.

5p4iw93

A Mathematical Model for Dispersion in the Direction

Of Flow in Porous Media
H. A. DEANS

ABSTRACT
A three-pararneter
mathematical
model for onedimensional
flow in porous media is developed,
The objective
of the mode[ is to predict accurately
the longitudinal
dispersion
associated
wit h the
flow of either gases or liquids over a wide range of
Reynolds
number.
A qualitative
analysis
of the model parameters
Published
experimental
pulse-response
is given,
curves are compared w itb results Predicted by the
model. Several general types of problems are given
for which the model can be used.

INTRODUCTION
The problem of multicomponent single-phase flow
through porous media is encountered in the study
of petroleum reservoirs,
gae chromatographic
and
ion-exchange
columns, industrial
fixed-bed contacters and elsewhere. These particular exampIes
span the wide range of flow conditions possible;
Reynolds numbers of less than 10+ are not unusual
in oil-production problems, while values in excese
of 103 are common in large fixed-bed operations.
The study of flow-dependent
transport phenomena
i,s complic~ted both by the changes in the character
of the flow over rhis. range, and by the irregularity y
of the flow boundaries inherent to porous media.
Dispersion
is one of the important phenomena
known to depend fundamentally on flow conditions
as weH as on fluid and, medium properties. As, used
in this paper, the term dispersion
refers to the
observed mixing of fIuid, elements of different composition which occurs in flow systems. The actual
mechanism may be one or more of a number listed
below. Only dispersion in the direction of the mean
flow (referred to as axial or longi~udinal dispersion
(or mixing) is considered
here, although lateral
dispersion ar)ses as part of certain coupled mechi
anisms.
1
.
M~CHANISljS FOR LONGITUDINAL
DiSperSiOn

A number of distinct

rnechaniams sre.knowns,s~

7t8

Originaf manuscript received in Soaiet y of Petroleum En@neers

office
%pt. 5, 1962. Revised
manuscript received
Jam 28,
1963. Pqer
presented
at Joint SPR.AtChE
Sytrponhn
held
Aug, 26.29, .1962, in Denver, COIO.
heferencee
given at end of pspert
.

RICE U.
HOUSTON,

TEX.

to contribute to the phenomenon of longitudinal

dispersion.
The more important of these are as
follows.
1. Molecular diffusion in the flow direction,
2, Turbulent (eel 1) mixing.
3. Lateral
transport
processes
coupled
with
velocity
and/or
residence
time distributions,
including: (a) t Taylor diffusion caused by the
interaction of velocity profiles in individual voids
with lateral molecular diffusion; (b) separation and
remixing or interdiffusion of streams, having different

velocities around particles; and (c) the coupling of

gross velocity profiles, caused by viscous instability
..
or inhomogeneous porosity, with Iateral dispersion.
4. Finite mass-transfer
rate between a porous
matrix and the flowing phase, and finite diffusion
rate inside eIements of the porous matrix.
It is a well documented fact that these mechanisms,
whether acting individually
or in combinations,
produce essentially
similar integral effects. The
observed dispersion can be described approximately
by solutions of the diffusion equation with a propetly
chosen dispersion coefficient.
Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg
and Sjenitzer. 7 AppiarentIy thr$se conditions are not
satisfied exactly in many real systems. %est fit
,
solutions of the diffusion equatibn often depart
appreciably from measured breakthrough curves for
the usual pulse- or step-forced experimental systems.
In particular, pulse response curves usuaHy show
some degree of asymmetry and [tailing
which
cannot be reproduced b y the one-parameter diffusion
model.
The
three-parameter
model proposed
herein
attempts to produce these effects in a realistic
manner. Asymmetry and ~ailing are predicted for
certsiru sets of parameter values, while for other
sets the new model agrees with the diffusion model.
VELOCITY Di?iPENDENCE OF DISPERSION
Molecular diffusion apparently controls at sufficiently low Reyuolds number in both gas and liquid
sYstems.2t3 At Re > 201 turbulent cell mixing is
dominant for gases flowing at Iow pressure; the
data of McHenry and Wilhelm8 show that the mixing
ceH is approximately
1 particle diameter long in
random sphere packs, On the other hand, the data
.
.. .
.
.

...-

tailing and asymmetry for pulsed systems. However,

cettqin basic advantages of the cell model should
be noted.
1. Serial solution of ordinary differential equations
is required, rather than solution of a boundary-value
partial differential equation.
2. Complications
such as additional
transport
phenomena, chemical reactions,
or flow ptofiles
can be added to the cell model without changing
its mathematical form or markedly increasing the
difficulty of obtaining solutions to the equations
for a single cell.
The addition of parameters to account for asymmerry, etc., can make use of these advantages
only if the basic form of the cell model is retained.
The procedure used here to add parameters is
based on the concept of capacitance 3 in a porous
medium, which implies the presence of a nonflowing
volume in the medium. If it is to have an effect on
the flowing stream, this stagnant volume must be
tonne cted to the flowing voIume by some sort of
resistance
to material transport. Hence, at least
two new parameters
are introduce~
a stagnant
voIume fraction, and a mass-transfer
factor, For
this simpIest modification of the celI model, the
equations for cell t Me

of other investigators 3*5 indicate that this limiting

situation is reached in liquids only at Re > 103 if
at all.
Fig, 1 is a replot of dispersion data from several
sources, reduced via the diffusion model, Of particular interest is the aImost linear dependence
of
~ . Re on velocity for liquids in the range 10-3 <
Re < K?. 315$10Effotw.2*4 to explain this behavior
in terms of the capillary diffusion effect of Taylorg
are otd y qua] itative, since # . Re is predicted to
vary with the square of velocity.
ALTERNATE

MATHEMATICAL MODELS

Several authors l-86 have pointed out the equivalence between the diffusion model and the series
of perfectly mixed cells in limiting cases. In the
latter model, the ith cell in the series is governed
by the simple material balance

-c, =

Cf-1

+ . . . . . . . . . . (1)

i = 1, 2, . . . . fi
where Ci is the concentration of a trace component
in the flowing stream and ~is dimensionless
time
based on the mean residence time in the mixing
ceJ1. If a mathematical pulse ~ (O+)& introduced
into the first cell at F = O+. the Nth cell will
produce a concentration
vs. time curve which is
closely approximated. by
-

:(2)

if ~ is chosen properly, and ~ is not too small.

E q. 2 is the anaIytical solution_of_the
d~fusion
eq~tion
for pulse forcing, with N, r and x being
the dittiensionless total Iength, of medium, time and
dispersion
modulus, respectively
(based on the
cell length). This equation is commonly. used to
obtain dispersion
coefficients
from experimental
pulse - response
curves.
The simple cell model also centsins one parameter,
which is the lengtlf of the mixing cell. Like the
diffusion model, it does not predict the observed

. -?WS

7/,-4

Ioa

/,

i.

LAO, C*,-U2,

+- RW.2 , H.-A,

If Z becomes very large, or / approaches zero,

Eqs, 3 and 4 will reduce to Eq. 1, whose limiting
behavior
is known. Gases at low pressure
are
probabIy characterized
by large ~ as will be discussed Iater.
The limit of large N for fixed path length L is
also interesting. This corresponds to a small value
of 1, the length of the mixing cell; in this case
Eqs. 3 and 4 may be approximated b y

SAND

-==(w)~+/~
ax

5A!I0

REF. 6, OASES, SPHtRtS

--

ETC.
REF.S, LIQUIDS,SPKRW$,

R*

FIG.

19 $

I
lot

ac*
f =a
dr

I
,.3

(C- C*),

OSXAN
.

.. .

r = 1, 2, .. . N

LIMITING BEHAVIOR OF THE

THREE-PARAMETER MODEL

------W.S,UQIJW,
iwrntt
---- REF.10, Uaulos. Wm

,/
/

sOCIETY

......

. (5)

. . . . . . . . ..(6).

.
OF
.-

.,

(4)

. . . . ..#

~..

,,6 p-

18

. . (3)

where f is the fraction of cell volume which is

nonflowing, Cf* is the tracer concentration in this
fraction, ~is a dimensiortlesa atass-transfer modulus
and F is again dimensionless
time based on the
mean residence time in the entire cell .volunie.

./

*.Re,

dCj *

-#&+/T

dCi *
f.~
= E(Cj-C~)

fry/
,/
+.=,:;

102

-cf=(I

(fi-z12

c(K3=&eq

la

c~1

PETROI.

. . .
EIJ.M ENGINEERS

JOIiRNAL
.-

----

. ...!.--

._

,,
..

..

where the longitudinal variable x, the total

a and r are now dimensionless
based
characteristic
length d.
The solution of Eqs. 5 and 6 for the pulse
ment conditions C(X,O) = C*(z, O) = (), O <
C(O, r) = 8(0+) is
N,

C(N, r) = e-d

a(r-N(l

. . . . . . . .

-/))

......

11(22)
=
z

includes

experix < N;

The velocity and mass transport in. an average

void in a porous medium are complicated functions
of position as well as Re and fluid properties. The
division of celI volume into flowing and stagnant
segments separated by a resistance is obviously an
extreme limit which can be justified only on the
grounds of simplicity. If the model is accepted, the
following assumptions
can be justified by dimensional cons ideations.
1. The velocity distribution,
hence R and ~/,
should depend on Re m-tly.
2. The resistance
factor, in which the mass
transport
is lumped, may depend on Re and the
Schmidc number. Z should decrease as Sc increases,
so that the capacitance effect will be more significant
for systems with large values of SC,
For gases (Sc on the order of unity), the capacitance
effect is apparently
insignificant,
The
limiting behavior at high Re c= be realized in the
cell model (Eq. 1) by letting N equal the ratio of
flow-path length to mixing-cell length. The latter
has been obkerveds to be approximately 1 partic~e
diameter in random sphere packs (i.e., Z = d, N = N,

(7)

unit impuhe function

= ]1 (iz) is the firstfirst kind of imaginary
z,

e2z
7=(8)

Under conditions such that I T-N I <<~N and ctN >> I,

tk square roots in Eq. 7 can be expsnded in the
form

.,

.,...

. . . . . . . ...

the latter

authors fit using Eq. 2.

ANALYSIS OF MODEL PARAMETERS

where ~(r - N( 1 -f) ) ia the

located at r = Af(l -/). Ii(z)
order Bessel function of the
argument. For large argument

length
on the

,,

(9)

etc. ),

Although the diffusion model is physically the

correct one at low R e, the cell model can be used
if ~ is allowed to vary with fluid properties. Agreement is obtain~d between the two models for long
flow paths if N = ~ PeL.
For liquids (Schmidr number on the order of 103),

The use of Eqs. 8 and g in E.q. 7 leads to

JL4!ll
C(N)

e 4(2)

0 (0)

This is the solution predicted by the diffusion

model for # = ~2/a, so that the three-parameter
model reduces to a one-parameter
limit in this
I

case,

Eq. 10 also predicts that the dispersing pulse

will move through the model with a dimensionless
ve]ocity of unity, rather than 1/(1-/), which is in
with experimental
observation.
agreement
This
paradoxical
behavior of the nonflowing volume is
encountered in a number of simiIar situations. ~
NUMERICAL
SOLUTION FOR SMALL
..
,

i
!
,
1
I

Eqs, 3 and 4 have been integrated numerically

on the Rice U. computer for a number of combinations
of the parameters ~ tt and h? Figs. 2 and 3 indicate
the variety of b~eakthrough-curve shapes avail abIe.
The curve for N = cu in Fig; 2 was computed from
Eq. 7.
Figs. 4 and 5 give best fits of experimen~al
curves publ i shed by Canberry and Brecton. 3 Fig. 4
.
MARCH,
..
.

196S
...

.;

1 -----

~~,=

r
FIG. 2

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RWERCNCE
3

RUN 13, .aml.

._

R,_

6La cm.
91.8 cm.
---+
lHIS WORti ,

f.,
. -. . . ..

-\

I
\

t
,,

.
-- . ~..
<i

-
k

R..oel

tc,,

N-294
R-106!

..

100

LL-

----CL,
Cfi

snhsr,,

-.

1)$-(

-~

- -4--

1.
/

t.
FIG,

FIG.

capacitance
is apparently the dominarit effect over
a wide range of I/e, The effective dispersion coefficient increases linearly with Re, beginning at
the lower limit of the molekular diffusivity at Re
on the order of 10-3, Z% seen in Fig. 1, # for liquids
remains significantly higher than the limiting value
for gases even at Re = 5 x 102.
Fig. 4 shows the extent to which experimental
cwves may depart from the cliffus ion model, ,In
this case, the best fit using the three-parameter
cell model gives (~2fla) = 4,3, which is more than
twice the value of @quoted by the authors? Attempts
to fit the curves in Fig. 5 with Eq. 2 leads to
different values of ~ for the two fIow-path lengths.
DETERMINATION OF PARAMETERS
USE OF THE MODEL

AND

T&e necessary data for ,a general determination

of N, ~ and E are not presently
available. Data on
gas systems can give little information, since the
capacit ante effect is small. Much of the liquid
data was taken under conditions such that the onedimensional
flow assumptions
are invalid;
the,
information obtained is characteristic
of the individual systems rather than porous media in general,
For a specific system, the model may be useful
even if the fIow is not one-dimensional.
The experimental curve in Fig. 4 is for a system with tube-toparticle diameter ratio of about 10. Lateral mixing,
coupled with gross velocity profile, probably contributed significantly
to the measured dispersion,
In many flow problems, dispersion may be safely
Some instances
where it must be
disregarded.
included
in reasonably
accurate manner are in:
calculations;
(z) certain
(I) miscible-displacement
chemical-reactor
design problems; end (3) chromatographic techniques
for measuring other trenspok
phenomena.
Most of the specific probIems in these categories
must be attacked by numerical methods in any case.
The three-parameter cell model can be used in place
of the basic. continuity equations in these calculations,

The

since it is quite amenabIe

model parameters

to generalization.

must be predetermined

for

the system of interest if dispersion

for accurately.

is to be accounted

NOMENCLATURE

Re = Reynolds

number, i7d/v where U = mean

interstitial velocity, d = a length parameter
character sti c of the porous matrix, and
v = kinematic viscosity of the fIowing fluid
Sc = Schmidt number, v/Din where Dm = a cheracteriatic molecuhr diffusivity
Peclet number, ZL/Dm where L =total length
of flow path
where
dispersion moduli, DE/Cd, or DE/ii,
DE = effective
long itudin al dispersion
coefficient, and 2 = length of a mixing cell
in the cell model
dimensionless
time, ti7d or tZ[
dimensionless
flow path Iength, L/c! or L/l
dimensionless mass-t&nsfer parameter, based
ondorl
.
fraction
of cell volume which ii nonflowing
f
REFERENCES
L

Aris, R.

and Amundsonz
N. R.: AfChE Jorm. (1957)
Vol. 3, 280,
R. J.; Rayne, J. R, end Terry, W, M., Jr.:
2. Blackwell,
~~Factor~ ~fluenc~g
the Efficiency
of Miscible
Displacement),
L
Trans.,
AIME (1959) Vol. 216,
3. Carberry,
J. J. and Bretton,
R, H.: AICbE Jour.
(195S) Vol. 4, 367.
4.

Coltina,
R. E;
Flow of Fluids Though
Porous
Materials, Reinhold Publishing
Cozp., N. Y. (1961).

R. A. tid White, R., R.: A1CM3 jour. (1958)

vol. 4, 16L
H. A. end Lapidus,
L.: AICbE Jorw, (1960),
6, Deana,
VOL 6, 663.
5. Ebach,

7. Klinkenberg,

A. and Sjenitzer,
(1956) vol.
5, 25S.
8, McHmry,
K. W. and Wilhelm,
(1957) vol. 3, 33.

F.:

R. H.: AIChE

Taylor, G, L: Proc., Roy. Sec.

151A, 42 L
D. U.: AICZIE
10. von Rosenberg,
55.
9.

Eng, Sci.

Cbem,

London
~osr.

Jour.

(1953)

(1956)

VOL

VOL
2,

***

2,
. .

sOCti

,,

TY

OF

..

P8TROLEUM

,,

,,

..

..-.

ENGINEERS

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