1614

Ind. Eng. Chem. Res. 2000, 39, 1614-1623

Extractive Distillation Solvent Characterization and Shortcut

Design Procedure for Methylcyclohexane-Toluene Mixtures
Peter G. Tiverios and Vincent Van Brunt*
Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, and
ONeal Engineering, 10 Falcon Crest Drive, Greenville, South Carolina 29607

A preliminary solvent screening tool for two-column extractive distillation flowsheets is described
whose results can be used to initialize process simulators. The tool uses shortcut approximations
to extractive distillation that accurately predict the relative column performance of alternative
solvents with rigorous simulations using the Aspen Plus process simulator. The activity coefficient
ratio of each feed component in the presence of the solvent, the boiling point difference between
the high boiler and the solvent, and an a priori heat integration criterion characterize potential
solvents. It was found that staging requirements for the flowsheets could be approximated using
4 times the number of stages predicted using the Fenske equation when it was applied over
each column section. Using these approximations resulted in a shortcut method for evaluating
and comparing alternative solvents and solvent families, predicting the staging requirements
and quickly determining the feasibility of completely heat integrating a flowsheet.
Background
Doherty and co-workers4,6,7,8,10 have extended our
understanding of azeotropic and extractive distillation.
Most of their work is based on azeotropic distillation
using geometric methods of nonlinear analysis incorporating residue curves. As described by Hoffman,1 the
path of a residue curve is essentially the distillation
path at total reflux, and accurate residue curves are
generally constructed from laboratory vapor liquid
equilibrium (VLE) data generated using a batch still.
Doherty constructs theoretical residue curves by combining a VLE model such as UNIFAC with a differential
material balance describing the dynamics of a still pot.
Generally, if a separation is possible at total reflux, then
the separation is physically possible and can be optimized by changing column parameters. Wahnschafft et
al.2 used residue curves to graphically construct pinch
point trajectories (e.g., Stichlmair et al.3) as separation
limits for establishing the feasibility of ternary separations with various entrainers based on achievable
bottoms and distillates. And most recently, Rooks et al.4
developed an equation-based approach rather than the
graphical approach for determining possible distillation
regions for homogeneous mixtures. Stichlmair and Fair5
summarize this work.
Once the feasibility of a separation is determined,
potential mass separating agents (MSA) can be evaluated further by considering energy requirements. Both
minimum solvent flow rates and minimum reflux ratios
can be used as indicators of a flowsheets energy
requirements. Levy et al.6,7 used tangent pinch points
to calculate minimum reflux ratios. Knapp et al.8
determined minimum entrainer flows using a geometric
method involving bifurcations of the finite difference
equations describing the middle section of the column.
Koehler et al.9 provided an excellent overview of evaluation techniques for determining minimum energy
* University of South Carolina. E-mail: 29208Vanbrunt@
engr.sc.edu.
ONeal Engineering. E-mail: Ptiverio@onealinc.com.

requirements of distillation flowsheets from approximation techniques to rigorous solutions. The approximation
techniques considered ranged from using Underwoods
method for both simple columns and extended for
complex columns to pinch point criteria for nonideal and
azeotropic mixtures (Koehler et al.,9 Levy et al.6,7). The
rigorous solutions range from tangent pinch point
criteria (Levy et al.,6 Fidkowski et al.10) to column
partitioning (Poellmann et al.11).
Introduction
By recognizing that narrowing the range of suitable
extractive distillation solvents using a shortcut procedure prior to rigorous simulation would save significant
time and energy, the goal of this work was to develop a
way to quickly screen alternative solvents for use in
extractive distillation flowsheets prior to their evaluation using residue curve maps, rigorous simulation, or
laboratory analysis. An additional goal was to explore
ways of determining staging requirements and whether
a heat-integrated flowsheet was possible.
An aliphatic-aromatic split was chosen to compliment the earlier Gerster et al.12 work that addressed
C3-C5 splits. Although a considerable amount of research has been done on the aliphatic-aromatic splits,
thermodynamic modeling packages such as UNIFAC
have not been adequately explored in the literature, and
it was felt that a re-evaluation of the early work was
warranted. In this work, the separation of toluene from
methylcyclohexane (MCH), a frequently used pedagogical example of extractive distillation, is analyzed with
the intent of characterizing potential extractive distillation solvents and developing a methodology for their
systematic evaluation. A representative group of solvents (listed in Table 1) was selected to evaluate in a
two column extractive distillation flowsheet (Figure 1).
The solvent screening method and preliminary design
procedure developed here is divided into the four steps
described in the following sections. First, an initial
screening of potential solvents begins by estimating
their effectiveness by using UNIFAC to approximate the

10.1021/ie990654k CCC: $19.00 2000 American Chemical Society

Published on Web 05/09/2000

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1615

Table 1
no.

solvent

classification

1
2
3
4
5
6
7
8
9

phenol
acetophenone
methyl n-amyl ketone
cyclohexanone
o-cresol
DMF
propylene glycol
furfural
aniline

aromatic, alcohol
aromatic
ketone
cyclic heterocycle, ketone
aromatic, alcohol
amide, ketone
glycol
heterocycle, aldehyde
aromatic, amine

2.15
1.96
1.47
1.43
1.90
5.01
4.94
2.12
2.35

1.33
1.02
0.88
0.88
1.27
1.82
2.74
1.26
1.23

Figure 1.

nonideality of the liquid phase and by calculating the

aliphatic-aromatic activity coefficient ratio in the presence of the solvent. Next, after a solvents separation
effectiveness and its impact on the activity coefficient
ratio of the solutes has been determined, the potential
for solvent recovery and its separability from the higher
boiling solute are evaluated by using the boiling point
difference between the solvent and the higher boiling
aromatic. Third, an approximation to the staging requirements is made, and last, the potential for heat
integrating the flowsheet is determined.
Preliminary Screening
The Shortcut Method. Steps 1 and 2. Initial
Solvent Screening. Characterizing solvents begins
with analysis of the mixture. The phase equilibrium is
described using eq 1, which assumes an ideal vapor
phase and accounts for only the nonideality of the liquid
phase.

yi iPisat
Ki ) )
xi
P

(1)

The relative volatility, defined as the ratio of the

equilibrium constants, describes the relative ease of
separation of component i from component j and is
approximated by eq 2.

Ki iPisat
)
Rij )
Kj P sat

(2)

j j

A mixture with a relative volatility close to 1.0 is

extremely difficult to fractionate without the use of a
mass separating agent; MCH and toluene have a
relative volatility of 1.004 at 1.0 atm. A good extractive

MCH/tol T
1.62
1.93
1.67
1.63
1.49
2.75
1.80
3.00
1.91

128
164
301
81
376
76
138
92
132

cascade I cascade II + III cascade IV + V

RMT
RTS
RMS
azeotrope
3.304
4.999
2.626
2.104
3.838
1.282
1.342
3.002
3.867

1.813
1.99
1.719
1.737
1.638
2.842
2.072
4.11
2.37

6.732
7.235
3.228
1.962
8.727
4.447
30.93
4.084
8.04

no
no
no
no
no
yes
yes
yes
no

solvent will increase the relative volatility by disproportionately modifying the respective liquid activity
coefficients to increase the activity coefficient ratio
(i/j). This can be achieved by increasing i versus j
or decreasing j versus i. In the first case, i > j, the
solvent preferentially rejects component i, increasing its
effective vapor pressure and chemically enhancing its
vaporization. In the second case, j < i, the solvent
preferentially reduces the volatility of component j
usually by enhanced secondary bonding. The effect of
the solvent on the MCH/tol ratio is usually considered
to be a measure of the enhanced interactions between
the solvent and toluene predominately resulting from
secondary or hydrogen bonding of the solvent with the
p orbitals of the toluene and are a function of its active
ligands.
Solvent characterization specific to the MCH-toluene
system was first investigated by Dunn et al.13 using
laboratory vapor-liquid equilibrium (VLE) data. For
initial screening, a mixture similar to the one used by
Dunn was considered, i.e., 20 mol % toluene, 20 mol %
MCH, and 60 mol % solvent at 234 F.
Figure 2 shows the effect of each solvent on the MCH
and toluene activity coefficients. In region 1, species i
(MCH) is preferentially rejected from the solvent whereas
species j (toluene) is retained and its solubility in the
solvent is enhanced. In region 3, the exact opposite effect
takes place: species j is rejected and species is solubility
is enhanced. In region 4, the solubility of both species
is enhanced in the solvent (both activity coefficients are
less than 1.0). Region 2 represents the region where the
presence of the solvent rejects both species and enhances
their volatility. It may be further divided into two
subregions above and below the 45 line. The region
above the line represents a preferential rejection of
component i relative to j; however, the solvent is
enhancing the volatility of both species. Below the line,
component j is rejected relative to component j. Note
that all of the solvents evaluated were either in region
1 or 2A, above the line; i.e., they increased the activity
coefficient ratio. Of particular interest is that only two
of the solvents lowered the activity coefficient of the
toluene. This graph clearly shows that all the others
increase the volatility of both species.
The success of each extractive solvent is not only
measured by its ability to increase the relative volatility
of a close boiling mixture but also by its ability to be
readily recovered from the bottoms stream. Solvents are
also characterized using the boiling point difference
between the solvent and the high boiler (toluene) as a
measure of stripping column performance (the ability
to separate the solvent from the high boiler) and the
activity coefficient ratio of the low and high boilers
(MCH and toluene) in the presence of the solvent as a
measure of extractive distillation column performance

1616

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000

Figure 2. Solvent characterization.

Figure 3. Methylcyclohexane-toluene separation ratio vs stripping factor.

(the ability to separate the low from high boiler in the

presence of the solvent). The hydrocarbon chain length
of these solvents has as great as or a greater impact on
their potential as solvents as the active ligand. The
active ligand affects the ratio, and the chain length
affects the T. In Figure 3, solvents are compared by
plotting the ratio versus T for each solvent in a
flowsheet with the ordinate inversely proportional to the
staging of the extraction column and the abscissa
inversely proportional to he staging of the stripping
column. The better solvents have the largest values of
both coordinates.
At the end of step 1, solvents that have both increased
the relative volatility between the solutes and have a
moderate boiling point differences between the high
boiler and themselves have been identified. In step 2,
these are further screened to identify potential processing problems by eliminating those solvents that form

azeotropes between the solvent and either solute. Azeotropic data references (Horsley,15 Gmehling et al.16) can
be consulted, and azeotropes can be predicted by use of
a thermodynamic model or determined in the laboratory.
Although activity generation is a prime consideration
when selecting a solvent so that separation of the
aliphatic from the aromatic is achieved, separation of
the solvent from the aromatic is equally important, and
Figure 3 indicates these relative affects. Furfural has
the highest impact on the ratio; however, it form
azeotropes with MCH and toluene, respectively, rendering recovery and purification of the feed components
impossible without increasing flowsheet complexity.
Flowsheets for organics that form heterogeneous azeotropes using liquid-liquid extraction are an alternative,
and membranes may be used as well (Seader and
Henley17).

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1617

Table 2. Cascades
cascade

description

function

I
II

top section of extractive column

middle section of extractive column

III

bottom section of extractive column

IV
V

rectifying section of stripping column

stripping section of stripping column

solvent recovery and aliphatic purity

separation of aromatic and aliphatic enhanced
by the solvent; toluene recovery
separation of aromatic and aliphatic enhanced
by the solvent; MCH recovery
solvent recovery, aromatic purity
aromatic recovery, solvent purity

Table 3. Extractive Distillation Column

solute solv.
distil.
solv.
staging
recovery (mol/h)
total
feed
feed
rate
rate
stages stage stage casc. I casc. II casc. III (mol/h) (mol/h) toluene MCH solv.
phenol
acetophenone
methyl n-amyl
ketone
cyclohexanone
o-cresol
DMF
propylene glycol
furfural
aniline

reboiler
duty
(BTU/h)

conden.
duty
(BTU/h)

reflux
ratio

100
74
98

70
42
61

31
12
38

31
12
38

39
30
23

30
32
37

51
50.25
50.5

330
330
330

49.99
49.65
49.96

49.61 328.6 6.12106 6.57106

49.71 329.8 4.75106 5.12106
49.79 329.3 6.88106 6.90106

86
99
39
43
88
60

50
79
21
33
58
42

32
8
3
4
18
26

32
8
3
4
18
26

18
71
18
29
40
16

36
20
18
10
30
18

50.5
50.1
68.75
58.25
615
52.5

330
330
330
330
330
330

49.55
49.75
49.99
49.99
49.69
49.99

49.67
49.57
49.32
49.66
49.48
49.64

329.6
329.7
310.6
321.4
318.3
327.2

6.47106
6.32106
2.85106
3.63106
3.64106
4.44106

6.44106
6.98106
3.60106
5.29106
3.92106
5.02106

12.0
9.4
13.0
12.0
13.2
3.9
7.0
5.0
8.5

Table 4. Stripping Column

recovery
staging

total feed
reflux
stages stage casc. IV casc. V ratio mol/h
phenol
acetophenone
methyl n-amyl
ketone
cyclohexanone
o-cresol
DMF
propylene glycol
furfural
aniline

toluene
%

solvent

mol frac.

mol/h

conden.
duty
(BTU/h)

reboiler
duty
(BTU/h)

15
18
28

8
7
16

7
11
12

8
7
16

8.8
7.4
13.6

49.99 99.98
49.58 99.16
49.32 98.64

0.990
0.993
0.990

325.31 7.12106 3.41106

327.49 6.09106 1.44106
326.01 1.22107 6.68106

28
17
80
36
30
13

9
9
75
3
22
9

19
8
5
33
9
4

9
9
75
3
22
9

15
7.4
7
4.6
7
6.2

49.50
49.55
47.15
48.50
49.48
49.08

0.990
0.991
0.970
0.960
0.989
0.990

326.30
326.73
301.28
308.54
314.8
323.93

Staging Requirements and Heat Integration

Shortcut Flowsheet Evaluation and Comparison
with Simulation. In this section, a shortcut approximation for staging requirements and heat integration of extractive distillation flowsheets are developed.
For the shortcut approximation, this flowsheet was
broken into five distinct cascades using pseudobinary
mixtures to approximate the behavior in each cascade.
These cascades are shown in Table 2. The model feed,
F, was taken to be a 50 mol/h MCH and a 50 mol/h
toluene stream that was introduced as a saturated
liquid into the extractive distillation column at an
appropriate feed location and a 330 mol/h solvent, S,
stream that was introduced at another arbitrary location above the feed stage. Both feed locations were later
optimized. The more volatile MCH was removed as a
liquid from the total overhead condenser of the extractive distillation column, and the toluene-solvent mixture was recovered from its bottoms. The bottoms was
then fed to the stripping column where the toluene was
removed as a liquid in a total overhead condenser and
the solvent was recovered from the bottoms. The stripping column bottoms was recycled back to the extractive
distillation column and used as the solvent feed with
sufficient fresh makeup solvent introduced to replace
the solvent loss in the two product streams.
The simulation specifications were allowed to float
whenever possible. Both columns were specified to

99.00
99.10
94.30
97.00
98.96
98.18

1.15107
6.05106
5.63106
4.05106
5.76106
5.14106

7.12106
1.29106
2.82106
2.02106
2.61106
1.23106

recov. col.
overhead strip. col.
conden.
reboiler
temp. (F) temp. (F)
412.3
412.6
412.5

369.9
405.4
314.2

412.7
412.6
378.8
374.4
403.8
411.7

323.7
405.9
312.6
370.7
332
372.2

operate at pressures sufficient to generate stream

temperatures that would allow heat integration of the
extractive distillation column overhead condenser with
the stripping column reboiler. The stripping column was
specified to operate at 14.7 psia (no vacuum systems
required), and the extractive distillation column was
specified to operate at 150 psia (standard materials of
construction-low pressure).
The flowsheet could have been configured by swapping column pressures and integrating the stripping
column condenser with the extractive distillation column reboiler. However, the respective heat duty of the
stripping column condenser was about half of the
extractive distillation column reboiler duty, and this
resulted in a flowsheet that could only be partially heat
integrated. The configuration chosen reduced the temperature of the stripping column to minimize the
possibility of solvent degradation. A minimum-approach
temperature difference of 10 F between the extractive
distillation column overhead condenser and the stripping column reboiler was used to create designs that
did not have excessive heat-transfer area. The staging,
feed locations, reflux ratio and distillate rate were
optimized until 99% of the MCH and toluene fed was
recovered, and each product purity was 99 mol % as
well. The simulation results are tabulated in Tables 3
and 4.
Step 3A. Pseudobinary Approximation. The shortcut procedure analyzed the flowsheet cascade by cascade

1618

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000

Figure 4. Recovery column section I simulated staging vs Fenske correlation.

and the relative volatility used in the Fenske equation

was developed using approximations to the mixture at
both ends of each respective cascade.
Cascade I was considered separately from the lower
two cascades in the extractive distillation tower. It
separates the low boiler from the solvent and was
analyzed using this pseudobinary mixture. The top of
cascade I was considered an essentially pure low boiler
(50 mol MCH) with the solvent present in infinite
dilution. In terms of concentrations, the distillate was
considered to have respective mole fractions of 0.99 and
0.01. The bottom of cascade I was assumed to be a
binary mixture of the solvent and the low boiler and
approximated using the relative flows fed to the column
(50 mol MCH and 330 mol of solvent). The relative
volatility used was the geometric average of the top and
bottom streams of cascade I. Cascades II and III
separate the low from the high boiler with the solvent
being removed with the high boiler in the bottoms
stream. A pseudobinary was assumed to be MCH and
toluene with the respective mole fraction ratios of 0.99/
0.01 at the top and 0.01/0.99 at the bottom. The relative
volatility was estimated using the mixed stream feed
composition (XMCH ) 0.12, Xtol ) 0.12, Xsol ) 0.76) at
its bubble point at the column pressure (150 psig). The
stripping column, cascades IV and V, separates the high
boiler from the solvent and was analyzed as a typical
binary separation with mole fraction ratios of 0.99/0.01
at the top and 0.01/0.99 at the bottom. The relative
volatility used was the geometric average of the feed
and bottom streams. Similar to cascade I, the bottom
stream relative volatility was calculated assuming
infinite dilution of the high boiler in solvent. The feed
stream properties for the stripping column were estimated at the extractive distillation column (cascade II
and III) bottoms stream condition.

Step 3B. Flowsheet Staging Requirements. The

staging requirements for each cascade from the simulation were predicted using the Fenske equation evaluated
with the pseudobinarys:

N)

ln[(XLB/XHB)TOP/(XLB/XHB)BOT]
ln R

(3)

The staging requirements used in the simulations and

those predicted by the pseudobinary Fenske equation
are plotted with respect to the R ratio in Figures 4-6.
Individual solvents are referred to by number (see Table
1) in these graphs. The pseudobinary Fenske equation
trends with the staging requirements predicted from the
simulation reasonably well. However, to accurately
predict staging and relative feed location, it had to be
applied to each column section in the extractive distillation column as described above rather than by a single
application over the entire column.
It has been the standard practice to use twice the
staging predicted by the Fenske equation when using
shortcut methods. Although the Fenske equation is
shown to trend with the simulation staging prediction,
this work shows the staging to be 3-4 times the staging
predicted by the Fenske equation rather than the
accepted rule of thumb.
An accurate forecast of staging requirements is essential for evaluating capital costs for competing solvents. As a consequence of this analysis, step 3B is to
conservatively predict the staging requirements for the
flowsheet column section by column section using 4
times the Fenske predictions, even though the trend was
from 3 to 4 times the minimum. The specific concentrations for each cascade and the staging for the flowsheet
is shown in Table 5.

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1619

Figure 5. Recovery column cascade II and III simulated staging vs Fenske correlation.

Figure 6. Stripping column: simulated staging vs Fenske correlation.

Table 5. Compositions and Relative Volatilities Used in the Fenske Equation and the Relationship between Prediction
vs Simulation
pseudobinary
cascade

XLB-TOP

XHB-TOP

XLB-BOT

XHB-BOT

LB

HB

Fenske correlation

I
II + III
IV + V

0.99
0.99
0.01

0.01
0.01
0.99

0.13
0.01
0.99

0.87
0.99
0.01

RM-S
RM-T
RT-S

MCH
MCH
toluene

solvent
toluene
solvent

Nsim ) 4NFenske
Nsim ) 3.75NFenske
Nsim ) 3NFenske

Step 3C. Flowsheet Heat Integration. The ability

to heat integrate the two columns can result in a 50%
reduction in operating costs. For the integration considered here between the extractive distillation condenser and the stripping column reboiler, an approxi-

mation to their duties is shown to result in a heat

integration criterion to quickly evaluate whether this
type of energy reduction is possible. For other configurations, a similar criterion can be developed and follows
by analogy to what is presented (see Appendix A). The

1620

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000

Figure 7. Heat integration criterion.

Figure 8. Heat integration simulated.

criterion can be written for the MCH-toluene system

as

Rtol-sol - 1
RMCH-sol - 1

)(

fMCH
fsol HMCH
>1
ftol
Hsol
1 + Rtol-sol
fsol

1 + RMCH-sol

(4)

This criterion only requires estimation of the relative

volatilities between the two solutes and the solvent, the
latent heats of vaporization for the components present
in the heat exchangers, and the relative feed flows of
MCH, toluene, and solvent. Although it was derived for

the MCH-toluene system, the criterion is general for

this heat integration scheme. In Figure 7, eq 4 is plotted
on the ordinate, the solvent number is plotted on the
abscissa, and the shortcut heat integration criterion
shows a one to one correspondence with the rigorous
simulation results. Thus, potential solvents can be
further screened by rejecting those that do not lend
themselves readily to heat integration, simply by evaluating eq 4.
The extractive distillation column condenser duties
and stripping column reboiler duties (generated from
the Aspen Plus simulations) are shown in Figure 8 with
respect to the temperature difference between these two
streams for each of the nine solvents that underwent
detailed design. Heat integration is not viable for every

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1621

Figure 9. Recovery column: solvent flow rate.

solvent due to either insufficient available energy from

the condenser or an insufficient temperature difference
between the condenser and the reboiler. Cyclohexanone
has its stripping column reboiler duty greater than its
recovery column condenser duty. Its negative energy
difference indicates that at these conditions it could not
be heat-integrated. Although propylene glycol, acetophenone, and o-cresol have sufficient energy to permit heat
integration, the stream temperature difference is insufficient and would result in excessive stripping column
reboiler surface area. This could be remedied by increasing the extractive distillation column operating
pressure and subsequently elevating its overhead condenser temperature. However, excessively high temperatures could cause thermal degradation of the components and may be impractical for other reasons as well.
Other Considerations. To evaluate whether the
optimization of solvent flow would influence the fixed
solvent flow results presented, the Aspen Plus simulator
was used to determine the optimum flow for each of the
nine representative solvents. The simulation specifications were relaxed to allow a wide range of solvent flows
to be evaluated in the previously configured columns
without further column optimization. The toluene product recovery and purity remained 99% in the stripping
column; however, the MCH purity (solvent recovery) and
the solvent recycle purity were permitted to be sloppy.
Figure 9 shows the dependence of the simulated
optimum solvent flows on the solute activity coefficient
ratio for the extractive distillation columns that were
previously optimized for staging, feed location, and
reflux using a fixed solvent flow rate. These simulations
reflect the strong dependence of optimized solvent flow
on solute activity coefficient ratio. However, it was
found, in general, that sloppy solvent splits increased
overall energy costs due to the additional separations
required to recover the solvent and should be discouraged. The solvent flow can be optimized without sacrificing the separation specifications, thereby reducing
solvent inventory, operating and capital costs.
Summary of the Screening Method. The screening
method, outlined in Figure 10, is as follows:

Figure 10. Solvent selection.

Step 1. Preliminary evaluation of the solvent by

plotting the ratio of solutes for each solvent (12%, 12%
mixture of solutes with 76% solvent can be used) versus
T between the high boiler and the solvent.

1622

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000

Step 2. Those solvents that form azeotropes with the

solutes are rejected.
Steps 3A and 3B. Staging is evaluated using pseudobinary mixtures with compositions shown in Table 5 and
the staging requirements of 4 times those predicted by
the Fenske equation individually applied to each cascade.
Step 3C. The potential for heat integration of each
flowsheet is evaluated using the criterion in eq 4. Those
that do not meet the criteria are rejected.
Step 4. Proceed to rigorous evaluation.
The results of the preliminary screening can be used
to initialize process simulators for more detailed analysis and optimization of the remaining solvents.
Conclusions
A preliminary solvent screening tool for extractive
distillation has been developed whose results can be
used to initialize process simulators. UNIFAC provided
a reliable tool to determine the relative behavior of
solutes and predict their activity coefficient ratio in the
presence of a solvent. This along with the temperature
difference between the high boiler and the solvent
enabled a graphical prescreening of potential solvents.
Both the hydrocarbon chain length of the solvent and
its active ligand end groups have significant effects on
a solvents influence on the solutes activity coefficient
ratio.
Although prescreening using the solute ratio is an
indicator of a solvents effectiveness, shortcut approximations to extractive distillation have been shown to
accurately predict the relative column performance
when compared to the rigorous simulations using Aspen
Plus. The staging requirements in extractive distillation
flowsheets are approximately four times that obtained
using the Fenske equation applied over each appropriate column section. The pseudobinary Fenske equation
was valid when applied over cascade I, cascades II and
III together, and cascades IV and V together because
each of these cascade groups essentially behaved as
binary separations.
Heat integration of the extractive distillation overhead condenser with the stripping column reboiler was
investigated, and an a priori heat integration criterion
using predicted relative volatilities was found to trend
and predict relatively rigorous simulation results. Heat
integration of the stripping column overhead condenser
with the extractive distillation column reboiler was
investigated but found insufficient for total heat integration for the MCH-toluene system. In addition,
solvent requirements were shown to be highly dependent on the activity coefficient ratio of the solutes in the
presence of the solvent.
In general, using shortcut approximations to prescreen extractive distillation solvents using physical
properties, predicted ratios using UNIFAC, and
predicted relative volatilities was found to be expedient
for both solvent screening and as an initiation tool prior
to rigorous simulation.
On the basis of the methodology described above, the
nine solvents were evaluated.
Azeotrope formation removed furfural, DMF, and
propylene glycol from consideration, and the inability
to heat integrate the flowsheet removed cyclohexanone
from consideration. Of the remaining solvents, acetophenone and then phenol appear to be the most favorable solvents when considering solvent flow require-

ments, overall staging requirements, and recovery of all

components. However, the acetophenone flowsheet would
both require raising the operating pressure of the
recovery column to elevate the overhead condenser
temperature and increase the differential temperature
between the two columns to optimize equipment size.
Appendix A
Developing a Shortcut Heat Integration Criterion. Cascade I in the extractive distillation column is
essentially a binary separation between the aliphatic
low boiler and the solvent and simultaneous solution
of the solvent feed stage q-line, the equilibrium expression for a binary, and the cascade I operating line results
in an expression for the minimum reflux. The equation
for the cascade I operating line equation is yi ) R/(R +
1)xi + xdi/(R + 1), and the q-line equation for the solvent
feed is yi ) q/(q - 1)xi + zf/(q - 1).

RmzF + qxD

)
Rm(1 - zF) + q(1 - xD)
R[xD(q - 1) + zF(Rm + 1)]
(Rm + 1)(1 - zF) + (q - 1)(1 - xD)

(A1)

Here R is the relative volatility of the low boiler (MCH)

with respect to the solvent, zF is the feed mole fraction
of MCH, and q is the traditional liquid quality of the
feed stream and is defined as

q)

HG - HF
HG - HL

(A2)

Equation A1 can be rigorously solved for Rm if the

feed quality and distillate fraction are known. In the
case of a saturated liquid feed at the bubble point (q )
1), eq A1 can be solved for the minimum reflux ratio in
terms of the separation factor, the feed composition, and
the distillate composition.

Rm )

1 - xD
1 xD
-R
R - 1 xF
1 - xF

(A3)

Further approximation of the distillate by a pure lowboiling stream (xD ) 1) results in the simplified relationship between the minimum reflux ratio, the effective
separation factor, and the feed composition.

Rm )

1
xF(R - 1)

(A4)

Energy and material balances for the top cascade relates

the condenser duty to the reflux ratio:

HVV ) hdD + hdL + Qc

(A5)

V)L+D

(A6)

Qc ) (R + 1)DHMCH

(A7)

Substitution of the reflux approximation, effective feed

flows for the feed, and relative volatility from eq A4 into
eq A7 results in an approximation for the condenser
duty in terms of predictable and known quantities.

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1623

Qc )

1
+
(RMCH-sol - 1)[mMCH/(mMCH + msol)]

1 mMCHHMCH (A8)
Here, m refers to the molar flow of a component in the
feed. Similar to the analysis of the condenser of the
extractive distillation column, the stripping column
reboiler duty was related to toluene and solvent flow.
Assuming a saturated liquid feed and minimal heat
effects in the stripper (constant molar overflow) results
in its rectifying section vapor flow rate equaling the
stripping section rate. Similar to the cascade I analysis
above, a mass balance around the rectifying section of
the stripping column results in an expression for the
vapor flow in terms of the reflux ratio and distillate flow
rate. The reboiler duty can be approximated by

Qr )

1
+ 1 mtolHsol
(Rtol-sol - 1)[mtol/(mtol + msol)]
(A9)

Heat integration for this scheme is possible only if the

extractive distillation column condenser duty is greater
than the stripping column reboiler duty.

Qc-r > Qr-strip or Qc-r/Qr-strip > 1

(A10)

Reducing eq A10 results in a compact criterion requirement for heat integration between the extractive distillation column condenser and the stripping column
reboiler.

( )(

fL
1 + RL sol
RH sol - 1
fsol HL
>1
RL sol - 1
fH Hsol
1 + RH sol
fsol

Notation

B ) column bottoms flow (mol/h)

D ) column distillate flow (mol/h)
fMCH ) feed rate of methylcyclohexane (mol/h)
ftol ) feed rate of toluene (mol/h)
fsol ) feed rate of solvent (mol/h)
m ) flow rate (mol/h)
F ) feed
HG ) enthalpy of the saturated vapor feed stream
HL ) enthalpy of the saturated liquid feed stream
HF ) enthalpy of the actual feed stream
HV ) enthalpy of vapor stream V
hd ) enthalpy of liquid distillate stream L or D
hL ) enthalpy of bottoms stream L or B
Ki ) equilibrium coefficient
L ) column liquid flow (mol/h)
Pisat ) component vapor pressure
P ) total pressure
Hvap ) heat of vaporization (HV - hd)
Hvap ) heat of vaporization (HV - hL)
HL ) heat of vaporization (HV - hL) of low boiler
Hsol ) heat of vaporization (HV - hL) of solvent
Qc ) condenser duty
Qr ) reboiler duty

(A11)

R ) reflux ratio (L/D)

S ) solvent
V ) column vapor flow (mol/h)
XLB ) low boiler mole fraction in pseudobinary
XHB ) high boiler mole fraction in pseudobinary
yi, xi ) vapor and liquid mole fractions, respectively
R ) relative volatility of LB/HB
RTS ) relative volatility of the toluene-solvent in the
stripping column
RMS ) relative volatility of the MCH-solvent in section I
of the extractive distillation column.
i ) liquid activity coefficient
i ) vapor fugacity in mixture; assume ideal vapor phase:
i ) 1

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Received for review September 1, 1999

Revised manuscript received January 27, 2000
Accepted January 29, 2000
IE990654K