Article

pubs.acs.org/IECR

Control and Prole Setting of Reactive Distillation Column for

Benzene Chloride Consecutive Reaction System
Cuimei Bo,, Jihai Tang, Mifen Cui, Kangkang Feng, Xu Qiao,*, and Furong Gao*,

College of Automation and Electrical Engineering, Nanjing University of Technology, Nanjing Xinmofan Road No. 5, Nanjing,
210009 China

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing
University of Technology, Nanjing, 210009 China

Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay,
Kowloon, Hong Kong

ABSTRACT: The purpose of this paper is to design and analyze the control structures of a consecutive reactive distillation
process. On the basis of the optimal economic design, a systematic framework for the design of the decentralized control
structure, controller parameter tuning, and setting proles under uncertainty disturbances is proposed for benzene chloride
production in a reactive distillation column. Its eectiveness and robustness are analyzed for disturbance resistance in terms of
changes of the production rate and the feed composition. Simulations indicate that better control performance can be obtained
by proper control loop pairing, tray location identication, and controller tuning. Furthermore, process performances are
compared for the three dierent prole setting cases in the forms of one-step, multistep, and quadratic function changes of the
product rate adjustment. The result shows that the process transient performance, such as overshoot, smoothness, and stability,
can be greatly aected by the set-point transition form, indicating that it is necessary to study the relevant production rate set-
point adjustment strategy.

1. INTRODUCTION to have a proper feedback control strategy to control the reactant

Traditionally, the two most important operations of chemical
processes, reaction and separation, are carried out separately in
dierent sections of a plant, using dierent equipment.
Nowadays, the process intensication technology is increasingly
practiced in the industry due to the economic and environmental
considerations.1,2 Reactive distillation is such an example of
process intensication. It is a process that combines reaction and
multicomponent separation in a unit, oering advantages over
the conventional multiunit processes in terms of catalyst usages,
reactive heat utilization, and cost saving.35 As reaction and
separation take place simultaneously in one column, the tray
temperatures are determined by the vaporliquid equilibrium of
the process. A lower temperature results in a lower specic
reaction rate; consequently, a large holdup will be required, while
a higher temperature may promote undesirable side reactions.
In such a reactive distillation, the interaction between the
simultaneous reaction and distillation introduces a much more
complex dynamic behavior compared to a conventional
multiunit process, leading to challenges in design, optimization,
and control of the process. Kaymak and Luyben6 quantitatively
compared the dynamic controllability of a reactive distillation
column against a conventional multiunit process, and they
concluded that its control is more dicult and its operability
region is smaller than that of a conventional multiunit process
because the reactive distillation column has fewer degrees of
control freedom. This is particularly true for the case of reactive
distillation column with two feed streams. In this case, a ratio of
the two reactants needs to be maintained for the column to
satisfy the stoichiometry. Luyben7 denes this type of operation
mode as neat operation mode. He suggested that it is necessary
ow rates inside the column.8,9 To do so, Al-Arfaj and Luyben
proposed six alternative control structures, all of which use a
composition controller in the reactive zone to satisfy the
stoichiometric balance between the reactants.10
Decentralized linear controllers with multiloop PI/PID
controllers are preferred in chemical processes not only because
of their easy practical implementation but also because good
performance can be obtained by appropriate control structure
design and parameter tuning. Online composition analysis is
expensive, dicult to maintain, and often plagued with a large
dead time. On the other side, the temperature relevant informa-
tion may be explored to infer composition with sucient
accuracy.11 Therefore, it is suggested that the product
composition is to be controlled indirectly by controlling a
suitable tray temperature as the temperature measurement is
usually much cheaper, faster, and more reliable than concen-
tration measurement. Owing to the complex dynamic interaction
of reaction kinetics, mass transfer, and thermodynamics, the
interaction often causes counteracting inuences on the process;
proper design and tuning of these controllers in a decentralized
structure are very important to the process performance in face of
a wide range of operating condition changes coupled with several
uncertain disturbances. In this study, the key issues are the
selection of a suitable tray temperature, the design of stable and
robust decentralized PI/PID controller structure, and tuning of
Received: March 8, 2013
Revised: October 5, 2013
Accepted: October 16, 2013
Published: October 16, 2013

2013 American Chemical Society 17465 dx.doi.org/10.1021/ie4007694 | Ind. Eng. Chem. Res. 2013, 52, 1746517474
Industrial & Engineering Chemistry Research
controller parameters.27 Luyben and Kaymak proposed two
alternative temperature control structures for a quaternary
reversible reaction process to replace their early proposed
composition control structures.12 Also recently, relevant process
control has been investigated with respect to eectiveness of feed
tray location,13,14 relative volatility ranking,18 multiplicity,19
controllability of control structure,1517 and plant-wide control
structure design.20,21 Furthermore, some nonlinear multivariable
control methods were also investigated aiming at the complex
interaction and nonlinear characteristic of reactive distillation.
For example, Daoutidis and co-workers applied nonlinear
multivariable control for ethyl acetate reactive distillation and
ethylene glycol reactive distillation column.22,23 Venkateswarlu
proposed a nonlinear model predictive control based on
stochastic optimization for an ethyl acetate reactive distillation
column with double-feed conguration involving an esterica-
tion reaction with azeotropism.24
All of the above works are conned to dynamic control for a
quaternary or ternary reversible reaction process; no relevant
work for the consecutive reaction process have been reported.
In the consecutive reaction, the main reaction with some side
reactions occur simultaneously. In the case where there are two
reactants, one is involved in an undesirable series reaction
(A + B C + D and C + B E + D). The higher selectivity of
the desired product C may be achieved using reactive distillation
technology, as the desired product C can be removed in a timely
fashion from the column through vaporliquid separation to
restrain the production of the byproduct D.25 As the reaction
kinetic in such cases is more complex than a reversible reaction
process, dynamic control for consecutive reactions in the
distillation column becomes a challenge when the selectivity as
well as the conversion are both considered.27
In this work, the dynamic design and simulation of a de-
centralized control structure is studied for benzene chlorine
consecutive reaction in a reactive distillation column based on
the optimal economic design. The eectiveness of the proposed
control structure is evaluated for the disturbance resistance
of changes in the feed rate and composition. Production rate is
often adjusted in response to changes of market, with three
dierent prole settings in the forms of one-step, multistep, and
quadratic parabola functions to represent changes of the product
rate are tested and compared to evaluate the performance of the
proposed control structure. The results show that the production
rate set-point transition form has an important eect on the
process dynamic performance.
2. REACTIVE DISTILLATION PROCESS
2.1. Consecutive Reaction. There are many important
industrial examples of consecutive reactions: chlorination,
oxidation, and nitration of a variety of hydrocarbons, etc.28 A
common consecutive reaction with two irreversible reactions is
the following:
main reaction A+BC+D (1)
side reaction C+BE+D (2)
The desired product is C, and the undesired byproduct is E;
the desired product C is produced by the rst reaction whose rate
depends on the concentrations of A and B in reaction section,
while C is consumed by the second reaction whose rate depends
on the concentrations of C and B. The reaction rates rc and rE can
be expressed by the following kinetic models
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E E
rC = A1 exp 1 CAC B + A 2 exp 2 C BCC
RT RT (3)
E
rE = A 2 exp 2 CCC B
RT (4)
where rC and rE are reaction rates of product C and E,
respectively, A1 and A2 are preexponential factors, E1 and E2 are
activation energy, R is the ideal-gas constant, and T is the reaction
temperature. In a reactive distillation process, a large excess of
reactant A should be used in the column, which will dilute the C
and B concentrations to suppress the undesirable side reaction. A
relatively higher selectivity to intermediate component C can be
obtained by maintaining a high concentration of reactant A and
low concentrations of reactants B and C in the reaction section.
These recycle streams increase the diculty of dynamic control
about the reactive distillation process.
2.2. Benzene Chloride Production. The benzene chloride
production in a reactive distillation column is used as the example
of the consecutive reaction with two irreversible reactions. Chlo-
robenzene can be produced from the reaction of toluene and
chlorine, while chlorobenzene will react further with chlorine to
produce the byproduct dichlorobenzene (mainly o-dichloro-
benzene, paracide). The chemical reaction is as follows:
main reaction Cl 2 + C6H6 C6H5Cl + HCl (5)
side reaction C6H5Cl + Cl 2 C6H4Cl 2 + HCl (6)
The product chlorine hydride is as an inert gas, which will not
aect the vaporliquid equilibrium. The benzene chlorination
kinetics with ferric trichloride as catalyst was discussed in refs 30
and 31. The kinetic equations for the benzene chloride con-
secutive reactions are shown in the following:
75.01 103
rC6H5Cl = 2.895 109 exp CC6H6C FeCl3CCl2
RT
82.99 103
+ 8.686 109 exp CC6H5ClC FeCl3CCl2
RT (7)
82.99 103
rC6H4Cl2 = 8.686 109 exp CC6H5ClC FeCl3CCl2
RT (8)
Here, R = 8.314 kJ/kmol/K. The reactions are highly exothermic
and occur in a suitable temperature T = 365 K. Some important
kinetic and vaporliquid phase equilibrium parameters for the
system are given in Table 1. The benzene chlorination system
belongs to an easy separation system of the raw material from
the product, which is ideal to use the reaction distillation
conguration.
2.3. Reactive Distillation Conguration. The optimal
steady state conguration parameters and operating parameters
can be obtained on the basis of an optimal economic design to
minimize the total annual cost, as reported in our previous
research works.29,32 The optimal conguration of the reactive
distillation column is given in Figure 1. In the conguration, the
light product, chlorine hydride (HCl), is removed from the top,
while the heavy products, chloride benzene (C6H5Cl) and
dichlorobenzene (C6H4Cl2), are taken out from the bottom. The
distillation column is divided into three sections: stripping
section Ns = 10, reaction zone NRS = 5, and rectifying section
NR = 1. The feed streams of chlorine and benzene are fed on the
sixth tray and second tray, respectively. The column pressure
is at atmospheric, the feed ow rates of benzene and chlorine are
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Table 1. Kinetic and VaporLiquid Phase Equilibrium

Parameters for System
param value
normal boiling C6H6 (353.1) < C6H5Cl (405.2) < C6H4Cl2 (453.4)
temperature (K)
ranking
suitable reaction 350365 K
temperature
reaction heat (kJ mol1), 123.78 (353 K)
main reaction
reaction heat (kJ mol1), 98.01 (353 K)
side reaction
heat of vaporization 45.90 (353 K)
(kJ mol1)
vapor pressure constants
ln Ps = Avp Bvp/(T + Cvp), Ps, bar; T, K
C6H6 C6H5Cl C6H4Cl2
Avp 9.28 9.45 9.66
Bvp 2788.5 3295.12 3798.23
Cvp 55.6 55.6 59.84

Figure 1. Optimum design of the reactive distillation column for

benzene chloride production.
Figure 2. Parameter prole curves of the steady state simulation.

FC6H6 = 10.2 kmol/h and FCl2 = 10 kmol/h, respectively, and the
reux ratio of the column is R = 3. Figure 2 shows the vapor
liquid phase ow rate proles, tray composition proles, and
temperature proles for such optimally designed column. It is
observed that the heavy product (chlorobenzene) proles
resemble the temperatures throughout the column. Therefore,
it is reasonable to estimate the composition using the tray
temperatures.
3. CONTROL STRUCTURE DESIGN AND SIMULATION
A poor control structure based on the optimal economic design
may result in a plant with poor control properties. It is important
to investigate the controllability, operability, and interaction
among multiloop PI/PID controllers.33 In this section, a sys-
tematic approach is used to design the decentralized control
structure for the benzene chlorine production in the reactive
distillation. There are three main control objectives: (1) main-
taining the product chlorobenzene purity higher than 0.96 kmol/
kmol; (2) keeping the selectivity of the product more than
0.99; (3) maintaining stoichiometric balance. When proper
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temperature proles are established, the higher conversion and
selectivity objectives can often be achieved.
3.1. Selection of Suitable Tray Temperatures. The key
issue in the temperature control is the tray location selection and
their pairing to control indirectly the composition. Singular value
decomposition (SVD) and relative gain array (RGA) methods34
are used to determine the variable pairings of the controlled and
manipulated variables. In the benzene chlorine process, there are
three main input variables, namely, the two feed rates FC6H6, FCl2,
and a vapor boilup, VS. While one of these three inputs is chosen
as the product rate, the other two inputs are used to control the
temperature of two trays. The relative gain array between these
three inputs and the outputs (the tray temperatures) is calculated
numerically on the basis of the optimal steady-state design.
Figure 4 gives the RGA results and their related SVD. It is shown
that the tray temperatures in the stripping section are sensitive
to these inputs. The steady-state gains between the stripping
tray temperature and the feed rate FC6H6 have the biggest
negative magnitude, while the very small gain of the fresh feed
stream FCl2 indicates small sensitivity to the changes in the FCl2.
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Industrial & Engineering Chemistry Research
Figure 3. Dual-temperature control structure for the reactive distillation
column.
Figure 4. Temperature RGA and SVD result for the benzene chloride
production.
Therefore, the fresh feed stream of benzene FC6H6 is chosen as the
production rate in the control structure. According to the SVD
results of Figure 4, the temperatures of the 11th tray and the13th
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tray are most sensitive to the changes in feed rate FCl2 and vapor
boilup Vs, respectively. In this case, the T11/FCl2 controller is
direct acting, while the T13/(V s) controller is reverse acting.
3.2. Design of Decentralized Control Structure.
According to the T11/FCl2 and T13/(V s) variable pairings, a dual-
temperature inferential control structure is proposed as shown in
Figure 3. In this conguration, the ratio of the two feed rates
(FCl2/FC6H6) is adjusted by tray temperature T11; tray temperature
T13 and bottom vapor rate VS are controlled by a cascade control
strategy. Thus, a correct ratio of the two feed streams can be
maintained in the neat operation mode. By timely removing
the product, chlorobenzene, from the column, the side reaction
is kept small. The higher product composition (xB,C6H5Cl =
0.964 kmol/kmol) and the selectivity (more than 0.992) can be
ensured by this dual-temperature inferential control structure. In
addition to this major design, there are some other basic control
loop designs, which are shown in Figure 3. The bottom level LB is
controlled by manipulating bottom ow rate FB (LB/FB control
loop), reux drum level LR is controlled by reux ow rate FR
(LR/FR control loop), and top pressure Ps is controlled by
hydrogen chloride gas recovery amount FD (Ps/FD control loop).
3.3. Controller Tuning. Multiloop PI/PID controllers with
dierent tuning technique have been reported. Most of these
tunings, such as the relay feedback tuning, TyreusLuyben
tuning, BLT tuning, and iterative continuous cyclic tuning, rely
on transfer functions to obtain response parameters as required
in ZieglerNichols-type tuning rules to determine controller
parameters.35 The dynamics of the reactive distillation exhibit
severe nonlinearity and loop interaction; they cannot be pre-
sented in terms of transfer functions, and thus, the traditional
tuning procedures are dicult to be applied to give satisfactory
performance. Detuning techniques are often performed to
preserve the system stability or to meet certain performance
specication. Recently, new retuning techniques based on the
stochastic search methods such as genetic algorithm (GA),36 or
mixed integer dynamic optimization (MIDO),37 have been
reported for applications in reactive distillation.
In this section, a new retuning based on stochastic dynamic
optimization against uncertainty disturbances is proposed for the
robustness improvement of the above dual-temperature control
structure, with the following optimization problem:
min (x(t ), xa(t ), u(t ), y(t ), , p)
p (9)
f (x( t ), x(t ), xa(t ), u(t ), y(t ), , p) t |t 0 , t f |
d
f (x(t ), x (t ), u(t ), y(t ), , p) t |t 0 , t f |
a a
g (x(t ), x (t ), u(t ), y(t ), , p , t ) 0
p k a k k k k t k |t 0 , t f |
s.t.
f (x( t ), x(t ), u(t ), y(t ), , p) = 0 t |t 0 , t f |
c
g (p) 0
c
(10)
Here, the objective function (.) is a suitable statistical measure
of the control system performance, fd(.) and fa(.) are dierential
algebraic equations modeling the process, gp(.) 0 represents a
set of inequality constraints of the process, fc(.) is the dynamic
equation for the dual-temperature controllers, gc(.) 0 rep-
resents inequality constraints for the controller parameters, x(t)
and xa(t) are the vector of dierential and algebraic variables, u(t)
is the vector of manipulated variables, y(t) is the vector of out-
put variables which are measured and to be controlled, and
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p represents the time-invariant control parameters (kj,i) in the Table 2. Control Structure Description of the Consecutive
vector form. is the uncertain disturbance assumed to follow Reactive Distillation Process
a continuous probability density function with the mean of
no. control loop target Kc (min)
and the covariance of over the nite domain . The dual-
temperature PI controllers are considered with the following 1 LR/FRR 0.32 m 10 60
general equations: 2 LB/FB 1.12 m 10 60
3 PS/FD 1 atm 20 12
1 t 4 T11/R (case 1) 362.5 K 3 35
uj(t ) = Kcjej(t ) + 0 ej(t ) dt + uj0(t ) T11/R (case 2) 362.5 K 10.5 30
j 5 T13/Vs (case 1) 380.3 K 8 45
T13/Vs (case 2) 380.3 K 3.5 30
j = 1, ..., Nu (11)

ej(t ) = ysp , j yj (t ) j = 1, ..., Nu (12)

kj min kj kj max j min j j max (13)

Here, kj and j are controller parameters to be searched; k , kmax, min

min, max are the upper and lower bounds of the controller
parameters, respectively.
The statistical objective function of the system performance
has the following form:

= E[J(p , , t )] + V [J(p , , t )] (14)

tf
J= 0 [(ysp y(t ))T Q (ysp y(t ))

+ (usp u(t ))T R(usp u(t ))] dt (15)

Here, E and V are the expectation and variance of the per-

formance index, respectively, and is weighting factor between
the two terms; y(t) represents the measurements of both tray
temperatures; ysp is the set points, and u(t) represents the vector
of manipulated variables, vapor boil-up rate Vs, and feed stream
ratio Rf. usp is the expected values of manipulated variable at the
steady state; Q and R are positive denite weighting matrices for
scaling purposes.
The expectation and variance of the performance index are
estimated using a sample average approach based on sigma point
method.39 The set of sigma points have the following forms:
set of sigma points:
0 =


i = + ( (n + ) )i i = 1 , ..., n

= ( (n + ) ) i = n + 1 , ..., 2n Figure 5. Open response of dual-temperature control for reactive
i i (16) distillation column.
weight: 2n

V [J ] = wi(E[J ] J(i))(E[J ] J(i))T

0 = i=0 (19)
n+

= The stochastic dynamic optimization problem may be converted to
i i = 1 , ..., n a deterministic one, which is solved by the deterministic algorithms
2( n + ) (17) using a sequential approach. Also, the lagrange multipliers for the
Here, and represent the mean and covariance of a random point constraints and other constraints may be used to solve the
disturbance condition , is a scaling parameter, and n is the optimization problem. All optimization computations are
number of uncertain disturbances. The expectation and the performed by the MATLAB optimization program.
variance of the performance index are given by All controllers are tuned rst using the TyreusLuyben
tuning method. Two cases are studied: in case 1, the tunings of
2n controllers are obtained by directly using the TyreusLuyben
E[J ] = wJi (i) tuning, and in case 2, the parameters of the dual-temperature
i=0 (18) controllers are retuned using the proposed stochastic
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Industrial & Engineering Chemistry Research
Figure 6. System response: 10% step changes in the feed stream of benzene (case 1, TyreusLuyben tuning; case 2, stochastic optimization retuning).
optimization method, in which the parameters of case 1 are set
as the initials. For illustration purposes, disturbances are
assumed to be the step functions, whose magnitude is described
by the normal probability distribution function (PDF), N(j, j),
j = 1,2, where j represents the disturbance variable of the
product rate or the feed composition. Assuming these two
disturbances are independent, the joint normal PDF is N(, ),
where is the mean vector and is the covariance matrix. The
covariance matrix is diagonal. There are four sigma points
(F = 10%,z = 5%) when the number of uncertain
disturbances n is set to 2. The optimal parameters of these
controllers are shown in Table 2.
3.4. Simulation and Discussion. The dynamic simulation
for the benzene chlorine process is simulated by the Aspen Plus
software with Aspen Dynamic modules. The eectiveness of
the proposed dual-temperature control structure is analyzed
by the uncertain disturbance resistance in terms of changes in
the production rate (FC6H6) and the feed compositions (zC6H6
and zCl2).
Before implementing the dual-temperature control structure
in simulation system of the benzene chlorine reaction, the open-
loop responses are tested rst through introducing a ow rate
change 10% in the benzene feed and a composition change 5%.
Also, three based control loops, such as LB/FB, LR/FR, and Ps/FD
loops, are implemented in the dynamic simulation in order to
maintain the system steadily running. The open-loop responses
of the process are shown in the Figure 5. Figure 5a shows the
responses of composition and tray 11th temperature against the
ow rate change 10%, in which product composition is greatly
reduced until it maintains a new steady state of 0.88 kmol/kmol
after about 5 h. Figure 5b shows their responses against the
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composition change 5%, in which the product composi-
tion maintains a new steady state of 0.95 kmol/kmol after
about 11 h.
Simulations are conducted for the designed control structure
with the dierent parameters as stated in case 1 and case 2.
In both cases, the process reaches steady-state with 1 h.
Disturbances of changes 10% step in the fresh stream of
benzene are introduced. The responses of the two manipulated
variables (FCl2 and Vs), the two controlled variables (T11 and T13),
and the bottom product compositions (xB,C6H5Cl, xB,C6H6) are
shown in Figure 6. The left curves show the responses of
the control system with the TyreusLuyben tuning parameters
(case 1), while the right curves show that of the control system
with the optimal parameters by the proposed retuning (case 2). It
shows that, with the increased feed rate of benzene FC6H6, the feed
rate of chlorine also increases to 12.2 kmol/h by the ratio control
strategy. A greater amount of energy is required to maintain
vaporliquid equilibrium in the column, and the vapor boilup VS
also is increased from 2.19 to 2.26 GJ/h. This result shows that
the 10% step disturbances can be handled well and the purity of
the product chlorobenzene (xB,C6H5Cl) can be maintained at the
desired value of 0.964 kmol/kmol. Moreover, the temperatures
of sensitive plate T11 and T13 can also recover to the ideal steady
state. At the same time, Figure 6 shows that the dynamic
responses of case 2 have been greatly improved as compared to
those of case 1 for the feed disturbance handling, with faster
response (as shown taking about 1 h for case 2 while almost 8 h
for case 1 for the bottom product composition to recover), a
smaller overshoot for tray temperatures T11, fdT13, and product
compositions xB,C6H5Cl, and a higher accuracy.
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Figure 7. System response: 5% step changes in feed stream composition zCl2,zC6H6 (case 1, TyreusLuyben tuning; case 2, stochastic optimization
retuning).

Table 3. Comparison of Dynamic Performance Indexes of Product Composition in Both Casesa

case 1 case 2
N disturbances % Ts ess IAE % Ts ess IAE
1 FC6H6 = 10% 0. 18 7 1.705 104 0.0112 0. 06 2.4 1.76 104 0.0037
2 FC6H6 = 10% 0. 07 7 1.002 104 0.0137 0. 02 2.15 1.57 104 0.0036
4 4
3 zC6H6 = 5% 0.033 9 8.560 10 0.0149 0.000 1.2 8.560 10 0.0164
4 zCl2 = 5% 0.027 7 1.023 104 0.0082 0.003 0.4 9.831 105 0.0019
5 one-step prole 0. 39 8 3.330 104 0.02018 0. 07 1.4 3.413 104 0.0071
6 three-step prole 0. 32 8.5 3.302 104 0.0197 0.027 1.3 3.413 104 0.0068
7 parabola prole 0. 29 8.5 3.257 104 0.0194 0.003 1.4 3.408 104 0.0065
a
Case 1: TyreusLuyben tuning. Case 2: stochastic optimization retuning. : overshoot. Ts: stabilization time. ess: steady state error. IAE: the integral
performance index of absolute value of error.

Other process performance tests are conducted with the feed
composition disturbances. A 5% impurity of chlorobenzene in
the feed of benzene (zC6H6) and a 5% impurity of chlorine
hydride (zCl2) in the feed of chlorine are introduced, respectively.
Figure 7 shows the responses rejecting these composition
disturbances. For a 5% composition disturbance in the benzene
feed, the process settles dynamically to the ideal steady state, and
the bottom product composition reaches the stable desired value
of 0.965 kmol/kmol. Production rate is decreased in response to
the impurity changes in the feed stream of benzene, the feed of FCl2
is also decreased to 9.7 kmol/h by the feed ratio control, and the
vapor boilup Vs is increased to 2.26 GJ/h to maintain the product
composition at the expected value. For the case of 5% impurity
introduced in the feed of chlorine, the feed rate FCl2 is increased to
10.62 kmol/h to satisfy the stoichiometry of the column, and the
vapor boilup Vs maintains at the steady-state of 2.22 GJ/h as
17471
production rate FC6H6 remains unchanged. The bottom product
composition xB,C6H5Cl is kept at the desired value 0.964 kmol/kmol.
Similarly, the dynamic performance of case 2 has been greatly
improved when compared to those of case 1 under the feed
composition disturbances against a dynamic response (about 1 h
for case 2 while almost 5 h for case 1 for product composition to
recover), smaller overshoot, and higher control accuracy. These
simulation results in Table 3 show that the feed rate disturbances
as well as the composition disturbances can be better handled by
the proposed retuning of the controller parameters.
4. PROFILE SETTING OF PRODUCTION RATE
Production rate is often changed in response to market demand.
Reactive distillation has inherent strong nonlinearity and
coupling; its operation is more dicult than that of a con-
ventional multiunit processes for the adjustment of production
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parabola function prole:

F0 0 t < t0

F F
Fset = F0 + 0 2 new (t t 0 T )2 t 0 t < t 0 + T
T
F
new t > t0 + T (22)

Figure 8. Three prole setting forms of the production rate FC6H6.
rate. It may result in loss of product quality, even lead to safety
issues if it is not properly operated.38,39 In this section, three
dierent set-point transition forms of the production rate
adjustment are tested and compared to evaluate the performance
of the proposed control structure.
4.1. Production Rate Set-Point Transition Forms. Three
prole setting forms of the changes of benzene chlorine
production in the reactive distillation column are constructed
with a one-step, multistep, or quadratic parabola function. They
are tested in the following simulation. The prole setting forms
are given as the following:
one-step prole:
F0
0 t < t0
Fset =
Fnew t t0
Here, F0 and Fnew are the original value and adjusted value of the
product rate, respectively, N is the step length of the multistep
prole, T1 is duration of each step, and T is the total transition
duration. The lengths of duration time T and T1 may be chosen
on the basis of the system dynamic characteristics, such as the
desired rise time, overshoot, and attenuation ratio, or may be
determined on the basis of certain form optimization.
In this section, these three set-point transition forms of a 20%
increase (FC6H6 = 2.04 kmol/h) in production rate are
introduced 1 h after the system reaches the steady-state. After
another 5 h, the process reaches again the new steady-state;
the production is decreased back to the original value through
the same three set-point transition forms, which are shown in
Figure 8. In the multistep prole setting form, the step length N is
set as 3 steps, and the duration time T1 is set as 1 h. While in the
quadratic parabola function prole form, the transition duration
T is set as 4 h.
4.2. Simulation and Discussion. The above prole setting
forms of production rate change are implemented, respectively,
into the simulation of the benzene chlorine process controlled

(20) with the above dual-temperature control structure. Changes in

multistep prole: production rate typically result in changes in product
compositions with a poor control structure or the inappropriate
F0 0 t < t0 parameter tuning, especially for reactive distillation. For a good

F F0 control structure and control tuning, with the product rate
Fset = F0 + k new t + (k 1)T t < t + kT
increasing, the feed rate of chlorine FCl2, vapor boilup Vs, and
N 0 1 0 1

Fnew t > t 0 + NT1 reux ow FR should also be increased accordingly to maintain
the material balance and energy balance; consequently, the
k = 1, 2 , ..., N (21) product compositions can maintain the optimal value. A 20%

Figure 9. Comparison with process transient performance of three prole setting forms (case 1, TyreusLuyben tuning; case 2, stochastic optimization retuning).

17472 dx.doi.org/10.1021/ie4007694 | Ind. Eng. Chem. Res. 2013, 52, 1746517474

Industrial & Engineering Chemistry Research
production rate adjustment is used as an example for the benzene
chloride reactive distillation to evaluate the process performances
under the above three set prole forms. The production rate set-
point transitions are, respectively, implemented and tested in
simulation system for the two cases with dierent tuning
parameter. In case 1, the parameters of the controllers keep the
same as the previous case, Loop T11/R: K = 3, = 35 min, and
Loop T13/(V s): K = 8, = 45 min, using the TyreusLuyben
tuning. Responses of the process under these three dierent
setting proles are shown in the left curves of Figure 9. The
results show that, with the product rate FC6H6 increasing, the feed
rate of chlorine FCl2 is increased accordingly to 10.2835 kmol/h
to maintain the material balance in the column, while vapor
boilup Vs is increased to 2.285 kmol/h to the energy balance.
Consequently, the product compositions can maintain the
optimal value of 0.964 kmol/kmol within 8 h for the three prole
forms. However, in the one-step prole case, the responses of the
tray temperature T13 and the bottom product composition xB,C6H6
have obvious uctuations with the bigger overshoot, which are
likely to cause the damage of the plates in industry operation. The
dynamic performances of the three-step prole form have been
improved greatly. In quadratic parabola function form, the best
process performance with the smallest overshoot and best
smoothness can be achieved.
In case 2, the parameters for the dual-temperature controllers
are retuned using the proposed optimization based on the new
optimal steady-state parameters which are achieved by the
economic optimum design. The parameters of case 1 serve as the
initials for the parameters optimization of case 2. The responses
under these three dierent setting proles are shown in the right
curves of Figure 9. The system responses have improved
signicantly as compared to these of case 1. For the one-step
prole, the output response curves of tray temperature T11, T13
and production composition xB,C6H5Cl have smaller overshot and
better stability than those of case 1. For the three-step prole and
parabola prole, the process responses are excellent with good
stability and precision. By comparing the performance indexes
(Tr, ess, and IAE of the composition response) of these dierent
prole forms under cases 1 and 2, as shown in Table 3, we
conclude that the close-loop dynamics are improved signicantly
by the propose retuning. They are strong functions of setting
proles.
5. CONCLUSION
A framework for design of a decentralized control structure, and
controller parameter tuning, has been proposed. The proposed
framework was successfully demonstrated and tested in
simulation control of benzene chloride consecutive reaction
system. It has been shown that the proposed control structure
with proposed selection of tray temperatures and their pairing is
very eective and has good robustness against the production
rate and the feed composition disturbances. Further, retuning of
the dual-temperature controllers by the proposed stochastic
dynamic optimization can result in superior control performance
even under several uncertainty disturbances. Three dierent set-
point transition forms for the production rate adjustment have
been tested in the simulation to evaluate the process control
performances. The results indicated that the dierent prole
setting forms have an important eect on the transient
performance of the proposed control structure. Therefore, the
17473
Article
production set-point transition strategy can be an important
study.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: qct@njut.edu.cn (X.Q.). Phone: 86-25-83172298 (X.Q.).
Fax: 86-25-83172298 (X.Q.).
*E-mail: kefgao@ust.hk (F.G.). Phone: 852-23587139 (F.G.).
Fax: 852-23580054 (F.G.).
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work is supported, in part, by the National Natural Science
Foundation of China (61203020, 21276126), Jiangsu Province
Natural Science Foundation (BK2011795), National Key
Technology Research and Development Program of the Ministry
of Science and Technology of China (2011BAE18B01), and
Jiangsu Province Six Domain Talent Peak Program.
NOMENCLATURE
ki = reaction rate constant of the reaction i
Avp,j = Antoine constant of component j
Bvp,j = Antoine constant of component j
Cvp,j = Antoine constant of component j
rC = reaction rate of product C (kmol/s)
rE = reaction rate of product E (kmol/s)
A1, A2 = pre-exponential factors
E1, E2 = activation energy (kJ/kmol)
FCl2 = feed ow rate of chlorine (kmol/h)
FC6H6 = feed ow rate of benzene (kmol/h)
Vs = vapor boilup (kJ/h)
zj = feed mole fraction of component j
zj = change in feed mole fraction of component j
xB,j = composition of component j in bottom product
xD,j = composition of component j in top product
PS = vapor pressure on tray i (atm)
FR = reux ow rate (kmol/h)
Kp = steady-state gain of temperature
Kp = steady-state gain of temperature dierence relate
Ti = temperature of tray i (K)
U = left singular vector matrix
E = expectation of the performance index
ei = error between set-points and output variable i
J = performance index
n = number of uncertain disturbances
Nu = number of potential manipulated variables
Nc = number of control loops
P = vector of continuous controller parameters
Q, R = weighting matrixes
V = variance of the performance index
x(t) = vector of dierential state variables
xa(t) = vector of algebraic variables
u(t) = vector of manipulated variables
y(t) = vector of measurements/output variables
ysp = set-points for output variables
R = covariance matrix
Kc = controller gain
F0 = original value of the product rate (kmol/h)
Fnew = expected value of the product rate (kmol/h)
N = the step length of multistep prole
k = the step number of multistep prole
dx.doi.org/10.1021/ie4007694 | Ind. Eng. Chem. Res. 2013, 52, 1746517474
Industrial & Engineering Chemistry Research Article

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