72 www.cepmagazine.

org August 2001 CEP

Reactions and Separations
ith new high-value, small-demand,
specialty chemicals continually com-
ing to market, there is an increased de-
sire to create adaptable processes that
enable the manufacture of a broad array of chemi-
cals. Semicontinuous distillation meets this need in
an efficient manner. This technology enables the
separation of a wide variety of mixtures that may
contain a large number of chemical species and ex-
hibit complex thermodynamic behavior.
Traditionally, distillation processes have been
designed to operate either in batch mode, where a
still is charged and light to heavier species are suc-
cessively removed in the distillate, or to run contin-
uously, where a column or a series of columns are
kept near steady state to separate a feed mixture. In
the former approach, process efficiency is sacri-
ficed for separation flexibility, whereas in the lat-
ter, the reverse applies.
Semicontinuous distillation represents a depar-
ture from these traditional approaches. Consider,
for example, the column and tank configuration in
Figure 1. By using this arrangement with a semi-
continuous policy, a wide variety of chemical mix-
tures can be separated efficiently. Mixtures that can
be split include binaries, near-ideal ternaries, low-
boiling azeotropes, and, with the use of an addi-
tional product tank, near-ideal quaternaries.
In semicontinuous distillation, the column, re-
boiler and condenser operate throughout the cam-
This processing strategy combines
the advantages of batch and continuous
operation, providing flexibility and
efficiency in a single design.
Bridge
Semicontinuous
Distillation
with
Gap
the
W
James R. Phimister and
Warren D. Seider,
University of Pennsylvania
T
1
D
1
S
1
S
10
S
9
S
2
S
6
S
7
S
8
S
4
S
3
S
5
T
2
T
3
T
4
T
5
I Figure 1. Column and tank conguration for semicontinuous distillation.
CEP August 2001 www.cepmagazine.org 73
paign, with a feed stream added constantly, while several
modes of operation are used cyclically. Each mode often
involves different feed tanks, feed compositions or prod-
uct vessels. These campaigns are, in principle, quite sim-
ple, and many have been found to be effective with unex-
pected consequences (15). Note that, prior to the publi-
cation of these papers, to our knowledge, no literature ex-
isted on semicontinuous distillation.
Two developments led to our close examination of
semicontinuous distillation. The first involved the intro-
duction of cyclic, batch-distillation processes, as exempli-
fied by Srensen and Skogestad (6), who showed how to
optimize a batch distillation process in which the reflux
drum was charged and discharged cyclically to reduce the
time to achieve high-purity product.
The second development was the use of new batch col-
umn configurations, including middle-vessel columns
(MVCs) (7), multi-vessel columns (8), and heat-integrat-
ed batch columns (9).
In view of these advances, and the emerging applica-
tions of non-steady-state processes, semicontinuous oper-
ation followed naturally. Indeed, its evolution is well
grounded and represents a significant advancement in
todays processing methods. We will illustrate how it
works and its advantages by considering the separation of
various types of mixtures.
Example 1: Near-ideal ternary mixture
Consider the separation of a near-ideal ternary mix-
ture of equimolar n-hexane, n-heptane, and n-octane. In
batch processing, the chemicals are separated in a col-
umn (Figure 2a). Initially, the still is charged and n-hex-
ane is collected in the distillate. Subsequently, a slop cut
(off-specification product) is taken, with n-heptane con-
centrated in the distillate. A further slop cut is used to re-
cover n-octane in the still. In continuous operation, either
direct or indirect column trains are used (Figure 2b and
Figure 2c, respectively).
In a semicontinuous setup, however, this separation is
accomplished in an MVC (Figure 3). This setup consists of
a column connected to a large middle vessel. The vessel
both feeds the column and receives a full-liquid sidedraw
from the tray above the feed tray. In the examples present-
ed here, the column consists of 25 stages including the re-
boiler. The authors (2) provide additional design and oper-
ating specications.
Each cycle of the semicontinuous campaign involves
three operating modes:
1. The equimolar ternary feed is charged to a nearly
empty middle vessel. Because the vessel continuously
feeds the column, the middle-vessel is never completely
emptied during the campaign.
2. The distillate, concentrated in n-hexane, is removed
continuously, although in diminishing amounts. The bot-
toms, consisting of n-octane, is also removed continuously
in diminishing quantities. The middle vessel becomes con-
centrated in the intermediate, n-heptane.
3. After the middle vessel becomes sufficiently concen-
trated in the intermediate, it is nearly emptied, and the
cycle returns to Mode 1.
Proles for a 240-h semicontinuous campaign are
shown in Figure 4. Throughout the run,
the distillate and bottoms compositions
were maintained near 98 mol% n-hex-
ane and 98 mol% n-octane, respective-
ly. (In this gure and in Figure 5, MF
stands for mole fraction.) During each
cycle, the middle-vessel became in-
creasingly concentrated in the interme-
diate, and upon achieving 98 mol% n-
heptane, the contents of the vessel were
removed as product. In this example,
the semicontinuous campaign separated
100 m
3
of feed in each cycle. With typi-
cal tray and tank holdups, three cycles
were completed in 222 h.
D
1
D
2
D
1
D
2
a. Batch b. Direct c. Indirect
I Figure 2. Separating a near-ideal ternary mixture.
Middle
Vessel
Middle
Tray
T
2
T
3
T
4
T
5
I Figure 3. Middle-vessel column set up for same separation as in Figure 2.
Example 2: Extractive distillation
The semicontinuous separation of a low-boiling
azeotropic mixture of acetone and methanol can be per-
formed, using water as an extractive agent, in the column-
tank conguration in Figure 1. One campaign, which is
similar to the batch distillation run by Safrit et al. (10), in-
volves three modes of operation:
1. Removal of methanol product after it concentrates in
the middle vessel.
2. Removal of acetone in the distillate.
3. Recovery of the extractive agent, water.
Mode 1 Charging and methanol production:
Stream S
1
(Figure 1), an equimolar mixture of acetone
and methanol, recharges the middle vessel (tank T
2
)
when it is nearly empty. Note that T
2
is never emptied,
since it continuously feeds the column. In this example,
T
2
is loaded initially with 50 m
3
of the acetone/methanol
mixture. Methanol concentrates in the middle vessel, as
the distillate. In this vessel, the mixture approaches the
low-boiling azeotrope of methanol and acetone (0.23 and
0.77 mole fractions at 55.4C) and is fed to T
2
. Water in
the bottoms is collected in T
5
(which is loaded initially
with 50 m
3
of water). When the methanol purity (0.98
mole fraction) is achieved in T
2
, its contents are dumped
into T
3
.
Mode 2 Extraction: After T
2
is nearly emptied, the
contents of tank T
1
are dumped into T
2
, and, hence, the
feed to the column is near the azeotropic composition.
Water is fed near the top of the
column in stream S
8
at a fixed
flowrate (2 m
3
/h); the set point of
the distillate composition con-
troller is adjusted to 0.02 mole
fraction methanol (assuming that
the mole fraction of the methanol
impurity in the distillate can be
measured accurately and instanta-
neously); and an acetone/water
distillate is collected in product
tank T
4
. As the extractive agent is
added, water and methanol con-
centrate in the middle vessel, the
mole fraction of water in the
sump meets its specification
(0.98), and water in the bottoms
product is sent to T
5
.
Mode 3 Water recovery:
After sufficient acetone is col-
lected in T
4
, the cycling of water
is discontinued. The setpoint of
the controller for the distillate
composition is returned to near
the azeotropic composition (0.75
mole fraction of acetone), and the
near-azeotropic distillate is sent
to T
1
in stream S
10
. Water, still present in the middle
vessel, continues to be removed in the bottoms product
until the water mole fraction in the sump falls below
0.96, after which the bottoms product valve is closed.
When the concentration of methanol is sufficiently high
in T
2
, its contents are collected in T
3
; tank T
2
is
recharged with the equimolar feed; and the process re-
turns to Mode 1.
Trajectories for the streams and tanks over the 240-h
(10-d) campaign are shown in Figures 5ag. Operation
over two cycles is shown, with the second cycle nearing
completion after 10 d.
Advantages and limitations
The benets of semicontinuous operation range from
improved performance, in which mixtures can be separated
more rapidly than batch processing, to economic consider-
ations, where less capital investment is usually needed than
for a continuous train, to advantages such as improved con-
troller performance.
Semicontinuous distillation captures many of the de-
sirable attributes of continuous and batch distillation.
From continuous processing, these include ease of
closed-loop control and the lack of slop cuts and column
dumping, and from batch processing, process flexibility
and lower investment costs. Further, thanks to the middle
vessel, it is easier to separate ternary mixtures using a
single column.
Reactions and Separations
74 www.cepmagazine.org/ August 2001 CEP
K
m
o
l
1000
500
0
0 50 100 150 200
n -hexane n -octane
n -heptane
Holdups
Middle Vessel (T
2
) Intermediate Product Vessel (T
5
)
Distillate Product Vessel (T
4
) Bottoms Product Vessel (T
3
)
M
F
1
0.5
0
0 50 100 150 200
Middle-vessel mole fractions.
Time, h
A.
B.
I Figure 4. Trajectories of tank holdups (A) and mole fractions in the middle vessel (B)
for the semicontinuous campaign performed in the setup in Figure 3.
Lastly, a decentralized distillate/bottoms conguration
for dual-composition control performs well. While this
conguration is rarely effective for a continuous column, it
facilitates the smooth operation of the cyclic semicontinu-
ous campaign (5). These, and other advantages, as well as
limitations, are summarized in the table.
Semicontinuous distillation is the most promising for
intermediate throughputs, where distillation campaigns are
likely to be operated for several days, up to a year. For low
production rates and short production cycles, batch distil-
lation is preferred, whereas continuous operation is pre-
ferred when:
Throughput is large and production times are long
Financial gains are obtained
through process automation
The design of a column or a
train can be optimized to perform
one separation.
Process comparison
Before considering a detailed
comparison of semicontinuous
with batch and continuous distil-
lation, recognize that, at first
glance, semicontinuous opera-
tion appears to be more competi-
tive with batch distillation than
with a train of continuous
columns. This is especially true
when it is envisioned that a pro-
cess will be operated for years.
In such cases, a continuous train
often proves to be a superior in-
vestment, since the design can
be optimized for the specific
separation. However, when the
life of a process is uncertain and
the throughput is not large, plant
flexibility becomes increasingly
important and semicontinuous
designs become competitive.
Just as it is difficult to use
quantitative criteria (economic or
otherwise) solely to determine
whether batch or continuous dis-
tillation is preferable for a specif-
ic separation, similarly, it is hard
to compare quantitatively semi-
continuous with continuous and
batch operations. To aid in this
comparison, it is helpful to con-
sider three criteria: capital invest-
ment, operating cost and plant
flexibility. In addition, criteria
such as toxicity or corrosiveness,
which are often not easily quantified, can greatly influ-
ence the decision process. These criteria are used here to
compare semicontinuous and batch distillation before a
comparison of semicontinuous and continuous methods
is considered. When appropriate, the previous example
involving the near-ideal ternary mixture is referred to.
Semicontinuous compared with batch
Capital cost A semicontinuous conguration usually
requires a larger capital investment than a batch column,
because two additional holding tanks are necessary, and a
more complex decentralized control system (involving sin-
gle loops) is implemented.
CEP August 2001 www.cepmagazine.org/ 75
M
1
Mode 1, M
2
: Mode 2, M
3
: Mode 3.
A Tank holdups.
Line styles: T
1
, T
2
, T
3
, T
4
, T
5

B Middle-vessel mole fractions.
C Distillate mole fractions.
Line styles (for B and C): acetone, methanol,
water
m
3
50
M
1
M
2
M
3
M
1
M
2
M
3
0
1
A.
B.
C.
D.
E.
F.
G.
M
F
0.5
0
M
F
0
K
m
o
l
/
h
20
40
0
K
m
o
l
/
h
150
100
50
0
m
3
10
5
0
K
m
o
l
/
h
50
100
150
0
0 50 100 150 200
Time, h
1
0.5
D Distillate flowrate.
E Bottoms flowrate.
F Sump and reflux drum holdups.
Line styles: sump,
reflux drum.
G Internal column flowrates.
Line styles: boilup rate,
reflux flowrate.

I Figure 5. Stream and tank trajectories for extractive distillation.
Operating cost Although capital costs are usually
somewhat larger for a semicontinuous setup, considerable
savings occur in operating costs. First, since no column
dumps and recharges are necessary, these labor-intensive
operations are avoided. Further, without dumps and
recharges, semicontinuous distillation proceeds more
rapidly, freeing-up the equipment for additional separa-
tions. Second, as discussed by Oppenheimer and
Srensen (11), continuous distillation normally requires
lower condenser and reboiler duties to achieve equivalent
separations compared with batch operations. Since the
condenser and reboiler do run continuously, semicontinu-
ous distillation normally requires lower duties to achieve
equivalent separations. Our simulations have further
confirmed this.
Flexibility Added flexibility is evident both in the
types of chemical mixtures that can be separated semi-
continuously, and in the operating schedules possible. As
an example of process flexibility, the extractive distilla-
tion in Example 2 would be difficult to perform in a batch
column, because of the large amounts of extractive agent
that would concentrate in the still. Regarding operating
policies, for a typical batch column, there is usually just
one policy to separate a near-ideal ternary mixture,
whereas several exist for semicontinuous setups. For ex-
ample, for separating the near-ideal ternary mixture (Ex-
ample 1), an alternative would be to remove n-hexane and
n-heptane successively in the distillate, and concentrate
n-octane in the bottoms.
Semicontinuous compared with continuous
Capital cost A semicontinuous arrangement that
involves just a single column is anticipated to have a
lower capital cost than a train of continuous columns.
The difference depends on the costs of additional hold-
ing tanks compared with those for
extra columns. Note that the semicon-
tinuous configuration has fewer con-
trollers, fewer heat exchangers, lower
material costs and less structural sup-
port than do two continuous columns
in series.
Operating cost This is usually
lower for a train of continuous
columns than for a semicontinuous
column. One reason is the added mix-
ing in semicontinuous installation,
which increases lost work and results
in higher utility costs. Another factor
is the difficulty of implementing heat
integration in a semicontinuous config-
uration, a practice commonly used in
continuous processing to reduce the
cost of utilities.
Flexibility Of the three operating
strategies, continuous fractionation is usually the least
flexible, with semicontinuous the most. This is perhaps
the dominant consideration in deciding whether to oper-
ate continuously or semicontinuously. When the demand
for products is anticipated to continue for an extended
period, surpassing the projected lifetime of the process,
continuous operation is favored. Here, column flexibili-
ty is not significant, and hence, one of the key advan-
tages of semicontinuous operation does not apply. On
the other hand, if the market is uncertain, especially
with regard to demand, the semicontinuous route be-
comes more attractive. Its attractiveness increases with
the degree of uncertainty.
Another issue is integrating a semicontinuous con-
figuration with the upstream and downstream unit oper-
ations in a process (2). Finally, continuous processes
run near steady state, and, consequently, may be ex-
pected to be easier to control. As will be discussed in
the next section, this may not be so, because a simple
decentralized control system also performs well in
semicontinuous distillation.
Decentralized control
Given the more complex operating policies in semicon-
tinuous runs, a centralized and model-based control strate-
gy would appear to be necessary. Yet, a decentralized pro-
portional-integral-derivative (PID) control system (involv-
ing single loops) works well, and surprisingly, the DB-con-
trol conguration is very effective (5).
This configuration, shown in Figure 6 for separating a
near-ideal ternary mixture, provides dual-composition
control throughout all modes of the semicontinuous
cycle. Most importantly, it maintains smooth, continuous
operation of the column in spite of the repeated switches
between modes.
Reactions and Separations
76 www.cepmagazine.org August 2001 CEP
Comparison of distillation processes
Batch Semicontinuous Continuous
Throughput Low Intermediate High
Flexible Yes Yes No
Automatic control Uncommon Possible Often
Investment Lowest Middle Highest
Heat integration No Possible Yes
Single column for ternary Yes Yes Not often*
separation
Slop cut required for ideal Often Occasionally N/A
ternary mixtures
* Separation of ternary mixtures in a single tower is possible with a liquid sidedraw
over a narrow range of ternary compositions.
To understand the success of the DB-conguration,
consider rst the difficulties encountered in continuous
distillation, which are rooted in the mass balance con-
straint between the ow rates of the feed, F, distillate, D,
and bottoms, B:
F = D + B
and the respective species balances. This causes the
composition controllers to be highly coupled, making
it difficult to control one composition when the
flowrate associated with the other composition con-
troller is temporarily reduced, causing the column to
become rapidly inoperable.
Consider the binary mixture fed to the continuous
column in Figure 7. When, for example, the composi-
tion of the bottoms falls below specification, the con-
trollers valve begins to close, increasing the volumetric
holdup in the sump. As a result, the boilup rate increas-
es, as does the amount of the heavy species in the over-
head vapor. This drives the distillate composition below
specification and increases the holdup in the reflux
drum, which increases the liquid reflux rate, further in-
creasing the sump holdup. Consequently, with liquid
continuously fed to the column, when the bottoms com-
position remains below specification, a spiral action
causes the reflux drum or sump to overflow, rendering
the column inoperable.
This spiral action does not occur for the semicon-
tinuous separation shown in Fig-
ure 6. As in continuous service,
when, for a binary feed, the bot-
toms composition drops below
specification, the bottoms
flowrate decreases, the holdup in
the sump increases, the vapor
boilup rate increases, and, owing
to the increase in the heavy
species in the distillate, the distil-
late flowrate decreases.
For semicontinuous setups,
however, the corresponding in-
crease in the reflux flowrate does
not impact the sump holdup.
Rather, due to the full-liquid sid-
edraw, this increased flow is
transferred to the middle vessel
and does not accumulate in the
column. This full-liquid sidedraw
enables the DB-control configu-
ration to reject composition dis-
turbances without sump and re-
flux drum overflows. Note that
these desirable control character-
istics extend to ternary and mul-
ticomponent mixtures as well.
Though illustrated here for a
binary feed, the DB-control configuration performs well
for multicomponent separations. This is so for highly
cyclic campaigns, such as the extractive distillation
shown previously.
CEP August 2001 www.cepmagazine.org 77
FC
LC CC
LC
CC
I Figure 7. Continuous column control arrangement.
T
2
T
3
T
5
LC
PC
CC
LC
CC Composition Controller
FC Flow Controller
LC Level Controller
PC Pressure Controller
CC
FC
LC
T
4
I Figure 6. Semicontinuous middle-vessel column with DB-conguration.
To sum up
When choosing process methods for distilling chem-
icals, a semicontinuous campaign is often an attractive
option. Moreover, in process design, other processes
may benefit from semicontinuous operation.
This type of distillation combines the advantages as-
sociated with batch and continuous operating cam-
paigns. Two attributes associated with batch distillation,
lower investment cost and flexibility, are retained in
semicontinuous distillation. Similar to continuous pro-
cesses, advantages such as process automation and not
requiring slop cuts or column dumps, are also advan-
tages of a semicontinuous policy.
However, a semicontinuous campaign is not simply
an amalgamation of batch and continuous processing.
For a near-ideal ternary mixture, there are instances
where a semicontinuous policy proves superior to a
batch or a semibatch one; for example, the separation of
three species in a single column which, when operated
continuously, is impractical. Further, semicontinuous
running of an MVC facilitates separations not easily
achieved using batch methods.
There are several attributes unique to semicontinu-
ous distillation. These include the flexibility of the
MVC in a campaign, the wide variety of chemical sys-
tems that can be separated efficiently and the utility of
the DB-control configuration. While these stand alone
in significance, they also contribute to the preference of
semicontinuous distillation over traditional methods for
many separations.
CEP
Reactions and Separations
78 www.cepmagazine.org August 2001 CEP
JAMES R. PHIMISTER is a co-leader of The Near-Miss Project at the Risk
Management and Decision Processes Center of the Wharton School,
Univ. of Pennsylvania, Philadelphia (Phone: (215) 732-3736; Fax: (215)
573-2130; E-mail: jphimist@wharton.upenn.edu; Website:
http://opim.wharton.upenn.edu/risk/nearmiss.html). He was recently
appointed the J. Herbert Holloman Fellow of the National Academy of
Engineering. He holds a bachelors of engineering and MS in chemical
engineering from the Univ. of Edinburgh, and an MS and PhD in
chemical engineering from the Univ. of Pennsylvania. His thesis topic
was semicontinuous distillation, for which he received a Merrill-Lynch
Innovation Award. He is a member of AIChE, the American Association
for the Advancement of Science and the American Chemical Society.
WARREN D. SEIDER is professor of chemical engineering at the Univ. of
Pennsylvania, Philadelphia (Phone: (215) 898-7953; Fax: (215) 573-
2093; E-mail: seider@seas.upenn.edu). He has contributed to process
analysis, simulation, design and control. He coauthored FLOWTRAN
Simulation An Introduction in 1974 and has coordinated the
design course at Penn for nearly 20 years, which involves projects
provided by many practicing engineers in the Philadelphia area. In
1999, he coauthored Process Design Principles: Synthesis, Analysis,
and Evaluation. He has authored or coauthored over 80 journal
articles and authored or edited six books. Seider was the recipient of
the AIChE Computing in Chemical Engineering Award in 1992. He
served as a director of AIChE from 19841986, has served as chairman
of the CAST Div., and is currently on the Publications Committee. He
helped to organize the CACHE (Computer Aids for Chemical
Engineering Education) Committee in 1969 and served as its chairman.
He received a BS from the Polytechnic Institute of Brooklyn, and an
MS and PhD from the Univ. of Michigan, all in chemical engineering.
Seider is a member of the editorial advisory board of Computers and
Chemical Engineering.
Literature Cited
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of a Middle-vessel Distillation Column, in Fifth International
Conference on Foundations of Computer Aided Process Design,
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AIChE, New York, pp. 302305 (2000).
2. Phimister, J. R., and W. D. Seider, Semicontinuous, Middle-
Vessel Distillation of Ternary Mixtures, AIChE J., 46 (8), pp.
15081520 (2000)
3. Phimister, J. R., and W. D. Seider, Semicontinuous, Middle-
Vessel, Extractive Distillation, Comput. Chem. Eng., 24, pp.
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4. Phimister, J. R., and W. D. Seider, Semicontinuous, Pressure-
Swing Distillation, Ind. Eng. Chem. Res., 39, pp. 122130
(2000).
5. Phimister, J. R., and W. D. Seider, Distillate-Bottoms Control
of Middle-Vessel Distillation Columns, Ind. Eng. Chem. Res.,
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6. Srensen, E., and S. Skogestad, Optimal Operating Policies of
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the International Federation of Automatic Control (IFAC) work-
shop, London (1992).
8. Skogestad, S., et al., Multi-vessel Batch Distillation, AIChE
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9. Hasebe, S., et al., Optimal Operation Policy for Total Reflux
and Multi-Effect Batch Distillation Systems, Comput. Chem.
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11. Oppenheimer, O., and E. Srensen, Comparative Energy Con-
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Eng., 21, pp. S529S534 (1997).
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