Math1 Comput.Modding, Vol. I I, pp. 19-21, 1988 0895.7177/88 $3.00 + 0.

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Printed in Great Britain Pergamon Press plc

MODELLING CHEMICAL SYSTEMS I

STATISTICAL MODELING OF FLUID-SOLID REACTIONS IN POROUS MEDIA

Muhammad Sahimi(') , Theodore T. Tsotsis(') and George R. Gavalas(*)

(1) Department of Chemical Engineering. University of Southern California,

Los Angeles, CA 90089-1211, USA
(2) Division of Chemical Engineering, California Institute of Technology,
Pasadena, CA 91125, USA

Abstract. We discuss statistical modeling of fluid-solid reaction

processes in porous media. We show that ideas from modern statistical
bhysics of diiordered media, such as the concepts of percolation theory,
aggregation processes, dynamic scaling and universality and random walk
representation of diffusion processes are potent tools for studvinq of
such processes in porous media. As exampl&,we briefly describe how such
ideas and concepts can be used fruitfully to model non-catalytic gas-solid
reactions processes, and the phenomenon of catalyst deactivation with pore
plugging. The application of our method to other problems of interest is
also discussed.

Keywords. Network modeling, percolation, dynamic scaling, random walk

processes

INTRODUCTION to be examined from both a macroscopic and a

Fluid-solid reactions in porous media have been
the subject of extensive experimental and
theoretical research activity in recent years
(for a review see, Sahimi.9. 1987). Such
processes occur commonly in many natural and
industrial processes and have important scien-
tific and technoloqical implications. Examoles
include catalyst deactivation (Sahimi and
Tsotsis 1985, 1987c), noncatalytic gas solid
reactions (Gavalas 1380, 1981, Sahimi and
Tsotsis 1987a,b), enzyme immobilizations
(Hossain et al. 1986), acid rock dissolution
(Daccord 19877. In some instances the product
is also a solid and the fluid reactant has to
diffuse through the product layer to reach the
unreacted solid. As a result, the available
pore volume decreases and at large conversions
pore plugging will occur. This is the case
with catalyst deactivation. In other instances
the chemical reaction consumes the solid matrix
of the porous medium leading eventually to
total consumption of the matrix, as in non-
catalytic gas solid reactions with pore volume
growth and acid rock dissolution.
A successful modeldescribingfluid-solid re-
actions in porous media has to account for the
important effect of the morphology of the
porous medium, i.e., its topology or connect-
edness - the way pores are connected to one
another, and its geometry - the shapes and
sizes of the pores. It is often true that in
such processes, the morphology plays a role
that is even more important than that of other
major influencing factors, since the fluid
reactants have to be transported into the pore
space before any reaction can take place at
all. Such transport processes are controlled
by the morphology of the porous medium. There-
fore, it must be intuitively clear that fluid-
solid reaction processes in porous media have
microscopic viewpoint, because of the existence
of several length scales that are usually
associated with morphological inhomogeneities.
Because of complexities of the structure of
porous media, there are difficulties with both
of these approaches. Macroscopic quantities
such as effective transport coefficients and
the effective reaction rate are defined as
averages of the corresponding microscopic
quantities (see, e.g., Whitaker 1967). But the
averages must be taken over a volume V which is
small compared to the volume of the porous
medium, but large compared to the volume of a
single pore, so that the variations in the
heterogeneitiesofthe pore space can be treated
properly. The role of the microscopic point of
view is to furnish models of transport and re-
action coefficients of porous media derived
from the morphological properties of the matrix
of the media.
To date, no microscopic theory which accounts
for all the effects present in porous media
has been established, and perhaps not even all
the effects have been identified. For reac-
tants that diffuse or flow in a porous medium
and react with the solid matrix of the medium,
one can in principle solve the equations of
transport and reaction. However, as the
boundaries between the fluid reactants and
matrix in typical porous media ai-3 so irregular,
practical and economical techniques are not
available for solving such problems - even in
the unlikely event that one knows the detailed
morphology of the porous mediu;:, and even if
the solution of the problem could be obtained
in such details, it would have more information
than needed usually - only macroscopic proper-
ties are of interest in most practical situa-
tions.
Attempts to model the macroscopic transport

19
20 Proc. 6th Int. Conf. on Mathematical
and reaction cofficients from the microstruc-
ture of porous media have usually involved
simplifications of the structure of the media
(such as representing the porous medium as a
bundle of parallel capillary tubes) which are
too severe to be useful for highly irregular,
multiolv connected oorous media. On the other
hand,'very recently'systematic procedures have
been developed (Mohantv 1981, Lin and Cohen
1982) to map, in princjple, .any disordered
porous medium onto an equivalent random network
of interconnected pore bodies (nodes) and pore
throats (bonds). This correspondence between a
disordered porous medium and a network of in-
terconnected pores,together with ideas from
modern statistical physics of disordered sys-
tems, such as the concepts of percolation
theory (for an introduction to percolation see.
Stauffer 1985), aggregation processes, scaling,
and random walk representation of diffusion
processes are potent tools for studying of
fluid-solid reactions in porous media. What
we intend to do in this paper is to briefly
describe our ongoing research on fluid-solid
reactions in porous media, and to demonstrate
the usefulness of modern statistical physics
of disordered media to the study of such
phenomena. In what follows we, first, describe
fluid-solid reactions that result in the
consumption of the solid matrix of the porous
media and the phenomenon of fragmentation
during such processes. We, then, describe
fluid-solid reactions that are accompanied
by pore plugging and the reduction of the
porosity of the pore space. Finally, we brief-
ly discuss the application of statistical
physics of disordered media to other problems
of interest in fluid-solid reaction.
FLUID-SOLID REACTIONS AND THE
PHENOMENON OF FRAGMENTATION
We, first, analyze the consumption of a porous
solid by a chemical reaction and the resulting
changes in the structure of the solid. We
assume that the porous solid can be represented
by a percolation cluster, i.e., each site of
a network belongs to the solid matrix with
probability p and, thus l-p represents the
porosity of the system. We, then, introduce
reaction molecules (e.g., oxygen) on the ex-
ternal surface of the network, far from the
solid matrix. These molecules perform an
unbiased random walk (which represents a diffu-
sion process) on the empty sites of the net-
work, and we assume that each empty site can
accept only one molecule. If a molecule hits
a solid site it reacts with it with probability
r, which essentially represents the reactivity
of the solid matrix. If reaction does take
place, the reactant molecule disappears and a
fraction of the solid site is consumed. Since
in our model we use finite lattices in order
to represent real systems (e.g., char particles
of micron size), each solid site should repre-
sent a macroscooic mass unit. Therefore. each
solid site has to be hit by the molecule; in a
reactive collision, 11 times (where I.1is a
parameter) before it is totally consumed.
The overall behavior of the system strongly
depends on r. If r - 1, then only the most
exposed partsofthe solid matrix are consumed
at the initial stages of the process. The net
effect is the removal of all irregularities
of the external surface of the solid matrix,
making its shape smooth and regular. As a
Modelling
result, no major breakup of the solid matrix
takes place and no fragments of appreciable
size are formed. On the other hand, if r is
small the reactant molecules are able to
penetrate deep into the pore space, and hit
and consume the weak points of the solid
matrix. As a result, for small r solid-matrix
fragmentation takes place and many clusters
with a wide variety of shapes and sizes appear.
It is clear that the limits r = 1 and r - 0
represent, respectively, the diffusion --
limited regime (i.e., the regime in which the
consumption of rate is limited by the rate of
diffusion of the reactants), and the kinetic
regime (i.e., the regime in which the consump-
tion is limited by the chemical reaction rate).
Therefore, our approach provides, for the
first time, a unified model for the reaction-
consumption process for both the diffusion-
limited and the kinetic reqimes. We summarize
here the important results-of our model; the
details are given in Sahimi and Tsotsis (1987a,
b). (1) In the kinetic regime there is a maxi-
mum in the reaction rate (fraction of solid
sites consumed perunitof time) at some well-
defined value of conversion (fraction of sites
consumed up to time t), in agreement with
experimental observations (Dutta and Wen 1977).
(2) The fragmentation phenomenon in the kinetic
regime occurs at some finite value of conver-
sion, again in agreement with the experimental
data. (3) The number ns of the fragments of
s-sites (per lattice sites) obeys a dynamic
scaling
t-ws-Tf(s/tz) , (1)
“s -
where w, z and T are universal critical expo-
nents that do not depend on the microscopic
details of the system. f(x) is the scaling (ur
cut off) function whose shape is also universal.
This dynamic scaling also agrees with ex eri-
mental observations (Sundbacketal. 1985 P. (4)
In the diffusion-limited regimzhe solid
surface loses its irregularities and, after
awhile, the solid matrix takes a spherical
shape and its radius shrinks uniformly. There-
fore, we have developed a unified model for
reaction-consumption processes in porous media,
whose predictions are all in agreement with
experimental observations.
FLUID-SOLID REACTIONS AND THE
PHENOMENON OF PORE PLUGGING
We now consider the phenomena of fluid-solid
reactions in porous media in which the product
of the reaction is also a solid, which ulti-
mately results in plugging of the pores. As
more pores plug, the accessible surface area
of the porous media decreases and,therefore,
the reaction rate. which is usually propor-
tional to the accessible surface area, also
decreases and ultimately vanishes. This is
similar to the phenomenon of catalyst deacti-
vation. This phenomenon is normally caused
by deposits (by a reaction, or d reaction
product) which covers the surface of catalyst
and frequently blocks its porous structure.
Many aspects of catalyst deactivation are
similar to those of non-catalytic gas-solid
reactions. In the case of gas-solid reactions
one deals with a char or a coal particle. In
catalyst deactivation one deals with a catalyst
particle which very often, as is also the case
with char and coal particles, has a tortuous
 Proc. 6th Int. C&J on Mathemutical Model& 21

porous structure. The main difference is that
in case of non-catalytic gas-solid reactions,
the reaction process consumes the solid-matrix;
this is rarelv true in catalvst deactivation.
However, in terms of the physical process, re-
gardless of such differences, ttie and effect of
the reaction process is in both cases the same.
The morphology of the porous medium, coal or
catalyst particle, changes as a function of
time.
problem. We have recently shown (Sahimi 1987,
Mojaradi and Sahimi 1987) how network modeling
of porous media, together with random walk
representation of diffusion processes can be
used to accurately estimate the effective
diffusivity of a reactive porous medium.
Related problems of hindered diffusion and
reaction in porous media, and acid rock dis-
solution are currently under study. The re-
sults will be reported in future papers.

Past modeling efforts of catalyst deactivation ACKNOWLEDGEMENTS

have paralleled those for modeling gas-solid
reaction systems. They have either utilized Two of us (M.S. and T.T.T.) gratefully acknow-
oversimplified models of the pore space of the leqe the partial support of this work bv the
catalyst, such as bundle of parallel pores, or donors of‘the Petroieum Research Fund (grants
pseudo-homogeneous descriptions in terms of 18950-67 and 18168-AC5,7), and the United
effective diffusivities and tortuositv factors. States Department of Energy.
Both approaches have a number of shortcomings.
For example, they fail to describe the effect REFERENCES
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the problem that can, in principle,'account for Process Des. Dev., E, 31.
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applicable to the deactivation process under Gavalas, G. R. (1981). WSciFTech. 4,
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Here, we briefly describe the essential fea- Hossain, Md. M., D. D. Do and J. E. Bailey
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sent the catalyst particle by a percolation Minnesota (1981).
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with coke and the reaction rate, which is
defined in terms of the amount of useful mate-
rial that is produced, decreases and ultimately
vanishes. It is also clear that the ratio
prd/pr is proportional to the selectivity of
the catalyst, while pr + prd is proportional
to its so-called sticking coefficient. Thus,
depending on the values of the probabilities
of different events, one may simulate the
deactivation process under any desired condi-
tions.
kinetic :~~i~~a~!l~~t~~y~< <e~~t??~t~~n!n i,"'
refer the interested reader to Sahimi and
Tsotsis (1987c) for more details.

OTHER APPLICATIONS

The techniques and ideas we described here can

be equally useful in modeling other aspects
and problems of fluid-solid reactions in porous
media. For example, estimating the effective
diffusivities of porous media under reactive
conditions is an important and unsolved