Chemical Engineering and Processing, 32 (1993) 233-244 233

Dynamic modelling of industrial SO, oxidation reactors.

Part II. Model of a reverse-flow reactor

K. Gosiewski
Institute of Inorganic Chemistry, ul. Sowiliskiego 11, 44-101 GIiwice (Poland)

(Received January 27, 1993)

Abstract

This paper presents the results of a computer simulation of a reverse-flow reactor. The results are compared with
experimental data quoted by other workers. The necessity to take into account gas-to-catalyst heat transfer is
stressed, so that quantitatively correct predictions may he obtained using the model. A brief description is given of
the way flow reversal has been incorporated in the model, and the possibility of the accumulation of errors occurring
during the calculations is mentioned. It is shown that the one-dimensional heterogeneous model of the bed makes
it possible to analyze the process with an accuracy sufficient for the preliminary selection of the parameters of the
reactor, whereas the homogeneous model leads to discrepancies which are too high. An analysis of the parametric
sensitivity of the model enables the formulation of practical conclusions concerning the design of such reactors.

Introduction 1. Reactors with periodically forced changes in the inlet

In Part I [la] of this series, equations have been
presented for a model involving a single pass of the
catalytic SOZ oxidation reactor with a fixed bed. Next,
verification of the model was given on the basis of a
comparison between the simulated and actual transients,
both for a single pass and for a whole SO, oxidation unit.
In reactors for stationary SO1 oxidation, the dynamic
states only occur in certain special cases and are there-
fore only of marginal importance in process engineer-
ing. Such states include the various cases involved in
the start-up of these installations (cf. Part I). Other
dynamic states which may be of interest in an analysis
of the process result from the reaction of industrial
metallurgical installations to the time-dependent oper-
ating conditions. This concerns, in particular, the reac-
tion of the process to the drop in concentration of SOZ
in the process gas which frequently occurs when the
oxidation unit cooperates with copper smelter convert-
ers. These cases are, however, similar to the ‘hot’ start-
ups discussed in detail in Part I.
A separate problem is that of a reactor operating under
a continuously forced non-stationary state. Analyses of
such set-ups, and especially their design, require some
reliable tools to describe their dynamics. In this case, the
dynamic states are no longer just an episode in the
operation of the installation, but constitute the normal
operating regime. Reactors operating under conditions
of forced non-stationary state conditions may be roughly
sub-divided into the following groups:
stream parameters (most often the reactant concen-
trations, but also pressures and temperatures).
2. Reactors with periodical changes in the direction of
flow through the bed, the so-called ‘reverse-flow
reactors’.
The literature concerning this problem is extensive.
Thus, even in 1984, a review paper by Renken [ lb]
provided a long list of references. Apparently, the
above two groups of reactors involve similar phenom-
ena, the former being mainly concerned with non-
stationary catalysis. To describe this properly, it is
necessary to analyze the phenomena occurring on a
microscale in a single pellet. However, as shown in the
literature, the improvement in the extent of conversion
achieved by the whole reactor in this group does not
usually exceed a few per cent. Some cases are also
mentioned where the overall effect may even be nega-
tive. Despite a number of references (see review article
[lb]), this mode of operation has not led to any serious
industrial applications.
The other group (reverse-flow reactors with numer-
ous industrial applications - cf. Matros [2,3c, 4,5],
Wojciechowski et al. [6, 71) includes apparatus in which
the direction of flow is periodically reversed. Such
arrangements involve the combination of a reactor and
a heat regenerator. A ‘cycle’ in such reverse-flow reac-
tors corresponds to the time during which the reaction
medium flows through the reactor in both directions.
The time of flow in one direction is called a ‘half-cycle’.

02552701/93/$6.00 0 1993 - Elsevier Sequoia. All rights reserved

234
Hence, it is a reactor involving an internal autothermal
recovery of heat along its regeneration path. This is the
classification which has been most frequently used in
recent publications (see, for example, Eigenberger and
Nieken [ 81, Matros [ 3c] and Froment [3b]).
Froment [3b] claims that dynamic surface phenom-
ena are not of crucial importance if the reversal cycle is
longer than 20 min. From a number of theoretical
studies and experiments performed in actual reactors by
Matros et al. [2, 3c, 4, 51, it has been shown that this
condition is usually fulfilled in the oxidation of SOa,
even with low SO2 concentrations in the inlet gas. The
important results obtained with such reactors arise
from the heat of reaction generated, coupled with heat
accumulation inside and heat transport within the bed.
At low reactant concentration, the reactor may be even
treated roughly as an ordinary heat regenerator
(Gosiewski and Sztaba [ 3d]). Thus, the model described
in Part I may be useful in analyzing phenomena taking
place in a reverse-flow reactor. Similar models, al-
though sometimes differing in important details, have
been employed by authors dealing with the mathemati-
cal description of such reactors (see, for example, refs.
2, 3b, c, e, 4, 5 and S-13).
Indeed the problem has been discussed in a large
number of papers, far outnumbering those concerned
with the start-up simulation investigated earlier. Thus,
the question arises whether it is worthwhile to carry out
an analysis of this problem. It appears that of the
numerous authors cited, only Eigenberger and Nieken
[8] have made any serious attempt to investigate the
effect of the model pafametet-s on the temperature and
conversion profiles along the bed in a systematic man-
ner. Their studies were restricted, however, to a homo-
geneous model. In what follows it will be shown that
the effect of the gas-to-catalyst heat transfer is most
important and should not be nbglected.
The object of the simuJations described in subsequent
sections of this paper is to determine the extent to
which the description, of the bed may be simplified
in modelling reverse-flow reactors. In the design of
such reactors for strongly exothermal reactions (e.g
the oxidation of SOZ), it is crucial to select reactor
parameters in such a way that values of the maximum
temperature, r,, , which are too high are avoided.
This problem has been discussed at length by Matros
(see, for example, ref. 2). In the interpretation of the
effect of the model parameters on the value of T,,,,,
insufficient attention appears to have been paid to the
intensity of the gas-to-pellet heat transfer. Matros [2]
has pointed frequently to the effect of the axial conduc-
tion of heat in the bed on. the value of T,,;, but has
neglected the even more important dependence on gas-
to-pellet heat transfer. The ‘possibility of influencing
T max and, consequently, the average conversion in the
reactor, by an appropriate choice of model parameters
(and also, of the reactor parameters) will be dealt
with when the parametric sensitivity of the model is
analyzed.
In a similar fashion to the simulation of the dynamic
states involved in the start-ups of SO, oxidation units,
the intention was to compare the present simulation
results with experimental data obtained in an industrial
reactor. However, a principal difficulty was the lack of
any experimental data of our own. A large number of
such data are given, however, in articles based on work
undertaken in the Institute of Catalysis at Novosibirsk,
e.g. refs. 2, 3a and 15, and concern both laboratory
experiments, pilot-plant tests (at a flow rate of c.
3000 SCM h-l) and several large-scale industrial instal-
lations with flow rates of 30 000-40 000 SCM h-’ [3a].
Hence, it was decided to use the data cited in the above
publications in testing our model. Unfortunately, for
the industrial reactors, it turned out that the number of
numerical parameters (e.g. the geometry of the reactors,
the volume of catalyst) was too small to justify any
serious model calculations. However, the laboratory [2]
and pilot-plant [3a, 151 experiments were described in
much greater detail and could therefore be employed in
simulated testings of the model.
Discussion of the model of the reverse-flow
reactor employed
General description of the model
For the purpose of numerical analysis, a mathemati-
cal model has been formulated which would make it
possible to simulate all of the variants of such a reactor
which are employed practically. The block diagram of a
‘generalized’ reverse-flow reactor is shown in Fig. 1.
The diagram contains four fixed-bed passes; heat ex-
change occurs in the middle of the reaction zone. Two
passes (the first and the last) may be packed with the
inert bed and act as heat regenerators. The middle
passes (2 and 3) are packed with the catalyst and form
the active zone of the reactor.
Heat transfer may be produced by the supply of heat
(heating the reacting medium) for very low concentra-
tions of reactants, or by the withdrawal of heat (cooling)
for moderately high concentrations. For intermediate
concentration values, when there is no heat exchanger,
the model assumes zero heat exchange in the middle of
the bed.
The block diagram of the model presented in Fig. 1
provides a particular generalization which makes it
possible to evaluate a reverse-flow reactor for all possi-
ble variants, i.e. both ‘with’ and ‘without’ the inert bed
at the reactor inlet and outlet, and also ‘with’ or
‘without’ cooling or heating in the middle of the bed.
 235

4 For t = 0:

&
v
1
Tk(X, 0) = T,(x, 0) = f(x) (4)
PASS 1
and to the simplified boundary conditions:
For x=0:

+=(I-&).a.[T,(O,t)-T,.] (5)

T.(O, t) = T@(t) and ~(0, t) = co(t) (6)

For x = L:
82-k
-_=O \ ,
ax
Some authors (see, for example, Eigenberger and
Nieken [Xl) use a homogeneous model to describe the
reverse-flow reactor. Thus, in order to assess the effect
of this simplification the following simplified form of
Fig. 1. Generalized block diagram of the model of a reverse-flow the differential heat balance was tested.
reactor. It was assumed that:
T(x, t) = T*(x, t) = Tk(X, t)
Model of the bed (catalyst or inert)
and consequently eqn. (8) was substituted for eqns. (1)
As a dynamic description of the bed, the heteroge-
and (2) in the model:
neous model has been employed (cf. Part I). The model
has been supplemented, however, with an additional
term allowing for the heat loss from the catalyst to the
surroundings. The introduction of this term arises from
The boundary conditions for this simplification as-
the fact that the simulations were also of concern to a
sume the following form:
small-scale laboratory reactor. Whereas in industrial or
even pilot reactors with diameters of several meters this For x = 0:
loss may be neglected, for the laboratory reactor de- and ~(0, t) = c,,(t)
T(0, t) = T,,(t) (9)
scribed by Matros [2] reliable results could not be
obtained unless the heat losses through the wall were For x = L:
taken into account. dT
For the sake of simplicity, it was assumed that heat -_=O (10)
ax
transfer to the environment occurs only from the cata-
lyst. The inclusion of such heat losses in the gas-phase with the initial condition:
heat balance has no appreciable effect on the numerical For t = 0:
results. The term which relates to heat transfer with the
surroundings [bold type in eqn. (2)] is the only modifi- T(x) = f(x) (11)
cation made with respect to the model discussed in Part The model for an inert bed differs from that for an
I of this series.
active (catalytic) bed only in the value of the reaction
rate, r, which is set equal to zero in the former case.
n,.C~.~+a.S.(T,-_T,)=O (1) The discussion of an expression describing the reac-
tion rate has been given in Part I of this series.
3%
e.---P,.C,.~+~.S.(7,-T,)+H.r.p,+
a

ax*
Model of interpass heat exchange
-2 .(Tk_ *.> =o
The interpass heat exchange is modelled as the with-
.ac+r.p,=o
ngax
drawal of a given amount of heat in a counter-current
heat exchanger disregarding the dynamics (this ap-
Equations (1) -( 3) are subject to the following initial proach is employed in the simulations described in later
conditions: sections of this paper). This amount can also be given
236
a priori in the model (options) as the temperature or
enthalpy difference between the stream leaving pass 2
and that entering pass 3.
The reactor bed has a much larger heat capacity than
a (usually small) heat exchanger or even the electric
heater used by Wojciechowski [7] in his reactors for the
catalytic combustion of organic substances. This may
provide the justification for neglecting the dynamics of
the heat exchanger in the model of the overall reactor,
in contrast to the approach employed in discussing the
start-ups of the SO, oxidation unit. An additional
argument for assuming cooling without any analysis of
the thermal dynamics of the heat exchanger is the lack
in the references mentioned (e.g. refs. 2 and 15) of any
data which could serve as a basis for evaluating the
dynamics of the heat exchanger.
Numerical method of solution of the overall model;
incorporation of flow reversal
For the simultaneous solution of the equations de-
scribing the overall model, the same numerical method
was employed as that used in the dynamic flowsheeting
system DYNAM outlined briefly in the previous part of
this series.
The essential modification in the model for the whole
reactor compared with the original DYNAM simulator
consists in taking the flow reversal into account. This
modification has already been introduced at the level of
the numerical model, which is based on difference equa-
tions and on a numerical formulation of the initial
conditions [eqn. (4)].
From the numerical point of view, flow reversal
constitutes a special case of discontinuity in the initial
and boundary conditions and requires inversion in the
direction of their integration. To simplify the numerical
procedure the reversal is modelled by “turning the
reactor upside down”, with the directions of flow and
integration kept unchanged. Also, the numbering of
passes in the model is reversed, as they are always
numbered along the direction of flow.
Such modelling of flow reversal requires:
1. Inversion of the ‘states’ of the passes at the moment
of reversal (matrix STATE 1). If the states of the passes
are determined unequivocally by the temperature
profile along a pass, this operation rewrites the temper-
atures calculated at the end of the preceding half-cycle
(new initial conditions) according to the following for-
mula:
T,(5 - i,j) = Tk(i, n -j + 1) (12)
where:
i = number of pass
i = actual number of mesh point along pass
n = total number of mesh points.
2. Rewriting the parameter matrices (PAR) describing
the passes according to the following formula:
PAR( 5 - i) = PAR(i) (13)
3. Rewriting the matrices of the parameters of the
streams (STREAM 1) for streams 2-6 at the moment
of reversal (new boundary conditions), according to:
STREAM l(m) = STREAM l( 7 - m) (14)
where:
m = number of stream (2 to 6)
Following the “turning” of the reactor, the number-
ing of the passes and streams is changed, while the
direction of integration is apparently unchanged.
Particular numerical properties of the reverse--ow
reactor
The “turning” of the reactor described in the foregoing
section introduces a particular positive feedback into the
numerical calculations. The feedback arises from the fact
that the parameters of the streams, as calculated at the
end of the preceding half-cycle, are always burdened with
a certain calculational error 6. This error is a sum of a
numerical error a,,, and a model error dmodwhich result,
for example, from all the necessary simplifications in-
volved in the mathematical description. The error may
be expressed by the following sum:
@,i=6i,i num + G&i (IS)
where
j = generalized number of parameter (in stream or at
a mesh point in the bed)
i = number of mesh point along the bed
In models without flow reversal, such as those for
unsteady states during start-ups of the SO, oxidation
plant, these errors would simply add to the final error
of simulation. The situation for models for reverse-flow
reactors is, however, different. At the moment of rever-
sal, these errors distort both the initial conditions [eqn.
(12)] and the boundary conditions [eqn. (14)] for the
next half-cycle of calculations.
This phenomenon is a numerical positive feedback,
and although it does not necessarily lead to the instabil-
ity of the method, it may result in much higher para-
metric sensitivity of the model, since the errors in the
subsequent computational cycles accumulate, in a simi-
lar fashion to the accumulation of heat in the reactor,
producing a so called ‘heat wave’.
These phenomena may be responsible for (amongst
other things) differences in the numerical results depend-
ing on the initial temperature profile along the reactor,
and thus, the number of cycles necessary to reach a state
in which the profiles for two consecutive cycles do not
differ from each other (this state will subsequently

be called a ‘quasi-stationary’ state). Consequently, the
numerical accuracy of the mathematical models of the
bed employed in describing a reverse-flow reactor has to
be higher than in modelling other unsteady states where
the above feedback does not occur. A similar accumula-
tion of numerical errors has been observed in simulating
unsteady states for metallurgical installations containing
two external loops of autothermal heat recovery, and
thus positive feedback loops as well.
‘Quasi-stationary’ state and a test for the consistency
of heat balance
Despite the fact that the reactor operates in a contin-
uously forced non-stationary state, the arbitrarily as-
sumed initial condition of eqn. (4) leads, after some
time, to the reactor operating in a state which may be
called ‘quasi-stationary’. This state arises when the
transients in consecutive cycles do not differ from one
another. Such a definition has been assumed by Eigen-
berger and Nieken [8], for example, who called this
state ‘stationary’. Although the definition seems quite
obvious, the name ‘quasi-stationary’ appears to be
more appropriate as the system is permanently dis-
turbed by the reversal of flow.
The approach to the quasi-stationary state from an
arbitrarily assumed initial state requires a large number
of cycles. This number depends on how much the
assumed initial temperature profile differs from that at
the beginning of a cycle in the quasi-stationary state. In
the simulations performed, this number varied from
several to c. 20 cycles. The stability of the method may
be tested by checking whether substantially different
initial states lead to the same quasi-stationary state. This
is a basic test for the numerical method employed. If a
considerable accumulation of the processing errors actu-
ally occurred, the result for the final quasi-stationary state
would depend strongly on the number of the cycles neces-
sary to attain this state. After the details of the model
had been perfected, no such phenomenon was found in
the simulations performed. This, however, is simply a test
of the numerical accuracy of the model and does not
constitute a proof of its physico-chemical correctness.
Another important test for both physico-chemical
and numerical correctness is a procedure which will be
called the ‘heat balance consistency test’. An alternative
definition of the quasi-stationary state is that it is a
state in which the first principle of thermodynamics is
fulfilled or, in other words,’ when the overall heat
balance for the reactor is satisfied during a half-cycle. If
there is no heat loss and/or heat exchange in the middle
of the reactor, this may be written as follows:
* f &I2
Bhb=Arti- ; T,,,(t) - dt - Ti, =0 (16)
( C s > discussed by Eigenberger and Nieken, this problem was
I overcome by applying additional compensation
237
where
c. -H
AT,,=“- * J&v (17)
c,
with the average conversion described as follows:
t+r,/2
x,, = f - X(t) - dt (18)
c s
t
The need to fulfill this condition has been stressed by
Matros [2]; however, he does not seem to have taken it
into account too seriously. In other papers dealing with
reverse-flow reactors, no mention has been made of
the necessity to meet such a requirement by a model
describing a reverse-flow reactor operating in the quasi-
stationary state. The author’s own experience with a
large number of numerical models for these reactors
suggests that the rigorous fulfillment of this condition is
extremely difficult due to the accumulation of the nu-
merical errors mentioned earlier. Computational prac-
tice shows that if S,, is less than 10% of AT,,, the
numerical results provided by the model may form a
sound basis for a discussion concerning the heat bal-
ance of the reactor. If, however, this value increases to
several tens of per cent, any model-based conclusions
have to be treated with caution. It must be pointed out
that a,,,, is, in a sense, a measure of the amount of ‘false’
heat which accumulates in the model due to the accumu-
lation of errors inherent in the model and/or numerical
errors [see eqn. ( 15)] rather than because of the physical
regeneration of heat within the bed. If the mathematical
model accumulates more or less heat than the physical
heat balance for the reactor would suggest, then any
attempt at reaching practical conclusions may be risky.
In the simulations discussed below, the error 6,,, in
most cases, did not exceed a few per cent of ATad.
Simulation results and discussion of the parametric
sensitivity of the model
A detailed discussion of the effect of the various
parameters employed in the model on the temperature
profiles in the quasi-stationary state has been presented
by Eigenberger and Nieken [8]. This effect was investi-
gated using a mathematical model and then compared
with experimental results obtained in a laboratory reac-
tor in which propane and methane underwent combus-
tion on a commercial catalyst to allow purification of
automotive exhaust gases. The reactor was 345 mm in
length and had an internal diameter of 50mm. The
article stressed the problem of the considerable losses of
heat through the walls of such a reactor. In the case
heating
238
through the external wall of the reactor. Good qualita-
tive agreement was obtained between the actual profiles
and those predicted by the model. With respect to the
quantitative agreement, the authors themselves admit-
ted that it was largely dependent on the correct level for
the compensation heating. The reactor operated at rela-
tively short reversal cycles (60-90 s).
As has already been mentioned, a wealth of experi-
mental data obtained in the Institute of Catalysis at
Novosibirsk concerning the oxidation of SO, has been
presented in refs. 2, 3a and 15, to mention only a few.
A particularly large number of the experimental results
obtained in a pilot plant have been reported in the
paper of Bunimovich et af. [3a]; the experimental data
have been compared with theoretical predictions. The
monograph by Matros [2] quotes, however, several
vastly differing models, and it is difficult to guess which
of them was actually employed for comparative pur-
poses in the calculations used by the Novosibirsk
group. From personal discussions with the authors, and
also from some comments presented in ref. 2, it may be
inferred that the majority of the calculations concerning
Tnlax and the degree of conversion were undertaken
using a simplified model assuming a so-called ‘sliding
regime’ in the form of ordinary differential equations.
Such a model, even if it leads to a satisfactory agree-
ment between the parameters mentioned, is incapable
of predicting either the transients or the temperature
and conversion profiles along the bed.
Numerical values of the parameters used in
the simulation
To determine the numerical values of the parameters
employed in the mathematical modelling, it is necessary
to have a certain amount of information concerning
both the experimental reactor and the catalyst used.
The data for the laboratory reactor were taken from
ref. 2, whereas those on the pilot reactor were from refs.
3a and 15. The author’s experience with the static
mathematical models for industrial reactors shows that
a kinetic equation describing the reaction rate over a
given type of commercial vanadium catalyst requires a
certain identifuzation of the equation to kinetic experi-
ments on this particular catalyst [20]. The problem of
the kinetic equation has been briefly discussed in Part I
of this series. For the catalyst described in ref. 3a, no
such data were available. This is certainly a weak point
in the simulations performed. As follows from the
studies, of Eigenberger (cf. ref. 8) and also from the
results presented below, the influence of the catalyst
kinetic parameters is most important; hence, a correct
determination of the reaction rate is essential. In the
calculations, an equation has been assumed and fitted
(identification according to the method given in ref. 20)
to a vanadium catalyst produced by PZChem Lubon in
Poland. For k in Boreskov’s equation in the form
presented in Part I of this series, the following experi-
mental formula (see ref. 20) was applied:
k = K, x exp (-4.95 + 15.0 x tin)
I
In the case discussed, the value of & in formula (19)
was taken as being that for moderately used Polish
catalysts; luckily, sufficient agreement was obtained de-
spite the fact that the experiments cited in ref. 3a were
carried out using an unknown Russian catalyst.
The numerical values of the model parameters are
given in Table 1. The values of GLwere estimated using
the formulae given in refs. 16 and 17, whereas those of
I, were based on refs. 18 and 19.
An analysis of the parametric sensitivity of the model;
a comparison between the heterogeneous and
homog?eous models
In ref. 3a, values have been given of the average
conversion in a cycle X,, and of the maximum temper-
ature T_, for a number of the operating regimes of the
pilot plant. The parameters of this plant have been
described both in refs. 3a and 15. The number of data
presented in these papers is sufficient for the purpose of
mathematical modelling of the process.
To test the model, the operation of the plant was
simulated for an inlet SO, concentration of 3.2%. The
model parameters used in calculations for this variant
are those in Table 1 corresponding to a flow rate of
3000 mz h-’ the variant itself being termed a ‘basic
variant’.
Calculations were undertaken to test the parametric
sensitivity of the model and were carried out neglecting
the heat losses to the surroundings. A comparison with
the experimental values presented in ref. 3a shows,
however, that such losses must have actually occurred
(TM, predicted was higher than the experimental
value). Calculations for the ‘basic variant’ data, but
with heat losses of c. 5% of the overall amount of heat
generated, led to good agreement (h, = 1 W m-i K-l;
T, = 10 “C).
Next a number of parameters which could have a
considerable effect on X,, and T,,,,, were varied sub-
stantially in order to study the parametric sensitivity of
 239

TABLE 1. Numerical values of the basic parameters of the model used in the simulation

Parameter Unit Simulation variable

1.3% so, 3.2% SO, 9.4% so,

Pilot act. [ 151 Laboratory act. [2] Pilot act. [3a] Pilot act. .[ 151

Flow rate m3 h-’ 2500 26 3000 2750

(under standard
conditions)
Inlet gas vol. % SO, 1.3 SO, 3.2 SO, 3.2 SO, 9.4
composition 02 10.0 02 12.5 02 12.5 0, 11.6
N, 88.7 N, 84.3 N* 84.3 N* 79:o
Reactor diameter m 1.55 0.175 2.0 2.8
Total bed height m 3.7 1.3 4.4 2.0
Catalyst pellet size mm cylinders cylinders cylinders cylinders
25 x 50 x 6 8x8x3 25 x 50 x 6 25 x 50 x 6
Heat transfer Wm-2K-’ 78 96 53 78
coefficient, a
Specific surface, S m* m-3 380 500 380 380
Effective conductivity, 1, W mm’ K-’ 1.0 0.5 1.0 0.833
Effective specific heat kJ kg-’ K-’ 3.5 2.5 3.5 3.5
of catalysis, Ck,cff
Bulk density of kg mm3 500 500 500 500
catalyst, p,
Heat of reaction, H kJ kmol-’ K-i 8.89 x IO” 8.89 x 104 8.89 x 104 8.89 x 104
Cycle time, 2, min 30 50 50 60

the model. In addition, simulation was carried out two-fold increase in this coefficient produces a visible
employing the homogeneous model, i.e. that which rise in the maximum temperature T,,,,, and a strong
completely neglects the gas-to-catalyst heat transfer re- drop in the average conversion X,,.
sistance. The results are listed in Table 2. In principle, The omission of the resistance to heat transfer from
they support the conclusions presented by Eigenberger the homogeneous model leads to a considerable dis-
and Nieken [S], especially regarding the effect of the crepancy between the values calculated and those found
reaction rate constant, which is difficult to understand experimentally. Additionally, it has been found that the
on purely intuitive grounds (the lower the value of K,,, homogeneous model is more. sensitive to AC than the
the higher the maximum temperature and the lower the heterogeneous model; thus, I the importance of this
average conversion X,,). An analogous conclusion con- parameter is sometimes over-estimated in cases where
cerns the effect of substituting the inert bed for the inlet the homogeneous model is employed. The predicted
and outlet sections of the active catalytic bed. Substitu- values of the temperature profile for the three different
tion of a certain volume of catalyst with an inert lengths of bed are shown in Fig. 2. For a bed of
material also leads to a substantial increase in T,,,,, and sufficient length, a flat ‘crest’ to the heat wave is formed
a decrease in X,,. Similarly as in ref. 8, a moderate along which no reaction occurs. A change in length
effect has been found for the axial dispersion which, in over a relatively wide range affects only the width of the
the case discussed, is represented by the effective heat heat wave, without any modification in the parameter
conductivity of the bed, 2,. A small influence has also values calculated.
been found for the following parameters: (i) inlet gas In the case studied, it was possible to shorten the bed
temperature, Tin; (ii) heat capacity of the bed (it affects down to c. 25% of the ‘basic’ value, virtually without any
only the velocity of movement of the heat wave; thus, effect on T,,,, and X,,. Further contraction of the bed
for a sufficiently long bed, it does not influence T,, or to 20% of the initial value (without changing the dura-
X,,); (iii) length of the bed (provided it is sufficiently tion of the cycle) led to the reaction being extinguished.
long); and (iv) duration of the cycle (provided it is not The computed conversion profiles along the bed for
too long, otherwise the reaction could be extinguished). the ‘basic variant’ as well as for the bed shortened to
An important conclusion of the analysis is the strong 50% and 25% are shown in Fig. 3. The first increase in
effect of the heat-transfer coefficient into the pellets, ~1. conversion is visible in that part of the bed correspond-
This effect has not been discussed either in ref. 8, where ing to the rising segment of the ‘heat wave’, while the
only the homogeneous model was used, or in ref. 2. A second (final) increase corresponds to the declining
240

TABLE 2. Values of X,, and T,, predicted by the model for

various values of the parameters relative to the ‘basic variant’

No. Description of the variant X” (-) T,, ( “C)

Heterogeneous model eqns. (I), (2) and (3)
1 Basic variant 0.92 575 s
‘ii 0.6
2 Basic variant, 0.93 540-560 ;
:
heat losses -5%
8
3 1, = 0 0.91 581 0.4
4 1, = 5 x n,, 0.94 567
=5Wm-‘K-1
0.2
5 Ti:,.= 250 “C 0.92 577
6 K” = 1/2K, 0.86 620
7 C, = 1.0 kJ kg-’ K-’ 0.92 590 0.0
8 L = 1/4L, 0.92 570 xc-1
= 1.1 In 2.2 4.4 L cm

9 a=2xa, 0.88 612 Fig. 3. Calculated conversion profiles along the bed for the ‘basic
=106Wm-2K-’ case’ and for the bed shortened to 50% (L = 2.2 m) and to 25%
10 t, = l/2&, 0.92 575 (L = 1.1 m), at the end of a ‘half cycle’.
= 25 min
11 t, = 2 x t,, 0.92 578
= 100 min Comparison between the predicted temperature profiles
12 inert = 2 x 0.55 m 0.47 737 along the bed and those measured in the laboratory
catal. = 2 x 0.55 m
reactor described in ref. 2
Homogeneous model eqns. (3) and (8) Figure 4 presents a comparison between the tempera-
13 Homogeneous mode1 with 0.84 658 ture profiles along the catalytic bed predicted by the
,&=,I,=1 Wm-‘K-r
14 Homogeneous model with 0.82 687
model [eqns. (l)-(7)] and the experimental profiles
I.= = 0 taken from the monograph of Matros [2]. The profiles
Data after Bunimovich et al. [3a]
shown correspond to three instants during a 50 min
15 Experimental data from 0.93 SO-550 quasi-stationary cycle, i.e. at the beginning of the cycle,
pilot plant at 8 min and at 15 min (cf. the description of the
16 Predicted by the 0.91 580 experiments in ref. 2). The points in Fig. 4 correspond
mathematical model to the measured values redrawn from the graph cited in
ref. 2, the broken line representing the profile calculated
without any losses of heat from the reactor while the
segment. The decreasing temperature allows one to solid line denotes the profiles estimated assuming heat
make use of the advantageous equilibrium conditions losses at an ambient temperature of 20 “C and with
for lower temperatures at the end of the bed, thus
assuring a very high final conversion.

x r-1
0.65 1.3 L un,

Fig. 4. Calculated (solid lines -with heat losses; broken

2.2 4.4 lines - without heat losses) and measured (points after ref. 2)
Fig. 2. Calculated temperature profiles along the bed for the temperature profiles along the bed of a laboratory reactor for
‘basic case’ (L = 4.4 m) and for the bed shortened to 50% 3.2% SO* and t, = 50 min, at the following instants: t = 0 (begin-
(L = 2.2 m) and to 25% (L = 1.1 m). at the end of a ‘half cycle’. ning of a cycle); t = 8 min; and t = 15 min.
 241

TABLE 3. Comparison of the measured conversions with those predicted by the mathematical model

Average Unit Simulation variable

conversion
1.3% so, 3.2% SO, 9.4% so2

Pilot act. [ 151 Laboratory act. [2] Pilot act. [3a] Pilot act. [ 151

Calculated _ 0.968 0.923 0.917 0.918

Measured - 0.95 0.94 0.91 0.896

the reactor-surroundings heat-transfer coefficient, hS,

equal to 3.5 W mm2 K-‘.
In his monograph, Matros [2] quotes heat losses in a
laboratory installation of up to 50%. In the simulation
described in the present paper, the value of the heat-
transfer coefficient, hS, was chosen in such a way that
the value of the maximum temperature, T,,, would be
close to that obtained in a laboratory installation. For
such a value of hS, based on a deviation of the average
increase in temperature in the reactor from AT,,, as
calculated from eqn. (16), it is possible to estimate the
heat losses relative to the overall amount of heat gener-
ated in the system. Such an estimation yields a value of Ol,,.,,.,,,,,,~,,,~,,,,,,,,!,.,. ,,,.0.5 ,,I,, ,,,,0.b ,,,,, -I
0.0 0.1 0.2 0.3 0.4 0.5 oh oh .o x C-J
up to 70% thus exceeding that given in ref. 2 (up to 1.85 3.7 L cm)

50%). This seems to be too high a value, although the Fig. 5. Calculated (lines) and measured (points after ref. 15)
experience with laboratory reactors shows that at small temperature profiles along the bed of a pilot reactor at the instant
reactor diameters, high temperatures and in the pres- of flow reversal (for 1.3% SO2 and t, = 30 min).
ence of a large number of metal elements in the bed
(e.g. thermocouples), these losses may indeed assume I” cl
high values. In addition, these elements strongly distort 800
the ‘theoretical’ temperature profile along the bed. 700
A comparison of the measured conversions with those
simulated in the present work is shown in Table 3. 600

s 500
s
Comparison between the predicted temperature pro$les b
f400
along the bed and those measured in a pilot reactor
I?!
described in refs. 2, 3 and 15 300

As in ref. 2, refs. 3 and 15 also contain sufficient 200

information to enable a comparison to be made be-
tween the simulation results and measurements pcr-
formed in a pilot plant operating at the gas flow rates ‘“r
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 x C-J
of 2500-3000 SCM h-l. In ref. 15, the experimental 1.0 2.0 L cm1

profiles have been given for a reactor operating at SO1
concentrations of 1.3 and 9.4% (in the latter case, with
cooling in the middle of the bed). The data used in the
simulations are again presented in Table 1. A compari-
son of the simulation results with the measured values
(taken from the graphs presented in ref. 15) is shown in
Figs. 5 and 6. For a concentration of 9.4%, an addi-
tional problem arises in estimating the amount of heat
withdrawn from the middle of the bed. It has been
assumed, therefore, that in accord with the flow sheet of
the installation discussed in ref. 15 cooling is carried
out in an indirect heat exchanger using a cold process
Fig. 6. Calculated (lines) and measured (points after ref. 15)
temperature profiles along the bed of a pilot reactor, with cooling
in the middle of the bed, at the instant of flow reversal (for 9.4%
SO, and t, = 60 min).
gas whose temperature is equal to the inlet temperature
to the reactor, i.e. 80 “C. The size of the exchanger was
selected in such a way that the cooling obtained might
be similar to that observed in the pilot plant (for a
heat-transfer coefficient of c. 15 W mm2 K-l, this condi-
tion would lead to an exchanger with an area of some
20 m’). The temperature drop in the middle of the bed
varies during the cycle; using the above assumptions,
however, its average value was equal to c. 90 “C.
Summary of the results against a background of the
literature information
The simulation calculations performed have been
based pn values of the coefficients characterizing the
gas-to-catalyst heat transfer, CI, and the effective heat
conductivity of the bed, I,, estimated according to known
literature correlations [ 16- 191calculated as a mean value
of two different formulae. Strictly speaking, the intensity
of gas-to-catalyst heat transfer is determined by the
product of the coefficient CIand the specific surface area
of the catalyst, S, i.e. (CXx S). Both a and & may be
evaluated using various literature formulae which, how-
ever, do not always strictly correspond to the conditions
prevailing in a given reactor. Their calculation may
therefore a priori contain considerable inaccuracies.
To date, attention has been paid mainly to the effect
of heat conductivity in the bed. In a number of publica-
tions (cf. for example, ref. 2), Matros has given approx-
imate relationships between the maximum temperature,
Tnlax2 and the parameters which describe the kinetics of
the reaction, AT,, and the effective heat conductivity in
the bed, il,. These relationships do not include the
parameters which characterize the intensity of the gas-
catalyst heat transfer, i.e. (CI x S). The simulations per-
formed revealed, however, that within the range of
values employed for these parameters their influence in
a reverse-flow reactor is quite considerable.
Simulations of various types of plant start-ups de-
scribed in Part I of this series did not demonstrate such
an important influence for (a x S) as in the case dis-
cussed, hence this effect must be connected with the
special nature of flow reversals in the reactor.
In ref. 2 as well as in other papers, it has been found
that a decrease in the maximum temperature may be
achieved by decreasing the linear velocity of the gas and
increasing & through increasing the pellet size. This
increase in size does indeed lead to a radical decrease in
Tmax. This, however, results more from the associated
decrease in both x and S than from an increase in 1,. For
the pellet sizes employed and values of the Re and Pr
numbers which actually occur in SO* oxidation reactors,
the same value of A, could well fall within the range of
0.5-1.5 W m-’ K-l. An increase in 1, up to the unreal-
istically high value of 5 W m-’ K-’ led to an effect in the
simulations performed which, although noticeable, was
too small to justify any definite conclusion about a
decisive influence of 1, on T_,. It may easily be seen
from the data presented in Table 1, that the product
(m x S) for realistically assumed values may change by
a factor of more than twofold with a change in the pellet
size (cf. the values for the SO* concentration of 3.2%).
From an analysis of the parametric sensitivity, it follows
that a twofold change in c1produces a substantial change
in T,,, and, consequently, in the average conversion
X,,. It may be concluded, therefore that the size of the
catalyst pellet influences the parameters of the process to
a greater extent through the change in the product
(U x S) than in any change in A,.
During simulation, a strong effect has been found
between the numerical structure of the model for the
reverse-flow reactor (positive information feedback) and
the accuracy of the calculations. Thus, it is essential that
a check of the accuracy should be carried out by testing
the consistency of the overall heat balance of the reactor.
The agreement reported in this paper between the
temperature profiles predicted and those measured is not
perfect. However, taking into account that only pub-
lished experimental data have been used, it is reasonable
to assume that the model employed is sufficiently reliable
for the preliminary design of the reverse-flow reactors.
It should be pointed out that a one-dimensional model
cannot be expected to yield ideal agreement with the
experimental results which themselves are usually bur-
dened with considerable measurement errors. The other
source of discrepancy may have been the exclusion from
the model of heat transfer through the elements of the
reactor body.
A number of publications have appeared which treat
the question just discussed as a purely numerical prob-
lem (cf. refs. 9-12). In this event, any physical conclu-
sions reached would seem to be doubtful. The
information given in ref. 12, that the ‘quasi-stationary’
state is reached after only 150-300 cycles suggests that,
when account is taken of the strong dependence of the
results on the initial conditions, the model has simply
produced a drift resulting from numerical errors.
A reverse-flow reactor for the oxidation of SOa has
also been simulated by Rakowski [ 141. The model was
investigated at an inlet temperature, TO, of c. 500 “C;
the value of T,,, obtained in the simulations exceeded
1000 “C. This suggests that a physical objective was
simulated under conditions of little practical impor-
tance. The lack of any physical verification of the
model, or at least an application of the ‘heat balance
consistency test’ proposed earlier, indicates little practi-
cal utility for the computer analysis performed.
Example: Most authors have found an essential inter-
relationship between the parameters describing the re-
action rate and the average conversion. On the other
hand, Gawdzik and Rakowski [9] have suggested that
the DamkGhler number (Da) does not affect the,
efficiency of the reactor, whereas Gupta and Bhatia [ 121
have found a strong effect for Da using the same model.
Such widely differing conclusions are not unusual when
the numerical analysis is not related to the actual
 243

characteristics of a given process. Over the range of taken in the application of inert sections of bed;
temperatures for which the process was analyzed in ref. they should be employed only in the case of reac-
14, the reaction rate was indeed rather small and, tions with a small heat effect (small ATad). In the
hence, the effect of Da may have been somewhat weak. oxidation of SO,, this concerns cases of lower
Such conclusions do not have, however, any practical reactant concentration.
significance. This may be illustrated by the fact that, 4. The heterogeneous model presented in this paper
according to ref. 14, the average conversion obtained [eqns. ( 1) -(7)] yields results which are sufficiently
for the process was 0.3, although from the numerous reliable for the preliminary design of reverse-flow
papers of Matros it follows that in this case we are reactors for SO2 oxidation.
dealing with reactors operating at conversions exceed-
ing 0.9. On the other hand, refs. 11 and 12 suggest that
an increase in the gas-catalyst heat transfer increases Acknowledgement
T,,, (thus agreeing with the conclusions of the present
paper), but that this also leads to a substantial increase The present analysis of the model of a reverse-flow
in conversion. Such a situation is possible when the reactor would have been impossible but for the papers
reaction in the bulk of the reactor occurs under condi- published by Professor Matros’ group from the Insti-
tions far removed from equilibrium - a condition tute of Catalysis in Novosibirsk [2, 3a, 151. The author
rarely met in this type of reactor. Such conclusions wishes, therefore, to acknowledge this fact and thank
should, therefore, never be regarded as ‘general’ the authors of these publications. He also hopes that
they will not object to the use made of their results in
Practical design conclusions the present article.
On the basis of the literature quoted and the tests
performed for the heterogeneous mathematical model,
some important practical conclusions may be formu- Nomenclature
lated:
c reactant ( SOZ) concentration, kmol
1. When the catalytic bed is sufhciently long, i.e. when kmol-’
a flat ‘heat wave’ crest is clearly formed, the final CiC gas specific heat, kJ kmol-’ K-’
conversion and the maximum temperature in the G catalyst specific heat, kJ kg-’ K-’
bed depend only weakly on a number of the model D reactor diameter, m
parameters. If, therefore, a judicious excess of cata- Da dimensionless Damkohler number
lyst is employed, no deterioration in the final conver- h, catalyst-surroundings heat-transfer co-
sion nor superheating may be feared; on the contrary, efficient, W me2 K-i
this leads to a stable operation irrespective of the H heat of reaction, kJ kmol-’
presence of possible disturbances in the process. K, reaction rate constant, h-’ Pa-’
2. Reaction occurs solely during the increasing and L reactor length, m
decreasing parts of the heat wave (Fig. 3) with 53 molar gas flux, kmol h-’ mm2
equilibrium prevailing along its crest. This produces PAR(i) matrix describing the parameters of the
a clear dependence of conversion on T,,,. Apart ith reactor pass
from the effect of linear velocity (cf. Matros [2]), r effective reaction rate, kmol kg-’ h-l
the basic factors affecting T,,, are the pellet size s specific catalyst surface area, m2 me3
and the catalyst activity. Thus, for higher SO, STREAM 1 matrix describing streams in the system
concentrations, a catalyst should be chosen which STATE 1 matrix describing the state of the reactor
has a greater granular size and good activity. These passes
two conditions may, to some extent, be contrary to t time, h
each other, although they do provide guidelines for T temperature, K or “C
the preparation of a catalyst for reverse-flow reac- Tmax maximum catalyst temperature, K or “C
tors. For very low concentrations, the catalyst used X axial coordinate, m
should be of a rather small pellet size. 2 =x/L dimensionless axial coordinate
3. The use of an inert bed results in the heat wave x conversion
slope occurring in a part where no reaction occurs. -&” average conversion
This leads to a substantial increase in T,,,,, and to
the contraction of that part of the bed in which Greek letters
reaction occurs and, in turn, to a decrease in the a gas-solid heat transfer coefficient,
average conversion. Hence, great care should be kJ m-* h-‘K-’
244

6 simulation error 5 Yu. S. Matros, A. S. Noskov, V. A. Chumachenko and 0. V.

adiabatic temperature rise, K Goldman, Theory and application of unsteady catalytic detox-
ATad
ication of effluent gases from sulfur dioxide, nitrogen oxides
P” catalyst bulk density, kg me3
and organic compounds, Chem. Eng. Sci., 43 (1988) 2061-
& effective heat conductivity,
2066.
kJ m-i h-’ K-i 6 J. Wojciechowski and J. Haber, .Z. Appl. Catal., 4 (1982)
E void fraction coefficient 275.
7 J. Wojciechowski, Swingtherm - a new method of catalytic
gas purification, Przem. Chem., 62 (1982) 502-504 (in Polish).
Subscripts 8 G. Eigenberger and V. Nieken, Catalytic combustion with
b basic variant periodic flow reversal, Chem. Eng. Sci. 43 (1988) 2109-
g gas 2115.
in reactor inlet 9 A. Gawdzik and L. Rakowski, Dynamic properties of the
k catalyst (solid phase) adiabatic tubular reactor with switch flow, Chem. Eng. Sci., 43
(1988) 3023-3030.
0 pass inlet (x = 0)
10 A. Gawdzik and L. Rakowski, The methods of analysis of
out reactor outlet the dynamic properties of the adiabatic tubular reactor
s surroundings with switch flow, Comput. Chem. Eng., 13 (1989) 1165-
1173.
11 S. K. Bhatia, Analysis of catalytic reactor operation
with periodic flow reversal, Chem. Eng. Sci., 46 (1991) 361-
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12 V. K. Gupta and S. K. Bhatia, Solution of cyclic profiles in
(a) K. Gosiewski, Dynamic modelling of industrial SO2 oxida- catalytic reactor operation with periodic flow reversal, Com-
tion reactors. Part I. Model of ‘hot’ and ‘cold’ start-ups of the put. Chem. Eng., 15 (1991) 2299237.
plant, Chem. Eng. Process., 32 (1993) 1 1 l- 129; (b) A. Renken, 13 J. Thullie and A. Burghardt, Methanol synthesis in a flow
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process for sulfuric acid production, Proc. Znt. Conf. Unsteady Epifanov, A. E. Popov, 0. N. Smimova and T. Yu.
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