Ind. Eng. Chem. Res.

2009, 48, 51855192 5185

Loop Reactor Design and Control for Reversible Exothermic Reactions

Roman Sheinman and Moshe Sheintuch*
Department of Chemical Engineering, Technion-I.I.T., Technion City, Haifa 32 000, Israel

The loop reactor, in the form composed of several units, with feed and exit ports switching, is investigated
for a reversible exothermic reaction like the synthesis of methanol. Unlike applications of VOC combustion,
which have been extensively investigated and experimentally tested, the maximal temperature here is limited
by equilibrium conditions and the advantage gained is due to the effectively periodic boundary conditions
that describe the system: due to the rotating nature of the system, the stream undergoes cooling as it leaves
the system, which in turn yields increasing conversions at an extent that depends on the parameters. We
show that the system exhibits the slow-switching asymptote and the complex many-domains pattern that was
identified for the irreversible case. The dynamic features within these domains are analyzed. Conversions are
comparable to those in the commercially applied reactor with interstage cooling. Control procedures are
suggested and tested.

1. Introduction
The loop reactor (LR), in the form composed of several units,
with switching of feed and exit ports between them (Figure 1),
is one of the suggested technological solutions for low-
concentration VOC combustion. This is one of the conceptual
solutions that combines a packed bed with enthalpy recuperation
like the reverse-flow reactor1-3 (RFR). The RFR and the LR
has been claimed to be advantageous for VOC combustion, due
the high temperature rise achieved, as well as for reversible
exothermic reaction, thanks to the spontaneous declining-
temperature zone that develops within the reactor. The purpose
of this work is to analyze the LR for the latter application.
The loop or ring reactor has been proposed by Matros4 and
was simulated for a case of two units by Haynes and Caram5
or for three units by Barresis group6,7 for the applications
described above. Sheintuch and Nekhamkina8-10 have general-
ized these results by studying the asymptotic solutions of a
many-units loop reactor in which a single exothermic reaction
occurs, showing the existence of a slow switching solution in
which the forcing switching velocity (Vsw ) L/sw, i.e., unit
length divided by switching time) and the spontaneous front
velocity (Vfr) are synchronized and the pattern is frozen in
moving coordinates. In that asymptote, the system is analogous
to a loop-shaped bed rotating in the direction opposite to the
flow at the speed of pulse propagation. The feed position is
fixed in time. Another asymptote, that of a fast switching
solution in which Vsw significantly exceeds Vfr, was also shown
to exist. Moreover, between these two asymptotes we recently
showed (Nekhamkina and Sheintuch11) the existence of many
finger like domains of complex frequency-locked solutions
that allow to extend significantly the operation condition domain,
rendering the LR scheme more attractive for practical imple-
mentation.
Comparison of the LR operation, within the slow-switching
domain, with the RFR12,13 led to the conclusion that its main
advantages are the significant reduction of the washout effect,
the autothermal behavior, and the nearly uniform catalyst
utilization. The main drawback of the LR is the very narrow
window of switching velocities that sustain the solution in the
frozen-patterns finger (see below). If control is incorporated,
this domain is quite wide, as we show below. The first
experimental implementations of the LR were recently reported
for an almost isothermal process (selective catalytic reduction,
NH3 + NO, Fissore et al.14) and for the VOC combustion
concept (ethylene oxidation, Madai and Sheintuch15).
The fast switching operation domain (Vsw > Vfr), for a three-
unit LR, was reported in a series of numerical studies;6-8,10
nonlinear dynamics and bifurcation analysis were conducted by
Russo et al.16-18 and Altimari et al.19 A brief analysis of
complex nonfrozen solutions in LR with different N was
conducted in our previous works.8,9
To understand the advantage gained in the LR for VOC
combustion, recall the effect of front velocity (Vfr) on the
maximal temperature (Tm) in a fixed bed reactor. For the case
of a single irreversible reaction in an ideal front (i.e., in an
infinitely long system) Tm and Vfr admit the following relations
(Wicke and Vortmeyer20):
VS - Vfr
Tm ) Tm - T0 ) Tad ,
VS - LeVfr
Tad - Tm
Vfr ) VS (1)
LeTad - LeTm
The peak temperature of a front (in a once-through catalytic
reactor) or of the rotating pulse (in a loop reactor) can be
increased significantly by pushing the front by increasing the
flow rate (Vs). Obviously, the front velocity cannot exceed the
thermal front velocity Vfr ) Vsw ) Vs/Le which corresponds to
an infinitely large temperature rise in the infinitely long system.
In a finite length once-through reactor, the pulse will eventually
leave the system and the extinguished state will prevail. Thus,
some form of matched boundary conditions or external periodic
forcing is required to sustain the periodic motion.
Figure 1. Representation of loop reactor operation, as a train of periodically
switched fixed beds (left) and as a rotating bed (right).

10.1021/ie801333w CCC: $40.75 2009 American Chemical Society

Published on Web 05/04/2009
5186 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009

In reversible reactions, on the other hand, the maximal Table 1. Summary of Dimensionless Parameters
temperature is limited by equilibrium conditions. The advantage parameter set I set II
gained here is due to the effectively periodic boundary condi-
exothermicity, B 16 5.5
tions that describe the system: the exit bed temperature is quite input temperature (T ) 100 C), in - 8.2 - 2.8
close to the feed temperature and, consequently, the stream input temperature (T ) 20 C), in - 15 - 5.0
undergoes cooling as it leaves the system. This cooling yields Peclet number for heat conduction, PeT 413 413
Peclet number for mass diffusion, PeC 390 390
increasing conversions at an extent that depends on the spatial Damkohler number, Da 0.017 11
rate of cooling, the flow rate, and the reaction kinetics. Lewis number, Le 29 29
The aim of the current work is to extend the information activation energy, 39 13
obtained for LR design for irreversible reactions, i.e., the two reaction enthalpy to activation energy, 1.6 2.9
ratio between direct and reverse reaction constants, 3.2 10 9.1 1010
8
asymptotes and the qualitative structure of the operating domain, reactor length, L 1/2 1/2
to designs for reversible reactions and use this understanding
to assess the advantages and shortcoming of such design. The be combined to eliminate the nonlinear reaction term and to
main alternative approaches for reversible exothermic reaction find that CCH3OH ) C0 - C.
are the interstage cooling or the counter-current autothermal In dimensionless form the model takes the form
designs, which require external or internal heat exchangers,
respectively. 1 2
Le + VS ) + Br(x, );
The structure of this work is the following: in the next section PeT 2
the model and its asymptotes are outlined, while their solutions x x 1 2x
are described in section 3 along with several control schemes. + VS ) + r(x, ) (5)
PeC 2
We use approximate kinetics, reduced from the detailed one as
described in the Appendix. where the reaction term is

( + )[1 - x{1 + exp( (1-+) )}]

2. Reactor Model 2
r(x, ) ) Da exp
In the simulations below we use an exothermic first-order
(6)
reversible, activated reaction. We use the kinetic and thermo-
dynamic parameters of the synthesis of methanol from CO and E2 A2
-H
hydrogen with the latter being in excess. Since the feed typically ) ) + 1; )
includes CO2 and water, this reaction is one of the three that E1 E1 A1
usually occur during catalytic methanol synthesis, and this was
the problem considered numerically by Velardi et al.6 To gain The boundary conditions are those of once-through operation,
some understanding, we assume only two reactants in the feed i.e., the Danckwerts BC, which are applied at the feed and exit
and that only one reaction occurs. port:

1 1 x
rA J ) in, ) V( - in), ) V(x - xin);
CO + 2H2 {\} CH3OH (-H) ) 9.071 104 Pe Pex
r-A mol
x
) out, ) )0 (7)

We shall assume that the feed includes 6.5% M of carbon while continuity is applied between the units; i.e., the system
monoxide in hydrogen. is modeled as a single continuous reactor. Here conventional
To simplify modeling, we assume that both direct and reverse notation is used:
reactions are of first order with Arrhenius dependence in
temperature. The transport coefficients (ke, Df) and thermody- z tu0 T - T0 Tin - T0
namic parameters (F, cp, and -H) are assumed to be constant. ) , ) , ) , in ) ,
z0 z0 T0 T0
Under these assumptions the enthalpy and mass balances in a
C u L E
one-dimensional homogeneous system may be written for each x ) 1 - , VS ) , L ) , ) ,
unit in the following form: C0 u0 z0 RT0
(-H)C0 Az0 (FCp)e
B) , Da ) exp(-), Le ) ,
T T 2T (FCp)fT0 u0 (FCp)f
(FCP)eff + (FCP)f u ) ke 2 + (-H)(1 - )r(C, T)
t z z (FCp)fz0u0 (FCp)fz0u0
(2) PeT ) , PeC ) (8)
ke Df

C C 2C Note that we use arbitrary values (u0, z0) for the fluid velocity
+u ) Df 2 - (1 - )r(C, T) (3)
t z z and the length scales in order to ensure that the corresponding
dimensionless values (L, V) can be varied as independent
r(CA, CB, T) ) k1(T)C - k2(T)(C0 - C); parameters. We choose u0 ) 1 m/s, z0 ) 1 m, and report
ki(T) ) Ai exp ( )
-Ea,i
RT
(4)
sometimes the dimensional reactor length and feed flow rate.
Typically, in our simulations, as well as in practical situations,
the ratio of solid to fluid heat capacities is large, Le . 1 (for
The rate equation has been reduced to a single-reactant this high-pressure case, Le ) 28.5) and PeT, PeC . 1.
presentation under the reasonable assumption that the mass- The parameters of the system were adopted from Velardi et
dispersion coefficients of the key reactant and product are al.6 and converted to a first-order presentation within a limited
identical and that a sufficiently long time has elapsed since the temperature range (see Appendix). The reference temperature
perturbation; under these conditions the two mass balances can T0 was chosen to be 200 C.

Figure 2. Bifurcation map showing domains of active solutions, in the plane of fluid vs switching velocity, for feed temperature of Tin ) 100 C (left) or
20 C (right). Both maps calculated for set I of parameters.
The many-port slow-switching asymptote was derived by
Nekhamkina and Sheintuch9 and was shown to converge to the
full model results as the number of ports is increased. In the
slow-switching domain, the system can obtain a stationary
solution in a moving coordinate system, ) - Vsw, with its
origin at the continuously moving feed position. The system at
the steady moving state is described by
1 2
- (Vs - VswLe) + B r(x, ) ) 0
PeT 2
1 2x x the second jump. This is unlike the case of irreversible reactions
- (Vs - Vsw) + r(x, ) ) 0 (9)
PeCF 2
with r(x, ) defined in eq 6 and subject to the following
boundary conditions:
1 x
at ) 0: Pe ) Vs(x - xin);
(| | )
C
1 significantly in their activation energies.
- ) VS(0 - in)
PeT )0 )L
at ) L:
x
|)L
) 0, x)1 ) x)0 (10)
3. Results
Following our previous study of irreversible reactions, we
draw domains of unextinguished solutions in the plane of fluid
velocity vs switching velocity. Figure 2 shows a grayscale plot
of the possible operating windows where the conversion is not
nil. Throughout this plane there exists another extinguished
solution, and in the white domains it is the only solution. The
maximal temperature is expected to fall approximately at Vsw
) Vs/Le, since the apparent convection term (eq 9) vanishes.
As expected the first domain (or finger or tongue) falls around
that value. Below, we elaborate further on the first domain and
the control required for safe operation. The other domains fall
around integer multiples of that value, i.e., Vsw ) nVS/Le, n )
1, 2,... (the seven lines drawn to guide the eye fall at VS ) VswLe/
n). For large n the domains are indistinguishable. At lower feed
temperature the same domain structure is still valid, but the
domains are narrower. Especially, the even n domains are very
narrow and may not be continuous.
The first domain yields simple periodic solutions with small
temporal variation in temperature, and in the limit of many
reactors while keeping the same length, it yields an asymptotic
solution that moves at constant shape and speed (see below).
Figure 3 presents the temperature or conversion spatial profiles,
as well as their phase plane presentations, for several switching
velocities within the slow-switching domain at u ) 1 m/s. It
Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009 5187
shows again that an ignited solution exists only for a limited
range of switching velocities (for fixed Vs), while outside this
domain the solution is extinguished. This domain exist around
Vsw ) u/Leu0 0.032. The largest temperature is limited by
equilibrium conditions, independent of the switching velocity.
The conversion jumps in two steps: at the entrance, due to the
high temperature generated there, and toward the exit due to
the cooling effect. The first jump is equilibrium-limited while
the second is limited by kinetics and the spatial temperature
gradient. Decreasing flow rate will increase the conversion in
where the temperature increases with feed flow rate. Increasing
switching velocity will lead somewhat higher conversions near
the right boundary of that domain. When plotting this data in
the phase plane we see that the second step (declining temper-
ature) follows the equilibrium line until the temperature is too
cold to sustain a reaction (Figure 3c). Note that there is no
qualitative differences between the two sets which differ
To avoid extinction, we should follow a constant u/Vsw ratio.
Plots of conversion along these lines, within the fingers in Figure
2a, show that the state is ignited almost for the whole domain
and the conversion declines with u (Figure 4) as expected from
the analysis of the second conversion jump above. Thus, while
a higher conversion can be achieved at lower flow rates in the
intermediate- and fast-switching domains, the throughput achieved
in the slow-switching domain is the largest, and the decision in
which domain to operate should be based on the ease of control,
as well as on the economics of reaction and separation.
Let us discuss the dynamic within the various fingers (Figure
5): the behavior is simple-periodic within the slow-switching
finger, showing one peak per cycle of the exit conversion and
a simple one-peak spatial profile. Fourier spectrum of exit
conversion exhibits the dominant frequency, which is the forcing
frequency, and its harmonics (Figure 6, column 1). This is also
evident from the spatiotemporal pattern (Figure 5a).
As we move to the other fingers, the temperature profile
exhibits a complex profile with several peaks (hot zones) within
the system, the exit conversion is multipeak or even aperiodic
and the spectrum includes more frequencies. At very high
switching velocities the system approaches the corresponding
asymptote showing a dominant frequency that is independent
of Vsw (Figure 6). This is also evident from the spatiotemporal
pattern (Figure 5c).
Numerical Solution of Quasi-Steady-State Problem. Com-
parison of the asymptotic model with simulation results of 32
units loop reactor of same total length (Figure 7) affirms again
the validity of the many-unit asymptote (see ref 9 for detailed
comparison). The asymptotic steady-state solution of eqs 9 and
5188 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009

Figure 3. Temperature (a) and conversion (b) profiles along the reactor for the slow-switching velocity solution, and their phase plane representation (c), for
set I (upper row) and set II (lower row). Tin ) 100 C for both sets.

Figure 4. Time-average conversion and production rate, along lines with constant VS/Vsw ratio (set I) shown in Figure 2a.

Figure 5. Examples of simple-periodic behavior within the slow-switching finger (a) and of more complex behaviors of frequency locked states (b,c),
showing the temperature in the time vs space plane. (a) Conditions are of the first slow-switching finger (Vsw ) 0.140 m/s; u ) 4.141 m/s), (b) of finger
number 4 (Vsw ) 0.140 m/s; u ) 1.236 m/s), and (c) of finger number 7 (Vsw ) 0.140 m/s; u ) 0.468 m/s).

10 was obtained by a 200-node finite-difference approach using traveling pulses; the slow-switching domain becomes nar-
Mathematica. rower with decreasing adiabatic temperature rise (Tad or
Control Design. The main drawback of the loop reactor is B) and forms a U- or V-shaped domain in the (B,Vsw) plane11
the narrow domain of switching velocities that support shown in Figure 8. Since not all parameters (especially Le)
 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009 5189

Figure 6. Comparison of dynamic behavior of LR at different operating regimes showing the temperature profile, the exit conversion temporal behavior, and
the Fourier transform of the signal, (set I, Tin ) 100 C). For all tests Vsw ) 0.140 m/s; u ) 4.1413, 1.7983, 1.4971, 1.2363, 0.952 16, 0.724 05, 0.468 27
m/s, respectively, for seven tests.
5190 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009
are known exactly, a control mechanism was simulated in
several numerical studies and was applied in the experimental
study. Barresi et al. (2002) suggested to use the switching velocity
as an actuator and simulated the behavior with the following
feedback control: For two consecutive reactors the feed is switched
from one reactor to the following when the temperature measured
at the entrance of the catalytic area in the second reactor reaches
Tsw2 (a threshold temperature) and the temperature at the entrance
of the first reactor past the feed drops below Tsw1. In practice it is
the former temperature (Tsw2) that triggered the switch. The
stability of a rotating pulse with a switching velocity controlled
to minimize the deviation of a reading T(z*), measured at certain
z*, from a certain set point Ts was recently studied in our group.8
The approaches described above require that two parameters
be determined (z*,Ts) or (z*,Tsw1) for proper design. Here we
want to design a control that identifies the pulse peak and
determines its velocity and tries to keep it at a constant distance
(on average) from the feed, thus reducing the number of control
parameters to one (z*, or the dimensionless *).
To identify the pulse peak, we note that we should see a
periodic signal from each of the thermocouples placed in the
reactor. These signals are masked by some noise. To filter out
the effect of noise and determine the pulse velocity we propose
the following steps:
1. The controller compares its temporal reading, within a
certain time interval, with a prespecified function, usually a
parabola. Once the peak is identified the program reports that
the hot spot has passed the sensor.
2. From knowledge of the temporal interval of peak passage
between adjacent sensors, the average velocity is calculated.
3. Using the present peak position and the average velocity
one of the following two control laws has been applied:
Proportional Control. The deviation of the estimated front
position from a certain set point is used to adjust Vsw according to
Figure 7. The asymptotic solution, compared to 32 reactors in loop model (set I). Vsw ) 1/Le, VS ) 1.
Figure 8. Testing the proportional (a) or proportional-integral control law (b): periodic ignited solutions obtained by decreasing B values are denoted in the
(B, Vsw) plane (set I); (c) shows the proportional-integral control law test on irreversible first-order reaction.
Vsw ) KP(peak - *) (11)
Recall that Vsw O(1/Le) and * O(1) so Kp O(1/Le).
Proportional-Integral (PI) Control. The switch velocity
is adjusted every switch like
Vsw,i+1 ) Vsw,i+1 + K1(*i - sp) + K2(*i - *i-1) (12)
where i is the peak position at the reactor. The drawback of
the proposed estimation algorithm is the measurement time lag.
The delay is induced because the measurement is updated only
when peak leaves the measurement window. Therefore, the time
delay is equal to the windows width. Reducing the window
width will reduce the delay, paying by reduced precision of
estimation.
The plot of operating domain is reconstructed now under
control in the plane of B vs Vsw: now Vsw is not fixed, but
rather the result of control. After pseudoperiodic conditions
are obtained the corresponding switch velocity was recorded
and plotted (Figure 8). Following an experiment of decreasing
feed concentration (or B), using the last point as initial
conditions for a new set, the locus of such pseudoperiodic
states was recorded until extinction occurred (Figure 8). The
extinction point in the closed-loop system is quite close to
that simulated for uncontrolled system (open loop) system
for proper choice of sensor location. The control is effective:
the lowest Tad that sustains a reaction is not strongly
dependent on the sensor position or threshold temperature.
Forcomparisonweshowasimilarfigureusingproportional-integral
control of irreversible reaction (using a set of parameters in
ref 8).
We analyzed the behavior of a loop reactor with a
reversible reaction. The reactor exhibits similar behavior to
the well-studied case of irreversible reaction, like the slow-
switching domain of frozen solution and multiple-switching
 Ind. Eng. Chem. Res., Vol. 48, No. 11, 2009 5191
domains of complex solutions (Figure 1). The domains have Table A1. Parameters Used in Simulations
a classical form of tongues that fall around constant values total length, L 0.5 m
of LeVsw/VS. void fraction, 0.4
Unlike the irreversible reactions, the temperature and catalyst density, FS 1750 kg m-3
catalyst specific heat, CP,S 1000 J kg-1 K-1
conversion of reversible reaction within the slow-switching catalyst thermal conductivity, S 0.33 W m-1 K-1
domain are limited by equilibrium conditions, which are pellet diameter, dp 0.0054 m
independent of the switching velocity. The conversion total pressure, P 5 MPa
superficial inlet flow rate, Fin 32.65 mol m-2 s-1
increases in two steps (Figure 2): at the entrance, due to the feed temperature 100 or 20 C
temperature rise, and is limited by equilibrium. The second av mol wt of feed, MW 4.02 g mol-1
jump happens toward the exit, due to the cooling effect, and feed density, FF 6.2593 kg m-3
is limited by kinetics and the spatial temperature gradient. feed specific heat, CP,F 7.3535 103 J kg-1 K-1
feed thermal conductivity, F 0.1917 W m-1 K-1
Decreasing flow rate will increase the conversion in the feed diffusivity, Dmx 0.0054 m2 s-1
second jump. This is unlike in the case of irreversible feed viscosity, 1.2964 10-4 Pa s
reactions where the temperature increases with feed flow rate.
Table A2. Kinetic Data
Increasing switching velocity will lead to somewhat higher
conversions near the right boundary of the slow-switching parameter set I set II
domain (Figure 3). reaction enthalpy (-H), J/mol 98385 90710
As we move to the other domains (tongues), the temper- pre-exponential constant kest, 7.379 1012 9.083 1010
ature profile becomes more complex featuring several peaks mol s-1 kgcatalyst-1
activation energy Ea,1, J/mol 153547 51800
(hot zones) within the system. The exit conversion is activation energy, back reaction 251932 142510
multipeak or even aperiodic, which is illustrated using Ea,-1, J/mol
frequency content of Fourier spectrum (Figure 5). At very set of concentrations that represent feed conditions (at P ) 25
high switching velocities the system approaches the corre- bar and pi ) Pyi)
sponding asymptote showing a dominant frequency that is
independent of switch velocity. yCO ) 0.045; yCO2 ) 0.018; yCH3OH ) 0.0065;
yH2O ) 0.002; yH2 ) 0.92
Appendix: Rate Expressions and Parameter Estimation
we plotted the term
The enthalpies and other physical properties are estimated
using Unisim, Peng-Robinson property prediction package.21 rA kpsAKCO pH3/22

( )
Another method, the Zudkevich-Joffee property prediction )
pCO KH2O
package, is the modification of Peng-Robinson method and (1 + KCO pCO + KCO2 pCO2) pH1/22 + pH2O
is designed to handle hydrogen-containing mixtures. The KH1/22
difference between the methods is less than 0.1%. The (A4)
catalyst properties and bed dimensions are those used by
Velardi et al.6 vs 1/T and determined the apparent activation energy within
The original rate equations for methanol synthesis on a ZnO/ the temperature range of 300-1200 K. This yielded the set of
CuO/Al2O3 catalyst were suggested by Graaf et al.22 Here we following parameters: kest ) 7.379 1012e-153547/(RT)
approximate them by a linear expression assuming hydrogen mol s-1 kgcatalyst-1. Note the high activation energy is due to
to be in excess. the temperature effect on adsorption equilibrium coefficients,
especially on KH2O (actual activation energy is due to kpsA and
KCO pCO pH2 2
kps,A KCO; see Table A2). The reaction enthalpy was set at Ea,1 -
rA ) Ea,-1 ) 98 385 J/mol, which is quite close to theoretical value
(1 + KCO pCO + KCO2 pCO2)[pH2 + (KH2O /KH1/22 )pH2O pH1/22 ] of reaction enthalpy 91000 J/mol.
-1
mol s-1 kgcatalyst (A1) Set II. Assuming that temperature is high so that the terms
KH2OpH2O , 1 and KCO2pCO2 , 1, the rate is
r-A pCH3OH KCO pCO pH2
kps,A
) (A2) rA ) (A6)
rA Kp,A pH2 2 pCO (1 + KCO pCO)

kps,A -1
) 2.69 107e-109900/(RT)mol s-1 kgcatalyst
KCO ) 7.99 10-7e58100/(RT) bar-1
KCO2 ) 1.02 10-7e67400/(RT) bar-1
Kp,A ) 105139/T-12.621 ) 2.3933 10-13e98385/(RT) bar-2
KH2O /KH1/22 ) 4.13 10-11e104500/(RT) bar-1/2 (A3)
We approximated the rate of the forward reaction as a first
order with respect to CO in the temperature range of
300-1200 K and re-estimate the activation energy and pre-
exponent factor by fitting the data for the forward reaction.
Parameters of reverse reaction are estimated from ratio of
reverse to direct reactions:
Set I. We assume that the denominator varies slowly with
conversion, so that it is mainly temperature dependent. For a
and it varies from zero order with apparent activation energy
of 109 000 J/mol, under feed conditions, to a first order with
apparent activation energy of 51 800 J/mol at sufficiently high
temperatures when KCOPCO , 1. We take the latter case since
it applies for most cases studied here where the catalyst is
operating at T > 600 K (e.g., Figure 4).
The kinetic data is presented in Table A2.
Acknowledgment
Work supported by the US-Israel Binational Science Founda-
tion. Moshe Sheintuch is a member of the Minerva Center of
Nonlinear Dynamics.
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ReceiVed for reView September 3, 2008
ReVised manuscript receiVed February 22, 2009
Accepted March 3, 2009
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