Chemical Engineering Science, 1970, Vol. 25, pp. 1503-I 5 16.

Pergamon Press.

Printed in Great Britain.

Parametric sensitivity and runaway in fixed bed catalytic reactors

R. J. VAN WELSENAERE
and G. F. FROMENT
Laboratorium voor Petrochemische Techniek, Rijksuniversiteit, Krygslaan 105, Gent, Belgium
6 April 1970)

(Received
Abstract-The

paper introduces two intrinsic criteria for runaway in fixed bed tubular reactors based
on the occurrence of characteristic points in the temperature profile along the reactor. Their transposition in the partial pressure-temperature
phase plane allows the derivation of some very simple
formulae for the prediction of the critical values for the operating variables. The results are compared
with those obtained from Barkelews empirical criterion. The namer also treats the related nroblem
of a hot spot which has to be limited for reasons other than runaway. The simple formulae mentioned
above can also be used in this case to determine the operating conditions.

WHEN AN exothermic
reaction is carried out
in a tubular reactor with constant wall temperature, a temperature rise of the reacting gases
leading to a so-called hot spot is practically
inevitable.
For reasons
of safety, catalyst
activity and process selectivity, the hot spot
temperature has to be maintained within given
limits. Yet, in many cases the hot spot temperature is very sensitive to relatively small changes
in the process variables such as inlet temperature or concentration
and wall temperature.
Therefore, if care is not taken, the temperature
may rise in an uncontrollable way- there may
be runaway. The study of this phenomenon is
an important part of reactor design and operation.
Bilous and Amundson[2]
have studied this
so-called
parametric
sensitivity
by a non
steady state approach which considered the
effect of a sinusoidal perturbation. The application of their method necessitates the knowledge
of one steady state profile of temperature and
concentration in the reactor, and this requires
numerical integration of the system of continuity
and energy equations. Barkelew [ 11 integrated
this system numerically for a very large number
of cases. From the results he derived, empirically,
a so-called stability criterion. It might be worthwhile to point out the improper use of the word
stability here. Clearly, there can be no question of instability sensu strictu; when the gas
and solid temperatures
are considered to be

equal the ideal tubular reactor is always stable

sense stricto. Therefore, the terms, parametric
sensitivity and runaway are to be preferred.
This paper presents intrinsic criteria for runaway in ideal tubular reactors from which limits
for the operating variables may be calculated.
The paper also treats the related problem of
limiting the hot spot for reasons other than runaway. It is believed that the simple methods
presented here- which do not require the use
of a computer-are
of value for initial stages of
design in which the operating conditions still
have to be fixed.
1. MATHEMATICAL
MODEL OF AN
TUBULAR
REACTOR

IDEAL

The continuity equation for one of the reacting components and the energy equation of a
one dimensional tubular reactor with constant
wall temperature, for a single reaction, constant
fluid density and no difference in temperature
and partial pressure between fluid and solid,
may be written:

(1)
td,=

&

c,

r-2..

cp. R

(T-TT,).

(2)

The following discussion will be based on an

irreversible reaction with 7 a : pseudo first order
rate equation:

1503

R. J. VAN
r

and

WELSENAERE

G.

F. FROMENT

pBO. e-(alT)+b_

The equations may then be written:

Sk?=_A
dz

. p

. e-(alT)+b

$f=B.p.e-

Ca/T)+b

(3)
_

( T

T,)

(4)

where:
A

=M-P.
PY

Pb .p*o;

BkAH).Pbapg.
ClJ

c=7&

2.U
c, . R

0.005

\
0.5
z.m

I
I.0

Fig. 1. Partial pressure profiles in the reactor illustrating the

sensitivity with respect to the inlet partial pressure.

forz=O:p=pO
T=

To= T,.

To illustrate the phenomenon

of parametric
sensitivity and runaway the system (3)-(4) was
integrated numerically
using a Runge-Kutta
technique, for a set of inlet conditions and with
the following fixed values of the parameters:
M = 29.48 kg/kmole; P = 1 atm;

Pa = 1,300 kg/m3; py = l-293 kg/m3;

(-AH) = 307.000 kcal/kmole;
c, = 0.323 kcal/m3. C; u = 3600 m/hr;
U = 82.7 kcal/m2. hr. C; R = 0.0125 m;
PB O = O-208 atm; a = 13.636 K-l;
b = 19.837.
U may be an overall coefficient, accounting for
resistance to convective
heat transfer at the
inner and outer wall and to conduction through
the wall itself or only an inner convection
coefficient. In the first case T, represents the
coolant temperature,
in the second the wall
temperature. In what follows wall temperature
will be used without really distinguishing
between both cases. The resulting partial pressure and temperature
profiles are shown in
Figs. 1 and 2 which illustrate the sensitivity
with respect to the inlet partial pressure.
Figure 3 illustrates the sensitivity with respect
to the inlet or wall temperature. It may be deduced from this figure and the corresponding

conversions that a too severe restriction of the

hot spot leads to excessive reactor lengths.
Generally,
the more important the hot spot,
the greater the risk of runaway, however.
Froment has already discussed this and pointed
out that dilution of the catalyst would be the
practical solution[3].
These aspects of the
problem will not be considered in the prespnt
paper, however.
An inspection of the temperature
profiles
of Figs. 2 and 3 shows how these may be
characterized
by two types of points, namely
the maximum and the inflexion points. In what
follows these characteristic
features, will be
translated into a p-T diagram. The analysis of
the curves in this diagram will enable certain
predictions
concerning the behaviour of the
reactor as a function of wall temperature, feed
temperature and composition, without any numerical integration or complicated calculations.
2. THE REACTOR
BEHAVIOUR
REPRESENTED
IN THE p-T PLANE

Dividing
equation:

(4) by (3) leads to the following

T-T,
dT=_E+C
A
A
*
p
.
dp

e-(a/T,+be

(5)

The trajectories
in the p-T diagram may be
obtained by numerical integration of (5) or from
the Figs. 1 and 2. Some are shown in Fig. 4.

1504

Fixed bed catalytic reactors

.y

675

!-

Fig. 2. Temperature profiles corresponding

to p-profiles of Fig. 1.

0.02

E
B
0

0.01

625

650

675
T,OK

Fig. 3. Temperature profiles in the reactor showing

sensitivity with respect to the inlet temperature.

the

1505

Fig. 4. p-T phase plane, showing trajectories, maxima-curve,

loci of inflexion points and the simplified curve p.,.

R. J. VAN WELSENAERE

and G. F. FROMENT

The loci of the maxima and the inflexion points

in the reactor temperature
profile, when represented in the p-T plane, will now be discussed
in detail.
The locus of the maxima

In the maximum of the reactor temperature

profile the following relation exists between
p and T:
B . pm . e--(alTm)+b- C . (T, - T,) = 0.

(6)

This relation may be obtained by setting dT/dz

equal to zero in (4). It is also valid in the temperature maximum of the trajectories in the p-T
plane, as can be seen by setting dT/dp equal to
zero in (5). When written explicitly with respect
to pm (6) becomes:
P?ll=B
_

Tm- Tto

Fig. 5. Maxima curves for a few wall temperatures.

plified curve.

Sim-

(7)

e-(alT,)+b

p-values beyond its maximum. A particular

importance may be ascribed to the trajectory
that intersects
the maxima curve in its
The only operating variable in this equation is I
maximum. Indeed, from there on a small inthe wall temperature, T,,,. The curve representcrease in p or To leads to an increase in the hot
ing the loci of the corresponding hot spot tempspot which is much more pronounced than before.
eratures and partial pressures, pm, is shown in It is proposed that a first objective criterion for
the p-T diagram of Fig. 5, for several values of
runaway be based upon the maximum of the
T,,.. From now on such a curve will be called
maxima curve. The criterion would then
the maxima curve.
state: The trajectory going through the maxiBy setting dp,ldT, = 0, two extrema are
mum of the maxima curve is considered as
found. The temperature
corresponding
to the
critical and therefore as locus of the critical
maximum of a maxima curve, TM, is given by:
inlet conditions for p and T corresponding to
a given wall temperature. This is a criterion for
T,=+[a-da.
(a-4T,)]
(8)
runaway based on an intrinsic property of the
system, not on an arbitrarily limited temperature
and the temperature corresponding to the miniincrease.
mum by:
C

d[a+da.

(a-4T,)].

(9)

For all practical values of the parameters the

minimum of the curve lies far beyond the temperature range of practical interest. Figure 4
shows how trajectories corresponding
to low
p-values intersect the maxima curve before
its maximum, and those corresponding to high

Locus of inflexion points of the reactor temperature profiles

The T(z)-curves of Fig. 2 reveal that the hot
spot becomes important when inflexion points
occur
before
the temperature
maximum.
Differentiating (4) with respect to z, equating
the result to zero and rearranging leads to the
following equation:

1506

Fixed bed catalytic reactors

(pi), or (pi)2 corresponds

Equation

(11) expresses

the relation

between

p and T at the point of inflexion in the T-z plane.

Before representing it in the p-T plane, the fol-

lowing groups
the notation:

will be introduced

pi . $.

e-(a/T$+b

to simplify

p *

g=A*(Ti)
t

To avoid inJexion points before the maximum

of the T(z)-curve,
and therefore runaway, the
p-T trajectory corresponding
to the chosen
conditions should not intersect the (pi)1 curve.
The critical trajectory is tangent to (pJl. It

l+&(Ti-Tw)=B*(Ti)
1

e-(a/Ti)+b

Ti-Tm=

B J * ( Ti)

C*(Ti).

(11) then reduces to:

A*.(p*)2-(B*+B*).p*+C*=0.

(12)

The solutions of this quadratic are given by:

P ?,2

(B*+B*)ad(B*+B*)2-4A*
=

to an inflexion point
in the T(z)-curve. As long as the trajectories
stay out of the (pi)r-(pi)2 region, the corresponding part of the T(z)-curve is concave upwards.
It is found that the intersection of the trajectories with (pi)2 always occurs after the intersection with the maxima-curve and therefore,
corresponds to the inflexion point beyond the
maximum in the T(z)-curve. Not all trajectories
have an intersection with (pi)13 however, just
like some T(z)-curves
do not have inflexion
points before their maximum. As soon as an
inflexion point of this type occurs, the hot spot
grows and there is runaway. Therefore, a second
objective criterion for runaway may be derived
from the occurence of inflexion points before
the T-z maximum. It may be stated as follows:

.C*

corresponds to two coinciding inflexion points

before the maximum of the T(z)-curve. This
second criterion too is based on an intrinsic
property of the system and not, for instance, on
an arbitrary choice of what would be called
runaway temperature.
The problem is now to predict the point of
tangency between the curve and the critical
trajectory, even if the latter is not availabletrajectories require numerical integration as can
be seen from (5). In the tangency point

2A*
(13)

dP d(Pih
-=-

so that

dT
(Pik2

pc2

(14)

c e-aTi+b

Figure 4 contains, by way of example, (p2)i and

(pi)2 corresponding to T, = 625K.
It follows from an investigation of the sign
of d2T/dz2 that the T(z)-curve is concave downwards as long as the corresponding trajectory
in the p-T plane is comprised between (pi)1
and (pi)2. An intersection of a trajectory with

dTi *

(15)

In the resulting equation, p has to be substituted

by the value of (p&, given by (14). An equation
in Ti only results, but it is implicit and laborious
trial and error is involved in its solution. To
avoid recourse to a computer and retain the
advantage of the present treatment
another
method was attempted for determining the temperature of the contact point. In Appendix I-l
it is shown that for practical values of the parameters B *( Ti) may be neglected with respect

1507

R. J. VAN WELSENAERE

to B *( Ti) so that (12) reduces to:

(16)

A*.(p*)z-B*.p*+c*=o
and(l3)to
(p,*

2,1,2

c*

B*&V(B*y-A*.

2A

and G. F. FROMENT

The next step is the calculation of the temperature corresponding to the contact point between
the p,-curve and the related critical trajectory.
Applying (15) to ps leads to the implicit Eq. (20),
from which (Ti)t may be calculated.

(17)

(20)

from which:

t =
(Pi,l)s=

P.3=

(pi,t)s =

B Ti
a _ @mi,+r,
c

BTi-Tw
s

a/(Ti)t

(21.a)
(2 1.b)

tw=a/T,

(18)

K = _A
c

eb-20

(22)

(19)

e-wTi)+b

It may be noted immediately that Eq. (19) for

(pls), is identical to (7), which is the expression
for the maxima-curve.
This means that the
maximum and the inflexion point beyond this
maximum would coincide and this is obviously
incorrect. For the purpose of this paper, however,
the inflexion point beyond the maximum is
less important and will not be discussed any
further.
It follows from (18) that ps is independent
of the wall temperature T,. It can be shown, by
eliminating T, between (7) and (8) that ps is
the locus of the maxima of the maxima-curves.
This is illustrated by Figs. 4 and 5. Both pz,l and
ps are represented
in Fig. 4. It is seen that the
true curve always lies above the simplified, as
is also apparent from Eq. (13). Therefore, the
use of ps is more conservative than the use of

Equation (20) is entirely general: all parameters

are grouped in K, t and t,. Some mathematical
aspects of (20) are discussed in Appendix I-2.
In order to facilitate the solution of (20) and
therefore the application proposed here, (20) has
been plotted in Fig. 6. Although this figure solves
+ 1-

+i , _

Y
C

cI-

Pi,l-

In Appendix I-l it is shown that the difference

between ps and pi,1 is sufficiently small to justify
further development on the basis of ps and even
that the difference decreases as T, increases,
so that predictions based on ps become more
reliable as the situation becomes more severe.
Consequently,
the second criterion may be
adapted
and stated as follows:
Runaway
occurs

when a trajectory

The critical trajectory

to the p,-curve.

intersects

-2

20

21

22

18

19

20

21

23

2,4

-4 I-

the ps curve.

is the one that is tangent

tw=19

I
22

Fig. 6. Plot for K, involved in the determination

conditions.

1508

I
23

of critical

Fixed bed catalytic reactors

the problem it has one drawback: it may require

interpolation with respect to c,. In Appendix
I-3 a method is developed to overcome this
difficulty. The following equation is derived:
In K(t,t,)

= in K,+ At = In K(t,,20)+

At

(23)

or
lnK,=lnK-At
where
A.1= t,-20
t,=

t-At.

(24)
(25)

Figure 7 represents lnK( t,., 20) as a function

oft,_
The procedure
for determining
(T,)t now
becomes: given 1nK (from (22)) and t, (from
(21.b)), At is calculated from (24), lnK, from
(23); then t, is obtained from Fig. 7, t from (25)
and finally (T& from (2 1.a). It should be noted
that the point of tangency is always situated
to the left of the maximum of the maxima
curve (Fig. 4). It follows that a trajectory going
through the tangency point intersects the ordinate at a lower point than the trajectory going
through the maximum of the maxima curve.
Therefore,
the second criterion is more conservative than the first.

3. CRITICAL

INLET

CONDITIONS

Upper and lower limits

The preceding two criteria for runaway were

derived from an analysis of intrinsic properties
of the T(z)-curves, translated in the p-T plane.
What remains to be done is to find the inlet
conditions which lead to the critical situations.
Rigorously this requires numerical back integration. Approximate values for the critical inlet
conditions may be obtained by simple extrapolations, however. Several ways of extrapolation are possible. Two ways were retained so as
to define an upper and a lower limit for the approximated critical inlet conditions. The discussion is mainly based upon equal inlet and wall
temperatures,
which is the situation generally
encountered in practice.
The lower limit is based upon the property
of the trajectories to start in the p-T plane with
an adiabatic slope for To = T, and to bend under
this line, due to heat exchange with the surroundings. Therefore, an adiabatic line starting from
a point on a critical trajectorycritical according to one of the criteria-leads
to a lower limit
for the critical inlet conditions. Indeed, in both
cases the critical trajectories through the critical
points start from inlet partial pressures which
are higher than those found from the adiabatic
lines. The following equation is easily derived:
(ph = ~c,+$Vc,-

(26)

To)

provided

-I -

T, s To s T,,.
per may be eliminated from (26) using either
(7) with T, = T, or (18) with Ti = T,,. The

latter choice is to be preferred since the expression obtained in this way is valid for the lower
limit derived from both criteria. Indeed, the
critical point according to the first criterion is
the maximum of the maxima-curve,
but as
such it is also a point of the ps curve, upon which
the modified second criterion is based. It follows
that:
Fig. 7. Plot for K,, involved in the determination of critical
conditions.

1509

(Poh =

a_
c

Tk
e-(a/Zc,)+b

+$(Tcr-

To).

(27)

R. J. VAN WELSENAERE

When To is lower than T, linear extrapolation

along an adiabatic cannot be used: the critical
trajectory becomes flatter and is intersected by
the adiabatic. This situation is less important,
however, since in that region the reactor mainly
acts as a heat exchanger. It is easily seen that
(p& is a decreasing function of T,,. Since the
value of T,, resulting from the modified second
criterion is lower than the T,,-value from the
first criterion, the modified second criterion will
give a higher value (p& > (p&. This, however, does not incriminate the statement that
the second criterion is more conservative than
the first: it is the method of extrapolation which
is responsible here.
Upper limits are based upon the following
observations:
as inflexion points of the trajectories only occur beyond T, or below the
maxima-curve,
tangents to trajectories taken
in points between T, and T, all intersect the
ordinate T = T, at values of p, which are higher
than the p of the trajectories themselves. This is
true in particular for the critical trajectory. Consider, for a fixed value of T, between T, and T,,
the tangents to all the trajectories, above the
critical. Their intercepts are determined by two
opposing effects: the higher the trajectory is
situated the lower the value of the slope of the
tangent. One of the trajectories will therefore
lead to a minimum intercept on the ordinate T,.
The corresponding PO-value, which is obviously
higher than that of the true critical trajectory, will
be the best possible approximation and is therefore considered as an upper limit for the inlet
partial pressure (PO),.
It is essential that only trajectories above the
critical are considered. At least one point of
the critical trajectory has to be known. The
critical point, already involved in the determination of the lower limit, is such a point.
In Appendix III the following formula is
derived for (p),, when To = T,
(~)u =

$( Tc,-

T,) .

[&j&z+I*(**)

It can be shown that (p), is an increasing func-

and G. F. FROMENT

tion of T,, for T, 6 T,, s TM. It follows that

the upper limit resulting from the fhst criterion
will be higher than the one obtained from the
modified second criterion. Consequently,
the
bandwidth or uncertainty of the predictions is
smaller with the modified second criterion than
with the first. The closer the point in which the
tangents to the trajectories are drawn is to T,
the better the upper limit of course. There are
other possibilities than starting from the vertical
through the critical points as was done here. The
extrapolation
would then become much more
elaborate, however, and this was not believed
to be justified, considering the objectives of
this work.
Mean values

An analysis of a series of numerical calculations revealed a rather curious rule. It was found
that the mean of upper and lower limits obtained
from either the first or the second criterion represents an excellent approximation for the true
critical inlet partial pressures. This is illustrated
in Fig. 8. Besides, but for the limits based on the
first criterion only and for To = T,, the mean
may be expressed analytically.
Again pc,. is
eliminated from (26), this time by making use of

0.03

6
'0

0.02

'0

0.01

I
600

650
T. (K)

Fig. 8. Upper and lower limits, mean and exact critical value
for the inlet partial pressure. Values derived from Barkelews
criterion are marked 43.

1510

Fixed bed catalytic reactors

(7) where T, takes the critical value TM, according to the first criterion. This leads to:

BTM
- Tw+$(TM-

(Poh=

T,).

T,, by T, in the upper limit (28). An example of

such a problem is given further in this paper.

e-taTM)+B

From (3 1) and the upper limit (28) with T,, = TM

the following equation is obtained for the mean:

&An =

$(TM-

5. COMPARISON
WITH
CRITERION

(2%

Tw)

BARKELEWS

As mentioned already, Barkelew derived a

runaway criterion from a large number of numerical integrations of the system-equations
(1)
and (2). He represented the results of the numerical computations in a diagram which is shown
in Fig. 9. r,/S is mainly related to the maximum
temperature in the reactor. N/S is the ratio of
the rate of heat transfer per unit volume at 7 = 1
to the rate of heat generation per unit volume at
T = 0. The parameter S corresponds to the value
r would reach if the reactants were fed at the
wall temperature and if the reactor were operated
adiabatically. The curves of constant S have
an envelope. Above the tangent to the envelope
T, changes rapidly with N/S. Below that point
it does not. The points of tangency therefore
correspond
to critical conditions.
Barkelew
modified the temperature dependence of the rate
coefficient in such way that it may be characterized by only one constant instead of two. Figure
10 shows some temperature profiles through the
reactor when the rate law of Section 1 is modified

l+f++$e-c:,TM,*j
(30)
or
(AT)%

l+Q+QZ

(31)

(*T)e,

where
(32)

(AT),, = $P,,
(AT),=

TM-T,

(33)

Q=~z$&i

(34)

and

Such an expression cannot be derived from the

second criterion, since in that case T,, is defined
by an implicit equation.
4. SUBCRITICAL

INLET

4-

S*32

CONDITIONS

0. 3.

There are cases in which the hot spot has to

be limited for reasons other than runaway. The
extrapolation techniques developed in the previous chapter can also be used to determine
subcritical inlet conditions. The problem could
be: given a wall temperature and an imposed
maximum temperature,
T,, which is the corresponding partial pressure?
The partial pressure at the point in the reactor
where T = T, is given by the maxima-curve.
When T, s TM the conditions for extrapolation
according to the techniques of Section 3 are
satisfied. It suffices to replace T,,, by T, in the
lower limit (31) and the mean value (29) and

In O.2x

1511

0, I -

0 O0.5

IO

I.5

2.0

N/S

Fig. 9. Barkelews diagram.

R. J. VAN WELSENAERE

proposed in this paper is slightly more conservative than Barkelews. What really matters for
practical purposes, however, are the inlet values
leading to these maximum temperatures
and
these involve, with the approach followed in the
present paper, some sort of extrapolation. Figure
8 shows critical inlet values, obtained by integrating numerically back, upper and lower limits
according to the first and second modified criterion and their mean values, all based upon the
true rate equation. In addition, Fig. 8 contains
the values obtained from Barkelews criterion,
using the modified rate equation. Barkelews
predictions
agree extremely well with these
based upon the present methods.

800

T, =628 OK 627

626

=0.017

6001

Fig. 10. Temperature

I
0.5
2. m

and G. F. FROMENT

atm

I
I.0

profiles in the reactor obtained with

simplified rate law.

the way Barkelew did. From a comparison of

these profiles with those of Fig. 3 it is seen how
the modified rate equation leads to runaway
well before the true rate equation.
It is of interest to compare Barkelews method
and results with those presented in this paper.
In order to do this it is necessary to represent
trajectories based on the modified rate equation
in the p-T plane. In an attempt to explain the
empirical
Barkelew-criterion
a relation was
sought between the points of tangency of the
S-curves and the envelope on one hand and
the corresponding trajectories in the p-T plane
on the other hand. It was observed that for all
S-values T, at the point of tangency was very
close to 1.275. No special meaning could be
assigned
to the corresponding
trajectories,
however.
The methods and criteria of the present paper
can also be applied with the modified rate equation. With Barkelews dimensionless notation
the first criterion leads to T, = 1, so that r,/S =
l/S. As indicated in Fig. 9 the corresponding
point on each S-curve lies a bit to the right of
the points of tangency between the S-curve and
the envelope. Consequently,
the first criterion

6. EXAMPLES

In the following examples, all the parameters,

except T, = To, T,, p and R, have been given
the values already mentioned in Section 1.
Example 1. Given the wall temperature T, =
625K and the reactor radius, R = 0.0125 m,
determine the maximum inlet partial pressure
p, permitting safe operation.
(a) First criterion
The critical maximum temperature, is given
by (8): T,, = TM = 656.6K. This means according to the first criterion, AT has to be limited to
31~6C in order to avoid runaway. What is the
corresponding pa?
From (26) a lower limit is obtained: (PO)~,~
=
0.01353 atm and from (28) an upper limit:
(PO)~,~= 0.01976 atm.
The lower limit is entirely safe. Exceeding
the upper limit will certainly lead to runaway.
This is in complete agreement with the results
shown in Fig. 2, obtained by numerical integration.
The mean value (PO)~,~= 0.01665 atm, is in
excellent agreement with the critical value,
(PO)cr.l= 0.01651 atm, obtained by integrating
numerically back from the critical point to T =
T,, i.e. the inlet.
(b) Second criterion
First the critical hot spot temperature has to
be calculated. The following steps are involved:

1512

Fixed bed catalytic reactors

from (21.b)

t, = 21.818
1nK = - 2.055
(24)
At= 1.8176
(23)
lnK, = - 3.873
Fig. 7 t, = 19.013
(25)
t = 20.83 1.

(22)

(21 .a) (Ti)t = 654*6K, SO that the AT has to

be limited to 29.6C. The lower limit for p. is
obtained from (26): (PO)~,~= O-01423 atm and
the upper limit from (28): (PO)~,~= O-01948 atm.
It can be seen the bandwidth is somewhat
smaller than that resulting from the first criterion.
Again the mean (PO),,~ = O-01686 atm is in excellent agreement
with the true critical value
results entirely
(PO)cr,z = 0.01641 atm. These
confirm those predicted by the first criterion.
If the inlet pressure is also given and the problem
is to check whether the given set of conditions
would lead to runaway, the critical inlet partial
pressure is calculated as before, and compared
with the given value.
Example 2. Same problem as before, but the
maximum temperature is also given, say T, =
640K.
This is a problem with subcritical conditions,
mentioned in Section 4, since the critical temperature corresponding
to a wall temperature of
T, = 625K, is TM = 654.6K. Formula (30) is
used to calculate the inlet partial pressure (p), =
0.01269 atm. The true value obtained by integrating numerically back from the point on the
maxima-curve,
corresponding to T, = 640K,
is p = 0.01201 atm. Numerical forward integration starting from (PO), yields a maximum temperature of T, = 641.5K. The precision of the
extrapolation based on (30) is excellent.
Example 3. Given
a radius R = O-0125 m
and p = 0.0075 atm determine the wall temperature which limits the hot spot to 675K.
For this maximum to be critical the wall temperature would have to be 641K and the inlet
partial pressure 0.01095 atm. Therefore,
the
maximum is subcritical. With p = O-0075 atm
it follows from (32) (AT),, = 312.6K; from (34)
Q = 3.094; from (31) (AT&= 22*9K and
finally from (33) T, = 652*2K.

A numerical integration starting from p =

0.0075 atm and To = T, = 652.2K yields a maximum temperature of 677K.
Example 4.
Given
p. = O-0125 atm,
T, =
625K, which would be the radius leading to
critical conditions?
TM = 656.6K
(AT&= 31.6K
(AT)ad = 521.09K.
(33) leads to the following equation:
Q2+Q-15*49=0
from which:
Q = 3.4675.
(34) gives: C = Qz . A . e-(aT.@b = 29,206.4
from which: R = 0.0175 m.
7. CONCLUSION

The two runaway criteria proposed in this

paper lead, through some simple extrapolation
techniques, to practically identical critical values
for the inlet, design or operating variables. These
values are in complete agreement with those
derived from numerical integration and with
those obtained from Barkelews diagram.
The method presented here is believed to be
easier to use since it is simple and straight forward, whereas Barkelews diagram requires
trial and error for most problems.

1513

NOTATION

a = 6,

b
B

where E activation
constant

frequency factor
=

(--AH) . Pb .
CP

c, specific heat
c=2.u
c, . R
K = $

eb-20

Peg

energy, R gas

R. J. VAN WELSENAERE

mean molecular weight

dimensionless
group
defined
by
Barkelew
p partial pressure of reactant
PtJO partial pressure of second component
P total pressure

and G. F. FROMENT

ps

Q=&&
r
R

reaction rate
reactor radius
dimensionless
Barkelew

group

defined

defined

by

of temperature profile
in reactor
1 lower limit
profile in
m maximum of temperature
reactor
m mean value if used in conjunction with
other subscripts
M maximum of maxima-curve
r reference value
simplified
S
upper limit
u
coolant or wall
W
0 inlet of reactor
1 first criterion
2 second criterion

by

adiabatic temperature rise

effective temperature rise
heat of reaction

Greek symbols
pb

group

Sub- or superscripts
cr critical value
i inflexion point

t=alT
T temperature

(AT)ad
(AT),
(-AH)

gas density
T dimensionless
Barkelew

bulk density

REFERENCES

[ 1] BARKELEW

C. H., Chem. Engng Prog. Symp. Ser. 1959 55 37.

[2] BILOUS 0. and AMUNDSON N. R., A.1.Ch.E. .I1 1956 2 116.
[3] FROMENT G. F., Ind. Engng Chem. 1967 59 (2) 18.

Ap=k%[l+/Gb].

APPENDIX I
PROPERTIES

OF (p,,),

I. 1 The difference between ~2,~and (pi,& = ps

The true locus of inflexion points before the maximum
is given by ( 14) the approximate by ( 18).
Before the latter may be used, it has to be checked if the
difference pi,i -pa = Ap, is sufficiently small. This difference
is rather difficult to handle, but an investigation in two characteristic points will suffice to illustrate its behaviour.
Considering the extrapolation techniques of Section 3 it
is clear that only the region between T, and T, is of practical
importance, For T = T,

(A-2)

This function has a minimum for a value of T,,, corresponding

to

02
t,-2

e-t+*0

2K

(A-3)

(A-1)

where tM= aIT, and K = (A/C)eb-*o.

The value of T .which follows from (A-3) lies aenerallv
far beyond the region of practical interest. Therefore it may
be stated that, at the maximum of the maxima-curve at
least, p decreases as T,,, increases, in other words that the
approximation
becomes more reliable as the situation
becomes more severe.

Since this value is much smaller than unity, B* may be

neglected with respect to B * . Ap is then given by

I-2 The temperature corresponding to the contact point of

the critical trajectory and (pi.&
From an investigation of the sign of the function (20) it
follows that, for practical values of the parameters (T,), <
T M.
For low values of T,, (TJr lies close to TM. As T, increases, ( TJr shifts to lower values and coincides with T,
when its value is given by:

Ap+AO
a
p is maximum for T = T.,, where B */B * is given by
-B* = _.A e-,a,TN)+b
B*
2C

1514

Fixed bed catalytic reactors

APPENDIX

(A-4)
UPPER
or
a

T=

b+ln$-ln

(A-5)

1-b

LIMIT FOR THE

CONDITIONS

from which ( TJt may be obtained by iteration. It is found

that ( Ti)r only equals T, far beyond the range of practical
interest.
It may be concluded that ( Ti)t based on pe is located
between T, and TM. Furthermore, it is easily demonstrated
that the tangent to ps at T = TM is steeper than the adiabatic
line through that point. It follows that an adiabatic line
starting from a point of (piJs between T, and T, always
lies above the adiabatic line starting from the maximum of
the maxima-curve.
This partly explains the narrower
limits predicted by the modified second criterion and discussed in Section 3. It should be added this is only true for
values of T, lower than those defined by (A-5), but this covers
the complete range of practical interest.

INLET

Consider the tanaents at the traiectories through the points

T = T,, and p = plrwhere

pb > pz,.

with T = T, the value of p. (pO) is

At the intersection
given by:

>

II

Tcr- Ttu

PO=P&--

dT

(A-8)

( dp 1 T=Tcr

or:

( Tw- TJ . P&
-C. Tw--Tw B
A e-a,Tc,,+bA .Pfr

P0 = Per

C-4-9)

or:

where;
o! = T,,-TT,

I-3. Unique plot for the modified Eq. (20)

In Fig. 6 the curves are limited by the points where t = rW,
because t > r, or ( TJt < Tw are not considered here. The
equation of the limiting curve is:
lnK* = r,-20+ln-

t -20

The lowest p is obtained for dpVdp& = 0, or

tic

which is very nearly a straight line with slope one for a very
wide range of im. Owing to the rather similar shape the fD
curves of Fig. 6 may be brought to coincide by a translation
parallel to this straight line.
It therefore suffices to draw only one curve e.g. that corresponding to tW= 20, which is shown in Fig. I.
The other curves then follow from:
lnK,(t,r,)=lnK,+Ar=lnK(t,,20)+Af

from which
B-r.p&=*vzjk

Since

is always negative, only the minus sign has to be considered,

so that

where

pf,=B+G

t=t,-20

r, = t-At.
This leads to:
The ratio between the real value of K and the approximation.
K,, is given by:
K

-=-.
K,

t-2

- t,
tr-2

-20

(P), = $ ( Tw - Tw) .

[ &k+y

CA-l)

I,--t(f,--t)

rw20-t,(t,-r)

where:
&.= t-tr,+20.
This ratio is practically always close to one.

Finally, it should be noted that the trajectories may have

inflexion points. Beyond these the tangents have a decreasing slope and this could lead to values of p which are too low.
These inflexion points however only occur beyond TM
whereas the tangents are only considered at T,,, which is
lower than or equal to T,.

Resume-Cet
article introduit deux crittres intrinseques pour lemballement dans les reacteurs
tubulaires a lit fixe, bases sur les points caracteristiques de la courbe de temperature le long du
rr5acteur. Leur transposition dans le plan de phase pression partielle- temperature permet de deriver
quelques formules t&s simples pour la prevision des valeurs critiques des variables operatoires. Les
resultats sont compares a ceux obtenus a Iaide du critere empirique de Barkelew. Larticle traite
Cgalement du problbme associt dun point chaud qui doit &tre limit6 pour des raisons autres que

1515

R. J. VAN WELSENAERE

and G. F. FROMENT

Iemballement. Les formules simples mentionnees ci-dessus peuvent &galement servir dans ce cas pour
determiner les conditions operataires.
Znsammenfassung-In
diesem Artikel werden zwei spezifische Kriterien fiir das Durchgehen in
Rohrreaktoren mit Festbetten, auf Grund des Auftretens charakteristischer
Punkte in Temperaturprofil entlang dem Reaktor, angefiihrt. Die Ubertragung derselben in die Partialdruck-Temperaturphasenebene gestattet die Ableitung einiger sehr einfacher Formeln fur die Voraussage der kritischen
Werte fur die Betriebsvariablen. Die Ergebnisse werden mit den aus Barkelews empirischem Kriterium
erhaltenen verghchen. Der Artikel behandelt ferner das verwandte Problem der iiberhitzten Stelle,
die aus anderen, nicht das Durchgehen betreffenden, Griinden begrenzt werden miissen. Die obenerwiihnten einfachen Formeln kijnnen such hier zur Bestimmung der Betriebsbedingungen angewendet
werden.

1516