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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)

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

(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

113

rous metallurgy, from pyrite or from other sulphide PS(C- C*) + rp, + .z*p, g = 0 (4)

ores. The heat of reaction is recovered to heat the cold

new gas (about 60 ‘C) leaving the scrubbers and elec- Equations ( 1) -(4) constitute the overall one-dimen-

trofilters, and to heat the gas after the interstage ab- sional model, assumed by many authors as a basis for

sorption (see above). further simplifications.

The two groups form a sufficiently large number of Practically, there is no universal kinetic model de-

possible connections of the reactor passes, the heat scribing adequately the reaction rate function r in eqns.

exchangers and the interstage absorber to justify the (2) and (4). The author’s experience has proved that

solution of the appropriate models using a single gen- Boreskov et al.3 [ 141 equation can be taken as a basis

eral computer program. for further approximation based on laboratory tests of

While the literature dealing with the modelling of the the catalyst samples employed. For the model dis-

reactor itself is abundant, the dynamics of the complete cussed, the following form of the reaction rate expres-

SO, oxidation plants has not been analysed properly. It sion has been taken:

seems that, apart from the earlier works published by r=kPb-W/2) 1-X

the author of the present paper and his co-workers

1 - @X/2) 1 -0.2X

[ 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 (5)

SO, has been well documented by Mann et a[. [2], in

spite of the fact that the simple mathematical models The original form of eqn. (5) given in ref. 14 is not

proposed by these authors, as well as that in ref. 13, do sufficient to describe r for the various commercial cata-

not meet the requirement of generality of the descrip- lysts, as then for the reaction rate constant k, an

tion. The dynamic flowsheeting simulator seems to be original Arrhenius type formula was not used. Instead a

an adequate tool in this case, if we do not intend to more complex function of temperature, identified indi-

build a complex model for a single and usually unique vidually for the particular industrial catalyst type and

installation. 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

The model of a single reactor bed separate problem which will not be discussed here in

detail. Generally the reaction rate r is a highly non-lin-

The model equations of a single reactor bed ear function of T, and i& where i? is a vector of local

An ideal plug flow is assumed, with negligible radial reactant concentrations

dispersion in the reactor. For reactors with large ratios r = f(T,, I?)

between the reactor diameter and the equivalent cata-

lyst pellet diameter, the assumption D/d,, 2> 1 is quite Equations ( 1) -(4) should have been supplemented

admissible. Hence the following heterogeneous heat and with appropriate initial and boundary conditions, but

mass balances can be written: for the sake of brevity this will be presented together

with simplified forms given below.

The heat balances

Before we go any further with the discussion and

for the gas phase: analysis of the model applied, we should answer the

question why, in this paper, the radial concentration

A.s~+ngCg~+~peCg~+aS(T~- T,) =0 (1) and temperature gradients are not taken into account in

any of the models discussed. Looking at the radial

for the solid phase: temperature profiles for the experimental reactor, given

by Mann et al. [3], one can see that even for the

PT laboratory scale the radial dispersion effect is significant

k - pu C, 2 + cxS(T, - T,) + Hrp, = 0 (2)

lk ax2 only for the case without the reaction. When the reac-

and mass balances tion occurs, the radial dispersion and wall effects are

much smaller. Moreover, the measurements of the hori-

for the gas phase: 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

for the solid phase: 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 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:

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

115

means that there are some regions along the reactor bed modelling the dynamics of the bed cooling. Some qual-

with the temperature enabling the immediate re-start of itative study of such a cooling process was carried out.

the reactor by supplying the hot gas with an appropri- A strict mathematical model of the cooling of the

ate SO, content. reactor bed would be very complicated, due to the

(2) The ‘cold start-up’ - that is, the start-up of the complicated ways of the heat outflow of the bed, when

reactor from its initial state when it is completely it is being cooled down. Additionally, one should de-

cooled down, first by using hot air from some external velop an individual model for any geometry of the

preheater and then by supplying the reactant when the reactor. Moreover, it seems impossible to provide reli-

reactor (or at least a part of it) has already been able quantitative parameters for such a model.

preheated to the appropriate reaction temperature For the analysis of the dynamic behaviour of the bed

(above 400 “C for the SOP oxidation case). during the ‘hot start-up’, the profile was estimated by a

The case of the ‘hot start-up’ was chosen as a subject trial and error method beginning with an initial steady

of investigation and identification of a single bed, as a state profile. The temperature of the bed was measured

first approach to the dynamic modelling problem. at -two points, namely for X Y 0.2 and X = 1, where the

During the ‘hot start-ups’ some interesting ‘oscilla- thermocouples were installed. The initial temperature

tions’ are observed. The simulation was expected to profile should fit these measurements at these points.

explain the nature of this phenomenon. For the com- The remaining part of the profile should have been

plete oxidation plant, both ‘cold’ and ‘hot’ start-ups estimated in such a way that an agreement could be

were investigated. obtained between the transients calculated with those

measured (at these two points) during the start-up

Identification of the model parameters for a single period. However, one should be aware of the fact that

reactor bed the assumption of the initial profile is the weakest point

To identify the model one should have not only the of the analysis. The initial profile taken for further

adequate mathematical equations, but also reliable val- simulation is shown in Fig. 3 as curve 1.

ues of the parameters used in the numerical calcula- Curve 2, also shown in this figure (dots), presents the

tions. Only few of the parameter values can be initial profile intentionally deformed, to test the sensitiv-

estimated with confidence. Others, like u or A,, have to ity of the transients to the initial profile shape; this will

be evaluated based on the relations taken from the be discussed further. As may be seen, the simulated tran-

literature. One can obtain different values of the sients are sensitive to the profile assumed, but this does

parameters, depending on a particular reference taken not change the time scale of the observed oscillations.

into account. Thus, an analysis of the sensitivity of the

results with respect .to these ‘uncertain’ parameters Problem of the heat capacity of the bed

seemed to be of particular importance. The parameter C, appearing in eqn. (2) should not

For the SO, oxidation reactor case, there are two be regarded simply as a physical specific heat of the

problems which should be treated with special care. catalyst.

These are: the initial temperature profile and the heat When the catalyst is heated up, the following pro-

capacity of the bed. cesses are observed:

The initial temperature profile (i.e. condition (9)) can Loci

_

be easily determined only for the ‘cold start-up’, when 620 150 min

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. 520

For the industrial reactor of dimensions such as, say,

3

those shown in Fig. 2(a), it is very difficult to measure

the initial profile. One can say that it is practically !i

s

impossible to realize this measurement in an industrial + 420

/

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 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.

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

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).

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

‘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

predictor [ 181).

Y(l + h,) =v(0 + V,{y(t + &)I (22) A comparison between several numerical methods,

In eqn. (21), the new value of the vector y for the both explicit and implicit, has been given in ref. 28.

next time step (t + h,) is calculated directly from the ln short, the numerical algorithm employed in the

value for the preceding step. In the case of eqn. (22), present work consists of the following steps:

when the function Fd cannot be uncoupled with respect

(1) Write the initial state of the installation streams

to y(t + h,) we have to resort to iterative methods. The

into the matrix STREAM 1, and that of the individual

uncoupling of eqn. (22) is either impossible or very

apparatus into the matrix STATE 1.

difficult (this concerns particularly the generally appli-

(2) Carry out the integration of all the apparatus for

cable software systems) and, consequently, the iteration

a single step h, - in any order, and write the new values

becomes a must.

(i.e. those for the time t + h,) for the streams and the

In ref. 27 the following classification of the sets of

individual apparatus into the matrices STREAM 2 and

equations has been given, depending on their stiffness

STATE 2, respectively.

coefficient:

(3) Write the values calculated into the final sets of

s = l-10: non-stiff problems, which may be the simulation results and check whether the actual

solved easily using the explicit meth- time does not exceed the fixed overall time of computa-

ods, tions. If it does ~ terminate the calculations, otherwise

S = 100-1000: moderately stiff problems rewrite the matrices STREAM 2 and STATE 2 into

STREAM 1 and STATE 1 and go back to step 2.

For S exceeding 1000 the explicit methods become

very inefficient, leading to instability and poor accuracy The flowsheeting software DYNAM, developed in

of the solutions. It should be mentioned that if the the Institute of Inorganic Chemistry by W. Klaudel and

system contains elements characterized by the spatially the author of the present paper, makes use of the above

distributed parameters and described by the partial algorithm.

equations, the stiffness coefficient usually increases; According to the classification presented, this al-

such elements may be formed by the individual reactor gorithm belongs to the group of the modular-simulta-

passes and heat exchangers in the installations whose neous methods.

simulation will be described later. In spite of this, in ln a numerical procedure thus formulated the prob-

the simulations discussed the application of an explicit, lem of the order of calculations, which is so important

simultaneous modular method did not result in any in the modular-sequential method of static simulators,

major problems. disappears altogether. Also, we do not have to inverse

The sequential modular method mentioned before sparse matrices of large dimensions. At the same time,

leads to additional iteration difficulties due to the tear- the description of the dynamic system is divided into

ing of streams. separate procedures concerning the dynamics of indi-

vidual apparatus and, consequently, the modular struc-

Dynamic flowsheeting simulator for the SO2 oxidation ture of the software can be retained. For the modules

plant characterized by complex dynamics (e.g. with a high

In ref. 11 a simple numerical procedure has been stiffness coefficient), the algorithm thus defined enables

proposed, employing the original idea of Klaudel and us to divide further the time step h,, imposed by the

based on the explicit Euler numerical formula with main integrator of the system, into smaller steps within

regard to the time derivative. The procedure enables the procedure describing a given module. It is also

non-iterative calculations to be performed for any topo- possible to use the semi-implicit method by performing

logical structure of chemical installations. The price the implicit integration inside the module; however, in

for this simplicity is the necessity of employing small the case discussed such measures were not necessary.

integration steps regarding both the time (h,) and the The starting point for coding the algorithm of the

spatial coordinates (h,), which leads to the prolonged DYNAM simulator is provided by the flowsheet of the

computing time. However, even using commonly acces- installation. Such a flowsheet for an actual plant is

sible fast 32-bit computers of the PC class, we obtain shown in Fig. 10. The dynamic simulation of this plant

maximum computing times not exceeding a couple of is an example of application of the method proposed.

hours for topologically complex structures. The flowsheet presented contains 24 calculating mod-

Although application of the explicit method is not ules coupled by means of 41 material flows. Twelve of

recommended for stiff sets of equations, the literature the modules (reactor passes, heat exchangers, absorber,

presents some examples of how these relatively simple sulphur burner and start-up furnace) are described by

methods have nevertheless been used for simulation the mathematical models of significant dynamics. The

121

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.

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

Air pass, revealed a high degree of mathematical complex-

Fig. 10. Flowsheet of an industrial SO, oxidation plant simulated ity. It seems, therefore, that a singular optimization for

in the present study. 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

others (mixing or splitting of the gas streams) are practical value. Moreover, for such a complicated prob-

treated as static elements. From the point of view of the lem (size of the system) we cannot resort to any suit-

start-up operation of the SO, oxidation plant, the most ably tested methods of formal optimization. Taking

essential dynamics is that of the reactor passes and the into account the long time necessary for the computer

interpass heat exchangers. The discussion carried out in simulation of a single start-up strategy, the heuristic-in-

the present work is focused solely on the start-ups of tuitive approach to the selection of the start-up proce-

the catalytic reactor equipped with interpass heat ex- dure has been chosen. Although this approach does not

changers and on the interstage absorption. The start-up guarantee that the results obtained will, in fact, be

(heating) of the sulphur furnace and of the heat utiliza- optimal, it does lead to conclusions which may be

tion boiler has been excluded from the analysis. This acceptable from the practical point of view.

enabled us to avoid modelling of the complex dynamics An additional practical restriction which has to be

of the boiler systems. taken into account in the start-up optimization is that

The equations used in simulating the shell-and-tube imposed by the producer of the catalyst and the lining,

heat exchangers are presented in Appendix B. The concerning the admissible rate of temperature increase

description of other dynamic elements of the system has in the reactor. At the initial stages of heating, when the

been omitted, as their effect on the transients of the temperature may increase fairly rapidly, it is easy to

system is less important. violate these restrictions. However, to simplify the sim-

The dynamic description as a complex structure ulation these restrictions have not been included in the

would be extremely tedious without the specialized tool model. In practice, the algorithm obtained by means of

provided by the DYNAM simulator. the simulation may be adapted to these limitations if we

122

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

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.

supplied from the start-up heater consisting of a gas [“Cl

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).

Fig. 12. Predicted and actual temperature transients in Phase 2 of

Phase 2: Start-up proper, which follows the discon- the start-up (start-up the reactor after the sulphur burner has

nection of the start-up heater. At the moment the been lit). Simulated - solid lines; measured - broken lines.

combustion of sulphur begins in the sulphur furnace

(FURNAC l), the gases containing SO, are supplied Phase 1 to Phase 2. The software developed enables one

through the boiler (BOILER 1) to the inlet of the first to take into account the change in topology during the

reactor pass (REACT 1). Lacking any reliable dynamic simulation.

model of the steam boiler it has been assumed for Phase Figure 11 presents the simulated and actual tran-

2 that the temperature of the gases leaving the boiler is sients of the outlet pass temperatures during Phase 1 of

constant. If the boiler has been properly heated in the start-up lasting 9.5 h. As may be seen, the actual

Phase 1, such an assumption is very close to reality, as transients agree well with those simulated for this phase

this temperature may indeed be kept constant by con- of the start-up operation.

trolling the flow through the boiler bypasses. Small Figure 12 shows the simulated and actual transients

perturbations of this temperature do not have any of the outlet pass temperatures for Phase 2, that is,

substantial effect on the start-up dynamics. In this after the sulphur burner has been ignited. The agree-

phase of the start-up, only about 20% of the gases flows ment between the transients is worse than in Phase 1;

through an interstage SO3 absorber (ABSORB l), this is due to the fact that the ignition procedure for the

whereas the remaining 80% is fed directly from the sulphur burner is by no means a step process and takes

fourth onto the fifth reactor pass (stream no. 22). in fact more than 1 h. During this process the yield of

As may be seen from the above description, the the burner changes constantly, and it is difficult to

topology of the system changes on passing from follow these changes properly in the model. For the

123

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).

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 Fig. 15. Predicted temperature transients during a ‘hot’ start-up

concentrations is quite satisfactory. It should be men- following the 4-h break.

tioned that the SO, emission in the plant studied is

particularly high. This results from a very low capacity mated for all the reactor passes after a break in the

of the start-up heater, which is unable to ensure the plant operation lasting for about 4 h; Fig. 15 shows the

heating of the installation to above 400 “C (673 K) temperature transients during the ‘hot’ start-up after the

during Phase 1. Consequently, the objective of the same break. Figure 16 presents a copy of the chart of a

simulation analysis has been not only to find an appro- conventional temperature recorder, revealing the actual

priaie start-up algorithm, but also to determine a cor- transients for the ‘hot’ start-up following a 4-h break.

rect heat efficiency of the start-up heater. Figure 17 gives the calculated SO, concentration tran-

sient after the fifth pass of the reactor related to the

Analysis of the ‘hot’ start-ups steady-state value. The transient recorded by an indus-

The model parameters obtained during the ‘cold’ trial SO2 analyser at the outlet from the plant has the

start-up identification described earlier were mostly em- shape analogous to that shown in Fig. 17. The values of

ployed in modelling the ‘hot’ start-ups. Only the de- concentration may, however, be much higher than those

grees of opening of bypasses in the heat exchangers and calculated if, due to poor thermal insulation of the re-

the effective specific heat of the catalyst had to be actor, the oxidation of SO2 does not occur at all for some

identified once again due to change in the operating time in the part of the gas flowing close to the cold wall.

conditions of the plant. As has been mentioned before,

in the modelling of the start-ups an additional problem SeIection qfsuitable start-up procedures for the ‘cold’

of estimating the initial temperature profile at the mo- and ‘hot’ start-ups

ment when the sulphur burner is switched on again In the heuristic ‘optimization’ of the start-ups slightly

arises. Figure 14 presents the temperature profiles esti- more degrees of freedom (decision variables) have been

124

5 (certain amount of hot air is fed directly onto pass

no. 5 via stream 29).

containing gas from the sulphur furnace.

lower capacity with, alternatively:

- normal flow of the gas and lower SO2 concentration

- decreased flow of the gas and normal SO, concentra-

tion.

normal load (normal gas flow and normal SO, concen-

tration).

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.

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

Fig. 18. 5.0

If

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

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

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-

St = r/&C,), Stanton num- bed reactor dynamics for SO, oxidation, Chem. Eng. Res.

ber Des., 64 (1986) 248-257.

4 P. Venkatchalam, L. Kershenbaum, E. Grossman and R.

STREAM 1, STREAM 2 matrices describing flows in

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apparatus in system before Sci., 27 (1972) 1909-1924.

and after integration step _

6 G. Eiaenberger._ Influence of the wall on the dvnamic behavior

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time, h (1974) 477-488; Adv. Chem. Ser. 133, Am. Chem. Sot., Wash-

= t/tmf, dimensionless time ington, DC.

conversion H. S. Weng, G. Eigenberger and J. B. Butts, Catalyst poison-

axial coordinate, m ing and fixed bed reactor dynamics, Chem. Eng. Sci., 30 (1975)

1341-1351.

=x/L, dimensionless H. Van Doesburg and W. A. De Jong, Dynamic behavior of

length an adiabatic fixed-bed methanor, Int. Symp. Chem. Reaction

Y vector variable describing Eng., Evanston, IL, (37) (1974) 489-504; Adv. Chem. Ser. 133,

state of system Am. Chem. Sot., Washington, DC.

K. W. Hansen and S. B. Jorgensen, Experimental investi-

partial derivatives of state

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variable with respect to spa- Int. Symp. Chem. Reaction Eng., Evanston, IL, (38) (1974)

tial coordinate 505-518; Adv. Chem. Ser. 133, Am. Chem. Sot., Washington,

DC.

Greek letters K. Gosiewski, Optimization of some type of an unsteady state

of SO, oxidation reactors, Proc. Int. Cong. Contr. Computers

31 gas-solid heat transfer co-

Dev. Chem. Eng. Ind. Chemistry, Paris, France, 1978.

efficient, kJ m-* h-l K-’ K. Gosiewski and W. Klaudel, A dynamic flowsheeting as a

PP molar gas density, kmol tool for a sulphuric acid plant start-up analysis, Proc. 6th Znt.

me3 Conf. Large Chem. Plants, Antwerp, Belgium, 1985.

128

12 K. Gosiewski and M. Moszczynski, Dynamic simulation of heat transport from the bed to the body was employed.

the start-up of SO, oxidation unit in sulph. acid plants (in The model assumes that the only mechanism through

Polish), Przem. Chem., 70 (1991) 422-425.

which the heat may be exchanged between the catalyst

13 J. C. Mishra and M. T. Sebastian, Mathematical modelling of

unsteady state process in SO, converter, Proc. Inr. Co& bed and the body of the reactor is radiation from the

Unsteady State Processes Catal., Novosibirsk, USSR, 1990, upper and lower surfaces of the catalyst bed. Such an

659-664. assumption results from the qualitative analysis of

14 G. K. Boreskov, M. G. Slink0 and V. S. Beskov, Volume of other mechanisms of the heat exchange. These mecha-

catalyst, stability and parametric sensitivity in sulfuric dioxide

nisms have a much smaller share in the overall amount

oxidation equipment, Khim. Prom., 3 (1968) 13- 18.

15 G. H. Tandy, The role of alkali sulphates in vanadium cata- of heat exchanged than radiation.

lysts for sulphur dioxide oxidation, J. Appl. Chem., (1956) The incorporation of radiation into the model

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:

potassium sulphate and vanadium pentoxide-potassium pyro-

sulphate systems, Zh. Obshch. Khim., 34 (1964) 23-29. & 2 - 2;; [TZ(O, t) - r&l = (1 -E)CI[T&JO, t) - TF]

17 V. HlavaEek, Analysis of a complex plant steady-state and

transient behavior, Comput. Chem. Eng., 1 (1977) 75-100. (A-l)

18 S. Bobrow, J. W. Ponton and A. I. Johnson, Simulation of the

transient behavior of complex chemical plants using a modu- a7-

lar approach, Cue. J. Chum. Eng., 49 (1971) 391-397.

C[TZ(O, f) - Ti”] = IV,“& at (A-2)

19 G. K. Patterson and R. B. Rozsa, DYNSYL: A general-pur-

pose dynamic simulator for them. processes, Comput. Chem. for x = L:

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

method for dynamic chemical plant simulation, Comput.

Chem. Eng., 14 (1990) 161-177. (A-3)

21 W. Marquardt, Dynamic process simulation - recent progress

and future challenges, in W. H. Ray and Y. Arkun (eds.), 3T..vr_

Proc. Chem. Process Control, 1991, 17-22.

CP-;Z(l, t) - ~4,,1 = MwLCwT$- (A-4)

22 M. Hillestad and T. Hertzberg, Dynamic simulation of chemi-

cal eng. systems by the sequential modular approach, Comput. Solving eqns. (6) (7), (8) subject to the above condi-

Chem. Eng., 10 (1986) 377-388. tions (A-l) -(A-4) we get the temperature transients

23 H. S. Kheshgi, Transient reactor analysis by approximate given in Fig. 4 as lines ‘b’.

Jacobian factorization, Comput. Chem. Eng., 14 (1990) 149-

156.

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

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

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