Chemical Engineering Science. Vol. 49. No. 248, pp. 546S.5472.

1994
Copyright 8 1995 Elscvier Scicncs Ltd
Printed in Crreat Britain. All rights reacrwd
wo9-251X/94 S7.00 + 0.00

0009-2509(94)00383-l

THE SIMULATED MOVING BED CHEMICAL REACTOR

THOMAS N. HAYNES and HUGO S. CARAM*

Department of Chemical Engineering, Lehigh University, Bethlehem, PA 18015, U.S.A.

(Received 9 May 1994; acceptedfor publication 5 October 1994)

Abstrati-A novel method of maintaining a transient cyclic steady state in a fixed bed tubular reactor is
examined. This process, the simulatedmoving bed chemical reactor, utilizesthe differencesin the thermal
and mass velocities of the system to maintain autothermal behavior within the reactor. This system can
process low calorific fuels and low temperature feed streams, is insensitive to minor disturbances, and
distributes the load evenly over all rhe catalyst in the bed. This work presents, for the first time, theoretical
resultsconcerning the operation of these systems. Both irreversibleand reversiblereactions are considered,
and comparisons are drawn betweenthe new process and the reverse flow reactor.

INTRODUCTION Operation of the simulated moving bed chemical

It is well known that dynamic operation can improve
the conversion and selectivity of chemical reactors.
Boreskov and Matros (1983) demonstrated that ben-
eficial transient operation can result when the gas feed
direction is periodically switched in heterogeneous
gas-solid tubular reactors. This system, the reverse
flow reactor, utilizes the “wrong way” phenomena
and thermal storage capacities of the catalyst bed to
generate autothermal behavior. Flow reversal is, how-
ever, not the only way to utilize these phenomena
(Matros, 1989). Matros has explored several other
methods of accomplishing sustained dynamic beha-
vior, which include configurations he called “the
rocker”, “the torus”, “the match” and “the wings”.
This paper examines, in more detail, “the torus”
scheme. This process, which the authors call either
the simulated moving bed chemical reactor or the
ring reactor, also uses the thermal storage capabil-
ities of the catalyst bed and the “wrong way” beha-
vior to maintain a favorable dynamic state.
Figure 1 shows a diagram of the simulated moving
bed reactor and illustrates its mechanical operation
for exothermic systems. To ignite the system, the
first reactor bed is preheated to a temperature where
the reaction rate is significant. By introducing a cold
reactant feed gas, a “wrong way” effect (Boreskov
and Slinko, 1965; Pinjala et al., 1988) is generated
and a temperature front with a high maximum tem-
perature develops. This temperature front moves
down the length of the first reactor bed and would
exit the system if no other measures were taken. In
this case, the reactor would extinguish. Reverse flow
operation prevents extinction by reversing the feed
direction before the front exits the reactor. On the
other hand, in the simulated moving bed reactor,
the temperature front is maintained by chasing it
around a ring of at least two reactors.
‘To whom correspondence should be addressed.
reactor can be separated into two phases. In the first
phase, the exit of the first reactor bed is connected
through a series of insulated pipes to the inlet of a
second reactor bed. This configuration is shown in
Fig. 1. Consequently, the exit gas of the first reactor
is used to preheat the second reactor bed. When the
temperature front passes out of the first reactor and
into the second reactor, the inlet to the system is
changed from the first bed to the second bed. At the
same point, the outlet of the second reactor is con-
nected to the inlet of the first reactor. This initiates the
second phase of the system and is demonstrated in
Fig. 1. In phase 2, the exit gas of the second reactor
is now used to reheat the first bed. When the tempera-
ture front exits the second reactor, the system is
switched back to the phase 1 configuration and the
whole cycle is repeated.
The simulated moving bed chemical reactor is an
addition to a growing class of processes that profits
from the differences in two wave velocities. In adia-
batic fixed bed reactors, the differences between the
speed of the thermal and mass waves are utilized to
generate autothermal behavior. In chromatographic
reactor systems, the differences in the speed of the
adsorption isotherms of the reactants and products
are utilized to achieve separation of the species and
to favor equilibrium conversion. A stable cyclic
steady state can be maintained by either reversing
the flow or simulating a moving bed. Thus, four dis-
tinct areas exist, which combine one of the two meth-
ods to accomplish one of the two objectives. The two
most researched systems are the reverse flow reactor
(Matros, 1989), which uses flow reversals to generate
autothermal behavior, and the simulated moving bed
chromatographic reactor (Ray et al., 1994), which
uses a simulated moving bed for chromatographic
separation. Recently, it was demonstrated that
reverse flow operation can be exploited for chromato-
graphic separation (Agar and Ruppel, 1988). Finally,

5465
5466 THOMAS N. HAYNES and HUGO S. CARAM

Insulation Insulation

Fig. 1. Switching mechanism of simulated moving bed reactor

the present paper examines using a simulated moving
bed for maintaining autothermal behavior.
MODELING
For the purposes of this study, a reduced version of
the homogeneous, or one-phase, model given by
Eigenberger and Nieken (1988) will be used. The
homogeneous model considers the gas and solid
phase to be at the same temperature. In addition,
the mass accumulation term of the mass balance is
neglected, axial mass dispersion is ignored, and all
parameters are considered to be constant. For an
adiabatic plug flow reactor, the mass balance can be
expressed as
where i = 1 indicates the first reactor and i = 2 indi-
cates the second reactor. The corresponding energy
balance is
6’Ti d’ Ti
Pb$b x = xs - “&P&g !?Y!
aZ
For eq. (2), the boundary conditions are the standard
Danckwert’s boundary conditions, except that the
feed temperature to each reactor is alternated
between the system feed temperature and the outlet
temperature of the other reactor. The complete set of
boundary conditions for each phase are:
Note that, although this model formulation allows for
variable lengths of each section of the ring reactor, we
will limit our focus to systems to where all the reactor
beds are identical (Li = L). Parameters for this model,
which describe the processing of a possible dilute
waste gas stream of volatile organic compounds, can
be found in Eigenberger and Nieken (1988). The
model parameters are reproduced in Table 1 and are
distinguished by a low adiabatic temperature rise of
50K.
Equations (1 j-(7) are integrated numerically using
a modified finite-difference method (Haynes et al.,
1992). The method represents the stiff linear portions
of the energy balance implicitly and the nonlinear
reaction rate explicitly. This introduces stability to
the solution, but avoids the requirement of a non-
(1) linear equation solver. The resulting set of equations
can be quickly solved for each time step by using a
slightly modified tri-diagonal matrix solver.
To insure ignition, a uniform high temperature
profile was chosen as the initial conditions for the
calculations. The reactor is now simulated until the
+ E(-AI%)r(Xi, 7-f) switching time is reached, at which point the bound-
ary conditions are switched to reflect the movement of
(2) the inlet and outlet of the gas stream. If the switching
continues long enough, a stable cyclic steady state is
approached, which satisfies
U(z, t) = U(z, c + 2t.y) (8)
It is convenient to define a pseudo-solids flow velo-
city of a system of N similar length beds (Li = L) as

Phase 1: Phase 2:

Xl(O,f) = 0 X1(0, t) = Xz(J52, t) (3)

x2 (0, t) = XI (G 17) X*(0,2) = 0 (4)

A- = vcpgcpg(Tl(O,r) - x dTl(O, t)
To) ~ = w~c~#I(O, t) ~ lz(L2, I)] (5)
az

A- = vq+cpg[T2(0, t) - T, (151,t)] AaT2(o,

~
a2
4
= YFP~c~~(T~(O,t) - 7-O) (6)

aq(G, 1) = o
t3Z
(7)
 The simulated moving bed chemical reactor 5467

Table 1. Parameters for the combustion of trace amounts of
volatile organic compounds in waste gas streams
0.121 mol/m3 206,000 J/mol
G (-AH)
66,512 J/m01 0.8
k” 29,732 s-’ ;, 2.06J/msK
L” 0.5m PhC&lb 2.0 x lo6 J/m3 K
T” 293 K P&G? 500 J/m3 K
” 1 mjs
3 = L/t*
where the switching time, ts, is constant for all beds.
This term is equivalent to the discretized solids velo-
city that is observed by a moving frame of reference
fixed at the temperature front. If the pseudo-solids
velocity is kept constant as the number of beds
approaches infinity, then the model will reduce to
that of a moving bed reactor which recycles the solids.
Directly related to the pseudo-solids velocity is the
net convective strength (NCS) of the system. The
NCS is a direct measure of the strength of the convec-
tion processes in the reactor and is given by
NCS = &CpsVc - &C,,bi
The value of (NCS)A T will give the flow sensible heat
between two points in the reactor which have tem-
perature difference AT. When the NCS is positive
(negative), then the heat capacity of the gas is larger
(smaller) than the heat capacity of the flow of solids,
and there will be a convective flow of energy in the
positive (negative) direction. Note that by proper
choice of the cycle time, and hence pseudo-solids
velocity, it is always possible to set NCS = 0. This is
the “convectionless” case.
IRREVERSIBLE REACTIONS
An important potential application of this technol-
ogy is the combustion of trace amounts of volatile
organic compounds in waste gas streams. This sys-
tem can be modeled using a simple, irreversible,
first-order reaction A -+ B. In this case, the reaction
rate for the model is r(X, T) = qk,eeRjRT( 1 - x).
For the parameters given in Table 1, the cyclic
steady state of the two bed “convectionless” ring
reactor is shown in Fig. 2. Since the two reactors are
identical and at cyclic steady state, both reactors see
the same set of temperature profiles, except for a
time delay equal to the switching time,
T1 (z, t) = Tz(z, t + tJ. A consequence of this beha-
vior is that, in the future, only one reactor bed need
be presented to fully explain the cyclic steady state.
The cyclic steady state shows several notable char-
acteristics (Matros, 1989). First, even though the gas
velocity is relatively high (= 1 m/s), the propagation
speed of the temperature profile is of the order of
1 mm/s. Thus, a large amount of gas can be processed
before switching is required. Second, the maximum
temperature of the reactor is high (1167 K) despite
the fact that the feed temperature is low (293 K) and
the adiabatic temperature rise is small (50K). Third,
part of the catalyst bed is used to preheat the feed and
(9) cool the effluent, which may eliminate some or all of
the need for external heat exchange.
An additional and important property, which has
not been previously mentioned, is also apparent from
Fig. 2. The temperature and conversion profiles show
that the reaction occurs within a relatively narrow
zone when compared to the overall reactor length.
This zone migrates throughout the entire length of
the reactor, which means that all of the catalyst will
be utilized uniformly. This feature is not present in
either the steady state or reverse flow reactor. Since
the thermal wave also propagates throughout the
entire body of the reactor, the “temperature load”
(10) of the ring reactor will also be more evenly distribu-
ted.
Comparison with the reverseflow reactor
There are two main processes which should be
examined as alternatives to the ring reactor: the
steady state system and the reverse flow reactor.
The ring reactor, and the reverse flow reactor for
that matter, utilize the available energy of reaction
more efficiently than the steady state system. Since
in the present case AT& = 50 K, ignition and reac-
tion could not be accomplished in a steady state sys-
tem, unless an external heat exchange system was also
considered along with the reactor. Therefore, a
simple and direct comparison against a steady state
system is not possible with the present case.
It is proper to compare the ring reactor with the
reverse flow reactor. Table 2 shows the results of the
calculations. The comparison was accomplished by
designing a “convectionless” ring reactor to achieve
99% average conversion with a AT,, of SOK. This
gave a total reactor length for both beds of 1.056m
and a switching time of 528 s. A reverse flow reactor
was then designed to produce an average of 99%
conversion with AT,,d = 50K and a cycle time of
528s. By equating the cycle time of the two pro-
cesses, variations in the switching losses can be kept
to a minimum. Notice that, at the beginning of phase

Table 2. Comparison between the reverse flow reactor and the ring reactor for an irreversible system

Length (m) Maximum Average Adiabatic Average Maximum load Cycle time
temperature temperature temperature conversion (mol/m3 s) (s)
(K) (K) rise (K) W)

Reverse flow reactor 0.902 1165.6 594.3 50 99 0.237 1056

Ring reactor 1.056 1175.9 583.8 50 99 0.116 1056
5468 THOMASN. HAYNES and HUGO S. CARAM

Fig. 2. Cyclic steady state of a simulated moving bed reactor.

- Simulated Moving Bed

120@
Chemical Reactor --. .
I _..*
(L = 1.056 m) / ‘.
; “;
,OOO- ._.......... f:
Reverse Flow Reactor
:’ ‘.
(L = 0.902 111) /\ ‘:,
Z

200!~,!~~,> 1,,,,,,,,,,,,,1,,,,,,,,,,,,,,,,,,,,1,,,1,,,,,

0 I). I 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Length (m)

Fig. 3. Temperature profiles in the reverse flow reactor and the ring reactor for an irreversible system. Both reactors provide
99% time-averaged conversion for a system with a AT,, = 50 K.

2 (l), the unreacted material accumulated in bed 1 (2)
will be swept out of the reactor.
Figure 3 shows a comparison of the two tempera-
ture profiles just prior to switching. There is a striking
resemblance between the temperature profiles in each
case. The main difference occurs because a longer tail
section of the reactor temperature profile is required
to keep the ring reactor stable. This is the main cause
of the extra reactor length that is necessary for opera-
tion with the simulated moving bed chemical reactor
 The simulatedmoving bed chemicalreactor 5469

and may represent a significant disadvantage of using
a ring reactor.
Evaluation of the performance of the two reactors
just based on length considerations is somewhat mis-
leading. The load of the catalyst can be defined as
y(z) = i ‘=Y=
r[X(z, a), T(r, (r)] dcl
(11)
tcyc J0
and can be important for comparison purposes. It is
especially important in systems where the catalyst
deactivation is a direct function of the load on the
catalyst. As can be observed from Fig. 4, the catalyst
load distribution for the ring reactor is nearly con-
stant except for a small end effect region. In addi-
tion, the load on the reverse flow reactor is much
less evenly distributed, and the maximum load in
the reverse flow reactor is much higher than that of
the ring reactor. Therefore, one would expect the
catalyst to deactivate more rapidly and more
unevenly in the reverse flow system than in the ring
system. This extended catalyst life may offset the cost
of the longer beds of the ring reactor, and will make
the ring reactor more comparable to the reverse flow
reactor. Further investigation and experimental
efforts are required for further evaluation of this
property.
Influence of the net convection
Figure 5 shows the influence of the pseudo-solids
velocity on the form of the cyclic steady state tem-
perature profiles. All bed lengths for the simulation
were 0.5m each, and the cycle time was varied to
obtain the desired pseudo-solids velocity. Curve B
of the figure shows the temperature profile which
was presented previously in Fig. 2. This is the case
where NCS = 0 and is the “convectionless” case.
For curve B, the reaction zone is located fairly close
to the inlet of the system when the inlet/outlet switch
occurs. This can lead to excessive energy losses and
can be eliminated by allowing for a slight convective
driving force. This is demonstrated in curves C and D
which show the cases where the NCS is 8 and 15.2 J/
m’s K respectively. In these cases, the small amount of
convective flux shifts the reaction zone deeper into the
reactor, which leads to lower energy losses and higher
temperatures. Too much net convection will even-
tually lead to serious convective heat losses and
would extinguish the system. The figure also shows
the case where the NCS is -4 J/m%K which means
that the net convection is in the negative direction. As
the figure shows, this quickly leads to lower tempcra-
tures and poorer performance.
The maximum temperature as a function of the
pseudo-solids velocity is shown in Fig. 6. The figure
also shows that the window of operation where igni-
tion can be maintained is relatively narrow and is
about 29s. This is in direct contrast to the reverse
flow reactor where the available window of opera-
tion of cycle times is much larger (w 500s;
Eigenberger and Nieken, 1988). In the reverse flow
reactor, this large window occurs because the equiva-
lent net convective strength is always zero and is not a
function of cycle time. Since the window of operation
is narrow, operation of the ring reactor will require
precise switching. However, if the control system has
the ability to make these precise switches, then the
cycle time can be. used to affect the shape of the
profile, which is not as easily done in a reverse flow
reactor.
REVERSIBLE REACTIONS
The important potential applications of both the
reverse flow reactor and the ring reactor are revers-
ible exothermic reaction systems which often have low

Reverse Flow Reactor

(L = 0.902 m)

Simulated Moving Bed

Chemical Reactor
(L = 1.056 m)

Length (m)
Fig. 4. The time-averagedcatalystload in each system.
5470 THOMAS
N. HAYNESand Huoo S. CARAM

Reactor 1 Profiles

Fig. 5. Influence of the pseudo-solids velocity upon the temperature profiles of the cyclic steady state. A, NCS = -4
J/m2 s K; B, NCS = 0; C, NCS = 8 J/m2 s K, D, NCS = 15.2 J/m2 s K.

“Convectionless” ;
Cafe w

Window of
Operation
29 Seconds

n
Pseudo-Solid Velocity (mm/s)
Fig. 6. The available window of operation.

adiabatic temperature rises. This includes the oxida-
tion of sulfur dioxide, the production of methanol, the
Claus process to produce elementary sulfur, and
ammonia synthesis. For the sake of generality, this
work only considers the simple A +P B reaction with
first-order kinetics [r(X, T) = k,qe-E’RT( 1 - x)-
/c,Pae-e’RT( q/c + X)] . Hypothetical parameters
for this system are available (Levenspiel, 1989) and
are presented in Table 3.
The conversion and temperature profiles for a ring
reactor and a reverse flow reactor of equal lengths are
presented in Fig. 7. In the case of the reversible sys-
tem, the ring reactor now begins to give higher con-
versions than the reverse flow reactor for the same
length reactor. In the example chosen, the time-aver-
aged outlet conversion for the ring reactor is 67.9%
and for the reverse flow reactor is 66.2%. The better
performance that is achieved in the ring reactor for
reversible systems can be attributed to the long tail
section of the temperature profile. The reaction will
come very close to equilibrium at the maximum tem-
perature of both systems. Then, as the temperature
drops along the trailing edge of the profile, an extra
push in conversion is obtained. In the reverse flow
reactor, the trailing edge profile is very steep and
the reactor rapidly becomes kinetically limited. On
 The simulated moving bed chemical reactor
I

Fig. 7. Cyclic steady states of the reverse flow and ring reactor for a reversible system.

tlet Conversion

600 700 800 900

Temperature (K)
Fig. 8. The trajectories of the reverse flow and ring reactor in the temperature conversion phase plane

Table 3. Parameters for the generic reversible reaction graph, the extra conversion is obtained. Notice that
both trajectories approximate the optimal trajectory
G 1 mol/m3 TO 293 K
0 mol/m3 1 m/s profile.
c;:
E 83,700 J/mol ;-/AH) 80,000 J/mol
167,400 J/m01 0.4
2 1.0966x lo6 1/s : 4.5 J/m s K CONCLUSIONS
k: 6.566 x 1O’Ol/s 1,328 J/m3K
PbCPb
The simulated moving bed chemical reactor is pri-
L 0.6m P.?CPR 1.0 x IO6J/m3K
marily applicable for mildly exothermic reaction sys-
tems and, therefore, can be considered an alternative
the other hand, the ring reactor shows a long smooth to the reverse flow reactor. Applications include, but
trailing edge and allows for higher conversion. The are not limited to, the combustion of volatile organic
conversion profiles in Fig. 7 show this behavior. compounds, the oxidation of sulfur dioxide, the pro-
This extra push in conversion can be better under- duction of methanol, the Claus process to produce
stood by examining the temperature conversion phase elementary sulfur, and ammonia synthesis. In gen-
plane in Fig. 8. Shown on the figure is the equilibrium eral, the reactor will favor reactions requiring high
restriction of the reaction, along with the optimal temperatures to enhance the reaction rate and lower
reactor trajectory. For both the systems, the system exit temperatures for high equilibrium outlet conver-
quickly approaches the equilibrium restriction sion. It is especially effective for low heating value
around 900 K. When the trailing edge of the tempera- mixtures, since it also provides a simple, inexpensive
ture profile is reached and the temperature drops, the and highly efficient integrated heat recovery system.
equilibrium restriction is relaxed. Under these circum- The major advantages of the simulated moving bed
stances, which occur after the “pinch point” in the reactor system are its autothermal behavior and its
5472 THOMASN. HAYNESand HUGO S. CARAM

nearly uniform catalyst utilization. It is, however, a Greek letters

very complex dynamic multibed system. There is only y time-averaged catalyst load, mol/m3s
a small window of cycle times in which the reactor can (-AH) heat of reaction, J/mol
maintain ignition. In addition, the reactor is less AT*,j (-AH)~/P,%E
stable than the reverse flow reactor and requires void fraction
longer beds in the irreversible reaction rate case. thermal axial dispersion, J/Km s
bulk density of catalyst bed, kg/m3
NOTATION density of gas stream, kg/m3
catalyst bed heat capacity, J/kg K
reactant gas heat capacity, J/kg K
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