Chemical

Engineering

Science,

1974. Vol. 29, pp. 747-751.

CATALYTIC

Pergamon

Press.

REACTIONS

Printed

in Great Britain

IN TRANSPORT

REACTORS

K. C. PRATT
Department of Chemical Engineering and Chemical Technology, Imperial College, London SW7 2BY,
England
(Received 21 August 1973)
Abstract-By
assuming plug flow of both gas and solids phases, and simple kinetics, a model of the
transport reactor has been prepared which accounts for the unsteady state behaviour of the catalyst
particles. Computational results are presented to show the influence of the major variables. As in a
steady state analysis, the Thiele modulus serves to indicate the catalyst effectiveness.

1. INTRODUCTION

2. THE MODEL

In a transport reactor, the catalyst or solid reactant

is carried through a pipeline by the reacting gases.
In principle the system presents many advantages
to the designer. For consecutive reactions, where
an intermediate product is desired, the close control
of residence time facilitates the maintenance of the
desired conversion level. Further, in contrast to
fixed and fluid bed reactors, the catalyst loading can
be varied independently
of the gas flow. Thus, in
the catalytic cracking of petroleum feedstocks,
where the conventional
fluid bed system is not
suited to the demands of fluctuating feedstock rate
and composition, up to 90 per cent of the cracking
may be done in a riser before entering the conventional dense phase system [ l-31.
In future applications, advantage could be taken
of the increased heat transfer rates in riser
systems 141to impose a temperature gradient on the
reaction, enabling an optimum path to be followed.
Also, since the gas flow is fully turbulent, ensuring
that the solids are well distributed, and reaction
conditions uniform at each point along the reactor,
the possibility of hotspots developing is remote.
Despite these advantages, little or no use has
been made of the transport reactor outside the petroleum industry, though the system should be
suited to other fast reaction or adsorption processes. The main reason for this neglect appears to be
a lack of operating and design experience. A few
experimental studies of non-catalytic reactions are
available[5-71, but there is a need for systematic
experimental
and theoretical study of catalytic
reactions in transport reactors. This work is an attempt to produce a model of the system, and must
account for the non-equilibrium
behaviour of the
catalyst particles.

We shall consider a system in which both particulate and gas phases are in plug flow. The catalyst
particles are spherical and of uniform size. For
simplicity, we assume that only a single reaction is
occurring, and that this reaction is first order, irreversible, and isothermal.
Considering an element of the reactor, if there is
no volume change during the reaction, a mass balance for the reacting component in the gas phase
leads to

747

Under the usual conditions of operation, experimental evidence suggests that axial diffusion can be
neglected[5], thus Eq. (1) becomes
u*_
dl

30(1-a)
Ry-

ac
arlrzR.

(2)

It should be noted that while the above results consider steady state operation in the gas phase, the
particles themselves do not attain steady state.
The mass balance equation for the particles is
E aC #C
--=2----D at
ar
Equations (2) and
ously subject to the
(a) At the entrance
cles are filled with

2 ac
rar

kc
D

(3) must be solved simultanefollowing boundary conditions.

to the reactor the catalyst partian inert diluent

C(O,r)=O

OSrSR.

(4)

748

K. C.

(b) The reacting component has a concentration

at the entrance to the reactor
c(0) = co = C(0, R).
(c) Spherical symmetry

cu

PRAIT
and
&Y

(5)

$+,O)=O.

M=~Q

mass transfer

c(t, R) = c(l).

resistance

30(1-o)
R
a

ac

arh

Equations
(3)-(S) are solved
Transforms[8], the solution is

using

(8)

groups given by

DL

p_U(1-4
u

(7)

The solution can be simplified by expressing Eq. (2)

in terms of a time derivative with respect to particle
motion, thus
Udc
--=---u dt

(18)

M, P, and 4 are dimensionless

in the particles

(d) There is no external

for the particles

= l-ficotfi.

(19)

m=R&

(21)

The group C#Jwill be recognised as the Thiele Modulus of the catalyst particles.
Finally, by making use of Eq. (7), we obtain the
concentration of the reacting component in the gas
phase as a function of the dimensionless length l/L,

Laplace

(22)
F, is given by Eq. (16).
3. COMPUTATIONAL

P =1+&&(1-o)-2u
(Y

--

&+&lJxo)

URZp,2
I( m
(10)

The kmsand p,s are the roots of

ff&$pn

= I-(k,R)cot(kR),

(11)

RESULTS

Using an iterative technique, the first 10 eigenvalues of the transcendental Eqs. (17) and (18) were
found for 5 values of rk2, namely, 1000, 100, 10, 1,
O-1, and 5 values of P; 0~1,0~05,0~025,0~01,0@05.
In practice, the series in Eqs. (15) and (22) converged rapidly, and only the first 4 eigenvalues were
used. A representative set of results is contained in
the figures accompanying this paper.

and
k;=-T epPn+ k

(12)

In order to express the solution in dimensionless

form we put
x. = k,R,
and

(13)

lZ2

4. DISCUSSION

In Figs. 1 and 2, conversion is plotted as a function of the parameter M, for various values of c$
and P. As the catalyst particles are not at steady
state, the quantity (1 -C/C&~
does not, strictly
speaking, represent the conversion. However, as
the volume of the reactor occupied by catalyst is

y. = 7
Thus the concentration
is given by

profile in a catalyst particle

and
F

=1+?p-y.+~y.2
2

2x.

6P xn

05)
I
0

The x.s and yns are the roots of

xn = - y. - &.

(17)

20

40

60

80

Fig. 1. Conversion as a function of the parameter

various values of P. 4 = 10.

I
loo M

M, for

749

Catalytic reactions in transport reactors

Con

0025

P.005

,o_

am

0005

08
06
04

In Fig. 4, a set of typical axial conversion profiles

of the reactant in the gas phase is presented. It can
be seen that the profile is almost linear at low catalyst circulations.
Of perhaps the greatest interest is the behaviour
of the catalyst particles themselves. Figures 5-8

02
COnV

lr,,:
0

200

400

600

800

1000 M

o-

0 025.

P-0 05

Fig. 2. Conversion as a function of the parameter M, for

various values of P. 4 = 1.
generally only of the order of 2 per cent, then (lC/G) gives a good approximation to the reactant
conversion.
Since the quantity R21Drepresents the time constant for diffusion, then the parameter M may be
thought of as being a measure of the number of
diffusion time constants which the particle spends
in the reactor. Thus, as expected, the effect of increasing M is to increase the conversion.
The
parameter P also has an obvious significance, indeed, it is easy to show that

02

04

06

OS

1O"L

Fig. 4. Axial conversion profiles for various values of P.

M = 5,d = 100.
CIC,

0 5IlL~Ol
I

P=&&

(23)

06

t
where p is the catalyst circulation ratio (weight of
catalyst circulated/weight of gas). Figure 3 isolates
the influence of catalyst circulation ratio, and demonstrates the diminishing return from increasing
catalyst circulation at conversions greater than 80
per cent.
From the designers point of view, a family of
curves similar to Figs. 1 and 2 would be the most
useful. Having selected the catalyst (hence d), and
the desired conversion, the designer can then determine corresponding values of reactor length and
catalyst circulation.
The optimum combination
would be determined by external factors, such as
power requirements, regeneration, and space limitations.

0.01

a02

0.03

0.04

02

0 L-

03

02

02

04

06

06

10 r/R

Fig. 5. Concentration profiles within the catalyst particle

at various values of 1/L. 4 = 100,P = 0.025, M = 5.

o a

a05 p

Fig. 3. Conversion as a function of the parameter P, for

various values of hf. I$ = 0.1,

Fig. 6. Concentration profiles within the catalyst particle

at various values of l/L. I$ = 10,P = 0.025, M = 20.

750

K. C.

TIC

-0-i .

IiL.01

02
0.6 0.3
0.4 -

04
05
06

02-

PRATT

given explicitly, it is difficult to test Eq. (15) for

convergence. However, as the values of l/L above
which convergence is obtained are so low, this is
not a practical problem in the use of Eq. (15). For
4 = 0.1, convergence was obtained above l/L =
040005,and the initial development of the profile is
shown in Fig. 9. It can be seen that C/c, rises to a
maximum at the centre of the particle, before decreasing as the particle traverses the reactor.

08
10
I
02

04

06

06

r/R

IO

Fig. 7. Concentration profiles within the catalyst particle

at various values of l/L. 4 = 1,P = 0.025, M = 100.

OS-

liL.0 1

Fig. 9. Development of the concentration lrofile within

the catalyst particle in the inlet region of the reactor. 4 =
0.1, P = 0.025, M = 1000.

02

06:

03
04.

04

02

04

06

08

10

r/R

Fig. 8. Concentration profiles within the catalyst particle

at various values of l/L. 4 = 0.1, P = 0.025, M = 1000.

display radial concentration profiles within the particles at various stages of their passage through the
reactor. Values of 4 range from 100 to 0.1. Consideration of steady state effectiveness factors [93, indicates that for values of 4 greater than about
unity, the rate is diffusion controlled. Examination
of Figs. 5-g shows that similar criteria will apply to
the unsteady state case treated here. The transition
from diffusion to reaction control over the range of
values of 4 is striking. For 4 = 100, it is clear that
only a fraction of the available catalyst is being utilised, while for 4= 0.1, the almost uniform concentration profiles indicate virtually full use of available active surface.
Some difficulty was experienced in obtaining
convergence of the series in Eq. (15) for very small
values of l/L, even when the number of eigenvalues used was increased. Since xn and y. are not

Finally, some mention should be made of the

fluid mechanics involved in the assumption of plug
flow in both the particulate and gas phases. As yet,
no basic theory has been successful in an a priori
prediction of two phase gas solids flow. Available
experimental
evidence [ 10, 1l] suggests that the
effect of added solids is to promote plug flow of the
gas phase. Solids concentration tends to be uniform
across the tube[l2], but a parabolic type velocity
profile results in a non-uniform mass velocity[ll].
At very high solids loadings, there is some evidence
of solids backmixing at the walls [13]. There is also
an implicit assumption that the particles are instantly accelerated to the velocity U, at t = 0. For
the size of particles likely to be encountered in
these systems, this is reasonable. The specification
of plug flow in the solids phase is perhaps the least
justified of the assumptions involved in this model.
However, no theory exists at the present time
which will give an adequate representation of the
solids velocity profile.
The existence of a non-uniform solids mass flux,
backmixing of solids, and the behaviour of the
catalyst particles in the mixing zone are problems
requiring further study.
CONCLUSIONS

This work has shown that a model of the trans-

port reactor operating under idealized conditions

can predict the influence of the major variables.

751

Catalytic reactions in transport reactors

Consideration of the results shows that the relationship between the Thiele modulus and the catalyst
effectiveness is similar to that obtained from a
steady state analysis. Further work is needed to
extend the model to cover situations which are
more kinetically realistic.
NOTATION
C

cu

c
D
E
k, P
k
1
L
M
P
r
r
t
t:
x.9 Y

concentration
of reactant in the reactor, g
mole/cm3
concentration
of reactant at reactor entrance, g mole/cm3
concentration of reactant in catalyst particle,
g mole/cm
effective diffusion coefficient of reactant in
the catalyst particles cm2/sec
axial dispersion coefficient cm*/sec
roots of Eqs. (11) and (12)
first order rate constant per unit volume of
catalyst pellet, set-
length along reactor, cm
length of reactor, cm
dimensionless group defined by Eq. (19)
dimensionless group defined by Eq. (20)
radial co-ordinate, cm
radius of catalyst particles, cm
time, set
particle velocity, cmlsec
interstitial gas velocity, cm/set
roots of Eqs. (17) and (18)

Greek symbols
a voidage in reactor

p
c
pp
ps

catalyst circulation,
voidage of catalyst
gas density, g/cm3
bulk density of a
g/cm
& Thiele modulus for

g catalyst/g gas
particle
single catalyst

particle,

catalyst (Eq. 21)

REFERENCIZS

[II BRYSON M. C., HULING G. P. and GLAUSSER

W. E., Hydroc. Proc. 1972 85.
121STROTHER C. W., VERMILLION W. L. and
CONNER A, J., Ibid. 89.
r31 PIERCE W. L., SOUTHER R. P., KAUFMAN T. G.
and RYAN D. F., Ibid. 92.
141SADEK S. E., Znd. Engng Chem. Proc. Des. Deu.
1972 11 133.
151JEPSON G., POLL A. and SMITH W., A.I.Ch.E.-I.
Chem. E. Joint meeting, London 13-17 June 1965.

t61 GAUVIN W. H. and GRAVEL J. J. O., Symposium

on the Interaction Between Fluids and Particles, p.
250. Instn Chem. Engrs London 1%2.
171YANNAPOULOS JT C., THEMELIS N. J. and
GAUVIN W. H.. Can. _I.&em. Ennnn 1%6 44 23 1.
Oxford
181CRANK J., 2% Mathematics of-D&ion.
University Press, London 1970.
191SAITERFIELD C. N., Mass Transfer in Heterogenous Catalysis. M.I.T. Press, Clinton 1970.
r101 DOIG I. D. and ROPER G. H., Znd. Engng Chem.
Fundls 1%7 6 247.
[III PRATT K. C., Ph.D. Thesis, University of Melbourne 1%9.
1121SO0 S. L., TREZEK G. J., DIMICK R. C. and
HOHNSTREITER G. F., Znd. Engng Chem. Fundls
1%4 3 98.
II31 VAN ZOONEN D., Symposium on the Interaction
Between Fluids and Particles p. 64. Instn Chem.
Engrs London 1%2.