Chemical Engineering Science, 1970, Vol. 25, pp. 173-l 85. Pergamon Press. Printed in Great Britain.

Modeling of chemical reactors - XVI?

Steady state axial heat and mass transfer in tubular
reactors
An analysis of the uniqueness of solutions
V. HLAVACEKS and H. HOFMANN
lnstitut fdr Technische Chemie I der Universitiit Erlangen-Niirnberg. W. Germany
(Received 1 April 1969)

Ahstraet-Numerical methods for the solution of steady state equations are reviewed and critically
discussed. A new technique is presented which, for the parameter study of a problem, enables one to
transform the boundary value problem to the initial value problem. Different criteria for testing of
uniqueness and multiplicity respectively are discussed. The necessary and sufficient conditions of
multiplicity and also analytical procedures providing an estimate of bounds of the DamkGhler numbers
where multiple solutions can occur. are presented. The mentioned criteria are presented for both an
adiabatic and nonisothermal-nonadiabatic case.

1. INTRODUCTION

of axial heat and mass transfer in

chemical tubular reactors is still intensively
studied. If a chemical reaction is accompanied
by heat effects then the behaviour of the system
is, in a transient state, described by a set of
parabolic partial differential equations. Numerical[ 1,2] and also rigorous analysis [3-51 of the
problem in question showed that in some cases
the mentioned equations may have more than
one steady state solution. Recently these theoretical conclusions were also confirmed experimentally. Wicke and coworkers [6,7] have shown for
the case of two highly exothermic
reactionsoxidation of CO and ethane by air-that
two
stable steady states can be verified: the former
when the rate determining step is the reaction
kinetics, the latter when the rate determining
step is the heat transfer (kinetic or heat transfer
regimes).
The aim of this and following papers is an attempt to investigate systematically problems
connected with multiplicity and stability of the
equations governing axial heat and mass transfer
and exothermic
reaction occuring in tubular
reactors. The current state of the mentioned
questions is reviewed in brief. On the basis of
an approximation, which enables one to transform
THE PROBLEM

a distributed parameter system into a lumped one,

criteria will be presented by which one is permitted to predict a priori-only from known parameters describing the system-the bounds where
multiple states might occur. The results of
these theoretical predictions are compared with
the exact numerical
values. For the practical
exploration of the regions of multiplicity an algorithm will be developed which enables one to
investigate the behaviour of the equations solely
on the basis of solutions
of an initial value
problem. The sufficient and necessary conditions
in the form of analytic
criteria will also be
presented.
2. HEAT AND MASS BALANCES:
APPROXIMATIONS

In this paper attention will be paid to a simple

reaction A + B accompanied
by the evolution
of heat. The assumptions underlying the developments are: no radial velocity
and concentration gradients in the reactor, the temperature
gradient may be described by use of a proper
value of the effective
radial conductivity[31],
absence of temperature and concentration gradients within and outside of a catalyst particle,
the properties of the reaction mixture may be
characterized by average values, the mechanism

tPart XV: J. Catal. In press.

.-. _ _
Sun leave from Department of Chemical Engineering, Technical University, Prague, 6, Czechoslovakia.

173

V. HLAVACEK and H. HOFMANN

of axial mixing can be described by means of a

single parameter in the Ficks or Fouriers law
respectively. For the sake of simplicity first
order kinetics is considered. Now, the heat and
mass balances may be written in the form:

t=

l;t>

(-AH)

--pvcv~+

e ax2

20

1:

7=O;O<f<
a2T

a0

0:

CA exp

aY
s=O

(7)

0 = M)
Y = Y(5)

(8)

by using the variables and parameters:

(1)

-F(T- T,) = pr,g

D a% _---U~-CAexp

pe,+

e a2

B=(-AfOCo .- E Da&o
PCJO RTo

where the boundary conditions are

A >

x = 0; t > 0: pvc,(T,,-T) =-keg

v(C,-C)
x =

1; t > 0:

E=l - P=----RT, PVC,

The Eqs. (5-8) contain in the general nonisothermal-nonadiabatic case nine independent
parameters: Pee, Pe,, B, Da, E, p, Be, yi, 8i, if
one assumes the initial conditions (8) in the form

ax-

0= 0i;
(4)

can be rendered dimensionless

at2 at

-P(O-O,)+BDa(l-y)

1 83 aY
9=----+Da(l-y)
a7 Pe, a(2 at

Y=Yi*

T = T(x)

at3 1 a20 a0

-=---a7 Pee

To)

s$ = xl1 7 = tvll.

ac- o

c = C(x).
The Eqs. (l-4)

e,=&(Tc-

(3)
~,

The initial conditions are:

x< 1:

0=&T-T,)

=-De%

aT_0 ax-

r=o;o<

pe,=g

e e

(2)

exp &
[

exp

[ 1

A genera1 analysis of Eqs. (5-g), due to the

great number of parameters and because of a
.
strong nonlinearity will be very complicated or
impossible. Therefore let us examine at first the
equations for the steady state and assume that
the Peclet numbers for heat and mass transfer

c5j

approximated in the form:

(6)

- =(
exp 1+&I

exp8.

5=0;7>

pe I9
e,Z

0:

at

aY
Pe,Y = ay
/

Frank-Kameneckij [8] and others [9, lo] have

shown that this approximation does not alter the
character of the solution. By these assumptions
the Eqs. (5-8) are simplified to:
174