1950

Ind. Eng. Chem. Res. 2000, 39, 1950-1954

PROCESS DESIGN AND CONTROL

Dynamic Simulation of Startup in Ethyl tert-Butyl Ether Reactive
Distillation with Input Multiplicity
Budi H. Bisowarno and Moses O. Tade *
School of Chemical Engineering, Curtin University of Technology, G.P.O. Box U 1987,
Perth WA 6845, Australia

Dynamic simulation is used to understand the effect of a startup policy on the ethyl tert-butyl
ether (ETBE) reactive distillation. Because input multiplicity is likely to occur in every reactive
distillation, its effects on startup are investigated. The ETBE reactive distillation is presented
as an example to show characteristic behaviors during startup of the ETBE column. It is found
that the dynamics of the startup condition are influenced by the given startup policy. An
understanding of the input multiplicity is a necessary requirement before performing the startup
operation to avoid excessive energy, to achieve a stable optimum process operation.
1. Introduction

Table 1. ETBE Column Simulation Input

Reactive distillation is a novel alternative to a typical

reactor and distillation combination.1 It offers advantages in chemical reaction by shifting the chemical
equilibrium and therefore increasing the total conversion and in separation by overcoming distillation boundaries. Economic advantages also result from direct
energy integration and reduction of equipment costs.
This technology is suitable for the production of ethyl
tert-butyl ether (ETBE), an important oxygenate with
better blending properties than methyl tert-butyl ether
(MTBE).2 ETBE is also a semirenewable oxygenate
because it is synthesized in a liquid-phase reaction
between isobutylene and ethanol that can be produced
from biomass such as agricultural waste.
Reactive distillation exhibits multiplicity phenomena,
which can be distinguished as input and output multiplicities and pseudomultiplicities.3 For output multiplicity, the different startup policies may bring the column
to an inappropriate operating condition. Both theoretical
analysis and experimental verification have been done
on tert-amyl methyl ether (TAME) synthesis.4,5 The
output multiplicity region was shifted according to the
operating conditions so that its existence could be
verified with the available laboratory column. Similar
phenomena were demonstrated using dynamic simulation for three different cases.6 However, there is no
reference in the open literature that discusses the
importance of input multiplicity during startup. The
input multiplicity has been known to impose more
practical control problems than that of output multiplicity in reactive distillation.7
The startup policy for reactive distillation was developed based on that of a typical distillation column.8 The
column was filled with a certain amount of feed, and
then the column was heated at total reflux. The reboiler
* To whom correspondence should be addressed. E-mail:
tadem@che.curtin.edu.au. Tel.: +61 8 9266 7704. Fax: +61 8
9266 3554.

feed conditions
temperature
rate
composition

30 C
0.76 L/min
29.1% ETBE
9.1% EtOH
7.3% iBut
54.5% nBut
overall excess EtOH 5.0 mol %

column specifications
rectification stages
reaction stages
stripping stages
total stages
feed stage
overhead pressure
reflux ratio (L/D)

2
3
5
10
6
950 kPa
5

duty was kept constant at its operating steady-state

value. Therefore, the column was brought into its stable
batch operation at its operating pressure before introduction of the additional feed and setting of the reflux
ratio/rate. Previous operation of the pilot unit showed
that the premixed feed, which has the same concentration as the feed, was the best mixture to stabilize the
column before introduction of the additional feed.9 The
reason was that the existing column temperature profile
was close to that of the steady-state condition so that
the startup condition would last for the shortest possible
time.
In this paper, the importance of input multiplicity
during startup is evaluated by using dynamic simulation. The transient responses of the reactive distillation
column are used to assess and understand the effects
of different variables during the startup operation. A
proposed best startup policy is presented.
2. Process Configuration and Mathematical
Model
The details of the ETBE reactive distillation pilotplant column are shown in Table 1. The column is
located in the School of Chemical Engineering, Curtin
University of Technology, Perth, Western Australia. The
column was modeled using the equation-based process
simulation package, SpeedUp.10 A rigorous expression
for ETBE reaction equilibrium was incorporated, and
the kinetic expression that is valid over a wide range
of ethanol concentrations was used.2 The side reactions

10.1021/ie9906417 CCC: $19.00 2000 American Chemical Society

Published on Web 05/09/2000

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1951

Figure 1. Input multiplicity region at 950 kPa and L/D ) 5.

were not modeled, because the system dynamics is not

significantly affected.11 The UNIFAC vapor-liquid equilibrium model was used to predict component activities
due to the strong nonideality of the reaction mixtures,
and the phase equilibrium calculations used recently
published vapor-liquid equilibrium data.12 Further
details of the mathematical model can be found in our
previous publications.1,11 Previous studies have shown
that this column shows input multiplicities and pseudomultiplicities, but there is no output multiplicity.13
3. Input Multiplicity and a Startup Policy
3.1. Input Multiplicity Region. The ETBE reactive
distillation column under study exhibits input multiplicity as shown in Figure 1. The optimum reboiler duty
with respect to ETBE purity was 8.45 kW at a constant
operating pressure of 950 kPa and a constant reflux
ratio of 5. The input multiplicity region below the
optimum condition is controlled by the separation
process while the reaction process controls that above
the optimum condition.3 Increasing the reboiler duty
increases separation so that the ETBE purity increases
in the separation-controlled region. However, increasing
the reboiler duty could reduce the ETBE purity because
it decreases the chemical equilibrium constant as shown
in the reaction-controlled region. Using the reboiler duty
as a manipulated variable could result in conflicting
effects on separation and reaction processes. It is likely
that other manipulated variables could produce similar
phenomena.
The input multiplicity results from the conflicting
effect of operating through the same manipulated vari-

able (e.g., reboiler duty or others). Therefore, its region

depends on the operating conditions. For example,
Figure 2 shows the effects of the operating pressure on
input multiplicity. At a constant operating pressure, the
reboiler duty was varied while either the reflux ratio
or the volumetric reflux rate was kept constant. The
results indicate that the input multiplicity region is
shifted to a lower reboiler duty for achieving the
optimum ETBE purity at the higher operating pressure.
This is reasonable because the reactive section temperature is also higher at a higher operating pressure so
that the reaction equilibrium is then lower at a constant
reboiler duty. As a result, the isobutylene conversion
as well as the ETBE purity decreases. Therefore, a lower
reboiler duty is needed to maintain the optimum ETBE
purity [Figure 2(left)]. This phenomenon is more important if the volumetric reflux rate is varied instead
of the reflux ratio as shown in Figure 2(right). This
result is important because the LV configuration, which
uses the reboiler duty to vary the vapor rate (V) and
volumetric reflux rate (L) as manipulated variables,
provides a better performance than the ratio configurations, including the (L/D)V configuration.11
Figure 2 also shows that the size of the input
multiplicity region is quite similar despite the different
operating pressures. Therefore, it could be speculated
that the input multiplicity always occurs in this reactive
distillation column for any operating condition. Several
reactive distillations that are obtained from any number
of either separation or reaction stages exhibit input
multiplicity as well. Figures 3-5 show the effect of a
different number of rectification, reactive, and stripping
stages on input multiplicity, respectively. These figures
show the input multiplicity regions resulting from one
and seven more rectification stages, two and five more
reactive stages, and one and four more stripping stages
than those in the column described in Table 1. Despite
the different reboiler duties that result in the input
multiplicity region, the size of the input multiplicity is
quite similar. Therefore, input multiplicity may occur
in every reactive distillation column.
3.2. Effects of Operating Pressure. Similar to a
typical distillation column, the ETBE reactive distillation column was filled with a mixed feed having the
same concentration as the feed. The column was then
stabilized through batch operation at total reflux, until
it reached a stable batch operation. At this point in the
startup, the chosen reboiler duty is critical in stabilizing
the batch operation because the optimum reboiler duty
depends on the targeted operating pressure. Figure 6

Figure 2. Input multiplicity region at L/D ) 5 (left) and L ) 2.5 L/min (right).

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

Figure 3. Input multiplicity for different rectification stages.

Figure 4. Input multiplicity for different reactive stages.

Figure 5. Input multiplicity for different stripping stages.

shows the responses of ETBE purity resulting from

different operating pressures when the reboiler duty
was kept constant at 8.45 kW during startup. Also, the
reflux ratio was held constant at 5 while the condenser
duty was allowed to vary.
Figure 6 shows that the existing ETBE purity is
higher at a lower operating pressure. This results from
lower column temperatures, including those in the
reactive section that increase the chemical equilibrium.
The ETBE purity responses that result from introduction of the additional feed present interesting results.
Although the stable batch operation results in higher
ETBE purity, the operating pressures below the opti-

mum result in a lower stable ETBE purity. Operating

pressures above the optimum also produce a slightly
lower stable ETBE purity despite the differences in the
original ETBE purity. These results indicate that a lack
of understanding of the input multiplicity could result
in an inefficient startup policy.
According to Figure 2, the optimum ETBE purity
could result from a different combination of the reboiler
duty and the operating pressure. Therefore, similar
responses for the ETBE purity, as shown in Figure 6,
could be derived for different constant reboiler duties.
This analysis indicates the possibility for implementing
a startup policy for the experimental work based on the
particular reactive distillation column. For example, a
lower reboiler duty could produce an optimum condition
with lower condenser duty as long as the column could
be run at a higher operating pressure.
At constant reboiler duty, a higher operating pressure
results in a lower condenser duty. Therefore, the
operating pressure that is too low uses an unnecessary
condenser duty. On the other hand, a high operating
pressure may result in a reboiler duty that is too large.
This analysis suggests that an understanding of the
input multiplicity could reduce the utilities required
during startup.
A lower reboiler duty (Figure 2) could result in an
optimum condition for ETBE purity at a higher operating pressure, which implies a lower condenser duty.
Although the ETBE purity responses are quite similar
during startup, the high operating pressure could reduce
the isobutylene conversion because of a lower chemical
equilibrium. Therefore, moderate operating pressures,
in the range of 700-1000 kPa, are suggested, because
these will maintain a balance between the utilities
required and high chemical equilibrium, necessary for
stable operation of this pilot-scale reactive distillation
column.
3.3. Effects of Reboiler Duty. Because the reboiler
duty is usually the main manipulated variable, it is
important to understand the effects of changes on the
responses of the reactive distillation column, especially
during the startup. The effect of the reboiler duty on
the transient condition during startup was studied at
a constant operating pressure (950 kPa) for both separation and reaction-controlled regions. The responses of
the ETBE purity during startup after the introduction
of the feed are shown in Figure 7.
Figure 7 shows that the ETBE purity increases
significantly and after that decreases before increasing
to a steady-state value. These phenomena could be
explained by noting the changes in the internal liquid
and vapor rates after introduction of the additional feed.
The fast initial increases in the ETBE purity result from
the introduction of additional reactants into the reactive
section. This change lasts for a short period of time
because the feed leaves the column almost entirely in
the bottom product because of the lack of an additional
heat supply. This results in less ethanol reacting with
isobutylene so that the conversion and therefore the
ETBE purity decrease. Without changes in the reboiler
duty, the operating pressure could also be kept constant
by changing the condenser duty. The condenser duty
decreases gradually with the increasing feed rate, and
the column temperature profile necessarily increases.
As a result, the ETBE purity increases continuously
until it reaches a steady-state value.
Figure 7 also shows that a larger reboiler duty results

Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1953

Figure 6. Responses of ETBE purity during startup at Qr ) 8.45 kW.

Figure 7. Responses of ETBE purity during startup at 950 kPa for separation-controlled (left) and reaction-controlled (right) regions.

Figure 8. Effect of multiplicity on responses of isobutylene conversion (left) and ETBE purity (right) during startup.

in a higher stable ETBE purity in the separationcontrolled region. On the other hand, the converse
applies in the reaction-controlled region. Besides, the
reactive distillation column is stabilized at relatively
similar times for different reboiler duties. Although the
stable batch operation produces higher ETBE purity,
the reboiler duty that is below the optimum value
results in lower ETBE purity in the stable continuous
operation. The reboiler duty that is above the optimum
also produces slightly lower stable ETBE purity. This
result indicates the importance of recognizing input

multiplicity. A similar behavior was also observed in the

isobutylene conversion responses.
Similar plots could also be constructed for other
constant operating pressures. Based on the response
shown in Figure 2, it would be expected that a lower
operating pressure requires a lower reboiler duty as
shown by the optimum operating condition. The lower
operating pressure also implies a lower condenser duty.
However, smaller internal rates inside the column that
result from lower reboiler and condenser duty could
increase the potential risk of flooding in the column and

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

reduce the availability of reactants in the reactive

section. Therefore, the isobutylene conversion as well
as the ETBE purity could decrease. As a result, any
attempt to minimize the utilities required should be
compromised with the reaction considerations.
The input multiplicity region shown in Figure 2 shows
that two reboiler duties result in the same ETBE purity
at certain operating conditions. For example, both
reboiler duties of 8.00 and 9.11 kW produce targeted
ETBE of 96 or 84.2 mol % at an operating pressure of
950 kPa and a reflux ratio of 5. The transient responses
of isobutylene conversion and ETBE purity during
startup for both situations stabilized at 8.00 and 9.11
kW after introduction of the additional feed (Figure 8).
Although the ETBE purity responses show that the
higher reboiler duty has a slightly better performance,
it produces a much lower isobutylene conversion. This
result indicates that the reactive distillation column
operation should be stabilized based on separation
consideration rather than reaction-controlled consideration, if there are difficulties in obtaining the optimum
condition.
4. Conclusions
Dynamic simulation is a useful tool for assessing and
understanding the transient responses of a reactive
distillation column during startup. The input multiplicity could increase or decrease the overall process
performance during startup depending on the chosen
operating condition. However, an understanding of the
input multiplicity could prevent stabilization of the
column at an inappropriate operating condition. The
startup study results recommend stabilization the
column at the optimum operating condition before
introduction of the additional feed. The results also show
that if there is a problem stabilizing the column at the
optimum operating condition, it could be stabilized in
the separation-controlled region rather than the reaction-controlled region. This startup policy would result
in the targeted ETBE purity within the shortest possible
time without using excessive energy.
Literature Cited
(1) Sneesby, M. G.; Tade, M. O.; Datta, R.; Smith, T. N. ETBE
Synthesis via Reactive Distillation: 1. Steady-State Simulation
and Design Aspects. Ind. Eng. Chem. Res. 1997, 36, 1855.

(2) Jensen, K. L.; Datta, R. Ethers from Ethanol. 1. Equilibrium

Thermodynamic Analysis of the Liquid-Phase Ethyl tert-Butyl
Ether Reaction. Ind. Eng. Chem. Res. 1995, 34, 392.
(3) Sneesby, M. G.; Tade, M. O.; Datta, R.; Smith, T. N.
Multiplicity and Pseudo-Multiplicity in MTBE and ETBE Reactive
Distillation. Trans. Inst. Chem. Eng. 1998, 76, Part A, 525.
(4) Mohl, K. D.; Kienle, A.; Gilles, E. D. Multiple Steady States
in a Reactive Distillation Column for the Production of the Fuel
Ether TAME. I. Theoretical Analysis. Chem. Eng. Technol. 1998,
21 (2), 133.
(5) Rapmund, P.; Sundmacher, K.; Hoffmann, U. Multiple
Steady States in a Reactive Distillation Column for the Production
of the Fuel Ether TAME. II. Experimental Validation. Chem. Eng.
Technol. 1998, 21 (2), 136.
(6) Scenna, N. J.; Ruiz, C. A.; Benz, S. J. Dynamic Simulation
of Start Up Procedures of Reactive Distillation Columns. Comput.
Chem. Eng. 1998, 22, Suppl., S719.
(7) Sneesby, M. G.; Tade, M. O.; Smith, T. N. Implication of
Steady-State Multiplicity for Operation and Control of Etherification Column. Proceedings of Distillation and Absorption 97,
Maactricht, The Netherlands, 1997.
(8) Kister, H. Z. Distillation Operation; McGraw-Hill Pub. Co.:
New York, 1990.
(9) Bisowarno, B. H.; Tade, M. O. Simulation of Start Up
Strategies in Reactive Distillation for ETBE Synthesis. CHEMECA
Conference 99, Newcastle-Australia, 1999.
(10) Aspen Technology Inc. The SpeedUp Users Manual;
Cambridge University Press: Cambridge, MA, 1993.
(11) Sneesby, M. G.; Tade, M. O.; Datta, R.; Smith, T. N. ETBE
Synthesis via Reactive Distillation: 2. Dynamic Simulation and
Control Aspects. Ind. Eng. Chem. Res. 1997, 36, 1870.
(12) Krahenbuhl, M. A.; Gmehling, J. A. Vapor Pressures of
Methyl tert-Butyl Ether, Ethyl tert-Butyl Ether, Isopropyl tertButyl Ether, tert-Amyl Methyl Ether and tert-Amyl Ethyl Ether.
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(13) Sneesby, M. G.; Tade, M. O.; Smith, T. N. Two-point control
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J. Process Control 1999, 9, 19.

Received for review August 26, 1999

Revised manuscript received March 22, 2000
Accepted March 24, 2000
IE9906417