1 = 99.9 mol %
become, suggesting that it is appropriate to select a higher pres- ethanol and x B2 = 99.9 mol % THF, respectively. The flow rates of
sure in the high-pressure column.32 However, the pressure should the two distillate streams, D1 = 64.3 kmol h−1 and D2 = 14.3 kmol
not be higher than that is compatible with heating steam. The h−1 , are calculated by the mass balance in the two columns. The
impact of pressure on the boiling point of the two components is obtained results are used as the initial values for the operating
shown in Table 3. Therefore, a medium-pressure stream of 10 atm is specifications in Aspen Plus. However, the corresponding TAC
selected in the high-pressure column for which the minimum tem- values are large, which requires us to find the optimal distillate flow
perature difference required in the reboiler is 20 K, which can sig- rates and the corresponding RRs to minimize the TAC.
nificantly reduce the energy costs. In addition, low-pressure steam
was used in the low-pressure column which is operated at 1 atm. Optimum distillate flow rates and RRs
When the distillate flow rate in the high-pressure column is 14.3
Calculation of distillate flow rates kmol h−1 , the RR value in the high-pressure column is so large
Empirically, the overhead distillate composition from the low- that it leads to an excessive energy cost when the desired purity
pressure column is slightly lower than that of the low-pressure is achieved. Therefore, the distillate flow rate D2 and the RRs in the
azeotrope, whereas the composition in the high-pressure column two columns are varied to find values that minimize the TAC on
is slightly higher than that of the high-pressure azeotrop.30 In the the premise that the desired purities are achieved. Figure 8 shows
literature, most design values for the composition of the distillate the effect of the RR pairs in the two columns on the TAC for each
streams are ∼2 mol % different from the corresponding minimum D2 flow rate. The minimum TAC is achieved at the 35-35-stage
azeotropic composition.33 For the mixture of THF and ethanol when the D2 flow rate is 32.5 kmol h−1 , RR1 is 1.80 and RR2
system, the azeotrope contains 85.82 mol % THF at 1 atm and the is 3.16. The corresponding content of THF in D2 is 51.4 mol %,

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Figure 10. Flowsheet of pressure-swing distillation for feed composition of 50 mol % THF.

which is significantly different from the above empirical value.


Figure 3 shows that the relative volatility is nearly equal to 1 Table 5. Design parameters and economics for extractive distillation
when the THF content ranges from 0 mol % THF to approximately and pressure-swing distillation
35.0 mol % at 10 atm, which makes the separation very difficult. To Extractive Pressure-swing
reduce the separation costs, the distillate flow rate D2 should be distillation distillation
increased, thus resulting in an increase in THF content.
C1 Diameter (m) 1.15 1.22
Stages 75 45
Optimum of NT s in the two columns
QC (kW) 1514 1920
The xy diagram shows that the 10 atm curve is close to the 45∘ line,
indicating difficult separation in the high-pressure column. The AC (m2 ) 61 79
optimization of NT in the high-pressure column is performed first. QR (kW) 1937 1873
When NT1 is temporarily fixed at 35, NT2 is varied from 25 to 55. The AR (m2 ) 52 41
flowsheets of the various column configurations are all optimized QCooler (kW) 1150 _
according to the procedures for the 35-35-stage case mentioned ACooler (m2 ) 29 _
above. Figure 9 shows the TAC for the 35–25, 35–35, 35–45 and Shell cost (106 $) 0.5004 0.3458
35-55-stage cases. It can be seen that the TAC reaches a minimum Heat exchanger cost 0.2652 0.2055
value when NT is 45 in the high-pressure column. When NT2 is fixed (106 $)
at 45, NT1 is varied from 25 to 55. Similar optimization procedures Capital (106 $) 0.7656 0.5597
are applied, and the global minimum TAC value is obtained for the Energy cost 0.4307 0.4165
case of 45-45-stage (Fig. 9). Detailed information can be found in (106 $ y−1 )
Table 4. C2 Diameter (m) 0.80 0.77
Stages 10 45
QC (kW) 595 878
Optimized process flowsheet AC (m2 ) 17 9
Figure 10 displays stream information, heat duties, equipment QR (kW) 1395 1214
sizes and operating conditions of the optimized process flowsheet. AR (m2 ) 37 89
For the optimized pressure-swing distillation system, the calcu-
Shell cost (106 $) 0.0577 0.2139
lated TAC is $1 014 300.
Heat exchanger cost 0.1217 0.1658
(106 $)
Possibility of heat integration Capital (106 $) 0.1794 0.3797
The two columns used in the pressure-swing distillation system Energy cost 0.3969 0.2875
had independent reboilers and condensers. The large temperature (106 $ y−1 )
difference between the condenser of the high-pressure column Total capital (106 $) 0.9450 0.9310
(424.7 K) and the reboiler of the low-pressure column (351.4 K) Total energy (106 $ y−1 ) 0.8276 0.7040
makes heat integration possible in pressure-swing distillation. TAC (106 $ y−1 ) 1.143 1.014
The heat duties are not the same (877.89 kW for the condenser

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Figure 11. Flowsheet of pressure-swing distillation for feed composition of 90 mol % THF.

of the high-pressure column and 1873.25 kW for the reboiler of


Table 6. Comparison of the two processes for the separation of a
the low-pressure column), so an auxiliary reboiler is required in mixture with a composition of 90 mol % THF
the low-pressure column. If heat integration is carried out for
pressure-swing distillation, the TAC value will be further reduced Feed to Feed to
to $810 100. high-pressure low-pressure
column column

COMPARISON OF EXTRACTIVE DISTILLATION C1 Diameter (m) 0.89 1.07


Stages 55 45
AND PRESSURE-SWING DISTILLATION QC (kW) 1009 1373
The design and the economic analyses of both processes are
QR (kW) 1567 1237
shown in Table 5. After the optimization of both distillation pro-
AC (m2 ) 10 14
cesses, it can be concluded that pressure-swing distillation exhibits
AR (m2 ) 34 27
better performance from the standpoint of economics. Moreover,
RR 4.83 0.15
using extractive distillation has the disadvantage of introducing
a solvent component into the system, which exists in the prod- D1 (kmol h−1 ) 22.5 140.1
uct streams as an impurity. Therefore, pressure-swing distillation is C2 Diameter (m) 0.46 0.92
more suitable than extractive distillation for the separation of THF Stages 25 45
and ethanol. QC (kW) 288 1034
QR (kW) 199 1633
AC (m2 ) 12 42
PRESSURE-SWING DISTILLATION SCHEMES AR (m2 ) 15 120
FOR DIFFERENT FEED COMPOSITION RR 1.59 1.91
D2 (kmol h−1 ) 12.6 50.0
All the studies mentioned above are focused on a mixture with
content 50 mol % THF and 50 mol % ethanol. It is noticed that Total capital (106 $) 0.5486 0.9074
the feed composition has an important influence on the sequence Total energy (106 $ y−1 ) 0.3955 0.6616
of high and low pressures of two columns in pressure-swing TAC (106 $ y−1 ) 0.578 0.964
distillation if the minimization of the TAC is considered during the
process design. Herein, the mixtures with different composition
(90 mol % THF and 10 mol % THF) separated by pressure-swing leading to a higher TAC value. For the former scheme, the TAC
distillation were investigated and optimized according to the value was $578 400, which is much smaller than that of the latter
procedures mentioned above (Fig. 11). Compared with the results ($964 100) (Table 6). Similarly, a suitable separation process of a
in Fig. 10, the main difference is that the mixture is added into the mixture containing 10 mol % THF and 90 mol % ethanol requires
high-pressure column first, which is based on the fact a mixture that the mixture is fed into the low-pressure column first and
with a content of 90 mol % THF is more easily separated at 10 atm, a much smaller TAC of $398,099 is obtained (Fig. 12). Thus, for
according to Fig. 3. On the other hand, separation can also be the various feed compositions, there are suitable pressure-swing
achieved if the mixture is added into the low-pressure column distillation schemes that show better performances with respect
first, however, more heat duties will be required in reboilers, to TAC values.

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Figure 12. Flowsheet of pressure-swing distillation for feed composition of 10 mol % THF.

CONCLUSIONS 10 Safrit BT, Westerberg AW, Diwekar U and Wahnschafft OM,


Extending continuous conventional and extractive distillation
Extractive distillation and pressure-swing distillation were inves- feasibility insights to batch distillation. Ind Eng Chem Res
tigated for separating a mixture of THF and ethanol. To obtain a 34:3257–3264 (1993).
minimum TAC value, the process parameters were optimized in the 11 Milani S, Optimization of solvent feed rate for maximum recovery of
two alternative processes. The results indicate that pressure-swing high purity top product in batch extractive distillation. Chem Eng
distillation could perform better than extractive distillation from Res Des 77:469–470 (1999).
12 Van Dyk B and Nieuwoudt I, Design of solvents for extractive distilla-
the standpoint of economics and product purity. Heat integration tion. Ind Eng Chem Res 39:1423–1429 (2000).
is possible for pressure-swing distillation and can further reduce 13 Lei Z, Zhang J and Chen B, Separation of aqueous isopropanol by reac-
the TAC. Pressure-swing distillation is further studied for separat- tive extractive distillation. J Chem Technol Biotechnol 77:1251–1254
ing mixtures with various compositions, and different schemes are (2002).
14 Ge Y, Zhang L, Yuan X, Geng W and Ji J, Selection of ionic liquids as
described to achieve minimum TAC.
entrainers for separation of (water + ethanol). J Chem Thermodyn
40:1248–1252 (2008).
15 Biglari M, Langstaff A and Elkamel A, The application of response sur-
REFERENCES face methodology for the optimization of an extractive distillation
1 Amelio A, Genduso G, Vreysen S, Luis P and Van der Bruggen B, process. J Pet Sci Technol 28:1788–1798 (2010).
Guidelines based on life cycle assessment for solvent selection 16 Luyben WL and Chien IL, Design and Control of Distillation Systems for
during the process design and evaluation of treatment alternatives. Separating Azeotropes. John Wiley & Sons, New York (2011).
Green Chem 16:3045–3063 (2014). 17 Yuan S, Yang W, Yin H and Chen Z, Separation of acetone–
2 Pandey RP and Shahi VK, Functionalized silica–chitosan hybrid tetrahydrofuran azeotropic mixture by continuous extractive
membrane for dehydration of ethanol/water azeotrope: effect distillation. J Chem Technol Biotechnol 88:1523–1528 (2013).
of cross-linking on structure and performance. J Membr Sci 18 Knapp JP and Doherty MF, A new pressure-swing-distillation process
444:116–126 (2013). for separating homogeneous azeotropic mixtures. Ind Eng Chem Res
3 Luis P, Amelio A, Vreysen S, Calabro V and Van der Bruggen B, Simu- 31:346–357 (1992).
lation and environmental evaluation of process design: distillation 19 Seiler M, Köhler D and Arlt W, Hyperbranched polymers: new selective
vs hybrid distillation–pervaporation for methanol/tetrahydrofuran solvents for extractive distillation and solvent extraction. Sep Purif
separation. Appl Energy 113:565–575 (2014). Technol 30:179–197 (2003).
4 Genduso G, Amelio A, Luis P, Bruggen B and Vreysen S, Separation 20 Seiler M, Jork C, Kavarnou A, Arlt W and Hirsch R, Separation of
of methanol-tetrahydrofuran mixtures by heteroazeotropic distilla- azeotropic mixtures using hyperbranched polymers or ionic liquids.
tion and pervaporation. AIChE J 60:2584–2595 (2014). AIChE J 50:2439–2454 (2004).
5 Gao C, Zhang M, Ding J, Pan F, Jiang Z, Li Y and Zhao J, Perva- 21 Wytze Meindersma G, Podt AJ and de Haan AB, Selection of ionic
poration dehydration of ethanol by hyaluronic acid/sodium liquids for the extraction of aromatic hydrocarbons from aro-
alginate two-active-layer composite membranes. Carbohydr Polym matic/aliphatic mixtures. Fuel Process Technol 87:59–70 (2005).
99:158–165 (2014). 22 Orchillés AV, Miguel PJ, Vercher E and Martínez-Andreu A, Ionic liquids
6 Randall M and Webb WA, Separation process. Ind Eng Chem as entrainers in extractive distillation: isobaric vapor–liquid equi-
31:227–232 (1939). libria for acetone + methanol + 1-ethyl-3-methylimidazolium triflu-
7 Perry RH, Azeotropic and extractive distillation. J Am Chem Soc oromethanesulfonate. J Chem Eng Data 52:141–147 (2007).
87:2079–2079 (1965). 23 Modla G, Energy saving methods for the separation of a minimum
8 Meirelles A, Weiss S and Herfurth H, Ethanol dehydration by extractive boiling point azeotrope using an intermediate entrainer. Energy
distillation. J Chem Technol Biotechnol 53:181–188 (1992). 50:103–109 (2013).
9 Arifin S and Chien I-L, Design and control of an isopropyl alcohol dehy- 24 Kiss AA, Suszwalak DJC and Ignat RM, Breaking azeotropes by
dration process via extractive distillation using dimethyl sulfoxide as azeotropic and extractive distillation in a dividing-wall column.
an entrainer. Ind Eng Chem Res 47:790–803 (2008). Chem Eng 35:1279–1284 (2013).

J Chem Technol Biotechnol (2014) © 2014 Society of Chemical Industry wileyonlinelibrary.com/jctb


www.soci.org Y Wang et al.

25 Zhang ZG, Huang DH, Lv M, Jia P, Sun DZ and Li WX, Entrainer 35 Muñoz R, Montón J, Burguet M and de la Torre J, Separation of
selection for separating tetrahydrofuran/water azeotropic mixture isobutyl alcohol and isobutyl acetate by extractive distillation and
by extractive distillation. Sep Purif Technol 122:73–77 (2014). pressure-swing distillation: simulation and optimization. Sep Purif
26 Chen Q and Gu ZG, Process design and optimization of extractive Technol 50:175–183 (2006).
distillation for butanol-isobutanol separation by Aspen Plus. Mod 36 Luyben WL, Comparison of extractive distillation and pressure-swing
Chem Ind 34:145–148 (2014). distillation for acetone-methanol separation. Ind Eng Chem Res
27 Phimister JR and Seider WD, Semicontinuous, pressure-swing distilla- 47:2696–2707 (2008).
tion. Ind Eng Chem Res 39:122–130 (2000). 37 Lladosa E, Montón JB and Burguet M, Separation of di-n-propyl ether
28 Repke JU, Klein A and Forner F, Homogeneous azeotropic distillation and n-propyl alcohol by extractive distillation and pressure-swing
in an energy-and mass-integrated pressure swing column system. distillation: computer simulation and economic optimization. Chem
Comput Chem Eng 18:757–762 (2004). Eng Process 50:1266–1274 (2011).
29 Repke JU, Forner F and Klein A, Separation of homogeneous 38 Modla G and Lang P, Removal and recovery of organic solvents
azeotropic mixtures by pressure swing distillation–analysis of from aqueous waste mixtures by extractive and pressure swing
the operation performance. Chem Eng Technol 28:1151–1157 distillation. Ind Eng Chem Res 51:11473–11481 (2012).
(2005). 39 Wang Q, Yu B and Xu C, Design and control of distillation system for
30 Repke JU, Klein A, Bogle D and Wozny G, Pressure swing batch methylal/methanol separation. Part 1: extractive distillation using
distillation for homogeneous azeotropic separation. Chem Eng Res dmf as an entrainer. Ind Eng Chem Res 51:1281–1292 (2012).
Des 85:492–501 (2007). 40 Yu B, Wang Q and Xu C, Design and control of distillation system for
31 Modla G, Pressure swing batch distillation by double column systems methylal/methanol separation. Part 2: pressure swing distillation
in closed mode. Comput Chem Eng 34:1640–1654 (2010). with full heat integration. Ind Eng Chem Res 51:1293–1310 (2012).
32 Wang Y, Cui P and Zhang Z, Heat-integrated pressure-swing distillation 41 Luyben WL, Comparison of extractive distillation and pressure-swing
process for separation of tetrahydrofuran/methanol with different distillation for acetone/chloroform separation. Comput Chem Eng
feed composition. Ind Eng Chem Res 53:7186–7194 (2014). 50:1–7 (2013).
33 Luyben WL, Pressure-swing distillation for minimum-and maximum- 42 Huang C, Separation of binary azeotrope tetrahydrofuran-ethanol by
boiling homogeneous azeotropes. Ind Eng Chem Res extractive distillation. ME Dissertation, Tianjin University, Tianjin,
51:10881–10886 (2012). Tianjin, (2008).
34 Luyben WL, Comparison of pressure-swing and extractive-distillation
methods for methanol-recovery systems in the tame reactive-
distillation process. Ind Eng Chem Res 44:5715–5725 (2005).

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