Journal of Process Control 24 (2014) 113–124

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Journal of Process Control

journal homepage: www.elsevier.com/locate/jprocont

Dynamics and control of benzene hydrogenation via reactive

distillation
Vishal Mahindrakar a , Juergen Hahn a,b,∗
a
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, United States
b
Department of Biomedical Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, United States

a r t i c l e i n f o a b s t r a c t

Article history: This work develops a dynamic, first principles-based model of a reactive distillation column used for ben-
Received 14 October 2013 zene hydrogenation of a reformate stream and investigates different control structures for this process.
Received in revised form 3 January 2014 The model is used initially to develop and evaluate a feedback control strategy which provides good reg-
Accepted 7 January 2014
ulatory performance for small disturbances, however, it tends to be sluggish for significant disturbances
Available online 28 February 2014
in the feed composition. In order to address this point, adding a feedforward controller to the feedback
structure has also been investigated. However, the feedforward controller can only be implemented if
Keywords:
composition measurements of the feed are taken. As online composition measurements are expensive
Reactive distillation
Packed column
in practice, several different scenarios have been investigated where samples of the feed are taken and
Dynamic modeling subsequently analyzed in a lab, as represented by measurement time delays. Simulation results show
Feedback control that adding feedforward control to the feedback scheme can be very beneficial for this process, however,
Feedforward control this is only the case if the composition disturbance measurements do not involve a significant time delay.

© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Automotive emissions are a significant contributor to poor air
quality [1]. As such, specifications for automobile fuels obtained
from petroleum have received increasing levels of attention from
the Environmental Protection Agency (EPA). Benzene is one of the
compounds that is regulated as it is a carcinogen and the EPA
requires all refiners to limit the amount of benzene in gasoline to
0.62 vol% [2]. While benzene in the gasoline pool results from a vari-
ety of sources, the main contributor is the reformer unit resulting
in significant amounts of benzene present in reformate streams.
As the reformate stream is used to boost octane rating, there are
economic objectives that have to be taken into account while com-
plying with environmental regulations.
One option to remove benzene is to hydrogenate in the presence
of a catalyst. However, a problem arises as the catalyst used for
the reaction is not exclusively selective for benzene, and toluene,
which is present in the reformate stream in considerable quantities,
will also be hydrogenated. Toluene hydrogenation is undesirable as
∗ Corresponding author at: Center for Biotechnology and Interdisciplinary Studies,
Rensselaer Polytechnic Institute, Troy, NY 12180, United States.
Tel.: +1 518 276 2138; fax: +1 518 276 3035.
E-mail address: hahnj@rpi.edu (J. Hahn).
toluene has a high octane rating (RON) and should be retained in
the final product.
Benzene (100 RON) + 2H2 → cyclohexane (83 RON) (1)
Toluene (120 RON) + 3H2 → methylcyclohexane (75 RON) (2)
In order to avoid problems related to the selectivity of the cata-
lyst, the reformate stream is split into light and heavy components
in the conventional process (Fig. 1a). As benzene is a reasonably
light component of this mixture, it is mostly concentrated in the
distillate, and accordingly, is hydrogenated before being sent to
the gasoline pool. The downside of this process is that a high cap-
ital investment is needed. Reactive distillation (Fig. 1b) offers an
alternative route for solving this problem. By combining reaction
with separation it is possible to selectively react one component in
a specified region of the column while suppressing unwanted reac-
tions of other components. Furthermore, additional savings can be
achieved as the heat of reaction can directly be used for separation
of the mixture.
While reactive distillation (RD) can have significant advantages
over traditional designs, there are also challenges that need
to be considered. The simultaneous presence of reaction and
separation phenomena can result in complex dynamic behavior.
Combining reaction and separation into a single vessel results in
fewer manipulated variables, thus increasing interactions between
control loops [3]. RD columns have been observed to be very
sensitive to changes in feed concentration. This is a crucial aspect

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114 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124

in the feed happen on a daily basis and a column operating under a

Notation feedback control can take several hours to return to an acceptable
steady states. This paper investigates these points by developing
a geometric surface area of packing per unit volume a detailed dynamic model, studying the dynamic behavior in
(m2 m−3 ) simulations, and developing a control scheme. Furthermore, the
A cross sectional area of column possibility of implementing a feedforward control scheme, in
CA concentration (mol m−3 ) addition to a feedback one, is investigated where it is taken into
dp packing particle diameter (m) account that feed composition measurements may involve time
ds column diameter (m) delays if the measurements are taken as samples analyzed in a lab.
D distillate flow rate (mol s−1 ) The outline of this paper is as follows. A literature review is
Ea reaction activation energy (J mol−1 ) presented in the following subsection and Section 2 presents pre-
F feed flow rate (mol s−1 ) liminary information. A detailed description of the model and
hi total liquid holdup based on empty column control structure is presented in Section 3. Section 4 discusses col-
(m3 m−3 ) umn responses to a series of commonly occurring disturbances.
Hlj molar enthalpy of liquid stream on stage j (J mol−1 ) Conclusions are given in Section 5.
Hvj molar enthalpy of vapor stream on stage j (J mol−1 )
HETP height equivalent to a theoretical stage (m) 1.1. Literature review
k reaction rate constant (mol s−1 kg−1 )
K wall factor Reactive distillation has received a lot of attention as part of
KA reaction adsorption coefficient (m3 mol−1) process intensification efforts in the last couple of decades. Employ-
KH reaction adsorption coefficient (m3 mol−1 ) ing reactive distillation can result in energy savings as the heat of
L liquid flow rate (mol s−1 ) reaction is directly used for separation of the mixture. Harmsen
M mass holdup (kg) [3] has reviewed commercial applications of reactive distillation.
Mlj liquid molar holdup on stage j (mol) Reactive distillation systems have been shown to reduce variable
Mvj vapor molar holdup on stage j (mol) cost, capital expenditure and energy requirements by 20% or more
N number of stages for some processes [3]. Also, since the heat of reaction is used for
P pressure (Pa) evaporation in a column, increased reaction rates can results in
P0,j dry column pressure drop across stage j (Pa) increased evaporation rates without significant changes of the tem-
Pj irrigated column pressure drop across stage j (Pa) perature. Thus, reactive distillation columns have been found to
Q external heat energy input (J) be less susceptible to runway behavior than conventional reactors
R reflux ratio [3]. Reactive distillation models have been surveyed extensively by
Rgas gas constant (J mol−1 K−1 ) Taylor and Krishna [5] and several articles describing dynamic mod-
Rev vapor Reynolds number els, and control structures [6–9] are available. A variety of different
rxn reaction rate (mol s−1 kg−1 ) applications of reactive distillation in refineries have been reported,
s Laplace variable such as processes involving ethers (MTBE, ETBE, and TAME [10]).
T0 reaction reference temperature (K) Sneesby et al. [11–13] have developed dynamic models for ETBE
Tj temperature on stage j (K) and MTBE, and also made general recommendations for control
V vapor flow rate (mol s−1 ) system design. Different control strategies for MTBE reactive dis-
u specific liquid load (m s−1 ) tillation columns were highlighted by Bartlett and Wahnschafft
x liquid mole fraction [14]. A number of authors have also explored the dynamics and
y vapor mole fraction control for reactive distillation of TAME [15–18]. However, despite
y* equilibrium vapor mole fraction these extensive efforts on reactive distillation in general, no papers
z feed mole fraction on benzene hydrogenation via reactive distillation can be found
in the open literature. This situation is especially peculiar as ben-
Greek letters zene hydrogenation is an important step in a refinery and several
ε packing void fraction RD columns used for benzene hydrogenation are in operation in
lj,i liquid fugacity coefficient of component i on stage j refineries throughout the world.
vj,i vapor fugacity coefficient of component i on stage j
cat catalyst density (kg m−3 ) 2. Preliminaries
 Murphree efficiency
 relative gain This section reviews preliminary information needed for the
 relative gain array remainder of the paper. Section 2.1 reviews existing modeling
transfer function time constant (s) approaches for reactive distillation columns, some of which will
c controller design parameter (s) be used in this work. Existing control strategies for reactive dis-

transfer function time delay (s) tillation columns are discussed in Section 2.2.1 and Section 2.2.3
resistance coefficient reviews the principles of feedforward control which will also be
used.
Subscripts
i component index 2.1. Packed column modeling
j stage index
Reactive distillation can be viewed as an extension of con-
ventional packed columns, where some of the packing includes a
for benzene hydrogenation as the concentration of some of the catalyst to facilitate a reaction taking place. A number of papers
main components in the feed can vary by 50% or more due to have discussed modeling of conventional packed columns. The
disturbances upstream from the column [4]. The importance of key methods used for packed columns are equilibrium (EQ) stage
addressing these disturbances is increased by the fact that changes modeling and non-equilibrium stage modeling (NEQ). In EQ stage
 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124 115

Fig. 1. Schematics of (a) conventional reaction/separation process and (b) reactive distillation.

models, the vapor and liquid phase are assumed to be in equi-
librium. NEQ stage models use rate-based equations to describe
the mass transfer occurring in conventional distillation columns.
NEQ stage models are generally based on the use of rigorous
Maxwell–Stefan equations for estimating heat and mass transfer
rates across the interface. Many papers have presented EQ models
[6,8,12,13,19–21] and NEQ models [16,17,20–22] for reactive dis-
tillation. Most of the NEQ models developed for reactive distillation
are generally steady state models [20–22]. However, Peng et al. [23]
have compared the results of dynamic NEQ and EQ model, and con-
cluded that the results are similar for their case. Contrary to this,
Baur [17] pointed out that the responses from the models may differ
quantitatively and the dynamics are influenced by column speci-
fications. NEQ models are generally more challenging to simulate
[17,23] and require thermodynamic properties for the calculation
of mass transfer coefficients and interfacial areas.
The dynamic behavior of a distillation column is strongly influ-
enced by fluid hydraulics in the column. This is even more so in
reactive distillation columns, as liquid hold-ups, and liquid res-
idence times are important for determining the conversion and
selectivity of the reactive distillation column. Very few dynamic
models consider both liquid and vapor holdup in the columns.
The vapor holdups are generally neglected because of the low
density of vapor in comparison to liquid. Also, considering vapor
holdups leads to additional computational difficulties in the model.
As such, most dynamic models consider only dynamic liquid hold
up or in some cases a constant liquid holdup [23]. However, Choe
and Luyben [24] suggest that vapor holdup should be considered
for dynamic models of columns operating at pressures greater
than 5–10 atm. Equations governing the vapor and liquid flows,
and hold-ups in a packed column have been discussed by many
papers: Bemer and Kalis [25] have given equations for liquid hold-
up and pressure drops in irrigated columns while Mackowiak [26]
has extensively reviewed methods for determining vapor flow in
packed columns.
multi-loop control system [27]. A major concern with multi-loop
control is the presence of process interactions, i.e., each manipu-
lated variable may affect multiple controlled variables, however,
these interactions are not taken into account for the control
structure design. Multi-loop control systems may not provide
satisfactory control in some scenarios and multivariable control
strategies, such as model predictive control and decoupling control
can provide better control. However, multi-loop control is the
most widely used control strategy for distillation columns because
of its simplicity, both in terms of maintenance and controller
tuning. As no work has been done on modeling and control of
benzene hydrogenation via reactive distillation, this work focuses
on traditional control strategies and advanced control will be
investigated in the future.
The commonly used control structures for reactive distillation
are similar to those of conventional distillation columns. Skogestad
and co-workers [28–30] have discussed the selection of controlled
and manipulated variables. Most distillation columns generally use
either a 4 × 4 control or a 5 × 5 control structure. These configura-
tions refer to the number of manipulated variables and the number
of controlled variables used. Eq. (3) presents the set of manipulated
variables u and controlled variables y that are used in 5 × 5 systems
in no particular order of correlation; see Fig. 2 for an illustration
of the variables. Columns having a 4 × 4 control system frequently

2.2. Control structure

2.2.1. Feedback control

Reactive distillation columns are systems with multiple inputs
and multiple outputs (MIMO). One approach to deal with MIMO
systems is to treat the control problem as separate individual
loops, i.e., assume that each manipulated variable affects only one
particular controlled variable and design a controller for each loop
separately. This type of control structure is also referred to as a Fig. 2. Conventional distillation column.
116 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124

do not use the pressure at the top of column, P1 , as a controlled The relative gains are arranged to form the matrix
variable [30]. ⎡ ⎤
11 12 ··· 1n
⎛ ⎞ ⎛x ⎞ ⎢ ···
⎥
L1 ⎢ 21 22 2n ⎥
=⎢ ⎥
1
⎢. ⎥ (5)
⎜ ⎟ ⎜x ⎟ .. .. ..
⎜ VN , QN ⎟ ⎜ N ⎟ ⎣ .. ⎦
⎜ ⎟ ⎜ ⎟ . . .
u=⎜
⎜ D ⎟
⎟ y=⎜ ⎟
⎜ M1 ⎟ (3) n1 n2 ··· nn
⎜ L ⎟ ⎜ ⎟
⎝ N ⎠ ⎝ MN ⎠ Controlled and manipulated variables are paired such that the
V2 , QD corresponding relative gains are positive and as close to one as
P1
possible. While the above definition of RGA may seem difficult to
estimate directly for real systems, the RGA can be determined from
The 5 × 5 system shown in Fig. 2 is generally used for columns an open-loop gain matrix. The procedure for computing the RGA
with a total condenser. For these columns, the pressure is typi- from an open-loop gain matrix, K, is given by
cally controlled by manipulating the condenser heat removal as
T
the condenser temperature and the column pressure are directly H = (K −1 ) (6)
linked for a total condenser. Partial condensers are used when there
=K ⊗H (7)
are very light components in the column feed that would require
a high column pressure or a low condenser temperature. In a col- where ⊗ denotes the Schur product (element by element multipli-
umn with a partial condenser, vapor is removed from the condenser cation) [27].
as a vapor stream. The pressure of the column is strongly influ- The controllers used for feedback control loops are generally
enced by the outlet vapor stream flow rate. Luyben [31] and Hori controllers of PID-type, where PI controllers are the most com-
and Skogestad [32] have discussed control structures for columns monly used ones. Luyben [31] has pointed out that flow controllers
with partial condensers. Sloley [33] has extensively reviewed con- that regulate the inventory of a column, e.g., the distillate and bot-
trol strategies that can be used for columns based on the type of tom flow, should be proportional-only controller as the inventory
condenser. in the column is sufficiently large to overcome the effect of offsets
Recycle loops in chemical plants are known to significantly alter that may occur due to the use of proportional-only controllers.
the control and dynamics of process networks [34–36]. Recycle
streams increase the overall time constants, thus “slowing down” 2.2.3. Feedforward control
its overall response [34]. Designing a control structure for process Feedback control does not take corrective action until after
networks with recycle can be challenging because recycle streams deviations in the controlled variables occur. As the effects of feed
can induce a time scale separation, where the dynamics of the pro- disturbances will only be detected after a while, this lack of predic-
cess evolves at a fast time scale, and the dynamics of the overall tive control can limit the overall column performance, especially if
process with recycle at a slower time scale [37]. Dynamical analy- the column includes large time constants or time delays. One option
sis and control of such process networks with recycle have received is to also include feedforward control in addition to feedback con-
considerable attention [37]. One of the first design procedures was trol in a control structure. Feedforward control systems measure
proposed by Buckley [38] and has been widely used in industry the disturbance variables and take corrective action before upsets
for many years [39]. The first step is to design a control struc- of the controlled variables can be recorded. The main disadvan-
ture that handles the inventory of the entire process (liquid levels tage of feedforward control is that the disturbance variable must
and gas pressures). This “hydraulic” structure provides smooth be measured online which is not always feasible, physically or for
flow rate changes. Fast-acting proportional-only level controllers economic reasons.
provide the most simple and most effective way to achieve this The basic idea for feedforward controller is to measure the
flow smoothing [39]. The second step is to close the “product qual- disturbance affecting the system and compute a change of the
ity” loops. These loops typically use slower proportional–integral manipulated variable such that the effect of the disturbance on
controllers to hold product streams as close to the specification the controlled variable is canceled by the change of the manipu-
as possible. Larsson and Skogestad [40] and Luyben et al. [41] have lated variable [44]. Feedforward controller designs are thus based
discussed plant-wide controller design procedures for a large num- on process models. A feedforward controller transfer function Gf
ber of measurements and control loops. When applied to a smaller for a system can be given by [27]
single unit scale, they mirror the steps that have been mentioned
Gd
above. Gf = − (8)
Gp Gmf

where Gd is the disturbance transfer function, Gp is the process

2.2.2. Relative gain array
An important general problem for a multi-loop control structure
is to pair the controlled variables and the manipulated variables.
Incorrect pairing may result in poor control performance and inter-
actions among controlled variables. One way to determine the
pairing is Bristol’s relative gain array (RGA) [42]. Bristol developed
the RGA as a systematic approach to measure the process inter-
actions and recommend an effective pairing of manipulated and
controlled variables. The relative gain between a controlled variable
yi and manipulated variable uj is defined as follows [27]:
(∂yi /∂uj )u open-loop gain
ij  = (4)
(∂yi /∂uj )y closed-loop gain
transfer function, and Gmf is the disturbance sensor/transmitter
transfer function. Sometimes modifications to the control law
shown in Eq. (8) need to be made to ensure that the resulting
controller is realizable [27].
Often, the dynamics between a process and a disturbance
are neglected and a simple static feedforward controller may be
designed if the responses are satisfactory. A static feedforward con-
troller is given by the ratio of gains of disturbance, process, and
measurement transfer functions [44]
Kd
Gf = − (9)
Kp Kmf
where Kd , Kp , and Kmf are gains of the disturbance, process, and
measurement transfer functions.
 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124 117

Table 1 equilibrium-based (EQ) stages and non-equilibrium-based (NEQ)

Feed composition for the RD column.
stages. NEQ models include more detail, but some of the model
Component Mole fraction parameters are usually not well known and it is unclear if NEQ
n-Butane C4 H10 0.0126 models provide a more accurate description than EQ-based mod-
n-Pentane C5 H12 0.0961 els. As such an equilibrium-based modeling approached is used
2,3-Dimethylpentane C7 H16 0.0116 in this work. Reaction kinetics for the catalyst section have been
3-Methylpentane C6 H14 0.0587 taken from Toppinen et al.’s [45] work on hydrogenation of ben-
n-Hexane C6 H14 0.0350
zene and other alkyl benzenes. Benzene hydrogenation columns
Benzene C6 H6 0.0826
Cyclohexane C6 H12 0.0000 operate at a relatively high pressure of 8 atm, and hence variable
3-Methylhexane C7 H16 0.0233 vapor holdups have been taken into account. Also, the feed stream
2,4-Dimethylpentane C7 H16 0.0234 has 15 components that need to be modeled, and some of these
n-Heptane C7 H16 0.0098
components are bound to have low concentrations in some stages
Toluene C7 H8 0.2814
m-Xylene C8 H10 0.2063 of column. If a dynamic model considers no vapor hydraulics, then
Cumene C9 H12 0.1594 the vapor flow rates are also dependent on the molar balances. This
Hydrogen H2 0.0000 creates a problem for the initialization of the model, as the stark dif-
Methylcyclohexane C7 H14 0.0000 ferences in the concentration of individual components may lead
to inaccurate estimation of flow rates. In the presence of vapor
hydraulics, the vapor flow rates are governed by the hydraulics
facilitating initialization of the model. Equations governing liq-
Feedforward control depends on the accuracy of the disturbance uid and vapor hydraulics have been adopted from Maćkowiak’s
measurement and on the accuracy of the model describing the pro- compilation [26] on packed bed fluid dynamics. The reflux drum
cess. As some inaccuracies cannot be avoided, feedforward control and the reboiler drum have been sized to have a residence time
by itself would often result in an offset. As a consequence, feed- for the liquid of approximately 5 min when the vessels are 50%
forward control is commonly combined with feedback control in full, based on the total amount of liquid entering or leaving the
practice [43]. vessels. Not all of the hydrogen fed to the column will react due
to disturbances in the feed composition. However, hydrogen is
3. RD column design and control an expensive resource and thus, almost all the unreacted hydro-
gen is recycled as vapor outlet stream of the partial condenser.
3.1. Development of dynamic model A recycle ratio of 0.99 has been used for the column. The equa-
tions of the model as well as the nomenclature can be found in
The RD column used in this benzene hydrogenation study is Appendix A.
a packed column with a throughput of 200,000 lb/h. The refor-
mate stream enters the column as feed which is processed into
benzene-free lights and heavy stream. The feed stream has 15 com-
ponents that need to be modeled and the feed composition is given 3.2. Control structure
in Table 1. The column has 70 theoretical stages which includes
a partial condenser and a reboiler. The column stages have been 3.2.1. Selection and pairing of controlled and manipulated
numbered from top to bottom in this investigation. The first stage variables
is the reflux drum and the last stage is the reboiler drum. The col- The set of controlled variables and manipulated variables need
umn model has 10 catalyst stages at the top, i.e., stage 2–stage 11. to be identified, in order to design a control structure. A degree
The feed to the column is added at stage 30. The reformate stream of freedom analysis gives the following set of seven manipulated
has a nominal benzene concentration of 6.0 vol% which is common variables that can be used for control:
in refineries [4]. It is expected that the feed benzene concentra-
tion may be as high as 11.0 vol% [4]. Hydrogen to the column is ⎛ ⎞
D
fed at stage 29 along with the unreacted hydrogen that is recycled
⎜ V1 ⎟
from the partial condenser. The column is required to meet EPA ⎜ ⎟
⎜L ⎟
specification of 0.62 vol% maximum benzene concentration at the ⎜ N ⎟
⎜ ⎟
outlet during regular operation. Note that the outlet benzene con- ⎜ ⎟
centration throughout this investigation refers to the total volume u = ⎜ FH2 ⎟ (10)
⎜ ⎟
percentage (vol%) taken over all the liquid streams (both distillate ⎜ Q1 ⎟
⎜ ⎟
and bottom) exiting the unit. ⎜ ⎟
The RD column is a packed column where a section of the col- ⎝ QN ⎠
umn is filled with catalyst. Industrial data regarding the packing R
details and type of catalyst used are unavailable as these are usually
kept a trade secret. Also, no publications on reactive distillation for
benzene hydrogenation are available in the open literature. Thus, When compared with (3), Eq. (10) has two additional manip-
in the absence of any sort of information regarding the packing, ulated variables: the reflux drum vapor stream flow rate V1 , and
a standard packing size (25 mm pall rings) and catalyst size has the fresh hydrogen feed flow rate FH2 . This is due to the pres-
been used in this work. The packing has been treated as equiv- ence of very light gases such as hydrogen in the system which
alent to theoretical trays and a height equivalent to theoretical has a very low bubble point temperature. Condensing hydrogen
packing (HETP) of 0.45 m has been used throughout the column. is economically infeasible, which necessitates the need for a par-
The diameter of the column has been determined by assuming tial condenser with a liquid outlet stream and a vapor outlet
that the vapor velocity reaches a maximum of 80% of the flooding stream.
limit [26]. Based on the vapor flow estimated in the column, the The first four manipulated variables of u are flow rates and
diameter of the column was estimated to be 2.8 m. Two different hence, they are part of the control loops that regulate the inven-
modeling methods are commonly used for each stage of a column: tory of the column. The influence of these variables on the
118 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124

corresponding controlled variables is straightforward and the

pairing can be performed as follows:

(11)

Even though the objective of an RD column is to maintain the

purity and conversion of the product streams, RD control is based
on temperature points instead of composition. This is because
composition analyzers are expensive to purchase and have high
maintenance costs [47]. They also introduce a delay in measure-
ments if chromatographic methods are used. Temperature sensors
are inexpensive, reliable and introduce small measurement lags.
Based on a degrees of freedom analysis, three temperature points
need to be selected for the remaining three manipulated vari-
ables. One of these control points should be somewhere above the
feed and one should be somewhere below the feed. One temper-
ature control point is selected at the top of the column to have
a measurement related to the top product that is located above
the reactive zone. Another of the temperature measurements is
selected approximately halfway between the feed and the bottom
of the column. Since the feed is at stage 30, a temperature mea-
surement at stage 55 is a reasonable choice and has been found
to be sensitive to changes in the manipulated variables. A third
temperature control point needs to be fixed at some point within
the column. Hori and Skogestad [46] and Luyben [47] have listed a
number of criteria for selecting the tray at which a temperature sen-
sor should be placed for column control. Conventional techniques Fig. 3. Schematic of feedback and feedforward control structure for the RD column.
are based, among others, on the slope of the temperature profile,
sensitivity to changes in manipulated variables, SVD analysis, tem-
perature invariance with changes in feed composition. However,
the temperature profile in the reactive zone of the column may control was fitted to transfer functions which were estimated using
affect the outcomes of these techniques. Therefore a more gen- the MATLAB system identification toolbox. Most of the responses
eral approach has been adopted here for selecting the temperature were fitted to first order plus time delay (FOPTD) transfer func-
control tray. The following three criteria have been used: tions. Some of the responses were fitted to second order transfer
functions in order to obtain a better fit and some of these responses
(i) Avoid trays near the feed tray: the temperature profile near also included a lead term. Table 2 shows the computed transfer
the feed tray is generally influenced by the enthalpy of the functions in response to step changes in the manipulated variables.
feed to the column and may not be as sensitive to changes in Based on these transfer functions, the RGA was determined
the manipulated variable. for the nominal operating conditions (feed benzene concentra-
(ii) Avoid trays near the top or the bottom of the column: since tion = 6 vol%). The RGA was also computed for the RD column at the
the distillate temperature and one temperature measurement extreme operating conditions, i.e., when the feed benzene concen-
below the feed have already been used as controlled variables, trations are 3 vol% and 11 vol%, since it is possible that the pairing
any temperature measurement near the top or bottom will be may change at different operating conditions. These results have
highly correlated with already selected measurements. been presented in Table 3 and it can be seen that the pairing of the
(iii) Avoid the catalyst zone: reactions occurring in the catalyst controlled and manipulated variables is unaffected by the investi-
zone are exothermic and this affects the temperature of the cat- gated changes in operating conditions.
alyst stages. A temperature control point should not be selected Based on RGA computed at the three operating conditions and
in this zone because the temperature is affected by reaction the discussion above, the pairing of manipulated and controlled
kinetics in addition to the regular dynamics due to separation. variables results in the following:

Based on these criteria the third temperature control point was

chosen to be between the catalyst zone and the feed state. Stage 19
was considered to be a good temperature control point and showed
significant sensitivity to step changes in the manipulated variables.
Thus, T19 was chosen as the third controlled variable.
The pairing of the remaining manipulated variables was done
via RGA analysis. Step input changes were given to the manipulated
variables of the model with some of the control loops open. Control
loops corresponding to the controlled variables liquid distillate (D), (12)
reflux drum vapor flow (V1 ), bottom flow (LN ), and fresh hydrogen
feed (FH2 ) are closed for determining the gain matrix. Simu- Fig. 3 gives a schematic of the control structure used for the
lated data obtained from this model involving partially open-loop column.
 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124 119

Table 2
Open loop transfer functions.

R QN Q1

−36.523(1 + 9632.8 s) 1.165 × 10−4 (1 + 6052.2 s) 1.0684 × 10−4

T1
1 + 2(0.901)(3548.8) s + (3548.8 s)
2
1 + 2(0.815)(3850.5 s) + (3850.5 s)
2 1 + 1887.1 s
−15.972 2.524 × 10−5 1.8704 × 10−5
T19
1 + 4564.7 s 1 + 5817.4 s (1 + 4555.3 s)(1 + 1834.3 s)
−10.502 1.4123 × 10−5 1.210 × 10−5
T55
1 + 3593.3 s (1 + 3081.3 s)(1 + 2259.4 s) 1 + 2(0.923)(3013.9) s + (3013.9 s)
2

Table 3
RGA for RD column at different feed benzene concentrations of (a) 6 vol%, (b) 3 vol%, and (c) 11 vol%.

(a) Feed benzene concentration of 6 vol% (b) Feed benzene concentration of 3 vol% (c) Feed benzene concentration of 11 vol%

R QN Q1 R QN Q1 R QN Q1

T1 −0.643 −0.157 1.800 −0.908 −0.026 1.933 −0.518 0.106 1.412

T19 −0.676 7.322 −5.646 −0.214 6.596 −5.382 −0.234 5.307 −4.073
T55 2.319 −6.165 4.846 2.122 −5.570 4.449 1.752 −4.413 3.661

3.2.2. Feedback controller design benzene concentrations for a significant period of time. As such it
Both the reflux drum and reboiler drum need controllers to reg- was hypothesized that adding feedforward action to this structure
ulate the flows and maintain specified liquid levels in the vessels. will improve the performance. The off-spec concentration of ben-
The reflux drum also holds vapor which needs to be regulated such zene in the product stream can be reduced if the flow of hydrogen
that the pressure of the column is maintained. Since the stream to the column is regulated according to the feed composition.
flow rates regulate the inventory of the column, P-only controllers Based on the disturbance variables, manipulated variables, and
have been used. These three proportional controllers were tuned controlled variables, Gp and Gd from Eq. (8) are defined as follows:
via Ziegler Nichols tuning relations. A PI controller was used for
maintaining the reflux drum outlet vapor flow rate V1 in order V1
Gp = (15)
to avoid an offset in the column pressure at the top (P1 ). PI con- FH2
trollers were also used for the temperature point control loops. All
the PI controllers were tuned using internal model control (IMC) V1
Gd = (16)
tuning relations [41]. The transfer functions shown in Table 2 were zC6 H6
used to compute the controller parameters for temperature control
loops. A transfer function (13) was obtained for the fresh hydrogen These transfer functions were determined using the MATLAB
feed (FH2 ) control loop by passing step change inputs to the model system identification toolbox on simulated data for open-loop step
without the recycle stream. responses:
V1 75.265
GPwithout recycle = = (13) 99.39
FH2 1 + 678.4 s Gp = (17)
1 + 3269.9 s
An IMC controller was designed based on transfer function (13)
which was determined for the distillation column without the −7.457 × 104
Gd = (18)
recycle loop in accordance with design procedure described for 1 + 3580.2 s
plant-wide control [38–40]. Table 4 shows the controller tuning
In order to keep the process realistic, feedforward control with
parameters that were derived and used for the control loops oper-
different levels of measurement delay
mf :
ating on the model. The values of c were chosen by adjusting the
desired speed of the closed-loop response. The faster the desired
Gmf = e−
mf s (19)
response, the lower the value of c . As faster response can lead
to larger overshoots, c needs to be chosen to achieve a trade-
off between speed of response and potential for overshoot. Chien were used for the measurement transfer function. Also, since the
and Fruehauf [48] have given the following general guideline to feedforward controller is represented by a lead-lag element, the
determine acceptable values of c for FOPTD systems, controller transfer function was augmented with a filter with a
time constant of 120 s in order to avoid large sudden changes in
> c >
(14) the manipulated variable. The resulting dynamic feedforward con-
troller is given by
where
is the time delay. The values of c chosen for the PI con-
trolled loops are listed in Table 4. 1 + 3269.9 s 1
Gf = 750.3 (20)
1 + 3580.2 s 1 + 120 s
3.3. Feedforward controller
If a static feedforward control law would be considered then this
Most conventional columns use feedback-only control [30]. would result in
As reactive distillation columns can be viewed as an exten-
sion of conventional columns, the first approach was to design a Gf = 750.3 (21)
feedback-only control structure, appropriately tune the controllers,
and observe the performance. However, as will be shown in Section Fig. 3 shows the control structure used for the column along
4, feed composition disturbances affect the column performance with the feedforward controller for controlling the fresh hydrogen
adversely, i.e., the product does not meet the specifications for feed.
120 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124

Table 4
Feedback controller settings.

Manipulated variable Controlled variable Kc i (s) c (s) Type of controller and tuning method used

1.766 × 107
Q1 T1 1887.1 110 PI (IMC)
c
2.305 × 108
QN T19 5817.4 582 PI (IMC)
c
342.15
R TN − 3593.3 610 PI (IMC)
c
9.013
FH2 V1 678.4 128.7 PI (IMC)
c
D h1 3340 – – P (Ziegler Nichols)
LN hN 3830 – – P (Ziegler Nichols)
V1 P1 −12.5 – – P (Ziegler Nichols)

Table 5
Steady state results for inlet and outlet streams.

Stream Feed Fresh hydrogen Distillate Bottom Vent

Phase Liquid Vapor Liquid Liquid Vapor

Temperature (K) 430.0 430.0 293.5 495.5 293.5
Pressure (kPa abs) 797.0 797.0 792.4 801.0 792.4
Total flow rate (mol s−1 ) 265.0 65.9 85.4 180.0 3.0

Component Mole fraction

n-Butane C4 H10 1.26E−02 – 3.87E−02 1.85E−28 1.31E−02

n-Pentane C5 H12 9.61E−02 – 2.97E−01 1.32E−17 2.35E−02
2,3-Dimethylpentane C7 H16 1.16E−02 – 3.58E−02 2.59E−11 1.32E−03
3-Methylpentane C6 H14 5.87E−02 – 1.82E−01 1.32E−09 5.33E−03
n-Hexane C6 H14 3.50E−02 – 1.08E−01 9.37E−09 2.56E−03
Benzene C6 H6 8.26E−02 – 1.09E−02 2.74E−05 2.14E−04
Cyclohexane C6 H12 – – 2.45E−01 6.26E−05 4.19E−03
3-Methylhexane C7 H16 2.33E−02 – 1.54E−02 2.70E−02 1.63E−04
2,4-Dimethylpentane C7 H16 2.34E−02 – 5.92E−02 6.27E−03 8.34E−04
n-Heptane C7 H16 9.77E−03 – 6.48E−05 1.43E−02 5.08E−07
Toluene C7 H8 2.81E−01 – 8.86E−07 4.14E−01 4.84E−09
m-Xylene C8 H10 2.06E−01 – 5.20E−14 3.04E−01 8.68E−17
Cumene C9 H12 1.59E−01 – 8.42E−18 2.35E−01 8.09E−21
Hydrogen H2 – 1.00E+00 7.10E−03 0.00E+00 9.49E−01
Methylcyclohexane C7 H14 – – 6.09E−06 1.88E−04 5.04E−08

Benzene conc. (vol%) 6.010 – 0.251 (combined) –

4. Investigation and comparison of different control
schemes for the column
4.1. Steady state results
The RD column model is assumed to initially operate at the same
steady state for any of the comparisons of different control schemes
made in this section. This steady state corresponds to nominal feed
(composition and temperature) being fed to the column, where the
benzene concentration is 6 vol%. Table 5 includes the steady state
values of all feed and product streams.
Fig. 4 depicts the profile of benzene and toluene concentration
at steady state in the column. The objective of the RD column is to
0.6
0.5
Mole fraction
Benzene molfraction
Toluene molfraction
react as much benzene as possible while minimizing the amount
of toluene entering the stage containing catalysts packing. It can be
seen that the benzene mole fraction increases along the height of
the column, until the reactive zone, where it decreases due to the
reaction. Very little toluene is present in the catalyst zone of the
RD column and as a result 99.8% of the toluene from the reformate
stream is retained in the bottom stream.
4.2. Feedback controller results
The rigorous model built in gPROMS was augmented with the
control structure shown in Fig. 3. The controllers specified in Table 4
were used for investigation. The model combined with the con-
trollers was subjected to changes in the inputs, representing step
disturbances that occur after 1hr, to evaluate the performance of
the control schemes. The set-points of all the controlled variables
remain unchanged throughout this investigation resulting in a reg-
ulatory control problem.
Fig. 5 depicts the benzene concentration in the product for the

0.4
Catalyst column under feedback-only control subjected to step changes in
Zone
0.3 the temperature of ±5 K (Fig. 5(a)) and the feed flow rate of ±5%
(Fig. 5(b)). The responses indicate that the effect of the disturbances
0.2
on the product benzene concentration is not significant, i.e., only
0.1 small changes can be seen in the benzene concentration and the
0 concentration stays far below the allowable limit.
10 20 30 40 50 60 70
Stage number
One of most common disturbances for the benzene hydrogena-
tion process is a change in the feed composition. The benzene
Fig. 4. Profiles of benzene and toluene in RD column. concentration in the reformate stream can increase up to a value
 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124
a)
0.26
Benzene vol%
0.255
0.25
0.245
0 5
Time (hours)
Fig. 5. Responses to step changes in (a) feed temperature and (b) feed flow rate.
of 11 vol% [4]. In order to evaluate such a scenario, a step change
was given to the feed benzene composition from 6 vol% to 11 vol%
and the concentrations of all other components were reduced pro-
portionally. The graphs in Fig. 6 labeled “feedback-only” show the
responses of the outlet benzene concentration and of the other
manipulated variables for a step change in the feed concentration.
The steady state benzene concentration meets the specifications.
However, it can be seen that the responses have significant over-
shoot and also a large settling time under a feedback-only control
scheme. This situation presents a clear opportunity for feedforward
control in order to minimize the effect of the disturbance on the
controlled variable.
4.3. Comparison of feedback and feedforward/feedback control
schemes
The simulations shown in Fig. 6 for feedback-only control
involve significant overshoot and as a result a considerable amount
of product does not meet the EPA specifications of 0.62 vol% [2] for
Fig. 6. Responses of controlled and manipulated variables for step change in feed composition: (a) benzene concentration of the product, (b) fresh H2 feed – FH2 , (c) condenser
duty – Q1 , (d) reboiler duty – QN , and (e) reflux ratio – R.
121
Feed temperature -5 K
b) 0.27
Feed flowrate +5%
Feed temperature +5K Feed flowrate -5%
Benzene vol%
0.26
0.25
0.24
10 15 0 5 10 15
Time (hours)
the benzene concentration. Use of feedforward control can reduce
the overshoot and settling time. All subfigures in Fig. 6 include a
comparison of the responses of the column for feedback-only con-
trol and feedforward–feedback control to a step disturbance in the
feed composition from 6 vol% to 11 vol% benzene. It can be clearly
seen that there is significant improvement in the response time
and the overshoot when feedforward control is added to the exist-
ing feedback control scheme. Additionally, the trajectories of all
manipulated variables also remain within reasonable bounds for
feedforward–feedback regulatory control.
While Fig. 6 shows the positive impact that the addition of feed-
forward control can have on the process, the simulation assumed
that concentration measurements are available instantaneously.
This is not a very realistic assumption in practice unless an online
analyzer is used. One commonly used alternative is that samples
from streams are taken and then analyzed in a lab, i.e., measure-
ments will only be available at discrete points in time and with
a certain time delay. As such, it is important to know how much
of an effect measurement time delay has on the performance of
122 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124

Feedback-only
1 FF-FB with continuous measurements
FF-FB with sampling time of 15min
FF-FB with sampling time of 30min
Benzene vol%
that is occurring at some point during the operation among all cases
is not occurring for the feedback-only control scheme but instead
for feedforward–feedback control with significant time delays. It

0.8 FF-FB with sampling time of 45min can be clearly seen from Table 6 that the larger the time delay for
FF-FB with sampling time of 60min
the composition measurement, the less of a benefit in the over-
0.6 all reduction of the offspec product can be achieved. At the same
time, the largest deviations from the target are occurring for long
0.4 measurement time delays. It is beyond the scope of this study to
evaluate these responses for different design specifications. How-
0.2
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
ever, in order to put the discussion of the performance for different
Time (hours) measurement delays into a more general perspective, it should be
pointed out that the dominant time constant of the systems is equal
Fig. 7. Response to step change in feed composition for feedback-only control and to 1.6 h. It can be concluded that the feedforward–feedback scheme
feedforward–feedback control for five different sampling times (continuous, 15 min, is superior to feedback-only control for the case of continuous mea-
30 min, 45 min, 60 min).
surements or measurements with a time delay of up to 15 min,
which corresponds to 15% of the dominant time constant. There is
the feedforward–feedback (FF–FB) control system. This case has only a marginal benefit to the feedforward–feedback scheme if the
been analyzed next. Fig. 7 shows a comparison of the responses for time delay is 30 min, corresponding to 31% of the dominant time
feedback-only control and combined feedforward–feedback con- constant, and it is questionable if there are any benefits of includ-
trol where the disturbance measurement transfer function Gmf uses ing feedforward control if the measurement time delay is 45 min
several different time delays corresponding to the sampling times. or more, corresponding to 46% of the dominant time constant.
As before, the step change disturbance occurs after an hour and the In addition to investigating a dynamic feedforward controller, a
system is initially at steady state. static feedforward controller has also been investigated. Table 6b
It can be clearly seen that longer measurement time delays sig- shows a comparison of the deviation values computed using the
nificantly degrade the advantages that the addition of feedforward static feedforward controller given by Eq. (21) instead of the
control has on the performance. In order to quantify the perfor- dynamic feedforward controller from Eq. (20). The results are close
mance of the responses shown in Fig. 7, a measure is defined to to those obtained by using a dynamic feedforward controller. In
quantify the area between the curve and the EPA specification of fact, the graphs of the responses overlap with those depicted in
0.62 vol% [2]: Fig. 7 for dynamic feedforward control and as such no separate fig-
 ∞ ure for the graphs is included. Thus, from an application point of
Dev = H(Bz vol% − 0.62) × (Bz vol% − 0.62) dt (22) view, a simple static feedforward controller could be used instead
0 of a dynamic feedforward controller without significant loss of per-
where H is the Heaviside function defined as formance.
 One last point to consider is that this investigation focused on
0, x < 0 step disturbances as these are the most common disturbances for
H(x) = (23)
1, x≥0 the scenario investigated in this work. As such, it was appropriate
to model the measurements occurring from lab samples as contin-
Table 6 shows a comparison of the deviation value computed
uous samples with a time delay instead of using discrete samples
from Eq. (22) for different sampling times. Not surprisingly, it can
with time delays as the two will return identical results for step
be concluded that feedforward control reduces the upset condition,
disturbances. However, it should be pointed out that if the benzene
as measured by Eq. (22), for all investigated cases. Similarly, it is also
concentration disturbances would have had a different nature than
not surprising that the best performance is achieved for the com-
a step, that it would have been required to use discrete sampling
bined feedforward–feedback control structure that uses an online
and time delays. This was not necessary for the cases investigated
composition analyzer. However, the largest benzene concentration
in this work, though.
It was one of the goals of this investigation to determine the
Table 6 benefit of using a control scheme that combines feedforward and
Deviations, as measured by Eq. (22), for (a) dynamic feedforward controllers and (b)
feedback control over a feedback-only control scheme. The simu-
static feedforward controllers.
lation results indicate that a significant benefit only exists if upsets
(a) in the feed composition can be quickly detected.
Control structure Dev % reduct. Max Bz
vol% 5. Conclusions
Feedback-only 1074 0.85
FF–FB with continuous measurements 423 61% 0.66 Benzene hydrogenation via reactive distillation is a process
FF–FB with sampling time of 15 min 559 48% 0.76 that has found significant use in the process industries. However,
FF–FB with sampling time of 30 min 756 30% 0.97
no models of this process can be found in the open litera-
FF–FB with sampling time of 45 min 874 19% 1.02
FF–FB with sampling time of 60 min 917 15% 0.94
ture. This paper addresses this point by developing a dynamic
equilibrium-based model for a reactive distillation column used
(b) for the hydrogenation of benzene. Simulations were carried out to
determine transfer functions between manipulated and controlled
Control structure Dev % reduct. Max Bz
vol% variables. Control loop pairing was performed using RGA analy-
sis and the feedback controllers were tuned via IMC tuning (PI)
Feedback-only 1074 0.85
FF–FB with continuous measurements 444 59% 0.67
and Ziegler Nichols tuning (P). a model-based feedforward con-
FF–FB with sampling time of 15 min 543 49% 0.74 troller was also designed to reduce upset conditions caused by
FF–FB with sampling time of 30 min 756 30% 1.04 disturbances.
FF–FB with sampling time of 45 min 888 17% 1.13 Simulations indicate that the column performance for feed tem-
FF–FB with sampling time of 60 min 939 13% 1.04
perature and feed flow rate disturbances remains acceptable for
 V. Mahindrakar, J. Hahn / Journal of Process Control 24 (2014) 113–124 123

∗
a feedback-only control scheme. However, the column has a sig- yj,i = yj+1,i (1 − ) + yj,i  (A11)
nificant settling time for disturbances in the feed composition.
Feedforward control can reduce these upset conditions resulting Energy balance
from feed disturbances. However, it was shown that the use of a d(Mlj Hlj + Mvj Hvj )
feedforward–feedback control scheme is only beneficial if the time = Vj+1 Hj+1 + Lj−1 Hlj−1 − Lj Hlj − Vj Hvj − Hrxn,j
dt
delay associated with the feed composition measurement is small.
(A12)
In summary, this paper (1) presented the first detailed model of
a reactive distillation column for the hydrogenation of benzene, (2) Flow rate and holdups
designed and evaluated a feedback control scheme for the column,
Liquid
and (3) investigated the benefit of using a feedforward/feedback
control structure for different sampling times of the feed composi- Mj vollj = hj (HETP)A (A13)
tion measurement.
2/3
hj = 0.34a1/3 uj (A14)
Acknowledgment
Vapor
The authors gratefully acknowledge partial financial support Pj A(HETP)(ε − hj ) = Mvj Rgas Tj (A15)
from the American Chemical Society - Petroleum Research Fund
(Grant PRF# 50978-ND9). P0,j (1 − ε) u2v v
= (A16)
HETP ε3 dp K
Appendix A. 150
= + 1.75 (A17)
Rev
A.1. Model
 −5
2hj
Condenser and reflux drum Pj = P0,j 1 − (A18)
dp a
Mass balance
Pj+1 = Pj + Pj (A19)
d(Ml1 + Mv1 )
= V2 − L1 − D − V1 (A1) Reaction rate
dt
kj,1 KA1 KH1 CAj,1 CHj
Component balances rxnj,Benzene = − (A20)
3
d(Ml1 x1,i + Mv1 y1,i ) (3KA1 CAj,1 + (KH1 CHj )1/2 + 1)
= V2 y2,i − L1 x1,i − V1 y1,i ∀i : 1 to n − 1 (A2)
dt kj,2 KA2 KH2 CAj,2 CHj

n

n rxnj,Toluene = − 3
(A21)
x1,i = 1; y1,i = 1 (A3) (3KA2 CAj,2 + (KH2 CHj )1/2 + 1)
i=1 i=1
  
Ea 1 1
ki,j = ki,0 exp − − (A22)
Vapor–liquid equilibrium Rgas Tj T0
x1,i l1,i = y1,i v1,i ∀i : 1 to n (A4) Reboiler
Energy balance Mass balance

0 = V2 Hv2 − V1 H0 + Q1 (A5) d(MlN )

= LN−1 − LN − VN (A23)
dt
d(Ml1 Hl1 + Mv1 Hv1 )
= V2 H0 − (L1 + D)Hl1 − V1 Hv1 (A6) Component balances
dt
d(MlN xN,i )
Packed section = LN−1 xN−1,i − LN xN,i − VN yN,i ∀i : 1 to n − 1 (A24)
dt
Plate j

n
Mass balance xN,i = 1 (A25)
d(Mlj + Mvj )  n i=1
= Vj+1 + Lj−1 − Vj − Lj + Ahj (HETP)cat rxnj,i (A7) Energy balance
dt
i=1
d(MlN HlN )
Component balances = LN−1 HlN−1 − (LN + VN )HlN (A26)
dt
d(Mlj xj,i + Mvj yj,i ) VN HlN − VN HvN + QN = 0 (A27)
= Fj zj,i + Vj+1 yj+1,i − Lj−1 xj−1,i − Vj yj,i − Lj xj,i
dt
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