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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.
0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(03)00103-9
2672
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)
Summation:
(2)
(3)
(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)
(6)
(7)
Njm = CtjL kL (xjI xj ) + xj
Vapourliquid equilibrium:
(8)
(9)
(10)
(11)
i=1
i=1
Ni;mj HP Li; j :
c
i=1
c
Ni;mj ;
(19)
Ni;mj :
(20)
i=1
c
(18)
i=1
c
i=1
c
i=1
i=1
c
2673
(13)
(21)
(22)
(23)
(24)
2674
Table 1
Dynamic rate-based models with di5erent complexities
Model
RB1
RB2
RB3
RB4
RB5
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
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.
Equilibrium
78
320
23,942
10
185
20
88
728
10
5.3
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).
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).
0.6
1
0.99
0.4
0.98
reactant conversion
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).
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 ).
0.5
0.6
0.48
0.55
0.46
0.5
0.44
0.45
reactant conversion
reactant conversion
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 ).
2678
0.72
model RB1
model RB3
model RB1
model RB3
0.7
reactant conversion
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
78
866
24,522
10
149
78
866
8532
10
36
2679
model RB1
model RB3
0.95
0.99
0.98
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. 13. Response of TAME purity from further simpli9ed model RB5
(D 9xed,+5% step change in QB ).
5. Conclusions
Dynamic rate-based and equilibrium models were developed for a packed reactive distillation column. The dynamic
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
Greek letters
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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