Computers &em. Engng, Vol. 15, No. 5, pp. 325-335, 1991 009%1354/91 $3.00 + 0.

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printedin Great Britain.All rights reserved Copyright0 1991 PergsmonPressPie

SIMULATION OF DYNAMICS AND PHASE

PATTERN CHANGES FOR AN AZEOTROPIC
DISTILLATION COLUMN

D. S. H. WONG, S. S. JANG~ and C. F. CHANG

Department of Chemical Engineering, National Tsing Hua University, Hsinchu, Taiwan 30043,
Republic of China

(Received I? August 1989; final revision received 1 September 1990;

received for publication 21 January 1991)

Abatraet-In this work, a dynamic model for an azeotropic distillation column capableof predictingthe
appearanceand disappearance of stageswithmultipleliquidphaseswas developed.The dynamicbehavior
of an azeotropicdistillationcolumn separatingethanol and water using benzeneas the entrainerwas
extensivelystudiedusingthismodel. Responsesof thecolumnto feedupsetsin flowrates and composition,
as well as changes in operating parameters such as aqueous refiux rate, reboiler duty and entrainer makeup
were simulated. Appearance of heterogeneous two-phase liquid in various equilibrium stages, and the
movement of the temperature front were predicted. Moreover, response of the column with temperature
of stage 23 being controlled by manipulating the aqueous reflux flowrate were simulated. It had been found
that the formation and disappearance of a heterogeneous two-liquid phase in stages inside the column
were critical to the dynamic behavior of the azeotropic column.

1. INTRODUCTION the column. The relation between two-phase steady

Azeotropic distillation has been commonly employed
as the process for separating species with close boiling
points or breaking azeotropes. In this process, the
relative volatilities between components to be separ-
ated is increased by adding an entrainer which forms
and azeotrope with one of the components. Such a
process usually involves heterogeneous liquid-tiquid
equilibrium in the condenser-decanter stage. Usually,
the organic phase is completely refluxed, white only
a portion of the aqueous phase is refluxed. However,
the performance of the column is very sensitive to
this reflux. Heterogeneous phase splitting may occur
near the top of the column. The temperature and
concentration profiles for such columns usually
exhibit steep fronts. There may be multiple steady
state solutions for a given set of design specifications.
The design and operation, as well as modeling of
azeotropic distillation processes, are therefore no easy
tasks.
Steady state simulation of heterogeneous
azeotropic distillation columns had been studied by
many authors, for example, Block and Hegner (1976),
Ross and Seider (1985) and Ferraris and Morbidelli
(1981). Magnussen et al. (1979) found multiple sol-
utions for a particular set of design specifications.
Kovach and Seider (1987a) and Prokopakis and
Seider (1983a) proposed a homotopy-continuation
optimization algorithm for designing the steady state
operating conditions for azeotropic columns without
considering vapor-liquid-liquid coexistence within
~To whom all correspondenceshould be addressed.
state solution multiplicity and a three-phase steady
state solution was discussed in terms of bifurcation
theory by Kingsley and Lucia (1988); who also used
the tunneling method for the optimization problem.
Design, optimization and minimum reflux of an
azeotropic distillation column were also studied by
Doherty and coworkers (Pham et al., 1989; Ryan and
Doherty, 1989). A critical aqueous reflux ratio was
identified by Widagdo ef al. (1989) using steady state
analysis and parameterization with respect to
aqueous reflux ratio.
Dynamic simulation for processes had been a
convenient tool to get better understanding of
performances. Dynamic simulation for conventional
distillation columns was extensively studied by many
investigators [e.g. Howard (1970), Ballard and
Brosilow (1978) etc.]. Dynamic simulation studies for
azeotropic columns were, however, much more
limited in scope. Prokopakis and Seider (1983b)
presented in dynamic simulation scheme which
assumed at1 stages in the column, except the con-
denser-decanter, operated with homogeneous liquid
phases. Dynamic behavior of an ethanol + water
column with benzene as the entrainer was discussed.
Rovagtio and Doherty (1990) demonstrated, using a
dynamic model, complex dynamic behavior due to
multiple steady states and parametric sensitivities, in
particular, with respect to small changes in column
pressure. However, the effect of changes in phase
pattern inside the column on the dynamic behavior
had not been studied in any detail.
Work on process control and operating strategy
for azeotropic columns had been limited due to

325
326 D. S. H. WONG et al.

the lack of an accurate physical model. Industrial 2. THEORY

practice for controlling azeotropic columns was 2.1. System equations
discussed by Bozehardt (1988). Kovach and Seider The schematic of an azeotropic distillation column
(1987b) reported results of experimental dynamic test is illustrated in Fig. 1, while a general equilibrium
for a set-butyl alcohol + water column with di-sec- stage in such a column with possible immiscible
butyl ether as the entrainer. They indicated that the liquid-liquid coexistence is represented in Fig. 2. If
temperature front in the azeotropic distillation the coexisting liquid phases were well mixed, an
column could be very sensitive to manipulation of the “overall” or “average” liquid phase could be defined
flowrate of the aqueous reflux stream. in terms of the individual phases as suggested by
In this work, our objective was primarily to study
Schuil and Boo1 (1985):
the dynamic behavior of an azeotropic distillation
column in which stages with a heterogeneous two- P, = rjx; + (1 - r,,x;, (1)
phase liquid might appear. A dynamic model for an
iGj = MT/rj = MT/(1 - rj), (2)
azeotropic distillation column capable of predicting
the appearance and disappearance of stages with E,. = Lp/r, = LB/(1 - rj). (3)
multiple liquid phases was developed. The integration
In the above and subsequent equations, the proper-
scheme proposed by Ballard and Brosilow (1978) was
ties of the organic, aqueous and average liquid phases
modified to accomodate the appearance of multiple
were represented by superscripts o, a and -, respect-
liquid phases. Phase separation was determined by
ively. The component species, the total number of
testing the stability of the average liquid phase using
species being C, were indiced by subscript i and
the tangent plane analysis proposed by Michelsen
properties of the column stages, with the condenser
(1982) and liquid-liquid equilibrium flash. The dy-
counted as stage 1 and the reboiler counted as stage
namic behavior of an azeotropic distillation column
S, were indiced by the subscript j.
separating ethanol and water using benzene as the
If we further assumed that the individual
entrainer was extensively studied using this model.
liquid phases were in equilibrium with each other
The effects of the appearance of a heterogeneous
and the vapor phases, overall K-values could be
two-phase liquid on the column dynamics were
defined:
further illustrated by examining the implementation
of an automated control loop that controlled the (4)
temperature front in the column by manipulating the
aqueous reflux rate. (5)

Fig. 1. Schematic illustration of a heterogeneous azeotropic distillation column.

 Simulation of dynamics and phase pattern changes 327

Fig. 2. Schematic illustration of an equilibrium stage in a heterogeneous azeotropic distillation column.

The overall liquid enthalpy of stage i could also be where WA,, WHj and WKj were characteristic par-
defmed as: ameters of the type of tray used; and pj was the
average density of the liquid phases present. It could
?$=r,hg+(l -r,)/zi”. (6) be seen from the above equation that mj, the average
Employing the above definitions of overall liquid molar holdup was a function of liquid flow but not
properties, the dynamic material balance (M), equi- vapor flow. The following assumptions were made to
librium (E), summation (S) and enthalpy balance simplify calculations: (i) the dependence of WKj on
(n) equations could be written as: liquid density [see Prokopakis and Seider (1983b)]
was neglected; and (ii) the partial derivatives amj/a&j
di@.
2 =Ej_,L;- y.+ y+,+l$ were negligibly small.
dt The methods used for physical properties esti-
d(li;i,n,) mation are described in Appendix A.
= L, _ , zz,,_ , - (L, + Rij Vj)Zij
dt Given the above equations and simplifying as-
sumptions, a semi-implicit-Rung+Kutta scheme
+Kfi+t c+~Pi~+,+Fjzij, (8) was adopted to integrate the system, as Ballard
y, = irijnij, (9) and Brosilow (1978) and Prokopakis and Seider
(1983b) did for a homogeneous distillation system.
(10) The MESH equations could be rearranged into the
following system of differential equations of changes
d(m.?L) in “average” liquid mole fraction and liquid
JI =Ej_,hi_, -L,li,- v,n, flowrates:
dt
+vj+,n,+, + Fiff4. + Qj, (11) dZ/dt = f(Z, V, #, T, M, L,, x,), (13)
for all the relevant species i from 1 to C and stages with
j from 2 to S.
In the above equation, the efficiency of a real stage
was neglected. However, a Murphree tray efficiency
could be included into the analysis without any (14)
difficulty if desired.
the function f is illustrated in Appendix B. In this
The hydrodynamics of the stage was described by
form the Jacobian matrix J could be approximated
the following modified form of the Frances weir
by a tridiagonal matrix.
equation:
The enthalpy balance equation could be reduced
m, = /i, WA,( Wn, + WKitff3), (12) into an algebraic equation for relating vapor
328
flowrates of all the stages except the decanter and the
reboiler:
O=C,jLj_, +C2jVj+C~jVj+I+C4jv
j=2,...,s-1.
The expressions for coefficients cy, crj, cy and cdjare
given in Appendix B.
For the reboiler, we assumed that the temperature
of the reboiler was at the bubble point of the
liquid. Furthermore, the molar holdup of the reboiler
was near constant due to large size and level
control action. Therefore, the vapor and liquid flow
of the reboiler were calculated by the following
equations:
v,= -(c,,L, + %)Czri,
L,=L,_1- vs.
The coefficients cls and cdr are the same as those
defined as in Appendix B.
For the condenser-decanter, the following assump-
tions were made, as suggested by Propkopakis and
Seider (1983b):
1. The decanter volumetric holdup was constant,
due to the large size and control action.
2. The temperature of the decanter was constant.
3. The two liquid phases in the decanter were in
equilibrium.
4. The two liquid phases were perfectly split, so
that the ratio of flowrates of the two liquid
phases out of the decanter and the amount of
holdup in the decanter were both equal to the
equilibrium phase fractions.
Using these assumptions, the following equations for
the condenser could be derived:
Q, = ~zW,(T,, YZ>- h, CT, 3 YJ.
The overall composition and flowrate of the refluxed
stream could then be calculated as:
1=, =L”,+crL;+F’,
fi, = (x~L~+x$aL~+x;I;“)/L,,
with xf and F being the composition and flowrate of
the entrainer makeup stream, and cxbeing the fraction
of aqueous phase overflow refluxed.
D. S. H. WONG et al.
2.2. Solution algorithm
The system equations were integrated by a third-
order semi-implicit-Runge-Rutta scheme (Seinfeld
et al., 1970) with the following steps:
(15) Step 1. For any iteration k in the integration
procedure:
AZ, =(O - 0.4358662rJk)-‘tf
x (Z”, Vk, Mk, T*, M*, c:, %:), (18)
was calculated with r being the size of
the time step and Jlkbeing the Jacobian
matrix.
Step 2. New values of J& for i=l,...,C
and j = 2, . . . , s; and Ej, for
j=2,...,S-1:
(16a)
Z=Zk+0.75AZ,, (19)
(16b)
were calculated. Then for each stage j:
Step 3. A tangent plane stability test suggested
by Michelsen (1982) at the temperature T,
(assumed to be Tf for the first time
through this step) for a given overall
liquid composition f, was performed. If
the average liquid phase was found to be
unstable, and isothermal liquid-liquid
flash calculation was performed; so that
rj, x$ and x,; could be found.
Step 4. A bubble point temperature calculation
for the liquid composition x; if
liquid-liquid separation was present to
find a new Tj. If this new Tj differed from
the assumed value of q, Steps 3 and 4
were repeated using the new value of Tj
until convergence to within a tolerance
level was achieved. If there was only one
homogeneous liquid phase, bubble point
temperature calculation was performed
to determine the new Tj. Individual and
(17a) “average” K-values, KG, Kjl, and Rij were
updated with the liquid-liquid flash and
bubble point temperature calculation.
(17b) Step 5. New values of V,, Ls were calculated
using equations (16a) and (16b) using new
values of L,_,, %, P,_,, T,, T,_,, Kb.
Step 6. New values of Vj were found using
equations (15) and (Bl3-B17) with
new values of Tj, Kij and Lj; for
j=2,...,s-1.
(17e) Step 7. NewvaluesofM,,j=2 ,..,, S-1,were
calculated using equations (12) with new
values of rj, xQ, x;, rj and Tj.
Step 8. The second correction in Z:
(17f) AZ* = (0 - 0.4358662rJIk)-‘zf
(17g) x (Z, V, R, T, M, Et, g:), (20)
were calculated with updated values of Z,
Vk, Ddk,Tk, M’, but unchanged values of
Jk and E, and Zi,.
 Simulationof dynamicsand phase patternchanges

Step 9. The third correction in Z:

AZ3 = (0 - 0.4358662rJk)- 1
x ( - 0.63020209 AZ, _ 3. 200Min

- 0.24233789 AZ,), (21)

were calculated using AZ1 and AZ,.
Step 10. The total correction in Z:
Zk + ’ = Zk + 1.037609496 AZ,
+ 0.83493048 AZ, + AZ3 , (22)
were calculated. 2 4 6 6 10 12 14 16 18 20 22 24 26
Step 11. Values of V,, L,, Vk+l, Tk+‘, xGkk+‘, STAGE NUMBER
s/c* I rk+‘, RI+’ ‘and &$+I were (a)
XiJ
updatbd &ing Steps 3-7.
Step 12. New values of m* ’ and ai+ ’ were 1.0
calculated by integrating equations (17a)
and (17b) with Euler’s method. An 3 200Min
isothermal liquid-liquid flash calculation 4. 2000Min
at the decanter temperature was per-
formed for this new overall liqiud com-
position to determine x? k+ ’ , x2’+’ and
kfl
?-I . The changes it the decanter
overtlow Ls, Lz and the reflux rate and
composition L, and %, were found using
equations (17c-f).
oc
This algorithm was carried out on a SUN 3160 4 6 8 10 12 14 16 18 20 22 24 26 ;
workstation, and the step sizes used for integration of STAGE NUMBER
the example problem discussed in the next section (b)
were 0.1 min for the first 60 min after initial step
change and 0.2 min for the rest of the time. Each time Fig. 3. Movement of column profiles with a +30% step
required the order of 1 CPU s. changein feed iiowrateand aqueousrefluxrate maintained
constant: (a) temperature;and (b) composition.
3. RESULTS AND DISCUSSION

3.1. The steady state base case
In this work, the dynamics of the azeotropic distil-
lation column for separating ethanol and water
with benzene as the entrainer, were simulated. This
column was similar to the one studied by Prokopakis
and Seider (1983b) and Rovaglio and Doherty (1990).
Under steady state operation, homogeneous liquid
phases were found in all states of the column. The
fronts of the temperature and composition profile
were found from stages 19 to 26.
3.2. Feedflowrate increase at constant aqueous refZux
rate
The dynamic changes of such an azeotropic
column given a +30% step change in feed flowrate
were studied with the aqueous reflux rate maintained
at the steady value. The changes in temperature and
composition profiles with time are illustrated in
Figs 3a and b. Both fronts first shifted downwards to
the reboiler and then upward, passing the original
position. Qualitatively similar observations were
reported by Prokopakis and Seider (1983b) using
a dynamic simulation without considering the possi-
bility of the existence of multiple liquid-liquid phases.
No heterogeneous liquid phases was found in our
simulation. This example demonstrated that our re-
sults were consistent with the previous study.
3.3. Feedfiowrate increase at constant aqueous reflux
ratio
If we maintained a constant reflux ratio for the
aqueous liquid out of the condenser-decanter stage,
instead of a constant aqueous reflux rate, the dynamic
behaviour of the column changes entirely. Tem-
perature and composition profile responses to a
+30% step change in feed flowrate are shown in
Figs 4a and b. Interestingly, the temperature and
composition fronts had two inverses, first shifting
towards the reboiler, then upward in about 200 min,
and then towards the reboiler again. For the stages
(21-25) at the front, double inverse responses were
observed.
The first downward shift of the temperature front
was believed to be an effect of washing out by the
increased feed liquid tlow, the magnitude of which
changes with tray design. The following upward shift
was explained by the decreased ratio of entrainer
to water. As the total amount of feed entering the
 D. S. H. WONG et al.

entrainer was holdup in stage 2 with the formation of

1. 0 Min two heterogeneous liquid phases.
2 5Min In this simulation case, the initial steady state
3. 200Min had no two-liquid stages inside the column, and in
4. 2000Min the final steady state, heterogeneous liquid-liquid
equilibrium was found on stage 2. Correspondingly,
the temperature front shifted downward. As the
347
-- t aqueous reflux rate increased, extraneous liquid
phases began to appear near the top of the column.
Figure 5 illustrated the changes in phase fraction

.
-2
..7 4 6 8 10 12 l4 16 18 20 22 24 26 28
for the first six stages below the condenser when
feed Aowrate was increased by 30, 40 and 50%.
We found that as more water was refluxed into
STAGE NUMBER the column, the number of stages with heterogeneous
(a) liquid phases increased. In some stages, a hetero-
geneous two-phase liquid appeared after a long time
delay, causing a long transition time from one steady
state to another. Furthermore, as the plait condition
(interface between stages with two-liquid phases
and one liquid phase) propagated down the column,
the temperature front shifted more towards the
reboiler.
Using dynamic test results performed for a
SBA + water column with DSBE as the entrainer,
Kovach and Seider (1978b) concluded that by

2 4 6 8 10 12 14 16 18 20 22 24 26 28
STAGE NUMBER
(b)
Fig. 4. Movement of column profiles with a +30% step
change in feed flowrateand aqueousrefluxratiomaintained
constant: (a) temperature;and (b) composition.

column increased, more benzene was required for u 1000 2ooo

entraining. Therefore, the amount of benzene near
the bottom part of the column decreased, and the
temperature and composition profiles shifted up-
wards. The increased flow of water to the upper part
of the column resulted first in an increase in aqueous
holdup in the condenser (as illustrated in Fig. Sa) in
the first 200min. During this period, the aqueous
overtlow did not increase appreciably, therefore, the
aqueous refiux rate remained relatively unchanged.
After the aqueous liquid holdup in the con-
denserdecanter had reached a certain limit, the
aqueous overflow began to increase. As the aqueous
reflux ratio was kept constant, the aqueous reflux rate
also increased. The aqueous phase of the condenser
consisted mainly of water saturated with entrainer
and ethanol. However, the ratio of entrainer to water
in this phase was higher, and the ratio of entrainer to
ethanol was much lower than those in the feed and
the entrainer makeup. Moreover, the reflux stream
was at room temperature. Therefore, the ultimate
effect of the increased aqueous phase refluxed into the 0 1000 2000
column was to push the temperature front down Fig. 5. Changesin liquid phase patternwith step increases
towards the reboiler. Although this downward shift in feed flowrate and aqueous reflux ratio maintained con-
was delayed as a certain amount of this water and stant: (a) +30%; (b) ~40%; and (c) +50%.
 Simulation of dynamics and phase pattern changes 331

increasing the aqueous reflux rate, the temperature _-.

: 1. OMin
front would be pushed towards the reboiler and the
number of stages with two liquid phases increased.
- 3. 5OMin
Appearance of a heterogeneous two-liquid phase
phenomenon was suggested and explained by steady
_ 52000Min
simulation results. Our dynamic simulation study
concurred with the observation.

3.4. Increase in water content of the feed

Figure 6a demonstrates the movement of the tem-

perature front when the initial steady state was upset
by a step increase in feed water content to 20 moi%. 6 10 14 18 22 26
In this simulation case, the aqueous reflux rate was (a)
maintained at a constant value. The initial downward
shift of the temperature front, observed in the pre-
vious case with feed flowrate upset, was not found as
GE 6 ( FEED STAGE)
the hydrodynamic washing out effect was absent. The
temperature front and domposition of the column in
this case shifted and stayed upward toward the
condenser. The phase pattern changes following
the upset in feed water content for the condenser- 0.8
decanter stage and stage 2 is illustrated in Fig. 6b.
Heterogeneous two-phase phenomena were observed
immediate1y as more water was introduced in the feed
stage (stage 6). However, the water was quickly
entrained to the condenser stage leading to a slight 500
decrease in the organic phase fraction in the decanter, (b)

Fig. 7. Responsesto an increasein feed water content to

20mol% with aqueous reflux ratio maintainedconstant:
(a) temperatureprofile; and (b) phase pattern.

leading to an upward movement of the temperature

front.
If the aqueous reflux ratio was maintained at a
constant value, the temperature front and compo-
sition of the column in this case first shifted upward
4. 200 Min
toward the condenser and then downward towards
5 2C0OMin
the reboiier as illustrated in Fig. 7a. The phase
pattern change following the upset in feed water
r.,‘.“.““‘.“..“.“.‘,l content for the condense-decanter and stages 2,4, 6
5 10 15 20 25
and 8 is illustrated in Fig. 7b. Similarly, hetero-
(0) geneous two-phase phenomena were observed almost
1 immediately in stage 2, as more water was introduced
1 in the feed stage. However, as more water appeared
TAGE 2 in the condenser, a strategy of maintaining a con-
stant reflux ratio resulted in an increase in aqueous
reflux rate. Liquid phase splitting followed shortly in
0.9 the stages near the top of the column. As the plait
STAGE 1 condition marched down the column, the tempera-
(CONDENSER DECANTER) ture front was also shifted towards the reboiler in the
/ new steady state.

““lLdLKz3
0 1000 2000
3.5. Movement of temperature front
aqueous rate and reboiler duty
with changes

In our problem formulation, there were three basic

in

operating degrees of freedom: the entrainer makeup

(b)
Fig. 6. Responsesto an increasein feed water content to rate, aqueous reflux rate and reboiier duty. Quality of
20mol% with aqueous retkx rate maintained constant: the separation was indicated by the movement of the
(a) temperature profile; and (b) phase pattern. temperature front. Therefore, the reaction curves of
332 D. S. H. WONG et al.

Temperature response of stage 23 353

aqueous reflux rate + 20 %
352

_ 351

346

345
-

-
;;z/
J,
0 0.2 a4 0.6 0.8 1.0 1.2 94 1.6 lB 2.0
I I 1 I I I I I I I
344
0 a2 0.4 0.6 08 1.0 12 ‘1.4 7.6 1.6 2.0
Time (103min)
( Thousands 1 Fig. 10. Temperature response of stage 23 to a 20% increase
Time ( minutes I in entrainer makeup.

Fig. 8. Temperatureresponsesof stage 23 to a 20% increase

in aqueous reflex rate. 3.6. Controlling the temperature front of aqueous
repUx rate

temperature of stage 23 with respect to changes in Results of our dynamic simulation indicated that
these operating variables were simulated. the column dynamic behavior was very complex. Due
If the aqueous reflux rate was increased by 2Q%, to complexity of the column’s dynamics, it is unlikely
a small initial hydrodynamic washing out effect that any simple control scheme could be used to
was observed followed by a prolonged decrease in regulate the performance of the column. In this study,
temperature, as shown in Fig. 8. This was due to the the aqueous reflux rate was considered as a manipu-
increase in aqueous reflux which was saturated with lating variable to control the process. It should be
benzene and at a lower temperature. emphasized that it was not the purpose of the follow-
Similarly, if the reboiler duty was increased by ing discussion to determine optimal control strategy.
20%, an initial (and more pronounced) hydro- Rather, we attempted to point out that nonideality of
dynamic entraining effect was observed due to the the process presented serious difficulties for designing
increase in vapour flow. This was followed by such control action. Furthermore, we would like to
a prolonged increase in temperature of stage 23, demonstrate the effect of phase pattern changes on
illustrated in Fig. 9. The response was found to be the dynamics of this process.
qualitatively similar, but in an opposite direction to In this study, the temperature of the 23rd stage
the one obtained with an increased aqueous reflux was controlled by a PI loop manipulating the
rate. aqueous reflux rate. Control tuning parameters were
Figure 10 demonstrates that if the entrainer obtained using a simulated reaction curve and the
makeup was increased by 20%) we observed a general Ziegler-Nichols method. The gain parameter rcfand
downward shift in temperature. The hydrodynamic the time constant 7i were determined to he -2.565
effect was absent in this case, as the entrainer makeup and 279, respectively.
rate was relatively small. Responses of this control setting to +30 and
In all three cases, homogeneity was found in +40% feed flowrate upset are illustrated in Fig. 11.
all stages in the column during the transition to
the new state.

I ( 8 I I1 Id I,

0 0.2 0.4 0.6 0.6 1.0 1.2 ‘1.4 16 1.8 20 3451 1

Time (103min) 0 2cOo 4ooo
Fig. 9. Temperature response of stage 23 to a 20% increase Fig. 11. Controlled response of temperature of stage 23 to
in reboiler duty. +30 and +40% step changes in the feed flow.
 Simulationof dynamics and phase pattern changes
501 I aqueous reflux rate, reboiler duty and entrainer
0 2ooo 4ocO
Fig. 12. Control action response (changes in aqueous reflux
rate) to f30 and +40% step changesin the feed flowrate.
It was clear that unstable oscillation was found
for the latter. This was found to bc attributable to
the appearance of a heterogeneous two-liquid
phase phenomenon for the top stages. Changes
in manipulating variable are illustrated in Fig. 12.
Phase pattern of stage 2 for the case of +40% step
change is given in Fig. 13. For the case with
+30% upset in feed flowrate, homogeneity was
maintained inside the column throughout the course
of transition, while periodic phase-splitting occurred
for the case with +40% upset in feed rate. In
general, the effect of increasing aqueous reflux
rate was to decrease the temperature of the column,
as recognized by the controller through the reaction
curve. However, the appearance of an extraneous
aqueous liquid on stage 2 would create a momentary
holdup of the water and entrainer. The effect of
the aqueous reflux rate on the temperature of
stage 23 would be minimized. This kind of change
in phase pattern resulted in overshooting and
oscillatory response. This argument was further
supported by the temperature response to 40%
in feed rate, simulated assuming that there was
no liquid-phase splitting inside the column. As
illustrated in Fig. 11, no oscillation was found in
this case.
1
L.I III
0.9
0.8
0 2000 4ooo
Fig. 13. Changes in phase pattern of step 2 with control
action responseto +40% change in the feed flowrate.
333
4. CONCLUSIONS
fn this study, a dynamic simulation algorithm for
an azeotropic distillation column capable of predict-
ing the appearance of heterogeneous liquid phases
was developed. Thus the changes in liquid phase
pattern of an azeotropic distillation column, and
the resulting effects on the dynamics of the column
could be followed. The dynamic response of an
ethanol + water column with benzene as the entrainer
to upsets in feed flowrate and feed composition
as well as changes in operating variables such as
makeup rate were simulated.
In our simulation, we found that apart from an
initial hydrodynamic effect, increasing the feed
flowrate or feed water content in an aqueous constant
reflux rate would shift the temperature front towards
the condenser. However, if the aqueous reflux ratio
was kept constant, the temperature front first shifted
upward and then downward, resulting in an inverse
response.
In our simulation, it was found that by refluxing
more of the aqueous product of the condenser-
decanter, the fronts of the temperature and com-
position profiles of the column could be pushed
downwards towards the reboiler. Similarly, results
could be achieved by a decrease in reboiler duty or an
increase in entrainer makeup.
The feasibility of controlling the operation quality
of the process by controlling the position of the
temperature front by manipulating the aqueous
reflux rate was investigated. It was found that the
appearance and disappearance of a heterogeneous
two-liquid phase phenomenon inside the column
would lead to instability of the operation. The com-
plexity of the column dynamics precluded any simple
control scheme.
Acknowledgement-The authors would like to thank the
National Science Council, Republic of China, for providing
financial support of this work through Grant No. NSC-77-
0402-EOO7-14.
NOMENCLATURE
a, b, c = Coefficientsin the transformed MESH
equations as defined in equations (13), (14),
(15) and Appendix B
C = Total number of component species
F = Feed flowrate. Gmol min-’
H = Vapor molar enthalpy, J Gmol-’
HF = Feed enthalpy, 3 Gmol-’
h = Liquid molar enthalpy, J Gmol-’
J = Jacobian matrix
K = Equilibrium K-value
L = Liquid flowrate, Gmol min-’
M = Liquid molar holdup, Gmol
Q = Heat exchange rate, J min-’
g = A numerical constant
r = Equilibrium fraction of the organic liquid
phase
S = Total number of equilibrium stages
T = Temperature of each stage K
334 D. S. H. WONG et al.

WA, Wff, WK = Parameters of the weir hydrodynamic Rovaglio M. and M. F. Doherty, Dynamics of hetero-
equation (12) geneous azeotropic distillation columns. AZChE Ji 36, 39
V = Vapor molar flowrate, Gmol min - ’ (1990).
x = Liquid mole fraction Ryan P. J. and M. F. Doherty, Design/optimization of
y = Vapor mole fraction ternary heterogeneous azeotropic distillation sequences.
z = Feed mole fraction AZChE Jf 35, 1592 (1989).
Schuil J. A. and K. K. Booi, Three-phase flash and distil-
Greek letters lation. Computers them. Engng 9, 295 (1985).
tc = Aqueous reflux ratio of the decanter Seinfeld J. H., L. Lapidus and M. Hwang, Review of
p = Liquid molar density, Gmol crnm3 numerical integration techniques for stiff ordinary differ-
r = Size of the integration time step ential equations. Znd. Engng Chem. Fundam. 9,266 (1970).
ri = Time constant of a PI controller Widagdo S., W. D. Seider and D. H. Sebastian, Bifurication
K, = Gain of a Pl controller analysis in heterogeneous azeotropic distillation. AZChE
JI 35, 1457 (1989).
Superscript
o = Organic liquid properties
APPENDIX A
a = Aqueous liquid properties
- = Average liquid properties In this study, the vapor phase was assumed to be ideal.
e = Entrainer Makeup Nonideal K-values of the liquid solution were calculated
k = Time step count using the UNIQUAC equation for activity coefficients
* = Pure component properties and the Antoine equation for saturation vapor pressure
for pure components. The enthalpies of the liquid and
Subscripts vapor phases were assumed to be the molar averages of the
gk = General species index pure component liquid and vapor enthalpies which were
ebw = Ethanol, benzene and water fitted as temperature polynomials, respectively. The para-
j = Stage index metric values of these pure component properties estimation
d = Decanter stage models were given by Reid et al. (1988). The parameters of
the UNIQUAC activity coefficient model were. given by
Prausnitz et nl. (1980). They were also tabulated in the table
REFERENCES of Propkopakis and Seider (1983a). The liquid densities were
calculated by the modified Rackett equation also described
Ballard D. M. and C. B. Brosilow, Dynamic simulation of in Reid ef al. (1988).
multicomponent distillation columns. Paper presented at
the AIChE Annl Meeting, Miami (1978).
Block U. and B. Hegner, AZChE Jl22, 582 (1976). APPENDIX B
Bozenhardt H. F., Modern control tricks solve distillation
The MESH equations defined in equations (7-12) could be
problems. Hydrocarbon Process. Mar. 47 (1988).
rearranged in the following forms:
Ferraris G. B. and M. Morbidelli, Distillation models for
two partially immiscible liquids. AZChE JI 27, 881 (1981). a..
Howard G. M., Unsteady state behavior of multicomponent --? = a,,&]_, + n,;jzij+ a3ii+ ,f,], , + 04ii’
dt
distillation columns: Fart 1: Simulation. AZChE JI 16,
i=l,..., C,j=2 ,..., S, (Bl)
1022 (1970).
Kingsley J. P. and A. Lucia, Simulation and optimization of with
three-phase distillation processes. Znd. Engng Chem. Res.
27, 1900 (1988). aI,,=Z;,_,ilc3,, (B2)
Kovach J. W. and W. D. Seider, Heterogeneous azeotropic a~,~= -[L;i-,+ V&- l)+&V,+,+F,]Jm,j, (B3)
distillation-homotopy continuation method. Computers
them. Engng II, 593 (1987a). %ij= ~+IKij+Ilmj, (B4)
Kovach J. W. and W. D. Seider, Heterogeneous azeotropic a,, = FjIij fiEfj, (B5)
distillation: experimental and simulation results. AZChE
JI 33, I300 (1987b).
and
Magnussen T., M. L. Michelsen and A. Fredenslund, dL-
Azeotropic distillation using UNIFAC. Inst. Chem. / = b,jLj_, + bzjLj + b, V, + b, Vj+ , + b,
dt
Engng Symp. Ser. 56, 4.211 (1979).
Michelsen M. L., The isothermal flash problem, Part I: j=2,...,S-

1,
L-2ij)/M,
stability. Fluid Phase Equil. 9, 1 (1982). with

;=*
Pham H. N.. P. J. Ryan and M. F. Doherty, Design and
minimum reflux for heterogeneous azeotropic distillation b,j = 1- 5 (amj/ an,)(a,_
columns. AZChE JI 35, 1585 (1989).
Prausnitz J. M., T. F. Andersen, E. A. Grens, C. A. Eckert, x [(2lr3i WKj/3)-‘( WHjq13 + WKj)]-‘, (B7)
R. Hsieh and J. P. O’Connell, Computer Calculations
for Multicomponent Vapor-Liquid and Liquid-Liquid
Equilibria. Prentice-Hall, Englewood Cliffs, New Jersey b,= -[2M,WK,/3)-‘(WH,q’3 + WK,I,)]-‘, (B8)
(1980).
Prokopakis G. J. and W. D. Seider, Feasible specification in
azeotropic distillation. AZChE JI 29, 49 (1983a).
Prokopakis G. J. and W. D. Seider, Dynamic simulation in
azeotropic distillation. AZChE JI 29, 1017 (1983b). x [(Zmj WKj/3)-‘( WNjLj13 + WKj~j,)I-‘, (B9)
Reid R. C., J. M. Prausnitz and B. E. Poling, Properties of

1
Gases and Liquid, 4th Edn. McGraw-Hill, New York
(1988). b+ = 1- 5 (a.Uj/ &i,)(K, - 1)%,/M,
Ross B. A. and W. D. Seider, Compurers them. Engng 5,295 i-l
(1985). x [(21c3 WK//3)-‘( WH,L;” + WKjLji)]-‘. (BlO)
 Simulation of dynamics and phase pattern changes 335

In equations (B12-B16), Ir$ denoted the liquid enthalpy

b, = 4 1- i: <ahiF,/an,)(f, - ~,,>/m, of species i at the temperature of stage j, calculated accord-
i=I 1 ing to the methods described in Appendix A. cp, was the
x [(2113iWK,/3)-‘(WH,qf’ + WK,L;,)]-‘. (B11) heat capacity of the “average” liquid phase at stage j,
Assuming that the variables V, K, M remained unchanged the derivative of the “average” liquid enthalpy with
over the integration. It was found to approximate a tridiag- respect to temperature, calculated according to the averag-
onal matrix. ing procedure described in equation (6) and methods
The coefficients of the algebraic enthalpy balance described in Appendix A. HF-, referred to the enthalpy of the
feed stream.

(B12)
equation (15) could be written as:

i=l
clj=

1 5 (h;+~~,g,j)(-i,j-*--,j) --cli,-l-_Ti,)Y
APPENDIX C

cy
= 5(h;
+C,S,)(R;,.-
[

1
The azeotropic column simulation example studied in this
I)?,) -(Rj_, -hi), (Bf3) work has 28 stages including the condenser-decanter (stage
[ i= I 1) and the reboiler (stage 28) with the feed stream at stage 6.

1
The feed stream contains 89Gmolmin-’ of ethanol and
c3j= 2 (h,:+C,,d;,)(R,*,x,*,--ij) -Cr;,+,-h;),
11 Gmol min-r of water at 298 K. The effective cross sec-
[
i=l tional area of each plate WAj is Q.23m2, the weir height
(B14) WHj 0.0254m. The height over weir coefficient WKj is

1
0.00508. The volume of reboiler and condenser holdup were
Cdj= --q 5 (h$ + c,si,)(z,- a,) both 1 m3. The steady state values of some of the

+(ffF,--j)
+
{L i= L operating variables are listed here: for the reboiler: V, =
426.5 mol min-I, xbz8= 9.809 + IO-‘, xwz8= 1.776 x 10-4,
Q,, (Bl5)
Q2s = 1.734 x 10’ J min-‘; for the condenser: xs = 0.2398,

@16)
>

i=l 1
x& = 0.6713, x; = 0.0889, x&, = 0.3762, x& = 0.0815,
6, = - Ki, 5 zij(aq a?) C& = 0.5423, L: = 312.8 mol min-‘, L.2 = 78.2 mol min-‘,
F’ = 1.829 mol min-‘, a = 0.74489.