Article

pubs.acs.org/IECR

Control of Rotating Wave Trains in a Loop Reactor

Pietro Altimari and Erasmo Mancusi*,,

Dipartimento di Chimica, Universita Sapienza di Roma, Piazzale Aldo Moro 5, 00185 Roma, Italia

Facolta dIngegneria, Universita del Sannio, Piazza Roma, 82100, Benevento, Italia

Departamento de Engenharia Qumica e de Alimentos, Universidade Federal de Santa Catarina, 88040-970, Florianopolis, SC, Brazil

ABSTRACT: A control strategy is proposed to stabilize thermal wave trains in networks of catalytic reactors with periodically
rotated inlet and outlet ports. The implemented approach entails updating the time between two successive port rotations based
on the current values of reaction- and thermal-front velocities. These latter values are estimated online by an algorithm derived
from geometric analysis of the spatiotemporal temperature pattern. Guidelines for the placement of temperature sensors and
controller design that enforce robust stability at regime and during startup are illustrated. The illustrated strategy is validated on a
simulated problem of controlling a loop reactor for the combustion of volatile organic compounds.

INTRODUCTION
Spatiotemporally varying patterns, such as traveling fronts and
periodic waves, can autonomously form in catalytic reactors as a
result of the interplay between reaction and transport.16 The
emergence of these solutions can lead to thermal runway and
reaction extinction and has therefore been considered a critical
concern for reactor operation.7,8 Numerous theoretical and
experimental studies over the past decades have thus focused
on the development of design and control methodologies
preventing the formation of spatiotemporally varying pat-
terns.9,10 Typically, stationary operation is targeted, and reactor
parameter values far from the stability boundaries of such
solutions are selected.
In contrast with such an approach, theoretical and
experimental evidence has been reported demonstrating the
possibility of purposefully exploiting spatiotemporally varying
patterns to optimize the performance of catalytic processes.11,12
The fundamental idea is to drive the motion of traveling fronts
and waves to construct a prescribed spatiotemporal pattern.13
This methodology has been demonstrated to be successful in
enhancing the yield and selectivity in reactiondiusion
systems.11,12,14 Scarce attention has been paid, however, to its
application in convectionreactiondiusion systems. This
class of systems congures the most appropriate modeling
framework to describe the dynamics of catalytic reactors and
thus represents an obligatory benchmark for testing the
reliability of the introduced control ideas.
Particular interest has been attracted in this context to the
application of a network of tubular catalytic reactors with
periodically rotated inlet and outlet ports.15,16 A schematic
description of the network, also referred to as a loop reactor or
a simulated moving-bed reactor, is shown in Figure 1. The
number of reactors rotated in the ow direction is dened as ns,
and the time between two successive modications of the
feeding sequence is referred to as the switching time .
The network is usually operated in T*-periodic regimes,
where T* is the time needed to recover the initial feeding
conguration, although multiperiodic, quasiperiodic, and
chaotic solutions can arise.1720 The emergence of high-
conversion solutions is governed by the interaction of traveling
temperature fronts with the periodic rotation of the inlet and
outlet ports. This rotation enables, for example, a reaction front
traveling in the ow direction to be trapped within the bed and
can thus ensure autothermal operation at low adiabatic
temperature rise. This has motivated signicant interest in
the application of such network technology to the combustion
of gaseous streams with low contents of volatile organic
compounds.18,2128 The eect of radial heat losses in the
system for a lean mixture of volatile compounds was analyzed
by Barresi et al.29 This latter application covers the largest
portion of the studies on such networks presented during the
past two decades.
Some studies have also provided indications about the
network potential to enhance the yield and/or selectivity in
reversible reactions or more complex reaction schemes. This
has been conrmed for the synthesis of methanol,3033 the
selective reduction of nitrogen oxides,3436 and the production
of synthesis gas through the coupling of partial oxidation and
steam reforming.37
Despite the satisfactory results obtained in these applications,
the fundamental mechanisms governing the emergence of high-
conversion regimes have only recently been identied, shedding
light on the actual network potential. Sheintuch and
Nekhamkina38 elucidated the fundamental role played by the
interaction between traveling fronts and periodic forcing. They
demonstrated the existence of single thermal waves traveling in
the ow direction for ns/Vth < < ns/Vfr, where Vfr and Vth are
the velocities of a reaction front and of a purely thermal front
(that is, a temperature front moving in the absence of reaction),
respectively. Experimental demonstration of this latter solution
regime was also reported in ref 39.
Subsequent studies were focused on the formation of trains
of traveling thermal waves with switching times of 0 < < ns/
Vth. These regimes allow the conversiontemperature pattern
minimizing the amount of catalyst needed to attain a prescribed
Received: April 4, 2013
Revised: July 10, 2013
Accepted: August 1, 2013
Published: August 1, 2013

2013 American Chemical Society 12134 dx.doi.org/10.1021/ie401067x | Ind. Eng. Chem. Res. 2013, 52, 1213412145
Industrial & Engineering Chemistry Research
Figure 1. Schematic representation of the network. Inlet and outlet ports are periodically rotated in a stepwise manner by ns reactors.
conversion in equilibrium-limited processes to be reproduced40
and can signicantly reduce the maximum temperature
experienced by the catalyst in combustion processes.41 Mancusi
et al.42 demonstrated that increasing ns can enlarge the values
and the range sustaining the emergence of thermal wave-train
solutions. This is of practical importance, as the achievement of
low switching times would require frequent modication of the
feeding sequence and, thus, cause damage to the external valve
system.
Altimari et al.43 later demonstrated the possibility of
controlling the structure of thermal wave trains. Innitely
many domains of thermal wave trains were demonstrated to
exist for any value of ns and any number of reactors composing
the network, and analytical approximations were derived for the
stability boundaries of the predicted solutions based on
geometric analysis of the spatiotemporal temperature pattern.
The analysis was extended to reversible exothermic reactions.40
The coexistence of wave-train solutions with low-conversion
multiperiodic and extinguished regimes was analyzed in ref 44.
The main obstacles to network operation around T*-periodic
wave-train regimes are the narrow switching time stability range
of such solutions and their coexistence with low-conversion
multiperiodic and extinguished regimes. Under these con-
ditions, external disturbances and model uncertainties can likely
cause network shutdown or transition to low-conversion
regimes. For this reason, the switching time cannot be xed
a priori but must be tightly controlled.
Several approaches have been developed for network control,
all of them concerned with single-wave solutions. The proposed
control strategies employ the switching time as a manipulated
variable and can be grouped into two dierent classes: (1)
strategies triggering switching when temperature values at one
or two prescribed axial positions cross certain thresholds and
(2) strategies updating the implemented switching time based
on an explicit feedback control law. Among the former group,
the strategy proposed by Barresi et al.45 entails switching when
the catalyst temperature at the beginning of the fed reactor falls
below a rst set point and the temperature at the inlet of the
subsequent reactor is above a second set point (signicantly
larger than the rst). Zahn et al.46 investigated the performance
of three dierent controllers, again falling in group 1,
concluding that the most eective approach, requiring the
minimum number of temperature sensors, is to install a
thermocouple at the end of each reactor and to switch when the
temperature at the end of the fed reactor becomes lower than a
prescribed set point. The feasibility and robustness of this
control strategy was also conrmed experimentally.
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A proportional feedback control law was proposed by
Smagina and Sheintuch,47 allowing the switching time to be
computed in response to the dierence between the catalyst
temperature at a prescribed axial position and a set-point value.
Stability analysis of the controlled network was also performed
on a simplied model reported earlier by Sheintuch and
Nekhamkina,38 providing indications for the selection of
controller parameters.
An analogous control structure was employed by Sheinman
and Sheintuch48 for the robust stabilization of the single-wave
solution of a network carrying out methanol synthesis. They
implemented a proportional controller and a proportional
derivative controller to update the switching time in response
to the dierence between the axial position reached by the
reaction front at the end of each cycle and a set-point value.
The set point was updated during each cycle based on the
online estimation of the reaction-front velocity. For this
purpose, an algorithm, whose detailed description was not
reported, was employed by the authors for the reconstruction
of the temperature pattern. Other advanced approaches, such as
the use of observers or soft sensors for forced unsteady-state
reactors, have been proposed to control a single traveling
temperature wave.4951
Even though they ensure the stability of the single-wave
solution, each of the aforementioned strategies is inadequate for
operating the network in wave-train regimes.52 A study
addressing the problem of stabilizing wave-train solutions was
recently presented.52 In that study, the proportional control
structure proposed by Sheinman and Sheintuch48 was
employed, and a controller design procedure enforcing the
stability of wave-train solutions was described. The imple-
mented control was adaptive as the set point was updated
during each cycle based on the estimated value of the reaction-
front velocity. Analytical relationships previously determined
for the stability limits of wave-train solutions43 were used for
this purpose.
The main limit of the approach presented in ref 52 is related
to the application of an approximate form for the expression of
the stability limits of wave-train solutions. These limits depend
on both the reaction- and thermal-front velocities, Vfr and Vth,
respectively. However, only Vfr was estimated online with the
approach described in ref 52, and a simplied form for the
expression of the stability limits was employed to update the set
point based on the assumption Vfr Vth. However, this
assumption is valid at zero adiabatic temperature rise, whereas
Vfr becomes signicantly lower than Vth as the adiabatic
temperature rise is increased. Because the minimum adiabatic
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Industrial & Engineering Chemistry Research Article

temperature rise sustaining autothermal operation increases z tu T T0 C

with the number of waves,41 diculties can be found as = , t* = 0 , = ,x=1 ,
L L T C0
solutions with increasing number of waves are considered.
A further weak point of the control method described in ref E u ( H )C0
= ,v= ,B= ,D
52 is related to the implemented startup strategy, which RT0 u0 (c p)f T0
imposes that network operation be started with the catalyst
AL (c p)eff (c p)f Lu0
uniformly heated at temperatures as high as possible. This a= exp( ), Le = , Peh = ,P
approach is based on the observation that higher initial u0 (c p)f ke
temperatures reduce the risk of transition of the controlled Lu0 L
network to multiperiodic and extinguished solutions. However, em = ,L= 0
there is no guarantee that increasing the initial temperature is Df N (2)
sucient to denitively rule out this risk. Danckwerts boundary conditions are applied at inlet and outlet
In this article, a control strategy overcoming the previous sections of each reactor and are modied after each switching
diculties is presented. In accordance with the proposed to take into account the permutation of the network feeding
approach, a switching time value ensuring stability of the sequence. The boundary conditions can be written in
prescribed solution is determined during each cycle based on dimensionless form as
estimated values of reaction- and thermal-front velocities.
Again, analytical relationships previously determined for the 1 xi
stability limits of wave-train solutions are used for this purpose, = [1 fi (t *)]x in fi (t *) xi 1(i 1, t *)
Pem 0
but unlike in ref 52, no proportional control is employed.
Because both the reaction- and thermal-front velocities are + xi(i 1, t *)
estimated during each cycle, the diculties related to the
1 i
application of an approximate form for the expression of the = [1 fi (t *)]in fi (t *) i 1(i 1, t *)
stability limits are overcome. Also, it is demonstrated that the Peh 0
proposed control strategy signicantly enhances robustness + i(i 1, t *)
during startup.
The rest of this article is structured as follows: The xi i
mathematical model of the network is described next. Then, = = 0, i = 1, ..., N
1
1
the stability characteristics and spatiotemporal temperature
pattern of wave-train solutions of the uncontrolled network are (3)
reviewed. Subsequently, the proposed control strategy and its where f i(t) = h{t* mod[(i 1)ns, N]}, mod(*, ) denotes
implementation are analyzed. Concluding remarks end the the standard modulo function,53 and h(t*) is the following
article. piecewise-constant periodic function

MATHEMATICAL MODEL
We consider networks of catalytic reactors organized in a loop


h(t ) =
t*
0 if 0 mod , N < 1

(see Figure 1 for a representative scheme). In the following t*

1 if mod , N > 1
discussion, the number of reactors composing the network is (4)
denoted as N. The inlet and outlet sections are periodically
rotated in the ow direction so as to jump ns reactors each time. It is worth noting that the implemented operating strategy
The number of shifted reactors, ns, is kept constant during (that is, ns) enters the mathematical model through the forcing
operation. The switching velocity is dened as Vsw = ns/. N function h(t*) in the boundary conditions 3.
1 switching strategies can be identied as ns varies between 1 The numerical analysis illustrated in the article was derived,
and N 1.43 unless otherwise specied, using the parameter values reported
A rst-order irreversible exothermic reaction is selected as in Table 1. We investigated parameter values capable of
representative of a large class of chemical processes. For the sustaining the formation of a reaction front moving at a
sake of simplicity, constant physical properties and negligible constant velocity in the ow direction, as these conditions are
interphase gradients are assumed. Mass and energy balances for of practical interest. Indeed, under stationary operation, the
the ith reactor unit can be then written as
Table 1. Dimensionless Parameter Valuesa
xi x 2
1 xi parameter value
+v i = 2
+ Da(1 x) exp i
t * Pem i + Damkohler number, Da 0.0129/N
dimensionless activation energy, 14.13
2
i 1 i dimensionless adiabatic temperature rise, B 4
Le +v i = + BDa(1 x) dimensionless feed temperature,b in 4.82
t * Peh 2
dimensionless velocity, v 1
exp i , i = 1, ..., N Lewis number, Le 800
i + Peclet number for heat conduction, Peh 312.5/N
(1) Peclet number for mass diusion, Pem 500/N

with the following denitions for dimensionless variables and a

Reference dimensional parameters: u0 = 0.5 m/s, L0 = 0.5 m, C0 = 1
parameters (see also the Nomenclature section) 103 kmol/m3, T0 = 293 C. bCorresponding to Tin = 100 C.

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Industrial & Engineering Chemistry Research
emergence of a reaction front traveling in the ow direction
causes extinction, and thus, periodic rotation of inlet and outlet
ports is required to attain high conversions.
The total length L0 of the network is maintained constant as
N is varied. Therefore, the Peclet and Damkohler number
values reported in Table 1 are scaled by N.
SPATIOTEMPORAL STRUCTURE OF WAVE-TRAIN
SOLUTIONS
Thermal waves are formed in the network by the interactions of
traveling temperature fronts with the rotating inlet and outlet
sections. To elucidate this mechanism, we analyze in Figure 2
Figure 2. T*-periodic two-wave solution (ns = 3 and N = 4 at =
830): (a) temperature prole predicted at one-half cycle and (b)
spatiotemporal temperature pattern, where blue and red identify cold
and hot regions, respectively. Each line separating such regions
describes the evolution of the axial position of a temperature front.
the spatiotemporal temperature pattern of a T*-periodic regime
corresponding to a train of two thermal waves. Vertical bold
segments are used to denote the positions of the inlet and
outlet sections during each cycle.
It is apparent from Figure 2 that the fresh reactants are
always fed after switching to a hot reactor section. This ensures
the formation of a new reaction front moving in the ow
direction with velocity Vfr and prevents transition to
extinguished or multiperiodic regimes. Owing to the displace-
ment of the reaction front, a cold region, ab, with a width of
Vfr is generated during each cycle (Figure 2). Two thermal
fronts then form after switching in a and b and move at
constant velocity Vth = 1/Le until reaching the network outlet
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section. This determines the warming of the cold region ab
generated during the previous cycle. The network energy
balance is closed, as a new cold region ab is generated at the
same time by displacement of the upstream reaction front.
The warming of cold region ab generated by displacement of
the reaction front is possible only if thermal fronts forming in a
and b reach the network outlet section during the same cycle.
For the pattern displayed in Figure 2, these two thermal fronts
must reach the network outlet section within a time interval
ranging between one and two cycles. This imposes the
condition that the distance covered in two cycles by the front
forming in a is larger than the axial position reached by the
network outlet section within the same time interval, that is,
2Vth 2. Analogously, it can be derived that the distance
covered by the front forming in b in a single cycle must be
lower than the axial position reached by the network outlet
section within the same time interval, that is, Vfr + Vth 2.
The derived inequalities can be manipulated to determine the
switching-time stability limits of the considered spatiotemporal
pattern leading to 1/Vth 2/(Vfr + Vth).
Innitely many T*-periodic wave-train regimes can be
generated as varies and the two fronts forming in a and b
reach the network outlet section after the same number of
cycles. In particular, a train of p thermal waves is found when
the fronts forming in a and b spend between p 1 and p cycles
traveling through the network. Again, the switching-time values
sustaining the emergence of such a solution can be determined
by the geometric analysis illustrated earlier. This gives
mod(nsp , N ) mod(nsp , N )
Vthp Vfr + Vth(p 1) (5)
The term mod(ns p, N) appearing in inequalities 5 denes
the axial position reached by the network outlet section within
p cycles. It is important to remark that values dened by
inequalities 5 can also sustain the emergence of multiperiodic
and extinguished solutions.44 There is therefore no guarantee
that a T*-periodic wave-train solution will be reached even
when parameter values fullling inequalities 5 are selected.
CONTROL OF ROTATING THERMAL WAVE TRAINS
In the following subsection, a strategy for network control is
illustrated. The objective is to bring the network to operate
around a prescribed T*-periodic wave-train regime and to
ensure stability in the presence of disturbance and model
uncertainties.
Control Strategy. In accordance with the analysis
presented in ref 43 and reviewed in the preceding section,
ensuring the stability of T*-periodic wave-train regimes requires
that inequalities 5 be satised. Once ns, N, and p are xed, this
objective can be achieved by varying the velocities of the
temperature fronts or the switching time . The velocities of the
temperature fronts can be modied by varying the feeding
conditions (e.g., feed temperature and composition). This
approach is less ecient than varying the switching time,
however. This latter variable can be instantaneously changed to
a prescribed value without any additional cost for network
operation, whereas modications in the feed characteristics
increase operation cost and take a nite time interval to be
introduced. These considerations suggest that switching time
should be employed as the manipulated variable. Obviously,
improved control performance could be attained by simulta-
neously manipulating the switching time and the feed
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Industrial & Engineering Chemistry Research
characteristics. However, the design of such a multivariable
control system goes beyond the scope of the present study. In
the following development, therefore, the switching time is
employed as the only manipulated variable.
When reaction- and thermal-front velocities are known,
inequalities 5 can be used to determine a switching-time value
ensuring stability. Owing to model uncertainties and dis-
turbances, variations in Vth and Vfr can occur, however, causing
the selected switching time to fall outside the stability range of
the prescribed solution. The approach we followed to prevent
this possibility was to update the switching time during each
cycle based on the current values of Vth and Vfr. Estimates for
these velocities were derived online and substituted into
inequalities 5 to determine the switching time. To enhance
robustness, the middle point of the stability range dened by
inequalities 5 was selected as the switching time i to be
implemented during the ith cycle. This gives the following
control law
mod(nsp , N ) 1 1
i = +
2 Vth, ip Vfr, i + Vth, i(p 1) (6)
where Vth,i and Vfr,i are the thermal- and reaction-front velocity
values, respectively, estimated during the ith cycle. The
problem to be solved is to determine Vth,i and Vfr,i. The
algorithm that we implemented for this purpose was derived
from the geometric analysis of the network spatiotemporal
pattern illustrated in the previous section.
Consider the wave-train solution displayed in Figure 2. Each
temperature front separates a region characterized by temper-
atures close to the feed temperature from a region where
signicantly larger temperature values are attained. Owing to
the attainment of large Peclet values (typically found in
industrial practice), temperature fronts are very steep, and
transitions between adjacent hot and cold regions take place
within a very narrow spatial interval. Under these conditions,
the instant at which any temperature front crosses a prescribed
axial position is marked by a sudden transition of in the
temperature at that position, T(), between a value close to the
feed temperature Tin and a value considerably larger than Tin. A
decreasing or rising temperature front is found when the
transition is accompanied by an increase or decrease in
temperature, respectively. In this framework, the reaction-front
velocity Vfr can be estimated by placing a thermocouple at a
distance from the inlet section of the fed reactor and
recording the time interval tfr* needed for the measured
temperature to reach Tin. Because the reaction front forms at
switching near the inlet of the fed reactor, it must be the case
that
Vfr =
tfr* (7)
In network operation, the feed section is periodically modied,
and an estimate for Vfr can therefore be derived during each
cycle provided that a thermocouple is installed at a distance
from the inlet of each reactor.
A schematic representation illustrating the approach
implemented to estimate Vfr is reported in Figure 3. The
spatiotemporal temperature pattern displayed in Figure 2 is
considered as a representative example, and the axial position of
each thermocouple is indicated. The time interval t*fr is
determined during the rst cycle by monitoring the temper-
ature measured by the thermocouple placed in the rst reactor,
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Figure 3. Geometry-based online estimation of reaction- and thermal-
front velocities. The spatiotemporal temperature pattern displayed in
Figure 2 is considered. The axial positions of the thermocouples used
are indicated by vertical dashed gray lines, while vertical bold gray
segments are used to denote the time intervals t*th and t*fr . The
instant at which a temperature front reaches the thermocouple placed
in the ith reactor is determined by thhe intersection between the front
spatiotemporal path and the vertical dashed gray line at = i + .
This allows t*th and t*fr to be computed during each cycle.
whereas the thermocouples placed in the fourth, third, and
second reactors allow t*fr to be determined during the second,
third, and fourth cycles, respectively.
This approach to estimate Vfr is identical to the one
employed in ref 52. We next demonstrate that Vth can be
estimated without introducing any additional thermocouple.
From geometric analysis of the spatiotemporal pattern, it is
known that a thermal front always forms at a switching in a
(Figure 3). If the kth cycle is considered, the point a is the inlet
section of the reactor fed during the (k 1)th cycle. To
estimate Vth, it is sucient to record the time interval tth *
needed for the thermal front forming in a to cover the distance
separating a from the subsequent thermocouple. This can
be computed as the time needed for the temperature measured
by the thermocouple at a distance from a to become larger
than Tin. It can thus be found that
Vth =
th* (8)
In Figure 3, t*th is determined during the rst cycle by
monitoring the temperature measured by the thermocouple
placed in the second reactor. The thermocouples placed in the
rst, fourth, and third reactors are then exploited to estimate
Vth during the second, third, and fourth cycles, respectively. It
should be noted that, because Vth > Vfr, a thermal front takes
less time than the reaction front to cover the distance ,
implying that tfr* > tth
*. This ensures that an estimate for Vth
is available during each cycle before Vfr is computed.
Inuence of Controller Parameters. Three parameters
need to be xed to implement the formulated control
algorithm: and two temperature limit values. Temperature
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Industrial & Engineering Chemistry Research Article

Figure 4. Impact of front deformation on the estimation of reaction- and thermal-front velocities: (a) snapshots of the reaction front crossing the
axial position * = 0.5, (b) snapshots of a decreasing thermal front crossing the axial position * = 0.5. Owing to the deformation induced by thermal
dispersion, the temperature T(*) is dierent from Tin at the time instant when the front crosses *.

Figure 5. Inuence of the limit temperature values Ts,1 and Ts,2 on the estimated reaction- and thermal-front velocities (a) Vfr and (b) Vth,
respectively. The displayed data were computed by numerical simulation of the controlled network. The reported Vfr and Vth values correspond to
the achievement of the two-wave T*-periodic regime illustrated in Figure 2.

limit values are required to determine the instant at which a
temperature front crosses the thermocouple axial position. The
passage of a rising temperature front, for example, must be
identied by recording the time instant at which the measured
temperature becomes lower than a limit value Ts,1 > Tin and not
when it reaches Tin. Because of the front deformation caused by
thermal dispersion and the nitely large reaction rate, the tail of
the front extends upstream in a wide spatial interval with
temperatures higher than Tin.41 The time needed for the
measured temperature to reach Tin is consequently longer than
the time needed for the front to cross the thermocouple axial
position. This is clearly shown in Figure 4a, where snapshots of
the reaction front crossing a prescribed axial position * are
displayed. It is apparent that the front has entirely crossed and
is far from * when T(*) = Tin, whereas it becomes
progressively closer to * as T(*) increases above Tin. Ts,1
values slightly larger than Tin must therefore be selected to
determine the instant at which the front crosses the
thermocouple axial position.
A second temperature limit value Ts,2 must be dened to
identify the passage of a decreasing thermal front. Because of
12139
the front deformation caused by thermal dispersion, the use of a
temperature T s,2 larger than Ts,1 is recommended, as
demonstrated in Figure 4b. The evolution of the thermal
front displayed in this latter gure indicates that Ts,2 values
exceedingly close to Tin would lead to an underestimation the
time needed to cross a prescribed axial position.
Increasing the enthalpy Peclet number, on the other hand,
makes each temperature front reducing the required dierences
between Ts,1, Ts,2, and Tin steeper. Because of the large Peclet
values found in industrial practice, the stability of the controlled
network is ensured within a wide range of variation of Ts,1 and
Ts,2. To conrm this statement, we analyze in Figure 5 the
eects of Ts,1 and Ts,2 on the Vfr and Vth values estimated with
the proposed algorithm. The results displayed in Figure 5 were
derived by numerical simulation of the controlled network
operated around the two-wave T*-periodic regime arising with
N = 4 and ns = 3. The curves displayed in Figure 5 can
therefore be considered stable branches of this latter solution.
The estimated Vfr value increases slightly with Ts,1 (Figure 5a).
This can be explained by noting that, because of the front
deformation caused by thermal dispersion (Figure 4a),
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Industrial & Engineering Chemistry Research
Figure 6. Startup of the controlled network; (a,c) temperature proles computed at one-half of each cycle under regime conditions and (b,d)
spatiotemporal temperature patterns. (a,b) Implementation of a 1 value fullling inequality 10 allows the T*-periodic ve waves solution arising with
N = 4 and ns = 3 to be reached. (c,d) Application of a 1 value violating inequality 10 leads to the emergence of a four-wave 5T*-periodic solution
coexisting with the prescribed T*-periodic one.
increasing Ts,1 determines a reduction in the time interval tfr*
needed for the temperature at to reach Ts,1. Figure 5a also
shows that the estimated Vfr value is barely aected by Ts,2. The
reason for this latter behavior is that the reaction front forms
near the network inlet section and travels in the ow direction
regardless of the implemented Ts,2 value.
Increasing Ts,2 causes an increase in the estimated Vth value
(Figure 5b) This eect can, again, be explained by analyzing the
front deformation induced by thermal dispersion. Vth is
estimated by evaluating the time interval tth * needed for the
thermal front forming in a to reach the thermocouple axial
position. This time interval increases with Ts,2 because of front
inection (Figure 4b). Larger Ts,1 values, on the other hand,
cause a reduction in the estimated Vfr, thereby decreasing the
implemented switching time, in accordance with eq 6. This, in
turn, causes a reduction in the maximum temperature attained
by the front forming in a,41 leading to a reduction in tth *.
It is important to remark that, in accordance with the results
displayed in Figure 5, the implemented control law can ensure
stabilization of wave-train solutions within a wide region of
temperature limit values Ts,1 and Ts,2.
The choice of must also be based on an analysis of the
evolution of the temperature fronts. must be lower than the
distance covered by the reaction front during a single cycle. The
fulllment of this requirement is essential to ensure that the
reaction front can cross the thermocouple axial position during
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each cycle. When implementing the illustrated control
algorithm, the distance covered by the reaction front during
the ith cycle is Vfr,ii, where i is dened by eq 6. The upper
bound for is therefore given by
mod(nsp , N ) 1 1
max = +
2 p 1 + (p 1) (9)
where = maxi(Vth,i/Vfr,i). max is therefore determined by the
type of regime (the p value in eq 9) to be stabilized and by .
Because Vfr,i and Vth,i depend on the reactor parameters, the
value of to be used in inequality 9 should be selected based
on the explored region of parameter space. At parameter values
of practical relevance, the inequality Vth,i 1.5Vfr,i is typically
fullled. Therefore, = 1.5 is generally sucient to determine
max.
Startup. A fundamental obstacle to network operation
around T*-periodic wave-train solutions is multistability.
Because of the coexistence of the target T*-periodic solution
with extinguished and low-conversion multiperiodic regimes,
temperature hot spots compromising catalyst activity and/or
reductions in the average conversion are likely to occur owing
to disturbances and/or model uncertainty. The most complex
step is in this framework startup. Because large variations in
temperature and concentration occur during this phase of
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Industrial & Engineering Chemistry Research
Figure 7. Evolution of the outlet temperature and switching time during startup, corresponding to the numerical simulations illustrated in (a,b)
Figure 6a,b and (c,d) Figure 6c,d. (a,c) Temperature and (b,d) switching-time values computed at the end of each cycle are reported. Consequently,
(a,b) a xed point is attained when the prescribed ve-wave T*-periodic solution is reached, whereas (c,d) a periodic evolution (with period = 5) is
found as a result of the emergence of the four-wave 5T*-periodic solution.
operation, the risk of transitions to undesired solutions is
signicantly greater than for operation at regime.
The approach typically followed for network startup is to
preheat the catalytic bed with a hot inert gas ow and
subsequently start to feed fresh reactants and to rotate inlet and
outlet sections. It was observed in ref 52 that increasing the
initial bed temperature reduced the risk of transitions to
extinguished and multiperiodic solutions. However, neither any
indication about the limit initial temperature to be imposed nor
any guarantee to reach the target solution was provided. We
next demonstrate that the control algorithm illustrated in the
previous section can successfully cause the network to operate
around any T*-periodic wave-train solution. The only
prerequisite to be fullled for this purpose is that the initial
bed temperature be large enough to ensure the formation of a
reaction front close to the network inlet.
To demonstrate the eectiveness of the formulated control
strategy for startup, the problem of bringing the network to the
ve-wave solution arising with N = 4 and ns = 3 is considered.
Adiabatic temperature rise values sustaining this latter solution
generate Vfr values signicantly larger than the corresponding
Vth values, making the application of the control strategy
proposed in ref 52 inadequate. The evolution of the
temperature prole resulting from implementation of control
law 6 during startup is displayed in Figure 6a,b. A reaction front
is formed at t* = 0 at the network inlet section and moves in
the ow direction during the rst cycle. By monitoring the
temperature at a distance < max from the inlet, an
estimate for Vfr,1 can be obtained. In contrast, no estimate for
Vth can be determined during the rst cycle as no thermal front
is present at this stage. This rules out the possibility of
computing 1 based on eq 6. It can be demonstrated that a
transition to the prescribed solution is ensured provided that
the following condition is fullled
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mod(nsp , N ) p 1 1 1
1 1 +
Vfr,1 2 p p 1 + 1/
(10)
Derivation of inequality 10 is reported in the Appendix. As
found for inequality 9, the value = 1.5 can be used, with
reactor parameter values of industrial relevance, to determine
an upper bound for 1. An estimate for such a bound, valid at
any set of reactor parameter values, can be derived in the limit
1/ 0. This limit corresponds to a thermal-front velocity that
is innitely larger than the reaction-front velocity and cannot
therefore be realized. It can nonetheless be imposed to
determine the theoretical minimum of the right-hand side of
inequality 10.
The pattern displayed in Figure 6a,b was generated by
implementing an underestimated 1 value computed based on
eq 10. In particular, the employed 1 value was selected to be
large enough to generate an upstream cold region ab and
signicantly lower than the minimum switching time ensuring
stability, that is, 1/Vth, computed with the actual Vth value.
Once the region ab had been created by displacement of the
reaction front, switching was performed, leading to the
formation of a thermal front in a. An estimate for Vth,2 was
derived during the second cycle by monitoring the temperature
at a distance from the inlet of the rst reactor. A new
reaction front also formed at the beginning of the second cycle,
and an estimate for Vfr,2 was determined by means of the
thermocouple placed in the fourth reactor. The switching time
2 was thus computed. Iterating this procedure enabled the
prescribed solution to be reached. The evolutions of the
switching time and of the network outlet temperature during
startup are reported in Figure 7a,b. It is apparent that about 50
cycles were needed to reach the prescribed regime and
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Industrial & Engineering Chemistry Research
Figure 8. Response of the controlled network to disturbances in the (ac) feed reactant concentration C0 and (df) gas velocity u. The illustrated
results describe the startup to the three-wave T*-periodic solution arising with N = 4 and ns = 3.
moderate deviations of the outlet temperature and switching
time from the corresponding regime values are found.
It is important to remark that, in accordance with the
illustrated analysis, no lower limit was found for 1. The
implementation of a 1 value even much lower than the
minimum value actually required to ensure stability is sucient
to reach the prescribed solution. In contrast, extinction or
transition to a coexisting multiperiodic solution was found
when 1 values not fullling inequality 10 were selected. This
latter circumstance is illustrated in Figure 6c,d. In this latter
case, the controller could not recover the error made during the
rst cycle, and a transition to a four-wave multiperiodic solution
was found even though i values enforcing stability were
implemented for all i > 1. The evolutions of the switching time
and the outlet temperature during startup are illustrated in
Figure 7c,d. It is worth noting that a multiperiodic solution with
a period of 5T* was attained, with the switching time oscillating
at regime within the stability range of the T*-periodic solution
displayed in Figure 6a,b. This was possible because of the
coexistence of the two displayed solutions.
The implementation of an underestimated 1 value is
recommended. It is nonetheless important that 1 be selected
large enough to generate a region ab at a temperature around
Tin. This is essential to form a thermal front in a and thus
estimate Vth during the second cycle.
Controller Performance. The ability of the formulated
control strategy to reject disturbances in the feed concentration
C0 and in the gas velocity u was analyzed. Variations in these
two parameters typically occur in industrial practice, causing
signicant changes in reaction- and thermal-front velocities.
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This can, in turn, cause transitions to multiperiodic or
extinguished solutions.
The eects of step variations in C0 and u are examined in
Figure 8. The problem of bringing the network to the T*-
periodic three-wave solution arising with N = 4 and ns = 3 is
considered. To analyze the ability of the controller to reject
disturbances both at regime and during startup, numerical
simulations were performed starting from a uniform initial
temperature prole with disturbances introduced before the
target T*-periodic regime was reached. Moreover, the
minimum C0 and u values considered in the numerical
simulation were selected close to the stability boundaries of
the target solution. It must be emphasized that the achievement
of such parameter values would make the target solution
unstable if an open-loop control strategy (i.e., an a priori xed
switching time) were implemented.
The evolutions of the network outlet temperature and
switching time reported in Figure 8 demonstrate the ability of
the controlled network to reject disturbances. The controller
modies the switching time to prevent that the stability
boundaries of the target solution are crossed. Large variations in
the outlet temperature were initially found corresponding to a
transition from the initial at temperature prole to a three-
wave temperature pattern. Also, a sudden increase in the
switching time was obtained following the rst cycle. Because
an underestimated 1 value was implemented, a sudden increase
in the switching time was observed as an estimate for Vth was
derived during the second cycle. Following the illustrated initial
transient, moderate variations in the outlet temperature and
switching time were ensured by the controller in response to
the introduced disturbances.
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Industrial & Engineering Chemistry Research
Figure 9. Response of the controlled network to disturbances in the (ac) feed reactant concentration C0 and (df) gas velocity u. The illustrated
results describe the startup to the ve-wave T*-periodic solution arising with N = 4 and ns = 3 and analyzed in Figure 6a,b.
The analysis of controller robustness was completed by
extending this numerical experiment to a solution characterized
by a larger number of temperature waves. This test was
essential to demonstrate the eectiveness of the proposed
control approach, as control diculties increase signicantly
with increasing number of waves. Indeed, increasing the
number of waves causes an increase in the number of coexisting
multiperiodic solutions and reduces the network stability range.
These two latter eects contribute to an increase in the risk of
transitions to undesired solutions.
The problem of bringing the network to the ve-wave
solution displayed in Figure 6a,b is considered. The evolutions
of the outlet temperature and switching time in response to
successive step variations in C0 and u are displayed in Figure 9.
Again, disturbances were introduced before the regime was
reached, and the C0 and u values imposed in the numerical
simulation were selected very close to the stability boundaries
of the target solution. Again, the controller eectively rejected
the disturbances. Following the initial transient, corresponding
to the transition from a at prole to a ve-wave temperature
pattern, oscillations of moderate amplitude were observed for
outlet temperature and switching time, and the target solution
was eventually attained.
CONCLUSIONS
A control strategy has been proposed to stabilize thermal wave
trains in a network of catalytic reactors with periodically rotated
inlet and outlet ports. The strategy relies on updating the
switching time during each cycle based on the current values of
the reaction- and thermal-front velocities. To estimate these
two velocities online, an algorithm was derived from geometric
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analysis of the network spatiotemporal temperature pattern.
The implementation of the illustrated control strategy for
network startup was analyzed. A procedure was presented in
this framework enabling the controlled network to be brought
to any T*-periodic wave-train solution. Numerical simulations
were used to demonstrate the eectiveness of the proposed
controller in rejecting disturbances both at regime and during
startup.
We conclude by noting the need for further investigation of
the impact of the implemented control strategy on the
spatiotemporal structure and stability of the loop reactor. In
particular, the eects of the values of controller parameters on
the stability limits of multiperiodic solution regimes coexisting
with the target T*-periodic regimes should be performed
through a detailed bifurcation analysis. This study can allow for
indications to be derived on how to design the proposed
control structure to reduce the risk of transitions to undesired
regimes.
APPENDIX: DERIVATION OF INEQUALITY 10
Stability limits derived for the uncontrolled network in ref 41
and reviewed in the section Spatiotemporal Structure of Wave-
Train Solutions of the present article apply almost unchanged
to the controlled network. The only dierence to be taken into
account in the analysis of the controlled network is the
possibility of variations in the reaction- and thermal-front
velocities. Any T*-periodic wave-train solution can be sustained
in the controlled network provided that the thermal fronts
forming in a and b (Figure 2) reach the network outlet section
during the same cycle. For a train of p thermal waves, this
imposes the following two conditions:41
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Industrial & Engineering Chemistry Research Article

First, the distance covered in p cycles by the thermal front q = number of reactors covered by a purely thermal front =
forming in a is greater than the distance (modulo the network mod(nsp,N)
length) covered during the same time interval by the network r = reaction rate
outlet section, that is R = gas constant
p+1 t = time
Vth,ii mod(nsp , N ) T = temperature
i=2 (11) t* = dimensionless time
T * = time needed to recover the initial feeding
Second, the distance covered in p 1 cycles by the thermal conguration (T*=N)
front forming in b is less than the distance (modulo the Tl = lowest maximum temperature of a temperature wave
network length) covered during the same time interval by the Tm = highest maximum temperature of a temperature wave
network outlet section, that is u = gas rate
p v = dimensionless gas ow rate
Vfr,11 + Vth,ii mod(nsp , N ) Vfr = dimensionless reaction-front velocity
i=2 (12) Vsw = dimensionless switching velocity
Vth = dimensionless purely thermal-front velocity
Inequalities 11 and 12 coincide with inequalities 5 in the case x = conversion
of constant reaction- and thermal-front velocities. Inequality 11 z = axial coordinate
involves only i values with i > 1. These latter values are
computed based on eq 6, as estimates for Vth,i and Vfr,i can be Greek Letters
derived during startup for all i > 1. This ensures the fulllment = maximum value assumed by the ratio of the thermal-
of inequality 11. Inequality 12, in contrast, involves switching front velocity to the reaction-front velocity = maxi (Vth,i/Vfr,i)
time 1, which cannot be computed based on eq 6 because of H = heat of reaction
the impossibility of estimating Vth,1 during startup. Inequality tfr* = time interval needed for the reaction front to cover
12 can be exploited to obtain an upper bound for 1. By the distance
replacing the implemented control law (eq 6) with i for i > 1, t*th = time interval needed for the thermal front to cover the
inequality 12 can be recast in the form distance
= distance of each thermocouple from the upstream
p
reactor inlet
Vfr,11 11 1 = reactor void fraction
1 + Vfr, i
mod(nsp , N ) 2 p p1+ = dimensionless activation energy
i=2
Vth, i
= dimensionless temperature
p 1 1 1 = density
1 + = dimensionless switch time
2 p p 1 + 1/ (13) = dimensionless axial coordinate
where = maxi(Vth,i/Vfr,i). Subscripts and Superscripts

AUTHOR INFORMATION
Corresponding Author
0 = reference conditions
f = uid
h = enthalpy
*E-mail: mancusi@unisannio.it (E.M.), pietro.altimari@ in = inlet
uniroma1.it (P.A.). m = mass
Notes max = maximum
The authors declare no competing nancial interest.

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