Chemical Engineering Science 58 (2003) 2671 2680

www.elsevier.com/locate/ces

Dynamic rate-based and equilibrium models for a packed reactive

distillation column
Jianjun Peng, Thomas F. Edgar , R. Bruce Eldridge
Department of Chemical Engineering, Separations Research Program, The University of Texas at Austin, Austin, TX 78712-1062, USA
Received 12 February 2002; accepted 3 January 2003

Abstract
Dynamic rate-based and equilibrium models were developed for a packed reactive distillation column for the production of tert-amyl
methyl ether (TAME). The two types of models, consisting of di5erential algebraic equations, were implemented in gPROMS and dynamic
simulations were carried out to study the dynamic behaviour of reactive distillation of the TAME system. The dynamic responses predicted
by the two types of models are similar in general, with some di5erences in steady-state values. The in7uence of manipulated variables,
such as distillate 7ow rate, re7ux ratio, and reboiler duty, on the dynamic responses of the controlled variables (reactant conversion and
product purity) was studied. The dynamic response of reactant conversion is very nonlinear and unconventional, but the response of product
purity is well approximated by a linear 9rst-order di5erential equation. The CPU time required to complete a dynamic simulation of the
rate-based model is at least an order of magnitude higher than that for the equilibrium model. Therefore, the dynamic rate-based model
is much more complicated than the equilibrium model, and simpli9cation of the rate-based model is necessary for the implementation
of model-based control. A new approach was proposed to simplify the dynamic rate-based model by assuming that the mass transfer
coe;cients are time invariant. This approach was demonstrated to be superior to the conventional simpli9cation methods. It can reduce
the number of equations by up to two-thirds and still accurately predicts the dynamic behaviour.
? 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Reactive distillation; Dynamic simulation; Modelling; Process control; Rate-based model; Nonlinear dynamics

1. Introduction
For some chemical processes, reactive distillation o5ers
many potential advantages over separate distillation plus reaction processes, such as higher conversion, reduced capital
cost and higher selectivity (Doherty & Buzad, 1992). For
a properly designed reactive distillation column, the reactant conversion can approach 100%. Several reactive distillation processes have been successfully commercialized.
The most spectacular example of reactive distillation is in
the production of methyl acetate (Taylor & Krishna, 2000).
The traditional process uses one reactor and nine distillation
columns. When reactive distillation is used, only one reactive distillation column is needed. The process is drastically
simpli9ed and the capital cost is greatly reduced by using
reactive distillation.

Corresponding author. Tel.: +1-512-371-3080;

fax: +1-512-471-7060.
E-mail addresses: edgar@mail.utexas.edu, tfedgar@che.utexas.edu
(T. F. Edgar).

However, it is much more di;cult to model, design

and control reactive distillation because of the complicated
interaction between reaction and distillation. Taylor and
Krishna (2000) made a comprehensive review on modelling
of reactive distillation with more than 300 references. Most
of the models published in the literature are steady-state
models. There are very few publications on dynamic modelling and control of reactive distillation in the literature
and the dynamic behaviour of reactive distillation is poorly
understood. Therefore, it is important to study this aspect
of reactive distillation in detail, in order to evaluate process
control approaches.
There are two di5erent types of dynamic models that
have been employed for reactive distillation: the equilibrium
model and the rate-based (nonequilibrium) model. Roat,
Downs, Vogel, and Doss (1986) discussed dynamic simulation of reactive distillation using an equilibrium model.
The control system equations were integrated with the column model equations. Ruiz, Basualdo, and Scenna (1995)
developed a generalized equilibrium model for the dynamic
simulation of multicomponent reactive distillation. Several

0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(03)00103-9

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J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

test problems were studied and used to compare the work

with those of others. A simulation package called REActive Distillation dYnamic Simulator (READYS) was used to
carry out the simulations. Perez-Cisneros, Schenk, Gani, and
Pilavachi (1996) proposed a di5erent approach to the equilibrium model by using chemical elements rather than the
real components. The chemical elements are the molecule
parts that remain invariant during the reaction, while the
real components are formed from di5erent combinations of
elements. Alejski and Duprat (1996) developed a dynamic
equilibrium model for a tray reactive distillation column.
Vapour holdup was ignored and di5erent levels of simpli9cation were tested against dynamic experiments for the production of ethyl acetate. It was found that the model which
contains hydraulic description of trays was the most accurate. A similar dynamic equilibrium model was developed by
Sneesby, Tade, Datta, and Smith (1997) for a tray reactive
distillation column for the production of ethyl tert-butyl ether
(ETBE). Chemical equilibrium on all the reactive stages and
constant enthalpy were assumed to simplify the model. The
model was implemented in SpeedUp and the open-loop response was simulated. It was pointed out that the interaction between the chemical and phase equilibrium in reactive distillation creates several unconventional control problems which do not generally occur with conventional distillation. Kreul, Gorak, Dittrich, and Barton (1996) developed
a dynamic rate-based model for a packed reactive distillation column for the production of methyl acetate. All the
important dynamic changes except the vapour holdup were
considered in the model. It was found that high-index problems may arise if the pressure drop is not related to vapour
and liquid 7owrates. The dynamic rate-based model was implemented into the ABACUSS large-scale equation-based
modelling environment. Dynamic experiments were carried
out and the results were compared to the simulation results. It was shown that the model is able to describe the
complex operation within the error margins of the experiment over the process time. Rapmund, Sundmacher, and
Ho5mann (1998) and Mohl et al. (1999) studied the multiple
steady states for the tert-amyl methyl ether (TAME) system
and veri9ed the existence of multiplicities experimentally.
They found that temporary changes in operating conditions
may derive the column to an undesired steady state. Baur,
Taylor, and Krishna (2001) proposed a dynamic rate-based
cell model for reactive distillation tray columns. Both the
liquid and vapour phases were divided into a number of contacting cells and the MaxwellStefan equations were used
to describe mass transfer. Liquid holdup, vapour holdup,
and energy holdup were all included in the model. A reactive distillation tray column for the production of ethylene
glycol was used to carry out dynamic simulations. It was
concluded that for proper description of the reactive distillation tray column dynamics, the nonequilibrium cell model
is essential. Vora and Daoutidis (2001) considered the dynamics and control of an ethyl acetate reactive distillation
column with 11 trays. Recently, Schneider, Noeres, Kreul,

and GNorak (2001) studied reactive batch distillation for the

methyl acetate system, using a two-9lm dynamic rate-based
model. Pilot plant batch experiments were carried out to validate the dynamic model and the agreement was reasonable.
It was pointed out that model reduction without signi9cant
loss of accuracy was necessary for the dynamic rate-based
model to be used in model-based control.
The purpose of this paper is to develop and compare
a dynamic rate-based model with a dynamic equilibrium
model and to develop appropriate simpli9cation approaches
for the dynamic rate-based model. Design speci9cations
for a packed reactive distillation column at the Separations Research Program at UT-Austin, or UT-SRP (Peng,
Lextrait, Edgar, & Eldridge, 2002) were used as the basis
to carry out dynamic simulations. The dynamic responses
of the controlled variables (product purity and reactant conversion) to a step change in the manipulated variables (re7ux rate, re7ux ratio, distillate rate, bottoms rate, and reboiler duty) were studied with both the dynamic rate-based
and equilibrium models. Di5erent approaches were used to
simplify the dynamic rate-based model, which in its original form is too complicated to be used directly in process
control.

2. Model development
The dynamic rate-based model is an extension of the
steady-state rate-based model (Peng et al., 2002). The
packed reactive distillation column is vertically divided into
a number of segments (Taylor & Krishna, 1993). The condenser and reboiler stages are numbered 1 and N , respectively. The following assumptions were made to simplify
the model.
(1) Each phase is perfectly mixed in each segment.
(2) Vapourliquid equilibrium is only assumed at the interface.
(3) At the liquidcatalyst interface, pseudo-homogeneous
reaction is assumed. Thus, reaction and di5usion inside
the catalyst have not been considered.
(4) The 9nite 7ux mass transfer coe;cients are assumed to
be the same as the low 7ux mass transfer coe;cients.
(5) The heat transfer coe;cients are assumed to be constant
for all segments.
(6) The condenser and the reboiler are treated as equilibrium stages.
(7) The pressure at the condenser is perfectly controlled.
(8) The level of the re7ux drum is perfectly controlled.
(9) The level of the reboiler is perfectly controlled.
Equations for the total condenser:
Molar component balances:
dMi;L1
= V2 yi; 2 (L1 + D)xi; 1 :
dt

(1)

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

Total energy balance:

dE1L
= V2 H2V (L1 + D)H1L Q1 :
dt
Summation:
c


xi; 1 1 = 0:

Summation:
(2)

(3)

Equations for the reboiler:

Molar component balances:
dMi;LN
= LN 1 xi; N 1 VN yi; N LN xi; N :
dt
Total energy balance:
dENL
= LN 1 HNL 1 VN HNV LN HNL :
dt
Summation:
c


xi; N 1 = 0;
yi; N 1 = 0:

(4)

i=1
c


i=1
c

xi; j 1 = 0;

(14)

yi; j 1 = 0;

(15)

xi;I j 1 = 0;

(16)

yi;I j 1 = 0:

(17)

i=1

(5)

Vapourliquid equilibrium at the vapourliquid interface:

yi;I j Ki; j xi;I j = 0:

(6)

Njm = CtjV kV (yj yjI ) + yj

(7)
Njm = CtjL kL (xjI xj ) + xj

Vapourliquid equilibrium:
(8)

Equations for the jth segment:

Molar component balances of the liquid phase:
dMi;Lj

= Lj1 xi; j1 + DT2 lj aj Ni;mj
dt
4
+ Fj xi;Fj Lj xi; j + Wj Ri; j :

(9)

Molar component balances of the vapour phase:

dMi;Vj

= Vj+1 yi; j+1 DT2 lj aj Ni;mj Vj yi; j :
dt
4
Energy balance for the liquid phase:
dEjL
L
+ Fj HjF Lj HjL Qj
= Lj1 Hj1
dt


c


 2
L
I
L
m PL
+ DT lj aj hj (Tj Tj ) +
Ni; j H i; j :
4

(10)

(11)

i=1

Energy balance for the vapour phase:

dEjV
V
Vj HjV
= Vj+1 Hj+1
dt


c


 2
V
V
I
m PV
DT lj aj hj (Tj Tj ) +
Ni; j H i; j : (12)
4
i=1

Energy balance at the vapourliquid interface:

c


hVj (TjV TjI ) +
Ni;mj HP Vi;j
i=1

i=1

Ni;mj HP Li; j :

c


i=1
c

Ni;mj ;

(19)

Ni;mj :

(20)

i=1

yi; N Ki; N xi; N = 0:

c

(18)

Mass transfer 7uxes:

i=1

= hLj (TjI TjL ) +

c


i=1
c

i=1

i=1
c

2673

(13)

De9nition of the holdups:


Mi;Lj = DT2 lj hLtj CtjL xi; j ;
4

Mi;Vj = DT2 lj (j hLtj )CtjV yi; j ;
4

EjL = DT2 lj hLtj CtjL HjL ;
4

EjV = DT2 lj (j hLtj )CtjV HjV :
4

(21)
(22)
(23)
(24)

The approach of Taylor and Krishna (1993) was followed

to calculate the mass transfer coe;cient matrices kL ; kV . The
kinetic model from Rihko, Kiviranta-Paakkonen, and Krause
(1997) was used to calculate the reaction rates for the TAME
system. The UNIQUAC equation was used to calculate the
liquid activity coe;cients with binary interaction parameters
from AspenPlus (Version 10.2). The hydraulic and mass
transfer models developed by Rocha, Bravo, and Fair (1993,
1996) were used to calculate hydraulics and mass transfer.
The dynamic rate-based model, which consists of a
set of di5erential algebraic equations, was implemented
in gPROMS. When the pressure and temperature at the
condenser were assumed to be 9xed, the index of the resulting di5erential algebraic equations (DAEs) is reported
by gPROMS to be greater than one and cannot be solved.
The index can be reduced to one by di5erent modi9cations
(see Table 1).
Model RB1, which is referred to as the full model throughout this paper, includes the liquid molar holdup, vapour molar holdup and liquid energy holdup. Only the vapour energy
holdup is neglected because of the index problem. Model
RB2 ignores the vapour molar holdup and keeps all the other

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J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

Table 1
Dynamic rate-based models with di5erent complexities

Model

RB1

RB2

RB3

RB4

RB5

Di5erential mass balance (condenser)

Di5erential energy balance (condenser)
Di5erential mass balance (reboiler)
Di5erential energy balance (reboiler)
Di5. liquid mass balance (segment)
Di5. vapour mass balance (segment)
Di5. liquid energy balance (segment)
Di5. vapour energy balance (segment)
Constant total molar holdup
Constant mass transfer coe;cients
Number of di5erential equations
Number of algebraic equations
Total number of equations

Yes
No
Yes
No
Yes
Yes
Yes
No
No
No
866
24,522
25,388

Yes
No
Yes
No
Yes
No
Yes
No
No
No
476
24,912
25,388

Yes
No
Yes
No
Yes
Yes
Yes
No
No
Yes
866
8532
9398

Yes
No
Yes
No
Yes
No
No
No
Yes
No
320
23,942
24,262

Yes
No
Yes
No
Yes
No
No
No
Yes
Yes
320
5596
5916

dynamics in the full model. The molar component balances

of the vapour phase (Eq. (10)) are changed from di5erential
equations to algebraic equations, while all the other equations in model RB1 are unchanged. Model RB3 keeps all the
dynamics in the full model, but the mass transfer coe;cients
are assumed to be constant. All equations used to calculate
the mass transfer coe;cients are dropped from model RB1.
Model RB4 ignores the energy holdup and the vapour molar holdup, and the total liquid molar holdup is assumed to
be constant. Di5erential equations (10), (11), and (12) are
replaced with the corresponding algebraic equations. Model
RB5, which is the simplest dynamic rate-based model in this
paper, is a further simpli9cation of model RB4, by assuming
that the mass transfer coe;cients are constant. All of these
models were used to evaluate which kind of simpli9cation
is the most e;cient and accurate.
The dynamic equilibrium model is an extension of the
steady-state equilibrium model (Peng et al., 2002). The hydraulic models developed by Rocha et al. (1993) were used
to calculate pressure drop and liquid holdup. When the pressure and temperature at the condenser were assumed to be
9xed, the index of the resulting DAEs is two and cannot
be solved in gPROMS either. The index can be reduced to
one by ignoring the energy holdup. However, the resulting
system of DAEs is very sti5 and only converges for a very
small (0.1%) step change in manipulated variables. When
constant total molar holdup is assumed at each stage, the
DAEs can be solved very e;ciently. Therefore, throughout
this paper, the total molar holdup is assumed to be constant
in the dynamic equilibrium model.

3. Rate-based vs. equilibrium models

The pilot plant reactive distillation column con9guration
(see Fig. 1) for the production of TAME at UT-SRP was
used as the basis for dynamic simulations. Dynamic experiments will be carried out in the future on this column

0.67 m Flexipac

4.72 m Katamax

1.2 m Flexipac
1.22 m Flexipac

TAME
B
Fig. 1. Con9guration of the pilot plant reactive distillation column at
UT-SRP.

to validate the dynamic models developed in this paper.

There are 9ve components in the TAME system: methanol,
2-methyl-1-butene (2M1B), 2-methyl-2-butene (2M2B),
TAME and n-pentane. Three reversible chemical reactions
take place in the reactive packing
2M1B + methanol
TAME;
2M2B + methanol
TAME;
2M1B
2M2B:

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

Table 2
Comparison of the CPU time between the rate-based and equilibrium
models
Rate-based

Equilibrium

Number of stages (segments)

Number of di5erential equations
Number of algebraic equations
Simulation duration (h)
Average CPU time (s)

78
320
23,942
10
185

20
88
728
10
5.3

The following speci9cations were made throughout this

paper:
(1) feed 7owrate: 0:2778 mol=s
(2) feed mole composition: methanol 0.26; 2M1B 0.007;
2M2B 0.07; TAME 0.1; n-pentane 0.563
(3) condenser pressure: 380 kPa
(4) condenser temperature: 342:15 K
(5) initial re7ux ratio: 2.2
(6) initial bottoms rate: 0:04167 mol=s.
To compare the dynamic rate-based model with the corresponding equilibrium model, the number of theoretical
stages in the equilibrium model was chosen such that the
TAME purity at the bottom is close to that predicted by
the rate-based model under the same steady-state speci9cations. The number of segments in the rate-based model
is 78 and the number of theoretical stages in the equilibrium model is 20 (not including condenser, reboiler). The
modi9ed dynamic rate-based model RB4 (see Table 1) was
used to compare with the dynamic equilibrium model, because the same assumptions on dynamics were assumed in
both models. When the pressure at the condenser, the levels of the re7ux drum and the reboiler were assumed to be
perfectly controlled, there are two controlled variables and
two manipulated variables. The controlled variables were
chosen to be the TAME purity at the bottom and reactant
conversion, because both product purity and reactant conversion should be controlled (Sneesby et al., 1997). The
reactant conversion is de9ned as the overall conversion of
2M1B and 2M2B (1(D(x2M1B; 1 +x2M2B; 1 )+LN (x2M1B; N +
F
F
x2M2B; N ))=(F(x2M1B
+ x2M2B
))). The two manipulated variables can be chosen from re7ux ratio (RR), re7ux rate (L),
distillate rate (D), reboiler heat duty (QB ), or bottoms rate
(B). Dynamic simulations were carried out by making a step
change in one manipulated variable and keeping the other
manipulated variable 9xed.
Dynamic simulations were performed with both the dynamic rate-based model and equilibrium model, by making
a step change in one of the manipulated variables. A comparison of the average CPU time of the two types of models
was listed in Table 2. The average CPU time of the dynamic
rate-based model is about 37 times that of the dynamic equilibrium model. It was found that the CPU time is approximately proportional to the number of equations.

1
equilibrium model
rate-based model RB4

0.95
0.9
TAME mole fraction

Model

2675

0.85
0.8
0.75
0.7
0.65
0.6

10

time, hr
Fig. 2. Comparison of dynamic response of the TAME purity between
rate-based and equilibrium models (QB 9xed, 10% step change in D).

The open-loop responses predicted by the rate-based

model and equilibrium model are similar for 20 dynamic
simulations, covering all the possible combinations of the
manipulated variables, and both positive and negative step
changes. However, even if the initial steady-state values of
the controlled variables were very close in the two types
of models, there is some di5erence in the new steady-state
values after a step change. The largest di5erence was found
when the reboiler heat duty (QB ) and the distillate rate
(D) were chosen to be the manipulated variables and a
negative 10% step change was made to the distillate rate.
The response of the TAME purity was shown in Fig. 2
and that of the reactant conversion was shown in Fig. 3. It
can be seen that the di5erence in the responses is predominantly caused by the di5erence in the new steady state.
Interestingly, the least di5erence was also found when the
same manipulated variables QB ; D were chosen, but a positive 10% step change was made to the distillate rate (see
Fig. 4). The open-loop response of the TAME purity is close
to 9rst order, but the response of the reactant conversion is
unconventional and highly nonlinear. Inverse response was
found in Fig. 3 and for other simulations. When the re7ux
rate (L) and the reboiler heat duty (QB ) were chosen to be
the manipulated variables and a negative 10% step change
was made to QB , the open-loop response of the reactant
conversion is highly unconventional (see Fig. 5). When the
same manipulated variables L; QB were used, but a positive
10% step change was made to QB , the response of the reactant conversion is totally di5erent (see Fig. 6), even the
shape of the response curve is changed completely. However, the responses predicted by the two types of models are
still similar. The size of the step change a5ects the dynamic

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

0.7

0.7

0.68

0.68

0.66

0.66

0.64

0.64

reactant conversion

reactant conversion

2676

0.62
0.6
0.58

0.62
0.6
0.58

0.56

0.56

0.54

0.54

0.52
0.5

0.52

equilibrium model
rate-based model RB4
0

0.5

10

equilibrium model
rate-based model RB4
0

10

time, hr

time, hr
Fig. 3. Comparison of dynamic response of reactant conversion between
rate-based and equilibrium models (QB 9xed, 10% step change in D).

Fig. 5. Unconventional response of reactant conversion (L 9xed, 10%

step change in QB ).

0.6

1
0.99

0.4

0.98
reactant conversion

TAME mole fraction

0.2

0.97
0.96
0.95
0.94
0.93
0.92

0.2
0.4
0.6

0.91
0.9

equilibrium model
rate-based model RB4
0

0.8

10

time, hr
Fig. 4. Comparison of dynamic response of the TAME purity between
rate-based and equilibrium models (QB 9xed, +10% step change in D).

responses signi9cantly. When the step change is smaller,

the dynamic responses are more conventional. The dynamic
response of the reactant conversion depends strongly on the
operating condition. When the feed composition in Fig. 5 is
changed, the dynamic response of the reactant conversion
(see Fig. 7) is quite di5erent from that in Fig. 5. However,
transition from one steady state to another steady state was
never found for all the simulations carried out in this work.

equilibrium model
rate-based model RB4
0

10

time, hr
Fig. 6. Di5erent response of reactant conversion for a positive step change
(L 9xed,+10% step change in QB ).

When the manipulated variables were changed back to the

initial values, exactly the same steady state was reached.
4. Simpli!cation of the dynamic rate-based model
The dynamic rate-based model (RB1) developed above
is much more complicated than the equilibrium model. It
would be infeasible to use this model in model-based control,

0.5

0.6

0.48

0.55

0.46

0.5

0.44

0.45

reactant conversion

reactant conversion

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

0.42
0.4
0.38
0.36

model RB1
model RB2

0.4
0.35
0.3
0.25

0.34

0.2

0.32
0.3

2677

equilibrium model
rate-based model RB4
0

0.15
0.1

10

time, hr
Fig. 7. Response of reactant conversion at a di5erent operating condition
(L 9xed, 10% step change in QB ).

10

time, hr
Fig. 8. In7uence of vapour holdup (L 9xed, +5% step change in QB ).

1
0.99
0.98
TAME mole fraction

where the model must be solved in real time, hence it is necessary to simplify the model. The common approach used in
the literature is to neglect some less important dynamics and
reduce the number of di5erential equations. However, this
will not change the total number of equations and therefore
cannot reduce the CPU time signi9cantly. For the dynamic
rate-based model, most of the equations (about 95%) are
algebraic equations. The majority of these algebraic equations were used to calculate the mass transfer coe;cients.
If the mass transfer coe;cients do not change much near
the steady state, they can be assumed to be constant, and all
equations used to calculate them can be deleted. In this way,
the total number of equations can be reduced drastically.
The relative importance of liquid molar holdup, vapour
molar holdup and energy holdup was examined. It was found
that vapour molar holdup is the least important parameter
and can be neglected. This is because the density of the
vapour phase is at least two orders of magnitude lower than
that of the liquid phase at low pressure. Even if the volume
of the vapour holdup in the column is much larger than that
of the liquid holdup, the total moles in the vapour holdup in
a segment are still much less than that in the liquid holdup.
For reactive distillation of the TAME system, and many
other systems, reactions only take place in the liquid phase.
Thus vapour holdup does not a5ect the reactions.
When the vapour holdup was neglected, very little difference was found between the simpli9ed model (RB2 in
Table 1) and the full model. The largest di5erence in the response of the reactant conversion is shown in Fig. 8. In other
cases, neglecting the vapour holdup resulted in almost the
same dynamic responses. However, neglecting the vapour
holdup does not reduce the CPU time noticeably.

0.97
0.96
0.95
0.94
0.93
0.92
0.91
0.9

model RB1
model RB4
0

10

time, hr
Fig. 9. In7uence of energy holdup and total molar holdup (D 9xed, 5%
step change in QB ).

When the energy holdup was neglected, the system of

DAEs was very di;cult to converge, even for a small step
change such as 1%. Further simpli9cation was needed to
improve the convergence. When the total molar holdup at
each segment was assumed to be constant, the convergence
of this simpli9ed model (RB4 in Table 1) is almost as good
as the full model. However, the dynamic responses could be
very di5erent from the full model (see Fig. 9) even though
the new steady-state values are the same.
It was found that neglecting dynamics is not a good way
to simplify the dynamic rate-based model. Even if the error

2678

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

0.72

model RB1
model RB3

model RB1
model RB3

0.7

reactant conversion

TAME mole fraction

0.9

0.8

0.7

0.6

0.5

0.4

0.68

0.66

0.64

0.62

0.6

10

time, hr
Fig. 10. Comparison of response of TAME purity between simpli9ed
model RB3 and full model RB1 (QB 9xed,+10% step change in L).

generated by neglecting dynamics is small, the CPU time required to complete the simulation is the same, or greater. In
some cases, neglecting dynamics could make the DAE system very sti5 and di;cult to converge. Therefore, it might
be a better approach to keep all the dynamics and try to
simplify the algebraic equations. Since the number of algebraic equations is much higher than the number of di5erential equations, there is more potential to reduce the CPU
time by simplifying the algebraic equations.
The majority of the algebraic equations in the rate-based
model are used only to calculate the mass transfer coe;cients. If these coe;cients do not change much near the
steady state, they can be assumed to be constant and all
the equations used to calculate the mass transfer coe;cients
can be dropped. To test this idea, the mass transfer coe;cients are assumed to be time invariant, with the values at
the initial steady state. All equations used to calculate the
mass transfer coe;cients were dropped from the model, and
all the dynamics were retained. This simpli9ed model is referred to as RB3 (see Table 1). A step change was made to
one manipulated variable, and the response was compared to
that from the full model (RB1). It is interesting to note that
the error generated by this simpli9cation is very small (see
Figs. 10 and 11), while the CPU time is reduced drastically
(see Table 3). In Fig. 10, the response of the TAME purity
from the simpli9ed model RB3 is identical to that from the
full model, even though the TAME purity changed drastically from 0.962 to 0.480 after a 10% step change in re7ux
rate L. In Fig. 11, the response of the reactant conversion
is very unconventional. However, the response predicted by
the simpli9ed model RB3 is still very close to that predicted
by the full model.

10

time, hr
Fig. 11. Comparison of response of reactant conversion between simpli9ed
model RB3 and full model RB1 (QB 9xed,+10% step change in L).
Table 3
CPU time of the simpli9ed model RB3
Model

Full
model RB1

Simpli9ed
model RB3

Number of stages (segments)

Number of di5erential equations
Number of algebraic equations
Simulation duration (h)
Average CPU time (s)

78
866
24,522
10
149

78
866
8532
10
36

A total of 20 dynamic simulations were carried out to

compare the simpli9ed model RB3 with the full model. It
was found that the responses predicted by the simpli9ed
model RB3 are very close to those predicted by the full
model. When the mass transfer coe;cients are assumed to
be time invariant, there will be a small error in the new
steady state after a step change. When there is signi9cant
change in the controlled variables, the error caused by this
simpli9cation is negligible. However, when the change in
the controlled variables is not signi9cant, the error becomes
more obvious, even though it is still small in absolute value.
The CPU time required by the simpli9ed model RB3 is
much less than that required by the full model (see Table 3).
The average CPU time in 20 dynamic simulations is only
24% of that required by the full model. This is because the
number of algebraic equations in model RB3 is reduced by
about two-thirds. Although the CPU time is still about six
times more than that in the equilibrium model, the di5erence
is mainly caused by the larger number of segments in the
rate-based model. There are 78 segments in the rate-based
model, while there are only 20 stages in the equilibrium
model.

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

2679

model RB1
model RB3

0.95

0.99
0.98
TAME mole fraction

TAME mole fraction

0.9
0.85
0.8
0.75
0.7

0.96
0.95
0.94
0.93
0.92

0.65
0.6

0.97

model RB1
model RB3
model RB5

0.91
0.9

10

time, hr

10

time, hr

Fig. 12. Comparison of response of TAME purity between simpli9ed

model RB3 and full model RB1 for a large step change (RR 9xed,+50%
step change in B).

Fig. 13. Response of TAME purity from further simpli9ed model RB5
(D 9xed,+5% step change in QB ).

The simpli9ed model RB3 is as robust as the full model.

When a larger step change was made, the responses predicted by model RB3 are still very close to those predicted
by the full model. However, convergence problems in both
the full model and the simpli9ed model RB3 may arise when
a larger step change is made. When the re7ux ratio is 9xed
and a +50% step change is made to the bottoms rate B, the
response of the TAME purity predicted by model RB3 is
still almost identical to that predicted by the full model (see
Fig. 12).
Further attempts were made to simplify the dynamic
rate-based model, but with less success. Index and convergence problems appeared in many cases. The reduction in
CPU time is not signi9cant, if any, and the deviation from
the full model becomes much more signi9cant. An example
is shown in Fig. 13, where model RB3 was further simpli9ed into model RB5 (see Table 1), by assuming that the total molar holdup is constant, and vapour holdup and energy
holdup were neglected. When the distillate rate D was 9xed
and a +5% step change was made to the reboiler duty QB ,
the CPU time required by model RB5 is only 10% less than
that required by model RB3. However, the deviation from
the full model is much more signi9cant than that in model
RB3. Considering both accuracy and computational time,
model RB3 is the best one for real-time implementation.

responses of the controlled variables (product purity and

reactant conversion) to a step change in the manipulated
variables (re7ux rate, re7ux ratio, distillate rate, bottoms
rate, and reboiler duty) were studied with both the dynamic
rate-based model and equilibrium model. It was found that
the open-loop responses predicted by the rate-based model
and equilibrium model are similar in general. However, even
if the initial steady-state values of the controlled variables
were very close in the two types of models, there are some
di5erences in the steady-state values after a step change.
The average CPU time of the dynamic rate-based model is
at least an order of magnitude more than that of the dynamic equilibrium model. It was found that the open-loop
response of the TAME purity is close to 9rst order, but the
response of the reactant conversion is unconventional and
highly nonlinear.
It was found that neglecting vapour molar holdup and
energy holdup can only reduce the CPU time slightly. In
some cases, neglecting dynamics will make the DAE system
very sti5 and di;cult to converge.
Instead of simplifying the dynamics, a di5erent approach was proposed to simplify the algebraic equations
in the dynamic rate-based model. When all the dynamics
are retained and the mass transfer coe;cients assumed to
be time invariant, the number of equations is reduced by
two-thirds while the dynamic responses are still very close
to those of the full model. The average CPU time required
by the simpli9ed model RB3 is only one-fourth of that
required by the full model. This simpli9ed model is as robust as the full model and performs well under large step
change (50%).

5. Conclusions
Dynamic rate-based and equilibrium models were developed for a packed reactive distillation column. The dynamic

2680

J. Peng et al. / Chemical Engineering Science 58 (2003) 2671 2680

Notation
a
c
Ct
D
DT
E
F
h
ht
H
HP
k
K
l
L
M
N
N
Q
R
t
T
V
W
x
y

e5ective speci9c area of the packing, m1

number of components
total molar concentration, mol=m3
distillate rate, mol=s
diameter of the column, m
energy holdup, J
feed 7owrate, mol=s
heat transfer coe;cients, W=m2 K
total liquid holdup
enthalpy, J=mol
partial enthalpy, J=mol
mass transfer coe;cient matrix, m=s
vapourliquid equilibrium constant
height of a segment, m
liquid 7owrate, mol=s
molar holdup, mol
total number of segments (stages)
mass 7ux matrix, mol=m2 s
heat loss, J=s
reaction rate, mol=kg
time, s
temperature, K
vapour 7owrate, mol=s
catalyst weight, kg
liquid mole fraction
vapour mole fraction

Greek letters



void fraction of the packing

3.1415926

Subscripts
i
j
t

component index
segment (stage) index
total

Superscripts
F
I
L
m
V

feed
interface
liquid phase
mass transfer
vapour phase

Acknowledgements
This project was partially supported by Aspen Technology, Inc. The 9rst author wants to thank Dr. Thomas
Badgwell for his suggestions and comments on this paper.

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