Chemical Engineering and Processing, 32 ( 1993) 111- 129 111

Dynamic modelling of industrial SO2 oxidation reactors

P&t I. Model of ‘hot’ and ‘cold’ start-ups of the plant

Krzysztof Gosiewski
Institute of Inorganic Chemistry, ul. Sowiriskiego 11, 44-101 Gliwice (Poland)

(Received July 14, 1992)

Abstract

The paper describes a comparison of some results computed using a mathematical dynamic model of a single reactor
bed with real temperature unsteady state transients, measured in a large industrial scale SO, oxidation reactor.
Problems of the dynamic modelling of complete oxidation plants, including a heat exchange section and a start-up
installation are discussed in the next section of the paper. As a basis for comparison some start-up dynamic
transients were analysed. The analysis shows that the model (two-phase model for heat transfer and homogeneous
model for mass transfer) is sufficient for qualitative analysis of the problem. The problems of obtaining reliable
parameters for simulation as well as parameter sensitivity of the model are also described. The plant is modelled
using the dynamic flowsheeting simulator DYNAM, whose algorithm is presented against a background of similar
simulators known from the literature.
The major part of the paper presents the results of the identification of the model based on an actual industrial
plant, together with the start-up analysis concerning the SO, oxidation plant. The analysis has been aimed at
minimizing both the emission of SO* during start-up and its duration. The results are given for the various modes
of the start-up operation.

Introduction

Jk
Inlet
The dynamic behaviour of SO2 oxidation reactors
can be readily described by the models developed in a
number of papers.
The two-phase heterogeneous model, well described
in the sixties and seventies, seems to be appropriate for
the solid bed reactors packed with vanadium catalyst
pellets. A good classification of such models was given
by Luebeck [l]. It would be beyond the scope of this
study to cite all the articles dealing with the models
similar to the one discussed here. We may quote only
some of them (Mann et al. [2, 31, Venkatchalam et al.
Outlet
[4], Eigenberger [5,6], Weng et al. [7], Van Doesburg
and De Jong [8] and Hansen and Jorgensen [9]). Fig. 1. SO, oxidation reactor with interpass cooling.
In spite of numerous publications, only a few of them
contain a comparison with experimental results; addi- experiments with laboratory tubes of diameter of sev-
tionally, it is very difficult to find a reliable comparison eral centimetres and height comparable with the indus-
of the computed results with the industrial plant un- trial scale, as was the case in the papers cited, must be
steady state transients rather than with the laboratory treated with caution if one wants to apply them to the
experiments. This paper deals with such a comparison industrial scale units. In particular, an analysis of the
for an SO, oxidation large-scale industrial reactor. influence of the reactor body on the dynamic transients
At present, such a reactor can have four to five should not be extended from the small to the large
passes (beds), as shown schematically in Fig. 1. Each scale. Figure 2 shows the bed which is the subject of the
bed is 0.5 to 1 m high with diameter from 5 to about numerical identification in this paper, compared with
12 m. It seems obvious that any conclusions based on the experimental reactor described by Mann et al. [3]. It

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

(4 Industrial reactor _ analysis and design of reactors operating in perma-
nent non-stationary state.
The SOa oxidation process is a very stable one;
therefore there are no real control problems with the
reactors discussed. Thus the model does not have to be
appropriate for control system analysis, and does not
have to be very precise for the signal frequencies neces-
sary to analyse the quality and stability of the control
system. The last two problems are, however, of growing
importance in the reactor analysis. Consequently, this
paper concerns the dynamic reactor model regarding, in
particular, the latter two items.
The aim of this paper is to test an agreement of some
I
well described mathematically process dynamics with
thermal insulation
b\;;ck the measured temperature transients in an industrial
lining
scale reactor, with special stress placed on the values of
(b) experimental reactor the model parameters which lead to sufficient consis-
of Mann et al. (1986) tency with real dynamic behaviour.
As a first step of the dynamic study attention was
focused on simulation of the first pass of the reactor.
The next section presents an attempt to apply the
above model to simulating the dynamics of a complete
SO* oxidation plant. Such a plant consists usually of 4
to 5 reactor passes, with interpass cooling using either
heat exchangers or the injection of cool gas.
The interpass cooling is usually carried out by means
of shell-and-tube heat exchangers. In some cases, the
cooling is performed using some selected parts of the
boiler such as preheaters, evaporators or steam super-
heaters. This case is somewhat more complicated and
thermal ’insulation has not been included in the present paper.
In modern plants the gas leaving a certain pass of the
Fig. 2. Relative size of a typical industrial reactor and of an
experimental one. reactor undergoes interstage absorption which, by re-
moving the reacted SO,, leads to higher conversions
after subsequent passes and, consequently, to a higher
illustrates the difference in size between the industrial final conversion. More often than not the interstage
scale reactors and those which are the subject of dy- absorption is carried out before the final pass, although
namic laboratory investigations. In many papers the the Lurgi company obtained quite satisfactory results
scale of the reactors analysed is comparable with that situating the absorber after the second pass in 4-pass
studied by Mann et al. in the paper cited above. reactors.
Obviously, the possibility of carrying out experiments The number of arrangements increases if the possible
in an industrial reactor is very limited. One could connections between the interpass heat exchangers are
analyse, however, the model equations even if the data taken into account. In general, from the point of view
available were highly incomplete. Despite many draw- of recovery of heat generated in the SO2 oxidation
backs of the industrial scale studies there is, however, reaction, two types of installation exist:
one advantage. The industrial reactors are much closer (1) Arrangement with a single autothermal loop. In
to adiabatic systems than any, even carefully prepared, this case the problem of the recovery of the heat of
laboratory installation. This is due to the much smaller reaction arises, which could be used to heat the cool
ratio between the wall surface and the volume of the gases leaving the interstage absorption (70-80 “C) up
catalyst. to the reaction temperature (above 400 “C). This group
The need for the mathematical dynamic reactor mod- comprises plants in which sulphuric acid is produced
els usually appears when solving one of the following from sulphur.
problems: (2) Arrangement with a double autothermal loop. This
- automatic control system analysis, setup comprises plants with two loops of recovery of
- plant start-up and shut down analysis, the heat of reaction. Usually, these are the plants

producing the acid from the flue gases in the non-fer-
rous metallurgy, from pyrite or from other sulphide
ores. The heat of reaction is recovered to heat the cold
new gas (about 60 ‘C) leaving the scrubbers and elec-
trofilters, and to heat the gas after the interstage ab-
sorption (see above).
The two groups form a sufficiently large number of
possible connections of the reactor passes, the heat
exchangers and the interstage absorber to justify the
solution of the appropriate models using a single gen-
eral computer program.
While the literature dealing with the modelling of the
reactor itself is abundant, the dynamics of the complete
SO, oxidation plants has not been analysed properly. It
seems that, apart from the earlier works published by
the author of the present paper and his co-workers
[ 10-121, only Mann et al. [2] and Mishra and Sebastian
[ 131 dealt with this problem. The need for analysing the
dynamic model in order to minimize the emission of
SO, has been well documented by Mann et a[. [2], in
spite of the fact that the simple mathematical models
proposed by these authors, as well as that in ref. 13, do
not meet the requirement of generality of the descrip-
tion. The dynamic flowsheeting simulator seems to be
an adequate tool in this case, if we do not intend to
build a complex model for a single and usually unique
installation.
The model of a single reactor bed
The model equations of a single reactor bed
An ideal plug flow is assumed, with negligible radial
dispersion in the reactor. For reactors with large ratios
between the reactor diameter and the equivalent cata-
lyst pellet diameter, the assumption D/d,, 2> 1 is quite
admissible. Hence the following heterogeneous heat and
mass balances can be written:
The heat balances
for the gas phase:
A.s~+ngCg~+~peCg~+aS(T~- T,) =0 (1)
for the solid phase:
PT
k - pu C, 2 + cxS(T, - T,) + Hrp, = 0 (2)
lk ax2
and mass balances
for the gas phase:
for the solid phase:
113
PS(C- C*) + rp, + .z*p, g = 0 (4)
Equations ( 1) -(4) constitute the overall one-dimen-
sional model, assumed by many authors as a basis for
further simplifications.
Practically, there is no universal kinetic model de-
scribing adequately the reaction rate function r in eqns.
(2) and (4). The author’s experience has proved that
Boreskov et al.3 [ 141 equation can be taken as a basis
for further approximation based on laboratory tests of
the catalyst samples employed. For the model dis-
cussed, the following form of the reaction rate expres-
sion has been taken:
r=kPb-W/2) 1-X
1 - @X/2) 1 -0.2X
(5)
The original form of eqn. (5) given in ref. 14 is not
sufficient to describe r for the various commercial cata-
lysts, as then for the reaction rate constant k, an
original Arrhenius type formula was not used. Instead a
more complex function of temperature, identified indi-
vidually for the particular industrial catalyst type and
operating conditions, was used. The identification uti-
lizes laboratory tests of the catalyst. Identification of
the reaction rate constant k for the above equation is a
separate problem which will not be discussed here in
detail. Generally the reaction rate r is a highly non-lin-
ear function of T, and i& where i? is a vector of local
reactant concentrations
r = f(T,, I?)
Equations ( 1) -(4) should have been supplemented
with appropriate initial and boundary conditions, but
for the sake of brevity this will be presented together
with simplified forms given below.
Before we go any further with the discussion and
analysis of the model applied, we should answer the
question why, in this paper, the radial concentration
and temperature gradients are not taken into account in
any of the models discussed. Looking at the radial
temperature profiles for the experimental reactor, given
by Mann et al. [3], one can see that even for the
laboratory scale the radial dispersion effect is significant
only for the case without the reaction. When the reac-
tion occurs, the radial dispersion and wall effects are
much smaller. Moreover, the measurements of the hori-
zontal cross-section temperature distribution carried
out for the industrial reactors have shown that there are
indeed some significant differences in the radial temper-
ature profiles, due to reasons which are difficult to take
into account mathematically. They were caused mainly
114

by random, non-uniform distribution of the flow rather n,C,[T,(L, t) - Tr’] =(1 -c)u[Tr’- T,(L, t)] (13)
than by the radial dispersion effects.
To simplify eqns. ( 1) -( 4) the following assumptions
aTk& 4
(1 - &)CI[Tk(L, t) - .yy = ny
were made: ax
For the mass balances: Elimination of TP’ from eqns. (13) and (14) gives
- homogeneous reactant concentration, that is, the the following form:
lack of mass transport resistance at the surface and
inside the catalyst particles (c = c*), ACP aTk(G t) = ngCg(1 - 4a
c
ax ( n
1 _[T,G 0 - T,(L, 01
E)u + c

- lack of the mass accumulation in the gas phase, g g

- lack of the axial dispersion term. (15)
For the heat balances:
It was shown, by solving numerically the above equa-
- substitution of the overall effective heat conductivity
tions, that for the case discussed, the application of the
2, for the catalyst, for the heat conductivity within the
simplified conditions ( 10a) and (15a), agreeing with
solid phase I, and the heat dispersion in the gas phase Danckwert’s condition, has no significant influence on
1, (for discussion see Eigenberger [ 5]),
the results, but leads to a simpler numerical procedure,
- lack of the heat accumulation in the gas phase.
and so it was used in the model instead of eqns. (10)
Taking the above into account we obtain the follow-
and (15).
ing model equations:
for x = 0:

T,(O, t) = p;(t) (104

for x = L:

O1k
ac
---0 (154
ax
y,-++rp,=O
ax The model eqns. (6), (7) and (8) can be presented in
The boundary and initial conditions for this sim- the following form, by introducing the usual dimension-
plified form will be as follows: less numbers:
jbr t =0: The heat balances:
Tk(x, 0) = T,(x, 0) = f(x) (9)
2 + St(SL)(T, - Tk) = 0 (gas phase) (16)
where f(x) is some arbitrary given initial temperature
distribution. This initial condition is of great impor- a”T,
--&$$+Bi $ (SL)(T,-Tk)+Da’=O
tance for the model adequacy. It will be discussed later ax2 0
in more detail.
(solid phase) (17)
for x = 0:
and molar reactant balance:
From the heat flux balance at the inlet cross-section
a(
surface for x = 0, a condition similar to that given in
ref. 1 for the two-phase model z =Da” (18)

n,C,[TF - T,(O, t)] = (1 - E)E[~; - T,(O, t)] (10) Results and discussion for a single reactor bed
From the practical point of view the start-up is an
aTk = (1 - &)CIITk(O,t) - TF]
1, - interesting case of an unsteady state, due to the exces-
(11)
ax sive pollution observed at that stage. This period, often
c(0, t) = c’“(t) (12) occurring in the existing full-scale industrial plants,
allows one to compare the computed results with the
for x = L:
real transients observed in the industrial reactor, thus
Usually the Danckwerts condition is taken for x = L. providing a good opportunity to identify the model
It should be emphasized, however, that this ‘classic’ experimentally.
condition concerns the case when for x > L, fluid flows Generally, there are two types of start-ups observed
to the space where Ae = 0. Since for the case discussed it in the industrial SO2 oxidation plants.
flows further through the ,ceramic pellets with Azp # 0, (1) The ‘hot start-up’ - that is, the start-up of the
this condition is not exactly fulfilled. Then the following reactor after some pause in the reactor operation, after
condition was taken as a first approach: which the reactor is only partially cooled down. This

means that there are some regions along the reactor bed
with the temperature enabling the immediate re-start of
the reactor by supplying the hot gas with an appropri-
ate SO, content.
(2) The ‘cold start-up’ - that is, the start-up of the
reactor from its initial state when it is completely
cooled down, first by using hot air from some external
preheater and then by supplying the reactant when the
reactor (or at least a part of it) has already been
preheated to the appropriate reaction temperature
(above 400 “C for the SOP oxidation case).
The case of the ‘hot start-up’ was chosen as a subject
of investigation and identification of a single bed, as a
first approach to the dynamic modelling problem.
During the ‘hot start-ups’ some interesting ‘oscilla-
tions’ are observed. The simulation was expected to
explain the nature of this phenomenon. For the com-
plete oxidation plant, both ‘cold’ and ‘hot’ start-ups
were investigated.
Identification of the model parameters for a single
reactor bed
To identify the model one should have not only the
adequate mathematical equations, but also reliable val-
ues of the parameters used in the numerical calcula-
tions. Only few of the parameter values can be
estimated with confidence. Others, like u or A,, have to
be evaluated based on the relations taken from the
literature. One can obtain different values of the
parameters, depending on a particular reference taken
into account. Thus, an analysis of the sensitivity of the
results with respect .to these ‘uncertain’ parameters
seemed to be of particular importance.
For the SO, oxidation reactor case, there are two
problems which should be treated with special care.
These are: the initial temperature profile and the heat
capacity of the bed.
Problem of the initial temperature profile
The initial temperature profile (i.e. condition (9)) can
be easily determined only for the ‘cold start-up’, when
the reactor bed is completely cooled down to some
ambient temperature. It is a trivial case. A more com-
plicated one is that when the reactor is started, from the
state of only partially cooled bed.
For the industrial reactor of dimensions such as, say,
those shown in Fig. 2(a), it is very difficult to measure
the initial profile. One can say that it is practically
impossible to realize this measurement in an industrial
environment taking into account the cost of the investi-
gation.
On the other hand it will be proved that the profile
has significant influence on the computed transients.
Theoretically the profile could be obtained numeri-
cally, from an already computed steady-state profile, by
115
modelling the dynamics of the bed cooling. Some qual-
itative study of such a cooling process was carried out.
A strict mathematical model of the cooling of the
reactor bed would be very complicated, due to the
complicated ways of the heat outflow of the bed, when
it is being cooled down. Additionally, one should de-
velop an individual model for any geometry of the
reactor. Moreover, it seems impossible to provide reli-
able quantitative parameters for such a model.
For the analysis of the dynamic behaviour of the bed
during the ‘hot start-up’, the profile was estimated by a
trial and error method beginning with an initial steady
state profile. The temperature of the bed was measured
at -two points, namely for X Y 0.2 and X = 1, where the
thermocouples were installed. The initial temperature
profile should fit these measurements at these points.
The remaining part of the profile should have been
estimated in such a way that an agreement could be
obtained between the transients calculated with those
measured (at these two points) during the start-up
period. However, one should be aware of the fact that
the assumption of the initial profile is the weakest point
of the analysis. The initial profile taken for further
simulation is shown in Fig. 3 as curve 1.
Curve 2, also shown in this figure (dots), presents the
initial profile intentionally deformed, to test the sensitiv-
ity of the transients to the initial profile shape; this will
be discussed further. As may be seen, the simulated tran-
sients are sensitive to the profile assumed, but this does
not change the time scale of the observed oscillations.
Problem of the heat capacity of the bed
The parameter C, appearing in eqn. (2) should not
be regarded simply as a physical specific heat of the
catalyst.
When the catalyst is heated up, the following pro-
cesses are observed:
Loci
_
620 150 min
520
3
!i
s
+ 420
.
/
Fig. 3. Temperature profiles along the reactor bed
116

_ melting of the active compounds of the catalyst (see TABLE 1. The set of parameters assumed for the ‘hot start-up’
Tandy [ 151 or Boreskov [ 16]), tests
- desorption of the gas compounds already adsorbed
Parameter Symbol Value
on the porous surface of the catalyst and adsorption of
the new compounds, Catalyst eff. spec. heat 5.5 kJ kg-’ K-’
_ in some cases evaporation of the moisture from the {Physical spec. heat) {-l.O5kJkg-‘K-‘}
catalyst can also occur to some extent. Heat of reaction 8.89 x lo4 kJ kmol-’
The above physico-chemical processes can signifi- Heat transfer coeff. 151 W m-2K-’
Eff. heat conductivity 0.465 W m-’ K-’
cantly increase the effective heat capacity of the bed Inlet molar flux 47.65 kmol mm2 hm’
over the simple physical specific heat effect of the solid Inlet gas composition:
bulk of the catalyst. Moreover, the heat capacity de- SO, lOvol%
pends on the range of temperature and composition of 0, 11 vol %
the gas supplied into the system. N, 79 vol %
Bed length L 0.48 m
Specifically, if we substitute some equivalent effective Reactor diameter D 8.6 m
value Ckeff for C,, this value will cause some additional Spec. catalyst surface s 568 m* m-3
non-linearity of the model, very difficult to allow for a Porosity of the bed 0.5
priori. To simplify the problem some rough simplifica- Bulk density of catal. P. 620 kg mm3
tion of the problem was assumed taking a constant
value of CkeWfor a wide range of temperatures and gas
compositions. The value of C, is virtually the only
uncertain parameter of the model influencing directly Results of simulation
the time scale of the process. It can be estimated simply Some real industrial catalyst temperature transients
by ‘adjusting’ the time scale of the computed transients of the ‘hot start-up’ run measured in an industrial
to get an agreement with the real ones, measured in the reactor are compared with the computed results in Fig.
industrial reactor. 4. The solid lines ‘a’ in the figure present the results
The identification of the Ckeff values was made for computed by solving eqns. (6), (7) and (8), while the
various reactors with different vanadium catalysts. It dots show the measured transients, recorded by the
turned out that the ratio Ckeff/Ck (where C, denotes industrial strip-chart recorder. The transients were
physical specific heat of the catalyst) can be ascribed to shown for the two points of the bed, 2 = 0.2 and R = 1,
one of the three groups of transients: corresponding to the points in the reactor where the
CkeR/Ck g 1, for heating of the catalyst with hot dry air thermocouples were installed. One can notice that the
up to the temperature of 400 “C, transients are of similar character with regard to the
C,,/C, g 2, for the start-up of the reaction after the ‘oscillations’. This ‘oscillatory’ transients can be ex-
bed has been preheated with dry hot air (i.e. during the plained when the movement of the temperature profile
‘cold start-up’), along the bed is observed (see the profiles for various
C,,/C, s 3-5, for the start-up of the reaction during
the ‘hot start-up’.
The differences in the ratio CkaK/Ck described above
are obvious if we remember that ‘cold start-up’ takes
place after a long break in the reactor operation. Before
such a pause the reactor is carefully purged with clean
and dry hot air, which significantly reduces the influ-
ence of the surface processes.

Parameters assumed .for the model

In order to test the model, the operation of an
industrial reactor was taken for simulation. The set of
parameters assumed for modelling is shown in Table 1. b
It was taken that the bed is cooled down to the
assumed initial temperature profile (see Fig. (3)-curve
1). The shape of the profile depends on the duration of
350 1~-1-rrl-r-I- l-r~~l-n-l-
the break in the reactor operation. Next, at the time 50 70
Time [minutes]
t = 0, the start-up begins simply by applying the full
flow rate and concentration of the gas containing the Fig. 4. Computed (lines) and measured (dots) temperature tran-
reactant. sients during a ‘hot start-up’.
 117

time moments, shown by broken lines in Fig. 3). cocl

Such character of the transients is caused by the ini-
tial profile (the line 1 in Fig. 3) having maximum
temperature inside the bed (i.e. for ;F-2 0.6).
To obtain an agreement between the time scale of
the process, the value of CkefT was corrected, until the
scale of computed transients agreed with the mea-
sured one. The agreement is worse as the transient
approaches the steady state, where the real transient
increase is ‘slower’ than that of the computed one.
This effect of ‘slowing down’ of the transients is
much more visible on the upper layer transient
(X = 0.2). One can assume that this effect is caused by
the heat accumulated in some ‘side heat capacity’.
The considerable mass of the body of the industrial
reactor can easily justify the effect observed. An at- Fig. 5. Computed temperature transients. Influence of E.
tempt has been made to include this effect in the
model. This is described in Appendix A. The results
of the simulation with the ‘side effect of the wall’ are
shown in Fig. 4 as the lines ‘b’. The consistency with
[“Cl
the real transients is better, but still far from an ideal 650
agreement. The conclusion of the test is that the ‘side
wall effect’ cannot be described by such a simple 600
model, but probably influences the approach of the
transient to the steady state. This influence is larger
for the upper parts of the first bed because of the
larger equivalent reactor body weight M,, (due to
the fact that the mass of the reactor roof is larger
than the equivalent part of the wall at the outlet of
the bed).

Parameter sensitivity of the model equations

350
Two parameters were considered as ‘uncertain’, 0
since they were calculated according to the data taken Time [minutss]

from the literature. These are the gas-solid heat trans- Fig. 6. Computed temperature transients. Influence of 1.
fer coefficient a and effective heat conductivity of the
bed 1,. The values given in Table 1 were calculated
as the ‘mean’ values of the parameters.
The influence of c( was studied by assuming the
values of u’ = 2a and IX”= 0.5a in the model.
To examine the influence of 1, the following values
were assumed:

0.65
The temperature transients thus calculated are shown
s
._
in Figs. 5 and 6, while the influence of the two tests
E
on the computed conversion is shown in Fig. 7.
9
There is a clear dependence of the results on the 0.60

two parameters. The amplitude of the temperature

‘oscillations’ is more sensitive to the GLvalue, but to
some extent it is also sensitive to the value of &.
Figure 7 shows, however, that the influence of the 0.55
da
two parameters on the computed conversions is smaller lima ~minutw 13
than the overall accuracy of the model. Fig. 7. Computed conversion transients. Influence of 1 and CC.
118

Sensitivity of the model to the initial temperature Model of the complete oxidation plant
proJile
The most questionable point of the simulation is the Mathematical simulation of the complete oxidation
assumption of the initial temperature profile along the plant needs special numerical tools to model the reactor
bed, at the beginning of the start-up. It seemed worth- passes together with an auxiliary installation and heat
while to test how sensitive the results are when the exchange system in order to include the mutual inter-
profile is deformed. Line 1 in Fig. 3 shows the profile connections of the process. This tool is described briefly
which gives the best agreement with the measured tran- in the following section.
sients. As may be seen, this initial profile is tangential
to the steady-state profile (line for t = 150 min in Numerical problems in the dynamic flowsheeting
Fig. 3), which is understandable from the practical simulators
viewpoint, since the most intense cooling occurs at both The need for dynamic flowsheeting simulators arose
ends of the bed. Line 2 shows the profile arbitrarily as a natural consequence, when static simulators be-
deformed, although agreeing with the measured temper- came available as commercial software products. In
atures at the points X z 0.2 and X = 1. The temperature the seventies numerous papers appeared concerning
and conversion transients for the two initial profiles the modelling of the dynamics of the complex chemical
(i.e. lines for profiles 1 and 2) are shown in Figs. 8 and plants. Although the review published by HlavaEek in
9. It may be seen that the computed transients are 1977 [17] quotes 130 articles and 5 books, only a few
clearly dependent on the initial temperature profile. of them contained information on the complete dy-
namic flowsheeting software systems. Probably, the
most general system dating back to this period is that
developed by Bobrow et al. [ 181 (DYNSYS); the other
papers dealt usually with numerical methods for
solving large numbers of ordinary and partial differ-
ential equations. While these methods are essential
in simulating the complex dynamic systems, they do
not provide any comprehensive treatment of the
problem.
It was only in the eighties that the rapid develop-
ment began of the complete software systems for simu-
lating complex chemical installations (e.g. DYNSYL,
PRODYC, DYSCO, REMUS and DYFLOW cited in
ref. 19, or the MUNICHEPS system described in ref.
20). The most recent review of Marquardt [21] presents
the state of the art and future challenges of dynamic
Fig. 8. Computed temperature transients. Influence of initial tem- process simulation in chemical engineering. It transpires
perature profile. from ref. 21 and other publications that, at present, the
dynamic modelling of large-scale systems is still being
C-l developed and rarely takes the form of fully commer-
cialized and generally applicable software, not requiring
a good computer background, similar to the systems of
the static flowsheeting simulation.
Mathematically, the problem of dynamic simulation
of a complex system consists of solving the set of n
equations with n unknowns; these equations may be as
.-s
follows:
F - partial differential equations (dynamic elements with
8 0.60 parameters distributed in space),
- ordinary differential equations (dynamic elements
with lumped parameters),
- algebraic equations.
If the set contains only algebraic equations or differ-
ential equations with spatial derivatives, the problem
Fig. 9. Computed conversion transients. Influence of initial tem- reduces to that of static modelling. Therefore the condi-
perature profile. tion for a problem to be dynamic rather than static is
 119

the existence of the time derivatives in at least part of The literature survey reveals that it is customary to
the equations. Generally, the problem of the dynamic employ methods based on the modules of already exist-
simulation may thus be formulated as follows: ing software systems used in the dynamic simulation of
large installations.
aY According to ref. 17, these methods may be further
at =Fd_vxx~yx~y>
0
divided into the following groups:
0= Fsi_~Y Y) _ simultaneous modular
XX? x9 (20)
- sequential modular.
The vector eqn. (19) describes the dynamic part of
In the former group, the equations are lumped to-
the system, whereas eqn. (20) describes its static com-
gether to form the modules usually corresponding to
ponent. The partial derivatives of the state variable y
individual apparatus or unit operations, and then inte-
with respect to the coordinate x may appear in the
grated simultaneously with respect to time employing a
functions Fd and F,. Usually, the number of apparatus single integration procedure. In the latter group the
and the complexity of the dynamic model for a large individual modules are integrated one after another
chemical plant result in a large dimension of the vectors according to an assumed sequence, often using different
in eqns. (19) and (20). integration procedures; this method is therefore an imi-
Similarly as for the static problems, the methods of tation of that employed in a number of static simula-
solution may be divided into two groups [22]: tors. However, while the sequential modular method
- equation-based methods, offers certain advantages in the case of static simula-
_ modular-based methods. tions, it has serious drawbacks when dealing with dy-
The equation-based methods seem to offer the sim- namic problems (iterative complications), which may be
plest way of tackling the problem, which reduces to a avoided by using a different method of solution (this
coherent set of equations of the type ( 19) and (20) and method, discussed later, is applied in modelling the SOa
then, upon employing an appropriate numerical proce- oxidation plant). The possibility of employing different
dure, to a set of algebraic equations which are solved integration methods for different modules seems to be
using any of the sparse matrix techniques. This appar- the only advantage of the sequential methods.
ently simple method of solution is, however, not always Equations of the type (19) may be solved using
employed in practice. The complexity of the solution various numerical procedures which, with respect to the
procedures for the sets of many differential equations, time derivative (a/&), may be divided into explicit
and especially the difficulties with solving the so-called methods and implicit ones. The theory of the numerical
stiff equations (see e.g. [20, 22-261) make it necessary methods shows that those based on an implicit form of
to carry out judicious decomposition of the whole the difference notation are absolutely stable and lead to
problem into smaller sets, which are then tackled using higher accuracy of the numerical solutions at larger
different numerical approaches. For instance, the linear values of the integration step. The implicit methods are
equations may be solved separately from the non-linear particularly useful in solving the stiff differential equa-
ones, or the stiff part may be separated from the tions. They have, however, a serious defect when deal-
non-stiff part. ing with the structures of complex topology. As follows
from ref. 25, only extremely simple structures, usually
described by a linear differential equation, may be
Note: The notion of low stiffness of the differential equations is
solved by means of non-iterative procedures. In the
known in the theory of the numerical methods used for solving majority of cases, especially when the installation con-
these equations. tains recycles of flows or information recycles, the so
If for eqn. (19) Jacobian is defined called ‘stream tearing’ has to be carried out, leading to
problems with the convergence of the iteration loops.
and if eigenvalues of the Jacobian contain both a real and an
Even a cursory examination of the problem suggests
imaginary part that for the non-linear equations which are usually
dealt with when describing chemical appliances, the
1, = ( l/si) + joi
necessity of employing an iteration loop makes the
the stiffness of the equations may be expressed using the so-called nature of the methods implicit with respect to the time
stiffness coefficient S which is given by the ratio of the largest to
derivative. This is clearly seen in simple numerical
the smallest value of ‘I~:
procedures formulated for the two methods (to simplify
S=Z the discussion the derivatives with respect to the spatial
variable x have been omitted from eqn. ( 19)):
In practice, this is the ratio of the largest to the smallest value - explicit procedure
of the time constant of the system. Numerical problems appear
for high values of S. Y(t + 4) =u(O + h,Fd{Y(4) (21)
120
_ implicit procedure
Y(l + h,) =v(0 + V,{y(t + &)I (22)
In eqn. (21), the new value of the vector y for the
next time step (t + h,) is calculated directly from the
value for the preceding step. In the case of eqn. (22),
when the function Fd cannot be uncoupled with respect
to y(t + h,) we have to resort to iterative methods. The
uncoupling of eqn. (22) is either impossible or very
difficult (this concerns particularly the generally appli-
cable software systems) and, consequently, the iteration
becomes a must.
In ref. 27 the following classification of the sets of
equations has been given, depending on their stiffness
coefficient:
s = l-10: non-stiff problems, which may be
solved easily using the explicit meth-
ods,
S = 100-1000: moderately stiff problems
For S exceeding 1000 the explicit methods become
very inefficient, leading to instability and poor accuracy
of the solutions. It should be mentioned that if the
system contains elements characterized by the spatially
distributed parameters and described by the partial
equations, the stiffness coefficient usually increases;
such elements may be formed by the individual reactor
passes and heat exchangers in the installations whose
simulation will be described later. In spite of this, in
the simulations discussed the application of an explicit,
simultaneous modular method did not result in any
major problems.
The sequential modular method mentioned before
leads to additional iteration difficulties due to the tear-
ing of streams.
Dynamic flowsheeting simulator for the SO2 oxidation
plant
In ref. 11 a simple numerical procedure has been
proposed, employing the original idea of Klaudel and
based on the explicit Euler numerical formula with
regard to the time derivative. The procedure enables
non-iterative calculations to be performed for any topo-
logical structure of chemical installations. The price
for this simplicity is the necessity of employing small
integration steps regarding both the time (h,) and the
spatial coordinates (h,), which leads to the prolonged
computing time. However, even using commonly acces-
sible fast 32-bit computers of the PC class, we obtain
maximum computing times not exceeding a couple of
hours for topologically complex structures.
Although application of the explicit method is not
recommended for stiff sets of equations, the literature
presents some examples of how these relatively simple
methods have nevertheless been used for simulation
purposes (e.g. explicit Euler [24] or explicit corrector-
predictor [ 181).
A comparison between several numerical methods,
both explicit and implicit, has been given in ref. 28.
ln short, the numerical algorithm employed in the
present work consists of the following steps:
(1) Write the initial state of the installation streams
into the matrix STREAM 1, and that of the individual
apparatus into the matrix STATE 1.
(2) Carry out the integration of all the apparatus for
a single step h, - in any order, and write the new values
(i.e. those for the time t + h,) for the streams and the
individual apparatus into the matrices STREAM 2 and
STATE 2, respectively.
(3) Write the values calculated into the final sets of
the simulation results and check whether the actual
time does not exceed the fixed overall time of computa-
tions. If it does ~ terminate the calculations, otherwise
rewrite the matrices STREAM 2 and STATE 2 into
STREAM 1 and STATE 1 and go back to step 2.
The flowsheeting software DYNAM, developed in
the Institute of Inorganic Chemistry by W. Klaudel and
the author of the present paper, makes use of the above
algorithm.
According to the classification presented, this al-
gorithm belongs to the group of the modular-simulta-
neous methods.
ln a numerical procedure thus formulated the prob-
lem of the order of calculations, which is so important
in the modular-sequential method of static simulators,
disappears altogether. Also, we do not have to inverse
sparse matrices of large dimensions. At the same time,
the description of the dynamic system is divided into
separate procedures concerning the dynamics of indi-
vidual apparatus and, consequently, the modular struc-
ture of the software can be retained. For the modules
characterized by complex dynamics (e.g. with a high
stiffness coefficient), the algorithm thus defined enables
us to divide further the time step h,, imposed by the
main integrator of the system, into smaller steps within
the procedure describing a given module. It is also
possible to use the semi-implicit method by performing
the implicit integration inside the module; however, in
the case discussed such measures were not necessary.
The starting point for coding the algorithm of the
DYNAM simulator is provided by the flowsheet of the
installation. Such a flowsheet for an actual plant is
shown in Fig. 10. The dynamic simulation of this plant
is an example of application of the method proposed.
The flowsheet presented contains 24 calculating mod-
ules coupled by means of 41 material flows. Twelve of
the modules (reactor passes, heat exchangers, absorber,
sulphur burner and start-up furnace) are described by
the mathematical models of significant dynamics. The

Air
Fig. 10. Flowsheet of an industrial SO, oxidation plant simulated
in the present study.
others (mixing or splitting of the gas streams) are
treated as static elements. From the point of view of the
start-up operation of the SO, oxidation plant, the most
essential dynamics is that of the reactor passes and the
interpass heat exchangers. The discussion carried out in
the present work is focused solely on the start-ups of
the catalytic reactor equipped with interpass heat ex-
changers and on the interstage absorption. The start-up
(heating) of the sulphur furnace and of the heat utiliza-
tion boiler has been excluded from the analysis. This
enabled us to avoid modelling of the complex dynamics
of the boiler systems.
The equations used in simulating the shell-and-tube
heat exchangers are presented in Appendix B. The
description of other dynamic elements of the system has
been omitted, as their effect on the transients of the
system is less important.
The dynamic description as a complex structure
would be extremely tedious without the specialized tool
provided by the DYNAM simulator.
121
The software has been developed as a so-called prob-
lem-oriented language, which makes it possible to code
the algorithm for the given flowsheet of the installation
in a simple and concise form, and then to carry out its
automatic translation into the standard FORTRAN 77.
The calculation results are given as tables which show
the state of the various streams at selected moments,
and also, as a special set which can be further processed
using general programs such as spreadsheets or graphi-
cal procedures.
Start -up problems in the sulphuric acid plant
Formulation of the problem
The problem is formulated as that of finding such a
mode of the start-up operation (i.e. an algorithm)
which would serve the dual purpose of maintaining the
SO, emission below the admissible level and decreasing
the start-up time to minimum. Only the heating of such
an SO2 oxidation plant which is equipped with a start-
up installation is taken into account. The installation
consists of a furnace fired with an available fuel (say,
fuel gas), and a heat exchanger heating the air stream
used to warm up the plant.
Theoretically, the problem could be reduced to a
rigorous task of minimizing the start-up time with the
constraint imposed on a maximum level of emission.
Since the decision variables are functions of time,
the original task reduces to a difficult variational prob-
lem. An attempt to formalize the optimization problem,
made by the author (see ref. 10) for a single reactor
pass, revealed a high degree of mathematical complex-
ity. It seems, therefore, that a singular optimization for
a plant analogous to that shown in Fig. 10 would entail
both formal mathematical difficulties and formidable
computing time and, consequently, would be of little
practical value. Moreover, for such a complicated prob-
lem (size of the system) we cannot resort to any suit-
ably tested methods of formal optimization. Taking
into account the long time necessary for the computer
simulation of a single start-up strategy, the heuristic-in-
tuitive approach to the selection of the start-up proce-
dure has been chosen. Although this approach does not
guarantee that the results obtained will, in fact, be
optimal, it does lead to conclusions which may be
acceptable from the practical point of view.
An additional practical restriction which has to be
taken into account in the start-up optimization is that
imposed by the producer of the catalyst and the lining,
concerning the admissible rate of temperature increase
in the reactor. At the initial stages of heating, when the
temperature may increase fairly rapidly, it is easy to
violate these restrictions. However, to simplify the sim-
ulation these restrictions have not been included in the
model. In practice, the algorithm obtained by means of
the simulation may be adapted to these limitations if we
122

intentionally slow down the heating process by supply-

ing less fuel and heating air.

300
Ident$cation of the model based on the simulation of
the ‘cold’ start-up 250
The dynamic model has been identified by comparing
the numerical results with the actual start-up data s 200
H
recorded by the strip-chart recorders. The decision
$150
parameters for identification included all the parame-
I-0
ters difficult to determine a priori and having an essen- 100
tial effect on the dynamic transients, namely the activity
coefficients for the catalyst, heat-transfer coefficients for 50

the exchangers, the degree of opening of bypasses in the

0
exchangers, etc. The main identification has been car- 0.0 2.0 4.0 6.0 8.0 10.0
Time [hours]
ried out by comparing the simulated transients with the
actual ones during the ‘cold’ start-up. For identification Fig. Il. Predicted and actual temperature transients in Phase 1 of
purposes, such a start-up has been divided into two the start-up (heating of the plant) simulated - solid lines; mea-
phases. sured ~ broken lines.

Phase 1: Heating the installation by the warm air

supplied from the start-up heater consisting of a gas
burner (BURNER 1) and a heat exchanger (H.EX 5).
During this phase, the sulphur furnace (FURNAC 1)
and the steam boiler (BOILER 1) are cut off from the
inlet into the first reactor pass (REACT 1) and are
heated by means of a separate gas burner located in the
sulphur furnace, whereas the combustion gases are dis-
charged into the atmosphere following the splitting of
the stream (SPLIT 5). As has already been mentioned,
the heating of the sulphur furnace and of the steam
boiler was not simulated. From the very start of the
heating, a part of the warm air (about 12%) leaving the
start-up heater was fed directly onto the fifth reactor
pass (stream no. 29).
Phase 2: Start-up proper, which follows the discon-
nection of the start-up heater. At the moment the
combustion of sulphur begins in the sulphur furnace
(FURNAC l), the gases containing SO, are supplied
through the boiler (BOILER 1) to the inlet of the first
reactor pass (REACT 1). Lacking any reliable dynamic
model of the steam boiler it has been assumed for Phase
2 that the temperature of the gases leaving the boiler is
constant. If the boiler has been properly heated in
Phase 1, such an assumption is very close to reality, as
this temperature may indeed be kept constant by con-
trolling the flow through the boiler bypasses. Small
perturbations of this temperature do not have any
substantial effect on the start-up dynamics. In this
phase of the start-up, only about 20% of the gases flows
through an interstage SO3 absorber (ABSORB l),
whereas the remaining 80% is fed directly from the
fourth onto the fifth reactor pass (stream no. 22).
As may be seen from the above description, the
topology of the system changes on passing from
[“Cl
Fig. 12. Predicted and actual temperature transients in Phase 2 of
the start-up (start-up the reactor after the sulphur burner has
been lit). Simulated - solid lines; measured - broken lines.
Phase 1 to Phase 2. The software developed enables one
to take into account the change in topology during the
simulation.
Figure 11 presents the simulated and actual tran-
sients of the outlet pass temperatures during Phase 1 of
the start-up lasting 9.5 h. As may be seen, the actual
transients agree well with those simulated for this phase
of the start-up operation.
Figure 12 shows the simulated and actual transients
of the outlet pass temperatures for Phase 2, that is,
after the sulphur burner has been ignited. The agree-
ment between the transients is worse than in Phase 1;
this is due to the fact that the ignition procedure for the
sulphur burner is by no means a step process and takes
in fact more than 1 h. During this process the yield of
the burner changes constantly, and it is difficult to
follow these changes properly in the model. For the
 123

Rslotlw axId pdtlon c-1 ii

Fig. 13. Predicted SO, concentration transients at the reactor Fig. 14. Estimated temperature profiles along the reactor passes
outlet during Phase 2 W~SUS values measured using chemical after the 4-h break.
analyses (dots).

identification purposes such a transient has been selected

for which the number of operator’s actions during the
ignition procedure was the least. It has been also assumed
in the modelling that the burner was started in two
stages; the first corresponded to about 10% of the burner
capacity and lasted for about 0.7 h, and was followed by
the burner reaching its full capacity. This is a serious
simplification, leading to poorer agreement between the
temperature transients in Phase 2 (such agreement is,
however, sufficient for analysing the start-up strategies).
Figure 13 presents a comparison between the SO,
concentration predicted at the outlet from the fifth -mrrmr -

reactor pass and several values measured during the 0.0 1.0 2.0 3.0 4.0- i?a Cho”$O

start-up operation. The agreement between the two
concentrations is quite satisfactory. It should be men-
tioned that the SO, emission in the plant studied is
particularly high. This results from a very low capacity
of the start-up heater, which is unable to ensure the
heating of the installation to above 400 “C (673 K)
during Phase 1. Consequently, the objective of the
simulation analysis has been not only to find an appro-
priaie start-up algorithm, but also to determine a cor-
rect heat efficiency of the start-up heater.
Analysis of the ‘hot’ start-ups
The model parameters obtained during the ‘cold’
start-up identification described earlier were mostly em-
ployed in modelling the ‘hot’ start-ups. Only the de-
grees of opening of bypasses in the heat exchangers and
the effective specific heat of the catalyst had to be
identified once again due to change in the operating
conditions of the plant. As has been mentioned before,
in the modelling of the start-ups an additional problem
of estimating the initial temperature profile at the mo-
ment when the sulphur burner is switched on again
arises. Figure 14 presents the temperature profiles esti-
Fig. 15. Predicted temperature transients during a ‘hot’ start-up
following the 4-h break.
mated for all the reactor passes after a break in the
plant operation lasting for about 4 h; Fig. 15 shows the
temperature transients during the ‘hot’ start-up after the
same break. Figure 16 presents a copy of the chart of a
conventional temperature recorder, revealing the actual
transients for the ‘hot’ start-up following a 4-h break.
Figure 17 gives the calculated SO, concentration tran-
sient after the fifth pass of the reactor related to the
steady-state value. The transient recorded by an indus-
trial SO2 analyser at the outlet from the plant has the
shape analogous to that shown in Fig. 17. The values of
concentration may, however, be much higher than those
calculated if, due to poor thermal insulation of the re-
actor, the oxidation of SO2 does not occur at all for some
time in the part of the gas flowing close to the cold wall.
SeIection qfsuitable start-up procedures for the ‘cold’
and ‘hot’ start-ups
In the heuristic ‘optimization’ of the start-ups slightly
more degrees of freedom (decision variables) have been
124

Stage 1.3. Simultaneous heating of passes nos. 1 and

5 (certain amount of hot air is fed directly onto pass
no. 5 via stream 29).

Phase 2 Starting up the reactor by means of SO,-

containing gas from the sulphur furnace.

Stuge 2.1. Operation of the sulphur furnace at a

lower capacity with, alternatively:
- normal flow of the gas and lower SO2 concentration
- decreased flow of the gas and normal SO, concentra-
tion.

Stage 2.2. Operation of the sulphur furnace under

normal load (normal gas flow and normal SO, concen-
tration).

Stage 2.3. Switching on the maximum flow through

the interstage absorber (ABSORB l), provided Stuges
2.1 and 2.2 were carried out at a partial or vanishingfZow
of streum no. 15.
Time[hours]

Fig. 16. Copy of chart of an industrial temperature recorder Procedure proposed for the ‘cold’ start-up
showing the temperatures of the ‘hot’ start-ups after the 4-h
Upon testing several intuitive start-up procedures,
break.
the following strategy for heating of the contact reactor
has been proposed.
(a) Carry out the heating with hot air in about 50%
of the normal flow (i.e. 15 000 standard cubic metres
per hour (SCMH) in the case discussed), gradually
increasing the amount of fuel to reach maximum heater
capacity (without exceeding the admissible rate of tem-
perature increase). The whole air flow should be di-
rected straight onto pass no. 1.
(b) Upon reaching the temperature of 350 “C
(623 K) at the outlet of pass no. 1, decrease the air flow
by about one third (down to 10 000 SCMH).
(c) When the outlet temperature from pass no. 2
has reached 420 “C (693 K), introduce 70% of the air
directly onto pass no. 5.
(d) When the outlet temperature from pass no. 5
has reached 410 “C (683 K), disconnect the start-up
Fig. 17. Predicted SO, concentration transients at the reactor installation swiftly, connect the furnace and the boiler,
outlet (relative to the steady state value) following the 4-h break. and then light the sulphur burner at the flows of the
sulphur and air equal to 50% of the normal values.
assumed to enable a more flexible approach to the (e) Some 3.5-4 h after the sulphur burner was
algorithm. Thus, in fact, the start-up strategy consisted started, switch to normal parameters.
of a larger number of stages defined as follows. The simulation results are shown in Figs. 18 and 19.
Figure 18 presents the temperature transients at the
Piruse I Heating by means of a start-up heater. outlet from the passes, whereas Fig. 19 gives the outlet
SO* concentration relative to the steady-state value.
Stage 1.1. Heating of the reactor pass no. 1 using a The heating of the installation takes about 7.3 h,
high flow of hot air at a lower temperature. whereupon the sulphur is ignited at a 50% load and
then, after 11 h, the load is increased up to its normal
Stage 1.2. Heating of pass no. 1 using a lower flow level. In practice, the necessity to meet all the require-
of hot air at a higher temperature. ments concerning the rate of the temperature increase
 125

200

Fig. 18. Temperature transients at the pass outlets predicted for Fig. 20. Temperature transients at the pass outlets predicted for
the algorithm proposed for the ‘cold’ start-ups. the algorithm proposed for the ‘hot’ start-ups following the 8-h
break.

C-l ing to the maximum capacity of the plant, without any

1.5, I I I I 1 danger of exceeding the admissible emission level.
-Ph& 2-I For the breaks of 2-12 h the algorithm is similar to
that proposed for the ‘cold’ start-up in Phase 2 (after
the lighting of the sulphur burner). For the start-ups
following the breaks longer than 12 h, immediately
after sulphur has been ignited, the operation should be
carried out with bypassing the interstage absorption
tower, until the outlet temperature on pass no. 1
reaches 600 “C (873 K). If the breaks exceed 24 h and
the temperatures of pass nos. 3 and 4 are higher than
410 “C (683 K), pass no. 5 should be heated for about
an hour using the hot air from the start-up heater. If
these temperatures are lower, the ‘cold’ start-up proce-
dure should be employed.
Fig. 19. SO, concentration transient at the reactor outlet (relative As an example, Figs. 20 and 21 show the temperature
to the steady-state value) predicted for the algorithm proposed for and the relative concentration for the proposed ‘hot’
the ‘cold’ start-ups.

C-l
in the lining and in the catalyst prolongs the heating 5.0

phase by 7-8 h compared with the case presented in

Fig. 18. 5.0
If

Procedure proposed for the ‘hot’ start -ups f 4.0

The simulations were performed for the start-up fol-

lowing breaks in the plant operation lasting for 2, 4, 8, $3.0

16, 24, 32 and 40 h. For each of these cases a number B

ty 2.0
of various start-up strategies were simulated. Since
fs
different algorithms have finally been proposed for the
1.0
various breaks, it is impossible to provide a detailed
description of all these algorithms in a single paper.
Thus, the simulation led to different start-up proce-
dures after breaks lasting for: below 2 h; 2-6 h; 6- 12 h;
12-24 h; 24-40 h. Fig. 21. SO, concentration transients at the reactor outlet (rela-
The ‘hot’ start-up carried out after the breaks shorter tive to the steady-state value) predicted for the algorithm pro-
than 2 h may be accomplished by the immediate switch- posed for the ‘hot’ start-ups following the 8-h break.
126

TABLE 2. The SO* emission (kg h-‘) expected for the start-up start-up of an industrial SO2 oxidation plant. The accu-
procedures selected using the computer simulation racy of the complex model of the plant seems to be
sufficient to yield strategies which could then serve as a
Parameter ‘Cold’ ‘Hot’ start-ups after the break lasting for:
start-up first approximation of the start-up experiments in an
2h 4h 8h 16h 24h 32h 40h actual installation. The algorithms proposed in the
present work could not be fully implemented in the
Average 13 32 16 17 22 25 33 27 plant studied because of the very low heat efficiency of
emission
the existing start-up section (it is to be modified in the
Maximum 27 45 36 45 59 63 173* 137*
emission near future). The verification has, however, been carried
out for the simplified algorithm more suitable for the
*NOTE: The admissible emission level is 100 kg h-’ existing (inadequate) heat efficiency, leading to an ex-
cellent agreement between the experiment and the nu-
merical predictions.
start-up algorithm, following an 8-h break. The concen- The results obtained using the computer modelling of
tration transient is compared with that occurring when the transient behaviour of the plant provide an impor-
a ‘jump’ start-up, that is, immediate switching to the tant guideline in dealing with actual start-ups. It follows
full yield, is applied. from the simulation performed that during the ‘cold’
Table 2 presents average and minimum emissions for start-ups and ‘hot’ start-ups after breaks shorter than
both the ‘cold’ and ‘hot’ start-up procedures after the 24 h, it should be possible to curb emission below the
various breaks in the plant operation. admissible levels. After breaks exceeding 24 h the emis-
It should be stressed that the emissions given in Table sions has to be controlled by means of the supplemen-
2 do not increase monotonically with the duration of tary heating of the reactor using an external heat source
the break, as for longer times, more complex start-up (start-up heater).
strategies are employed.
The emission values shown in Table 2 do not take
into account the increased emission resulting from the Acknowledgements
enhanced cooling of the catalyst near the reactor wall.
The author is grateful to all his collaborators for
their help in completing the study. Special thanks are
Conclusions due to Dr Witold Klaudel, who worked out the DY-
NAM flowsheeting simulator software, and to Mr
The model described here gives temperature and con- Marek Moszczynski, who tested tens of the start-up
version transients similar to those measured in large strategies.
industrial reactors, if the physical specific heat of the
catalyst is replaced by an effective value, incorporating
all heat-consuming effects occurring in the catalyst. Nomenclature
The agreement of the model is not very good, since
there is a visible influence of some large ‘side’ heat a, b inlet SO, and 0, concentra-
capacity effect. This effect is stronger for the upper tion respectively, kmol
layers, closer to the gas inlet. kmol-’
The model with the parameter values appropriate for Bi =aD/L,, Biot number
the large scale industrial reactor is sensitive to the a and C reactant (SO*) concentra-
1, values, but the influence of these parameters is not tion, kmol kmol-’
very significant when start-ups of the plant are consid- C* reactant concentration at
ered. Much larger is the influence of an (generally the catalyst surface, kmol
unknown) initial temperature profile on the final simu- kmol-’
lation results. c, gas specific heat, kJ
The model can be used for a qualitative analysis of kmol-’ K-’
the start-up of an SO, oxidation plant. G catalyst specific heat, kJ
Despite the fact that the model does not provide a very kg-’ K-’
precise description of the process simulated it seemed C heat radiation constant,
sufficient for finding the best start-up procedure for the kJ h-’ K-4
complete system at the stage of qualitative analysis. D reactor diameter, m
The dynamic flowsheeting simulation makes it possi- Dar = Hrp,L2/(& r,,), 1st Dam-
ble to analyse the control algorithms concerning the kiihler number
 127

Da” =w,W,, IInd Damkiih- P” catalyst bulk density, kg mm3

ler number heat conductivity, kJ m-’
d -l equivalent catalyst pellet di- h-1 K-l
ameter, m E void fraction coefficient
Fo = Iz,q,,-/(L2Ckpu), Fourier kf =P”G/QS, characteristic
number time for reference, h
functions describing dy-
namic and static part of sys-
Subscripts
tem
e, eff effective
H heat of reaction, kJ kmol-’
gas
h integration step with respect
f catalyst (solid phase)
to time, s
W reactor wall
spatial increment for nu-
Ewztyon
Superscripts
reaction constant, CP catalyst pellets
h-’ Pa-’ in bed inlet (x = 0-)
equilibrium constant, Pa-0,5 out bed outlet (x = L+)
reactor length, m
equivalents of the body
mass at inlet and outlet of
References
bed, kg
% molar gas flux, kmol h-’ 1 B. Liibeck, Comparison of continuous models for description
mm2 of dynamic properties of catalytic solid bed reactors, Chem
r effective reaction rate, kmol Eng. .I., 7 (1974) 29-40.
kg-’ h-’ 2 R. Mann, I. J. Gardner and C. Morris, Reactor dynamics and
P total pressure, Pa strategies for minimising SO* emissions during start-up of a
contact sulfuric acid plant, Chem. Eng. Sri., 3.5 (1980) 185-
S specific catalyst surface, 192.
m2 me3 3 R. Mann, E. Stavridis and K. Djamarani, Experimental fixed-
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128

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14 G. K. Boreskov, M. G. Slink0 and V. S. Beskov, Volume of other mechanisms of the heat exchange. These mecha-
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68-14. modifies only the boundary conditions:
16 G. K. Boreskov, W. W. Illaronov, R. P. Ozierov and E. W.
Kildisheva, Chemical interaction in the vanadium pentoxide- for x = 0:
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sulphate systems, Zh. Obshch. Khim., 34 (1964) 23-29. & 2 - 2;; [TZ(O, t) - r&l = (1 -E)CI[T&JO, t) - TF]
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19 G. K. Patterson and R. B. Rozsa, DYNSYL: A general-pur-
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Eng., 4 ( 1980) l-20.
20 J. C. Fagley and B. Camahan. The sequential clustered &. 2 = (1 _&)CI[Tk(‘L, t) - TF,] -s [Ti(L* t) - T4,J
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21 W. Marquardt, Dynamic process simulation - recent progress
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22 M. Hillestad and T. Hertzberg, Dynamic simulation of chemi-
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23 H. S. Kheshgi, Transient reactor analysis by approximate given in Fig. 4 as lines ‘b’.
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24 Y. Ch. Liu and C. B. Brosilow, Simulation of large scale
Appendix B
dynamic systems, Comput. Chem. Eng., II (1987) 241-253.
2.5 J. W. Ponton, Dynamic process simulation using flowsheet
structure, Comput. Chem. Eng., 7 (1983) 13-17 D_vnamic model of a counter current gas gas heat
26 J. W. Ponton and V. Vasek, A two-level approach to chemical exchanger (with dominating thermal capacity of the
plant and process simulation, Comput. Chem. Eng., JO (1986) W&l)
277-286.
The model has been reduced to that of an equivalent
27 J. C. Heydweiller, R. F. Sinovec and L. T. Fan, Dynamic
simulation of them. processes described by distributed and shell-and-tube exchanger by assuming that the condi-
lumped parameter models, Comput. Chem. Eng., 1 (1977) tions in all tubes are uniform. It is assumed that the
125-131. accumulation of heat in the shell and the tube them-
28 R. S. H. Mah, S. Michaelson and R. W. H. Sargent, Dynamic selves is high enough to justify the omission of the
behaviour of multi-component multi-stage systems. Numerical
accumulation in two gaseous media. The axial conduc-
methods for solution, Chem. Eng. Sci., 17 (1962) 619-639.
29 J. C. Heydweiller and R. F. Sinovec, The influence of A-stabil- tion of heat along the exchanger is also neglected.
ity on the efficiency of stiff integrators, Comput. Chem. Eng., 6 Thus, the balance equations may be written as fol-
(1982) 185-188. lows:
30 S. Kuru and A. W. Westerberg, A Newton-Raphson based
strategy for exploiting latency in dynamic simulation, Comput. v, c, _ + (T, - T&d, ~1,= 0 (B-1)
Chem: Eng., 9-(1985) 175-182. 3X

(T, - T&d, a, + (T, - T,)nd,cc, - -

at
m,c, = 0 (B-2)
Appendix A
vzcz2 + (T, - T&rd,cc, + (T, - Ts)nd,a, = 0 (B-3)
An analysis of influence of the reactor body
To analyse how the reactor body influences the dy- aT
(7;; - T&d,cr, - 2 m,c, = 0 (B-4)
namic start-up transients, a very simple model of the at
 129

subject to the following initial conditions (t = 0) m unit mass of shell or tube, kg m-’
temperature, K
TdO9 4 =“A(42 Ts(O, 4 =f,G) (B-5) f
gas flow rate, kmol h-’
and the boundary conditions u heat transfer coefficient, kJ m-* h-’ K-’
for x = 0 TI (& 0) = CPI(t) (B-6) cp temperature transients imposed at inlets, K
for x = L T,(t, L) = 92(t) (B-7)
Subscripts
where: 1 inside of tube
C specific heat, kJ mol-’ K-’ for gas; kJ kg-’ K-’ for 2 inside of shell
material of shell or tube 3 outside surface of shell
d diameter, m t tube
f initial temperature profile assumed, K S shell