Chem. Eng. Technol. 2006, 29, No.

10, 1137–1154 1137

Sachidanandam Athimathi1 Research Article

Thota K. Radhakrishnan1

1
National Institute of
Control System Design for a Single Feed ETBE
Technology, Tiruchirappalli, Reactive Distillation Column
India.

Reactive distillation (RD) is advantageous for the Ethyl Tert-Butyl Ether (ETBE)
synthesis. The steady state model of an ETBE reactive distillation column created
using the simulator HYSYS is analyzed to synthesize effective control structures.
Since the column exhibits input multiplicity with the dual process objectives of
ETBE RD (isobutene conversion and ETBE purity), inferential variables are
selected. A control structure that organizes a sensitive tray temperature in the
stripping section using the reboiler duty and maintains the temperature differ-
ence of reactive trays using the reflux flow, is found to be most suitable. A decen-
tralized PI controller and constrained Model Predictive Controller (MPC) are
implemented, and performances are compared for set point tracking and distur-
bance rejection. MPC control algorithms are implemented in MATLAB and inter-
faced with HYSYS. Constrained MPC (CMPC) is found to be effective for load
disturbance rejection, which frequently occurs in the single feed configuration.

Keywords: Columns, Kinetics, Modelling, Reactive Distillation

Received: August 8, 2005; revised: June 2, 2006; accepted: June 13, 2006
DOI: 10.1002/ceat.200500274

1 Introduction be eliminated, which improves process selectivity. The forma-

Process intensification is an area of growing interest, which is
defined as any chemical engineering development that leads to
a substantially smaller, cleaner, and more energy efficient tech-
nology. An excellent example of process intensification is reac-
tive distillation, which provides an alternative to conventional
processing schemes that include, for instance, a reactor fol-
lowed by a distillation column in chemical production by
combining reaction and separation.
Reactive distillation (RD) has many advantages over conven-
tional processes. The most important advantage of RD for
equilibrium-controlled reactions is the elimination of conver-
sion limitations by continuous removal of products from the
reaction zone. It reduces the capital cost as two stage processes
occur in a single device. Such integration leads to lower costs
for pumps, piping and instrumentation. For exothermic reac-
tions, the reaction heat can be used for the vaporization of
liquids, which in turn reduces the reboiler duties and conse-
quently reduces the energy costs. The maximum temperature
in the reaction zone is limited to the boiling point of the reac-
tion mixture, so that the danger of hot spot formation on the
catalyst is significantly reduced. As the products or reactants
are continually removed, the occurrence of side reactions can
– dynamic simulator, SpeedUp, and the effects of different
Correspondence: T. K. Radhakrishnan (radha@nitt.edu), National
Institute of Technology, Tiruchirappalli, India.
tion of azeotropes is also prevented, thereby reducing the com-
plexity of separation procedures. Due to the advantages of RD
over conventional processes, it has become increasingly popu-
lar in recent years. However, RD involves considerable uncer-
tainties and displays complex behavior such as high nonlinear-
ity, strong interactions, multiplicity and time delay, due to the
functional integration of reaction and separation, and the dy-
namic complexities. RD is exceptionally difficult to operate
and control, resulting in the requirement for a systematic study
of its control.
The literature with respect to the control of reactive distilla-
tion is not as abundant as in other areas such as analysis of the
steady state of RD. Bock et al. [1] studied the design and con-
trol of reactive distillation including recovery systems. In this
paper, the etherification of myristic acid using RD is investi-
gated. Steady state and dynamic sensitivity of manipulated
variables are analyzed for control structure synthesis. The tem-
perature in the reactive tray is selected for the maintenance of
purity. The recycling does not lead to instability of the system.
The quality of the product stream is maintained by using two
SISO control loops, since the system is sluggish.
Considerable efforts have been undertaken in the control of
ETBE Reactive distillation columns. Sneesby et al. [2] studied
steady state simulation of an ETBE column and design aspects.
In that work, column simulation was performed using a
design parameters were studied. The authors also reported on
dynamic simulation and control aspects. They identified both

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1138 S. Athimathi et al.
ether purity and isobutylene conversion as process objectives
and suggested the use of control configuration alone to manip-
ulate the reboiler duty [3]. As the one point control scheme
suffers from the disadvantage of low process gain between the
temperature controller set point and the ether purity, they also
studied two point control of the ETBE column. The combined
composition and conversion control scheme is implemented
on the ETBE column using the inferential conversion model
and the LV control configuration. The authors found that a
two point control is more effective in feed disturbance rejec-
tion and in optimizing the isobutylene conversion compared
to one point control [4].
Loperenal et al. [5] studied the control problem in the ethyl-
ene glycol system. The presence of input multiplicities was
revealed. A first-order output-feedback compensator was
designed, which was shown to be equivalent to a PI controller.
Al-Arfaj and Luyben [6] reviewed the control of RD. They
explored the closed-loop control of an ideal two product RD.
Six alternative control structures were evaluated via rigorous
dynamic simulation. The interaction between design and con-
trol was illustrated by the impact of holdup in the reactive
zone. Stoichiometric amounts of fresh feeds are also desirable
for a double feed column. The authors studied real two prod-
uct systems and basing the studies on three different control
structures, they concluded that the tray temperature control
avoids nonlinearity, which normally occurs for composition
control [7]. They demonstrated that adding additional trays in
a RD does not degrade performance, provided the specified
degrees of freedom are chosen appropriately [8]. Three chemi-
cal systems (hypothetical, ETBE and methyl acetate) were cho-
sen for their studies. The authors showed that a simple single
temperature PI structure provides effective control for ethylene
glycol rather than using an advanced nonlinear inverse-based
controller [9]. They demonstrated that effective dynamic con-
trol is provided by a control structure that uses two tempera-
tures to maintain the purity of both product streams. They
also studied control of ETBE reactive distillation in which
Sneesby’s single feed configuration is optimized and control
structures for both double feed and single feed are studied
[10]. They found that tray temperature management provides
better control over composition for the single feed process.
However, they used only single end control in order to main-
tain ETBE purity.
A robust nonlinear control scheme consisting of a nonlinear
state feedback and a robust observer has been designed [11].
In order to compensate for steady state observer offsets, an
outer control loop with a simple PI controller was implemen-
ted. From the simulation studies, the authors found that the
nonlinear controller exhibits better performance compared to
a well-tuned linear controller, even in the presence of unknown
input delays, thereby proving its robustness.
Wang et al. [12] studied the effect of interaction multiplicity
on control system design for a MTBE reactive distillation col-
umn. Though the column exhibits steady state multiplicities,
they explained that linear control is still possible by selecting
appropriately controlled and manipulated variable pairing.
Engel and Frenholz studied the control of methyl acetate
reactive distillation [13]. They found that strong interactions
and process nonlinearity makes the control problem more dif-
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154
ficult. For satisfactory control, a carefully tuned interacting
multivariable controller is required. Better results are obtained
by using a model predictive controller.
Bisowarno et al. [14] investigated model gain scheduling for
inferential one point control of an ethyl tert-butyl ether reac-
tive distillation column. They studied the directionality of the
process gain, which cannot be well controlled by using stan-
dard PI control with fixed parameters, and found that the
problem can be overcome for a wide range of operating condi-
tions by using a gain scheduled PI controller. However, model
gain scheduling demands preprogramming or online identifi-
cation of the process gain.
Pattern based predictive control for ETBE on a pilot scale
RD column in which the maintenance of the purity of product
(ETBE) is performed using pattern based fuzzy prediction has
been reported [15]. The authors used only single point control
where the purity at the bottom is controlled using reflux flow.
Kaymak et al. [16] compared control of conventional pro-
cesses with a RD process for the production of Butyl Acetate.
For a selected plant wide control structure, both processes are
effectively controlled using conventional PI controllers that
manage the addition of fresh feeds and stabilize recycle flow
rates.
Recently, Khaledi and Young [17] employed two point con-
trol of ETBE using model predictive control. The HYSYS 3.1
simulator is used to simulate the column and the control is
implemented by using inbuilt features such as the uncon-
strained DMC module in HYSYS. The authors showed that,
for the variation of manipulated variables in certain regions,
the reverse reaction occurs.
The control of RD columns has been performed using a
decentralized PI controller, as well as an adaptive and fuzzy
controller with single or dual composition control. It has been
shown that a multivariable controller is necessary for satis-
factory operation. The product purity is controlled by main-
taining either temperature or composition. It has also been
shown that for variations of manipulated variables in certain
regions, reverse reactions takes place and RD exhibits input
multiplicity. Since the reverse reaction occurs for positive
change in reboiler heat flow and negative change in reflux mo-
lar flow from nominal steady state values, it is necessary to im-
pose constraints for better control. The advantage of using
MPC in the processing industry is due to its multivariable ex-
tension and constraint handling capabilities. Moreover, MPC
has been applied previously without constraints on a single
feed configuration of Sneesby’s column, which is a laboratory-
sized column. In this work, an industrial scale optimized single
feed configuration having 30 trays is used [10], and mainly fo-
cuses on control of single feed ETBE columns using a decen-
tralized PI controller and multivariable CMPC. The controller
performances are compared and evaluated.
2 ETBE Reactive Distillation
The reactive distillation process for ETBE differs from the con-
ventional process in the combination of the second reaction
stage (adiabatic) with the purification column and the elimi-
nation of some peripheral equipment. The pretreatment stage
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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1139

is unaffected. The operation of the first reaction stage can also (CH3)2C=CH2 + H2O > (CH3)3COH (3)
remain unchanged. The RD column is, therefore, actually a
hybrid column that contains a reactive distillation section and However, this side reaction is essentially eliminated when
two non-reactive distillation sections. Under such conditions, ethanol is in excess over the isobutene.
the majority of the reaction (ca. 80 %) is performed in an iso-
thermal, tubular reactor operating at moderate temperature
conditions, ca. 65 °C. The feed to the RD column should, 2.2 Reaction Kinetics
therefore, be rich in ETBE but still contain some ethanol and
isobutene. The products from the bottoms and overheads of The reaction kinetics for the liquid-phase synthesis of
the reactive distillation column are ETBE with some ethanol, ETBE based on the Langmuir-Hinshelwood-Hougen-Watson
and non-reactive hydrocarbon with a small amount of isobu- (LHHW) model are given below [2]e].
tene and ethanol, respectively. The distillate products may or – Reaction equilibrium constant:
may not require further processing depending on the compo-
sition and the refinery configuration. The advantages of using 4060:59
ln KETBE ˆ 10:387 ‡ 2:89055 lnT 0:0191544T
RD for ETBE manufacture in comparison to the conventional T
process are: ‡5:28586
10 5 T 2 5:32977
10 8 T 3 (4)
– RD produces a higher overall isobutene conversion for
ETBE, providing if some excess ethanol is used and the over-
all fuel purity (defined as the ether concentration plus the – Adsorption equilibrium constant:
ethanol concentration in the bottoms) is 97.89 %, which is 1323:1
comparable to the conventional process; lnKA ˆ 1:0707 ‡ (5)
T
– No additional reboiler duty is required for RD, since the
heat generated by the exothermic reaction offsets the reboi- – Reaction rate constant (mol/h/g of catalyst):
ler heat input and contributes to product separation;  
60:4
103
– Additional savings can be realized from the effective elimi- krate ˆ 7:418
1012 exp (6)
nation of ethanol from the distillate product (reduced to RT
1–2 ppm compared to the conventional process). This is – Generalized rate equation (mol/h):
potentially a decisive advantage of RD since it removes the
 
requirement to install ethanol recovery equipment. aETBE
Mcat krate a2EtOH aiBut
KETBE
rETBE ˆ (7)
…1 ‡ KA aEtOH †3
2.1 Process Description
ai = cixi (8)
The ETBE synthesis reaction is the reversible etherification of
ethanol and isobutylene on an acid catalyst, such as the acidic where ai is the activity, ci is the liquid activity coefficient, xi is
ion-exchange resin, Amberlyst 15, see Eq. (1). The reaction is the liquid mole fraction, R is the gas constant (J/mol K), Mcat
equilibrium limited at high temperatures (above 80 °C) and is the mass of the catalyst (g), and T is the temperature (K).
very slow at low temperatures (below 60 °C): Since the chemical reaction is very fast in the case of ETBE,
the heterogeneous reaction kinetic model can be neglected as
(CH3)2C=CH2 + C2H5OH > (CH3)3COC2H5 (1) it will not create any modeling error [17]. Chemical equilibri-
um is expected in all reactive trays, which can be defined by
ETBE in RD can be synthesized by using either a single feed the reaction equilibrium constant given by Eq. (4).
or double feed configuration. In double feed, two fresh reac-
tant streams are used, whereas in the single feed configuration,
the majority of the reaction is performed in an isothermal, 2.3 Steady State Profile from Aspen HYSYS 2004
tubular reactor operating at moderate conditions. This removes
the significant quantity of heat liberated in the reactor itself In this work, the optimal single feed, industrial scale steady
rather than affecting the reaction equilibrium in the distillation, state design is used [10]. The column consists of 30 trays
and therefore, also reduces the catalyst loading in the trays. (including partial reboiler and total condenser). There are
Two side reactions exist in ETBE synthesis. One is the di- 7 reactive stages present in between 7 rectifying trays and
merization of isobutylene to form diisobutylene (DIB) with 14 stripping trays, as shown in Fig. 1. The feed stream from
the chemical structure [(CH3)2C=CH2]2. In the presence of the upstream chemical reactor enters the column just below
any water traces in the reaction environment, another side re- the reactive trays. The steady state simulation is performed
action is the hydration of isobutylene to form isobutene (iso- using Aspen HYSYS 2004 [18]. The fluid package used is the
butyl alcohol) with the chemical structure (CH3)3COH. The UNIQUAC model for the liquid phase and ideal gas for the
side reactions are expressed by the following equations: gaseous phase, and the UNIFAC parameter are also used by
setting a binary coefficient. The steady-state simulation is per-
(CH3)2C=CH2 + (CH3)2C=CH2 > [(CH3)2C=CH2]2 (2) formed by using a sparse continuation solver. The equilibrium

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1140 S. Athimathi et al. Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154

3 Control Structure Synthesis

Figure 1. Optimal steady state design of a single feed configura-
tion.
reaction kinetics based on the equilibrium constant, is added
at each reactive stage. The composition profile obtained is
shown Fig. 2.
From Fig. 2, the distillate contains mainly n-butene and the
bottom contains mostly ETBE. Since the chemically inert
n-butene is much lighter than ETBE, any unreacted isobutene
is found mostly in the distillate. The excess ethanol will typi-
cally be removed in the bottoms as it is present in excess and
be blended with ETBE. The isobutene conversion rate in the
column alone is 48.9 % and the overall process (pre-reactor/
column) conversion is 89.7 %. The ETBE production rate and
purity in the bottoms are 5000 kg/h and 83.8 mol.-% ETBE,
respectively.
1
0.9
0.8
Composition, mole fr.
Systematic steady state analyses are conducted to synthesize
effective control structures for an ETBE reactive distillation
column. A control structure refers to the number of control
loops and the specific input-output pairing used in the loops.
Potential input variables are the reflux rates, reflux ratio, reboi-
ler duty, reboil ratio, distillate rate, bottoms rate, and the fresh
feeds. Potential output variables are the easily measurable vari-
ables such as tray/stream temperatures and compositions.
There are several possible input (manipulated) variables and
output (controlled) variables even in a simple RD column.
Usually, the control structure is synthesized based on the pro-
cess objectives of the RD column.
Reactive distillation combines the functionality of both the
reaction and purification stages of a process, and the main
operating objective for a reactive distillation column should
reflect both roles. In a reactor, the principal process objective,
which maximizes profitability, is conversion of the limiting
reactant, while in distillation it is separation, which is normally
measured by the product purity. Thus, for the ETBE RD
column, the combinations of the above factors are process
objectives, i.e., isobutene conversion and ETBE purity.
Control of reactive distillation is challenging because of its
complex dynamics resulting from the integrated functionalities
of reaction and separation. In the design of such a control sys-
tem, the selection of the control structure is the most crucial
decision. The approach taken is to study the effect of varying
the input handles about their base case values, on the column
outputs, to identify potential input-output pairings. Pairings
that are sensitive, avoid multiplicities and give almost linear
input-output relationships are then short-listed. This simple
philosophy for control structure synthesis is performed on a
single feed ETBE RD system in this work.
3.1 Selection of the Manipulated Variable
Distillation control configurations are often described with ref-
erence to the two manipulated variables, which are not used to
control the column inventory. The LV, LB and DV schemes are
the most practical combinations since they provide one
manipulated variable at each end of the column, thereby mini-
mizing lags. The most widely used control configuration in
industrial practice, the LV configuration is selected here [4],
although the LB scheme could also have been used.
3.2 Selection of the Controlled Variable

0.7 ETBE
0.6 i-butene
0.5 The controlled variable, which is used to ensure that the
1-butene
0.4 column consistently meets the process objectives, should have
ethanol
0.3 several characteristics, i.e., linearity, sensitivity, and responsive-
0.2 ness. Linearity refers to the relationship between the selected
0.1 controlled variable and the manipulated variable. Sensitivity
0
refers to the extent that the controlled variable must be
0 5 10 15 20 25 30
changed to vary the overall column operating condition. Re-
Stage number
sponsiveness refers to the relationship between the controlled
Figure 2. Steady state compositional profile for different trays. variable and the manipulated variable, which is used to pro-

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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1141

vide that control, and is a measure of both the dead time and rates that give the same conversion and composition in the
dynamic lags between the two variables. ETBE system, respectively, thus exhibiting input multiplicity
with both the process objectives. The presence of multiplicities
is common in reactive distillation and has been reported for
3.2.1 Steady State Multiplicities many RD columns [19]. The more economical design is the
one with the lower reflux flow rate and lower reboiler heat in-
The ETBE process exhibits the phenomenon of multiple steady puts (lower energy consumption). Although, Aspen HYSYS
states, which increases the difficulties for operation and con- 2004 is used, as discussed in Sec. 3.3, the comparable steady
trol. Multiplicity of steady states normally occurs as either in- state profile of Al-Arfaj and Luyben [10] is obtained. The con-
put multiplicity or output multiplicity. Input multiplicity oc- sequences of input multiplicity are not as severe as output
curs when two or more sets of input variables produce the multiplicity. However, input multiplicity results in a change in
same output condition. Output multiplicity occurs when one the sign of the process gain around the nominal operating con-
set of process input variables results in two or more sets of dition, leading to control instability. Directionality of a chemi-
process output variables. cal process means that a vector of inputs is amplified in a dif-
The presence of input and output multiplicities may cause ferent manner depending on the direction. Directionality of
operation and control problems. The control structure chosen the process gain has been known to create a considerably com-
must avoid output multiplicities to ensure that the column plex design of the control system for multivariable processes.
does not drift from a high conversion steady state to a low As the ETBE purity and conversion exhibit bidirectionality of
conversion steady state. However, it will be shown that even process gain and nonlinearity for changes in reboiler duty,
though the states of the column exhibit multiplicities, simple alternate control variables are required. Also, the direct mea-
linear control is still feasible, if both controlled and manipu- surement of isobutene conversion is not recommended as it
lated variables with a one-to-one relationship can be identi- requires complex feed, bottom and top composition analyzers
fied. and a calculation module.
Figs. 3 and 4 are obtained by changing the reflux flow
(1 kg mole/h) and reboiler heat duty (50 kW) in open-loop. It
shows that there are two reboiler heat inputs and reflux flow 3.2.2 Selection of Inferential Variable for ETBE Purity

Due to the presence of multiplicities in process objectives, in-

ferential controlled variables (temperature or composition)
60 0.9 which infer the process objectives, have to be synthesized. The
Conversion
ibutene-Conversion(%)

50
ETBE purity 0.85 reboiler temperature has a strong correlation with the ether
Bottom ETBE mole fr

purity but is also non-monotonic with respect to the reboiler

40 0.8
duty. Then the tray temperature is selected based on sensitiv-
30 0.75 ity. From the steady state temperature profile, Fig. 5, the lower
stripping section is sensitive (i.e., from tray 1 to tray 4). The
20 0.7
open-loop tray temperature sensitivity with respect to the
10 0.65 reboiler duty is obtained by stepping the reboiler heat duty in
the steady state mode.
0 0.6
The change in tray temperature for changes in reboiler heat
3000 3200 3400 3600 3800 4000
duty (0.5 %) for all trays plotted in Fig. 6 shows that the most
qr(KW)
sensitive tray is tray 1. In order to select the most appropriate
Figure 3. Input multiplicity of reboiler heat duty with conversion tray, an open-loop step test is performed in dynamic mode.
and purity. For a positive 0.5 % change in reboiler heat flow, the responses

100 0.95
140
90
ibutene conversion( % )

Conversion
130
80 0.9
Bottom ETBE mole fr

ETBE purity
120
Temperature ( C )

70
60 0.85 110
50 100
40 0.8 90
30
80
20 0.75
10 70
0 0.7 60
515 520 525 530 535 540 50
Reflux flow (kgmole/hr) 0 5 10 15 20 25 30
Stage number
Figure 4. Input multiplicity of reflux molar flow with conversion
and purity. Figure 5. Temperature profile on different trays.

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1142 S. Athimathi et al. Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154

of different stripping stage temperatures are monitored and it lated variable (reboiler heat) is varied around the operating
is found that the sensitivity decreases with increases in tray point. From the response shown in Fig. 7, a one-to-one rela-
number. For the entire stripping tray above stage 5, the tem- tionship exists between these two variables and has positive
perature has a much larger dead time, and hence, low respon- gain. This graph shows that temperature is a nonlinear func-
siveness. Thus, even though tray 1 is more sensitive, tray 3 is tion of reboiler duty, but the gain is constant over the range of
selected as the optimal tray, having appreciable sensitivity. interest (64–71 °C). On analyzing the correlation between the
The selected inferential variable should be linear, sensitive process objective (ETBE purity) and the controlled variable
and unidirectional in nature with the manipulated variable (tray 3 temperature), Fig. 8, a one-to-one relationship exists
and process objective. In order to achieve this, the manipu- around the operating range of 64–71 °C and has unidirectional
gain. Therefore, the stage 3 temperature is an appropriate con-
trolled variable to infer the bottom product ETBE purity.
Change in temp per change in qr

50
45
40 3.2.3 Selection of an Inferential Variable for Conversion
35
30 An inferential variable for conversion can either be the top
25 product composition or tray temperature. For the double feed
20 configuration, ethanol is selected instead of conversion, as the
15 control variable to control the impurity at the top [10]. How-
10 ever, for the single feed configuration, the ethanol mole frac-
5 tion exhibits bidirectionality and multiplicity in the operating
0 range of reflux flow, as shown in Fig. 9. Also, tray temperature
0 5 10 15 20 25 30 in the rectification section is not sensitive, as shown in Fig. 5.
Stage number Another inferential variable for isobutene conversion
Figure 6. Steady state temperature sensitivities (From open-loop analyzed is the reaction zone temperature difference [17]. From
step test). Fig. 10, the reactive zone temperature difference (DT = T21–
T15), has a linear relationship in the region between 0.6 °C–

135
125 0.18 0.0000003
distillate-
0.16
115 ibutene 0.00000025

Ethanol mole fr
0.14
ibutene mole fr

distillate-
105 0.12 0.0000002
T3 ( C )

ethanol
95 0.1
0.00000015
85 0.08
0.06 0.0000001
75
0.04
65 0.00000005
0.02
55 0 0
2900 3100 3300 3500 3700 3900 4100 510 515 520 525 530 535 540
Reboiler heat( KW ) Reflux flow (kgmol/hr)
Figure 7. Relationship between the manipulated variable (qr) Figure 9. Input multiplicity of reflux flow with ethanol impurity
and the selected inferential variable (T3). and isobutene at top.

1 100
0.9 90
0.8
Purity ( mass frac)

80
0.7 70
conversion

0.6 60
0.5 50
0.4 40
0.3 30
0.2 20
0.1 10
0 0
60 80 100 120 140 0 10 20 30 40
T3 ( C ) DT( C)

Figure 8. Relationship between the process objective (purity) Figure 10. Relationship between inferential variable (DT) and
and the selected inferential variables (T3). process objective (conversion).

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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1143

15 °C. Moreover, the reaction zone DT has a one-to-one rela- kp e hd s

tionship with reflux flow. Also, with different gain magnitudes,
it always has the same sign for the gain, as shown in Fig. 11.
3.3 Process Model Identification
The open-loop step test is performed with both manipulated
variables for different magnitudes, and the corresponding
changes in the controlled variables are recorded. From the
graph, the transfer function matrix is generated. Before per-
forming this step test, the inventory controllers are implemen-
ted. The reboiler liquid level and condenser liquid level are
controlled by the bottoms molar flow and distillate molar flow,
respectively, using a simple proportional controller. In order to
maintain the column pressure, the condenser pressure is con-
trolled by the condenser cooling duty, using a PI controller.
These three inventory controllers are tuned independently by
auto tuning. The method consists of inserting an on-off relay
in the feedback loop. The only parameter that needs to be spe-
cified is the height of the relay. The loop starts to oscillate
around the set point with the controller output switching
every time the process variable crosses the set point. The ulti-
mate controller gain and ultimate period are obtained. Then
the Zeigler-Nichols tuning method is used to calculate the
controller parameters from the ultimate gain and period [20].
45
40
35
30
DT ( C )
gˆ
…ss ‡ 1†
The FOPDT model reasonably describes the process gain,
time constant and effective delay time of the process, although
it cannot capture all of the features of a higher order model. In
general, it is step response data, which is fitted with these
models. The model is operated with the Identification Toolbox
of MATLAB, with a best fit value of ca. 90 %.
For different values of reflux flow variation, the controlled
variable is fitted to a first order transfer function and the static
gain, time constant and dead time are calculated and plotted.
The response of the process objectives for a 5 % change in
reflux flow is shown in Fig. 12. From Fig. 13, it can be seen
that there are large variations in gain, time constant and dead
time for a negative change in reflux flow. The above two prob-
lems suggest the need to use a multivariable constrained model
based controller design for control of the RD column. A simi-
lar step test is conducted for reboiler heat flow, as shown in
Fig. 14. For a positive change in reboiler heat flow, the transfer
function parameter shows large changes, as shown in Fig. 15.
In this region, the conversion drops drastically and reverse re-
action may even take place. This indicates that constraint for
positive change in reboiler heat flow is required and a model-
based controller is necessary for satisfactory operation. An
approximate transfer function matrix is found to be:
2 3
  0:018722e 1:25s
2:51093e 19s
 
DT L
ˆ4 …0:583s‡1†
0:010528e 0:5s
…0:001s‡1†
2:52875e 1:5:5s
5 (9)
T3 qr
…0:17s‡1† …0:001s‡1†
3.4 Check for Pairing and Stability

25
20 Relative gain array (RGA) proposed by Bristol is a means of
15 measuring steady state interaction. The RGA for this process is
10 found be (2.26 –1.26;–1.26 2.26). It can be seen from the RGA
5 values that the interaction in the selected control structure is
0 severe. However, from the Niederlinski index (NI = 2.26), the
495 515 535 555 575 595 pairing in a diagonal fashion is a closed stable loop [22].
Reflux Rate Hence, the selected control structure is appropriate. Thus, the
Figure 11. Relationship between manipulated variable (reflux ETBE purity in the bottom is maintained by controlling T3 in
flow) and selected inferential variable (DT). the stripping zone by manipulating the reboiler heat flow, and

For different magnitudes of reflux 1.04 555 68 555

flow change, both controlled variables 67
1.03 550 T3 550
are recorded. It is found that for large DT
66
Reflux molar flow

flow (kgmol/hr)

negative changes in reflux flow, both

Reflux molar

1.02 545 545

65
(kgmol/hr)

Reflux Reflux
DT ( C )

the conversion and purity drop drasti-

T3(C)

1.01 flow 540 64 flow 540

cally. Negative conversion (reverse re-
action) is even observed for negative 63
1 535 535
changes in reflux flow. This suggests 62
0.99 530 530
the need for a controller with con- 61
straint handling capability. For positive 0.98 525 60 525
changes in reflux flow, the response 0 500 1000 1500 0 500 1000 1500
can be fitted to a first order with dead a) Time( Sec) b) Time(sec)
time (FOPDT) model:
Figure 12. Open-loop step 5 % change in reflux molar flow; a) Step response of DT; b) Step
response of stage temperature.

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1144 S. Athimathi et al. Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154

500

400
Tp(min),Kp(%/%)

Kp-DT
300 Tp- DT
Kp-T3
200
Tp-T3

100

0
-2 0 2 4 6
-100

-200
a) Reflux change(%)

1400

1200
Td-T3
1000
Td- DT
Deadtime(min)

800

600
400

200
0
Figure 14. Open-loop step negative 5 % change in reboiler heat
-2 0 2 4 6 flow; a) step response of DT; b) step response of stage tempera-
-200
ture.
b) Reflux change(%)

Figure 13. Transfer function parameters for different molar reflux
flow rates; a) time constant & gain; b) dead time.
isobutene conversion is maintained by controlling the reaction
zone temperature difference (DT) by manipulation of the re-
flux molar flow, (L), at the top.
Morari Indexes of Integral controllability (MIC) given as
MIC=k‰G‡ …0† Š, where k[G] = Eigen values of the matrix G and
G‡…0† = a plant steady-state gain matrix, with the sign adjusted
so that all diagonal elements have positive signs [23]. If all the
SISO controllers contain integral action and have positive loop
gains, a negative value of any of the Eigen values of G‡
…0† shows
that the variable pairing will produce an unstable closed-loop
system. MIC for this system are found to be 0.0082 and
2.5392. The positive values of the Eigen values show that the
pairing will produce a stable closed-loop system.
By calculating the condition number of the system at steady
state, it can be determined whether or not the system is ill-
conditioned [22]. The condition number is defined as the ratio
between the maximum and minimum singular values of the
system. The singular values are s1 =0.0333 and s2 = 0.0038 and
the condition number is 8.7632. Since the condition number is
not too large, the system is not ill-conditioned. Thus, the final
control structure is:
– ETBE purity in the bottom is maintained by controlling the
3rd stage temperature in the stripping zone by manipulating
the reboiler heat flow;
– isobutene conversion is maintained by controlling the reac-
tion zone temperature difference in the reaction zone by
manipulating the reflux molar flow at the top.
4 Control System Studies
4.1 Decentralized PI Controller
Most industrial control systems use the multi-loop SISO diag-
onal control structure or decentralized controller, since it has
the most simple and understandable structure. Operators and
plant engineers can use it and modify it when necessary. It
does not require an expert in applied mathematics to design
and maintain it. In addition, the performance of these diago-
nal controller structures is usually quite adequate for process
control applications. Decentralized PI control is a desirable
controller structure for multivariable systems because of its
corresponding hardware and design simplicity [23]. Decentra-
lized control systems can also be designed to achieve levels of
fault tolerance that may be difficult to obtain in a centralized
multivariable control system. The decentralized PI controller
for the ETBE column is synthesized by using the relay feed
back method [20] and is implemented in HYSYS as shown in
Fig. 16. Using the ultimate gain and frequency obtained, the
Ziegler Nichols setting is applied, to obtain the diagonal con-
trollers.

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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1145

600 6000

500 5000
Kp-DT
K p ( % /% ) , T p ( m in )
Td-DT

Dead tim e Td( m in)

Tp-DT 400 Td-T3 4000
Kp-T3
Tp-T3
300 3000

200 2000

100 1000

0 0
-6 -4 -2 -6 -4 -2 0 2
-100 0 2
-1000
a) qr change(%) b) Reboiler heat flow change(%)

Figure 15. Transfer function parameters for different reboiler heat flows; a) time constant & gain; b) dead time.

Figure 16. Decentralized PI controller in an ETBE column.

 1 
The Biggest Log-modulus Tuning (BLT) technique, which is GC;11 ≡ 0:156 1 ‡
2:73 s
basically a procedure for detuning the control parameters to  1 
account for the interaction among the control loops, is applied GC;22 ≡ 0:482 1 ‡ (10)
for detuning the PI controllers [22]. For a detuning factor of 1:96 s
1.51, the final controller setting is obtained:

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1146 S. Athimathi et al. Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154

4.2 Model Based Predictive Control ulow ≤ u(t + j/t) ≤ uhigh

25 ≤u1 (t + j/t) ≤ 100 (12)
Model predictive control is arguably the most popular model 0 ≤u2 (t + j/t) ≤ 75
based algorithm currently used in the chemical process indus-
try [24]. A large part of MPC’s appeal is drawn from an intui- These constraints are expressed in matrix form for all pro-
tive use of a finite step response (or convolution) model of the jections as:
process, a quadratic performance objective over a finite predic- 2 3
uhigh …1† u…t 1†
tion horizon, and optimal manipulated input moves com- 6 .. 7
puted as the solution to a least squares problem. Because of its   6 . 7
6 7
IL 6 u …m† u…t 1† 7
popularity and acceptance by industry, this section focuses on Du…t† ≤ 6 high 7 (13)
IL 6 u…t 1† u …1† 7
implementing MPC. 6 low 7
The objective of a MPC controller is to drive the output as 4 5
close to the set point as possible in a least-squares sense with u…t 1† ulow …m†
the possibility of the inclusion of a penalty term on the input where IL is the identity matrix.
moves. Therefore, the manipulated variables selected, mini- The optimization problem with a quadratic objective and
mize the quadratic objective that considers the minimization linear inequalities can be defined by a Quadratic Program. By
of future errors including the control effort. The solution to converting to the standard QP formulation the Constrained
the minimization of the cost function is: MPC (CMPC) problem becomes:
X
p X
m
Jˆ k^y…t ‡ j=t† w…t ‡ j†k2 R ‡ kDu…t ‡ j 1†k2 Q minDu(t+m)Du(t + m)THDu(t + m) – g(t + j/t)Du(t + m) (14)
jˆ1 jˆ1 (11)

subject to: u1,min ≤ u1(t + j/t) ≤ u1,max and u2,min ≤

u2(t + j/t) ≤ u2,max.
There are three types of process constraints:
– Manipulated Variable Constraints: These are
hard limits on inputs u(k) to into consideration,
e.g., valve saturation constraints;
– Manipulated Variable Rate Constraints: These
are hard limits on the size of the manipulated
variable moves Du(k) to directly enhance the
rate of change of the manipulated variables;
– Output Variable Constraints: Hard or soft limits
on the outputs of the system are imposed, e.g.,
to avoid overshoots and undershoots.
In the ETBE column, for a positive change in
the reboiler heat flow and for a negative change in
the reflux molar flow, the conversion and purity
dropped drastically. Hence, it is necessary to im-
pose constraints on manipulated variables in these
regions. For reflux molar flow, a constraint is im-
posed for negative change, where the lower limit is
25 % from the steady state value and there is no
constraint for a higher limit. The constraint for a
positive change in the reboiler heat flow is imple-
mented in a similar manner. The higher limit for
reboiler heat flow is 25 % from the steady state val-
ue. These values are chosen to avoid input multi-
plicities in the process, when it is closer to the
nominal operating conditions.
The solution vector of MPC contains not only
the current moves to be implemented but also the
moves for the future m intervals of time. Although
violations can be avoided by only constraining the
move to be implemented, constraints on future
moves can be used to allow the algorithm to antici-
pate and prevent future violations, thereby pro-
ducing a better overall response. The manipulated Figure 17. a) Software communication pathway; b) MPC controller in an ETBE
variable value at a future time is constrained to be: column.

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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1147

Table 1. Tuning parameters for constrained MPC. and the gradient vector is:

Tuning Parameters Values g(t + j/t) = 2 GTRTRE(t + j/t) (16)

Number of inputs/outputs 2
where R and Q are the error and control increments weighting
Control interval 40 s
matrices (usually diagonal matrices of dimension of 2p × 2p
Model horizon 50 and 2m × 2m, respectively). Here the first m elements of R are
tuned for DT and the next m elements are set for T3. The con-
Prediction Horizon (p) 3
trol weightings, Q, are also taken in similar fashion for the ma-
Control Horizon (m) 2 nipulated variables. The constrained optimization is per-
Reference Trajectory () 1 formed using the function quadprog in the MATLAB
optimization toolbox.
Positive-definite weighting function The CMPC algorithm is implemented in MATLAB, which is
For manipulated variable (Q) [1.5–1] linked with HYSYS using the COM (Common Object Model)
principle. Both HYSYS and MATLAB contain such links, and
For controlled variable (R) [0.5–0.5]
it is possible to use both links simultaneously in order to ex-
ploit the strengths of both for better design and control of
chemical processes. The 2 × 2 CMPC controller is implemen-
where the Hessian of the QP is: ted in the ETBE column, as shown in Fig. 17. This illustrates
the basic communication pathway when the two programs are
H = GTRTRG + QTQ (15) linked using the active server principle.

a) b)

c) d)
Figure 18. Negative set point change in DT. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobutene Conver-
sion; d) ETBE purity (Bottom product).

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1148 S. Athimathi et al.
The initial tuning parameters for DMC are obtained using
Shridhar and Cooper tuning procedures [25]. They are fine
tuned by trial and error and the optimal parameters are given
in Tab. 1.
5 Results and Discussion
5.1 Comparison of PI and CMPC Controllers
The performance of CMPC is evaluated and compared with
that of decentralized the PI controller for the RD column. Both
set point tracking and disturbance rejection responses are con-
sidered and the responses of the two controllers are compared
for these disturbances based on Integral Square Error values.
5.1.1 Set Point Tracking of Reaction Zone Temperature
Difference
In order to check the performance of a controller for set point
tracking, a positive set point change is introduced, where the
reaction zone temperature difference (DT) is stepped to 1.6 °C.
a)
c)
Figure 19. Positive set point change in T3. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobutene Conver-
sion; d) ETBE purity (Bottom product).
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154
Similarly, a negative set point change is also introduced, where
the DT is stepped to 0.8 °C. The CMPC controller tracks the
set point moderately faster than the PI controller. The over-
shoot is greatly reduced in CMPC for the Stage 3 temperature.
However, for CMPC the set point tracking is not smoother for
positive changes. The process variables are controlled in a sim-
ilar fashion for both the controllers. A similar response is ob-
served for a negative step change in the DT, as shown in
Fig. 18. For negative step changes, overshoot and undershoot
in process variables are very much less for CMPC.
5.1.2 Set Point Tracking of Stage 3 Temperature
For a set point change in stage 3 temperature (T3), the CMPC
is sluggish when compared with the PI controller. CMPC also
has a high overshoot for positive changes in T3 (67.49–71 °C)
as shown in Figs. 19a)–19d). But for negative changes in T3
(67.49–64 °C), the CMPC settles faster but the response is
oscillatory and has high overshoot as shown in Figs. 20a)–
20d). Here the purity increases with increases in T3, and vice
versa.
b)
d)
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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154
a)
c)
Figure 20. Negative set point change in T3. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobutene Conver-
sion; d) ETBE purity (Bottom product).
5.1.3 Rejection of Feed Rate Disturbances
In order to check the performances of disturbance rejection,
± 10 % changes in feed molar flow are introduced to the ETBE
column. The control performances are illustrated in
Figs. 21a)–21d) and in Figs. 22a)–22d). For both the changes,
the CMPC has a shorter settling time, though the response is
not smoother. The overshoots in DT are similar for both con-
trollers, but with CMPC, the overshoot in T3 is smaller. Both
the process objectives are maintained around the set point.
Undershoot for purity is greatly reduced in CMPC.
5.1.4 Rejection of Feed Temperature Disturbances
The feed stream comes from the upstream reactor and also the
reaction is exothermic in nature. This causes frequent feed
temperature disturbances in the column. For ± 20 % change in
feed temperature, the responses of different controllers are
plotted in Figs. 23a)–23d) and Figs. 24a)–24d). The CMPC
controller is aggressive for feed temperature disturbances caus-
ing shorter settling time but higher overshoot.
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Reactive distillation 1149
b)
d)
5.1.5 Rejection of Feed Composition Disturbances
The composition disturbance is introduced where the isobu-
tene molar fractional composition increases from 0.07–0.15.
From Figs. 25a)–25d), both the controllers settle almost at the
same time but the CMPC has less overshoot compared with
PI. The conversion drops drastically to 20 % and the purity is
increased to 85 % for both controllers. Similarly, negative
change in isobutene is introduced by increasing the ethanol
composition. The CMPC settles faster than the PI controller
and the overshoot is same for both the controllers.
5.1.6 Comparison Based on ISE
The Integral Square Error (ISE) for different set points and
load disturbances for DT and T3 are calculated and tabulated
in Tab. 2. In set point tracking, the closed-loop performance
of the decentralized PI is better for set point change in stage 3
temperature, but is poor for set point change in reaction zone
temperature. For load disturbances, which occur more fre-
quently in chemical processes, CMPC effectively rejects the
feed rate disturbances and feed composition disturbances.
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1150 S. Athimathi et al.
a)
c)
Figure 21. Positive step change in feed. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobutene Conversion;
d) ETBE purity (Bottom product).
6 Conclusions
In this study, steady-state analyses are performed to synthesize
the control strategy of an ETBE reactive distillation column.
The key points to controlling the column are to maintain the
quality of the bottom product, and to maintain isobutene con-
version. Although input state multiplicities occur in the col-
umn, linear control is still possible since suitably controlled
and manipulated variable pairings are found, which exhibit no
multiplicities.
A decentralized PI controller is implemented using the
HYSYS subroutine. The CMPC algorithm is implemented in
MATLAB, which is linked with HYSYS using the COM princi-
ple. Since HYSYS and MATLAB contain such links, it is possi-
ble to use both links simultaneously. Thus, any type of control
algorithm can be implemented for better design and control of
chemical processes. The performances are compared for the set
point tracking and load disturbances. The decentralized PI
controller is effective for set point tracking except for set point
change in reaction zone temperature difference. From Tab. 2,
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154
b)
d)
one can see that ISE values are lower for CMPC. As the feed
stream is coming from the upstream reactor, feed disturbances
will occur frequently in reactive distillation. Hence, it is re-
quired that the controller should reject the load disturbances
effectively. CMPC rejects the load disturbances effectively ex-
cept for feed temperature disturbances. However, the feed tem-
perature is cooled to ca. room temperature before entering the
column and thus, the effect of this disturbance is less in the
column. Therefore, the CMPC controller is recommended for
the control of a reactive distillation process as it is effective for
both set point and load disturbance rejection.
Acknowlegements
T. K. Radhakrishnan thanks the TEQIP, NPIU, Government of
India for the support given to him to complete the work at the
National Taiwan University, Taiwan. The discussions with Prof.
C. C. Yu are gratefully acknowledged.
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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1151

a) b)

c) d)
Figure 22. Negative step change in feed molar flow rate. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobu-
tene Conversion; d) ETBE purity (Bottom product).

Table 2. Comparison of ISE values.

DISTURBANCES Decentralized PI Constraint MP

ISE for ISE for Sum of ISE for ISE for Sum of
Top Loop Bottom Loop ISE Top Loop Bottom Loop ISE

Positive set point change in DT 3.63 635.45 639.08 4.0 59 63.0

Positive set point change in T3 0.002 13.73 13.74 0.08 38.96 39.04
Positive 10 % feed change 0.23 79.23 79.46 0.36 33.61 33.97
Positive feed composition change (isobutene) 0.08 12.92 13.0 0.04 6.69 6.73
Positive change in feed temperature 0.01 12.7 12.71 0.01 16.13 16.14
Negative set point change in DT 0.64 105.57 106.21 0.56 73.80 74.36
Negative set point change in T3 0.005 37.59 37.59 0.008 118.95 118.97
Negative change in feed 0.27 89.84 90.11 0.217 12.21 12.43
Negative change in feed temperature 0.01 10.99 11 0.014 20.74 20.76
Negative change in feed comp. (isobutene) 0.74 112.41 113.15 0.217 86.61 86.82

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1152 S. Athimathi et al. Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154

a) b)

c) d)
Figure 23. Positive step change in feed temperature. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobutene
Conversion; d) ETBE purity (Bottom product).

a) b)

c) d)

Figure 24. Negative step change in feed temperature. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) isobutene
Conversion; d) ETBE purity (Bottom product).

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Chem. Eng. Technol. 2006, 29, No. 10, 1137–1154 Reactive distillation 1153

a) b)

c) d)
Figure 25. Positive step change in feed molar composition. a) Reaction zone temperature difference; b) stage 3 temperature (T3); c) iso-
butene Conversion; d) ETBE purity (Bottom product).

Symbols used p [–] prediction horizon

qr [–] reboiler heat duty
ai [–] activity Q [–] weighting matrix for control
DT [–] reaction zone temperature moves
difference rETBE [–] generalized rate equation
E(t+j/t) [–] future error R [J/mol K] gas constant
g [–] process transfer function R [–] weighting matrix for predicted
g(t+j/t) [–] gradient vector errors
G [–] transfer function matrix T [K] temperature
Gc,11, Gc,22 [–] controller transfer function T3 [–] stage 3 temperature
G‡…0† [–] steady state gain matrix u [–] control signal
H [–] Hessian of the QP xi [–] liquid mole fraction
J [–] cost function
kp [–] steady state gain Greek Symbols
KA [–] adsorption equilibrium constant cI [–] activity coefficient
Kc [–] controller gain hd [–] process dead time
KETBE [–] reaction equilibrium constant s [–] time constant
krate [–] reaction rate constant si [–] integral time
L [–] reflux flow rate k [–] eigen value
Lcm [–] closed-loop log modulus r [–] singular values
m [–] control horizon
Mcat [g] mass of catalyst

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1154 S. Athimathi et al.
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