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5p4iw93

A Mathematical Model for Dispersion in the Direction


Of Flow in Porous Media
H. A. DEANS ‘
I RICE U.
HOUSTON, TEX.

ABSTRACT to contribute to the phenomenon of longitudinal


A three-pararneter mathematical model for one- dispersion. The more important of these are as ~
dimensional flow in porous media is developed, follows.
The objective of the mode[ is to predict accurately 1. Molecular diffusion in the flow direction,
the longitudinal dispersion associated wit h the 2, Turbulent (eel 1) mixing.
flow of either gases or liquids over a wide range of 3. Lateral transport processes coupled with
Reynolds number. velocity and/or residence time distributions,
A qualitative analysis of the model parameters including: (a) t ‘Taylor” diffusion caused by the
is given, Published experimental pulse-response interaction of velocity profiles in individual voids
curves are compared w itb results Predicted by the with lateral molecular diffusion; (b) separation and
model. Several general types of problems are given remixing or interdiffusion of streams, having different ‘
for which the model can be used. velocities around particles; and (c) the coupling of
gross velocity profiles, caused by viscous instability ..
INTRODUCTION or inhomogeneous porosity, with I’ateral dispersion.
4. Finite mass-transfer rate between a porous
The problem of multicomponent single-phase flow
matrix and the flowing phase, and finite diffusion
through porous media is encountered in the study
rate inside eIements of the porous matrix.
of petroleum reservoirs, gae chromatographic and
It is a well documented fact that these mechanisms,
ion-exchange columns, industrial fixed-bed con-
whether acting individually or in combinations,
tacters and elsewhere. These particular exampIes
produce essentially similar integral effects. The
span the wide range of flow conditions possible;
observed dispersion can be described approximately s
, Reynolds numbers of less than 10+ are not “unusual
by solutions of the diffusion equation with a propetly
in oil-production problems, while values in excese
chosen dispersion coefficient.
of 103 are common in large fixed-bed operations.
Necessary conditions for equivalence between dis-
The study of flow-dependent transport phenomena
persion and diffusion are discussed by Klinkenberg
i,s complic~ted both by the changes in the character
and Sjenitzer. 7 AppiarentIy thr$se conditions are not
of the flow over rhis. range, and by the irregularity y
satisfied exactly in many real systems. ‘%est fit”
of the flow boundaries inherent to porous media. solutions of the diffusion equatibn often depart ,
Dispersion is one of the important phenomena appreciably from measured breakthrough curves for
known to depend fundamentally on flow conditions the usual pulse- or step-forced experimental systems.
as weH as on fluid and, medium properties. As, used In particular, pulse response curves usuaHy show
in this paper, the term “dispersion” refers to the some degree of asymmetry and [‘tailing” which
observed mixing of fIuid, elements of different com- cannot be reproduced b y the one-parameter diffusion
position which occurs in flow systems. The actual model.
mechanism may be one or more of a number listed The three-parameter model proposed herein
below. Only dispersion in the direction of the mean attempts to produce these effects in a realistic
flow (referred to as axial or longi~udinal dispersion manner. Asymmetry and ~ailing are predicted for
(or mixing) is considered here, although lateral certsiru” sets of parameter values, while for other
dispersion ar’)ses as part of certain coupled mech- sets the new model agrees with the diffusion model.
anisms. i
1“
.
VELOCITY Di?iPENDENCE OF DISPERSION
M~CHANISljS FOR LONGITUDINAL
DiSperSiOn Molecular diffusion apparently controls at suffic-
iently low Reyuolds number in both gas and liquid
A number of distinct rnechaniams sre.knowns,s~ 7t8
sYstems.2t3 At Re > 201 turbulent cell mixing is
Originaf manuscript received in Soaiet y of Petroleum En@neers dominant for gases flowing at Iow pressure; the
office %pt. 5, 1962. Revised manuscript received Jam 28, data of McHenry and Wilhelm8 show that the mixing
1963. Pqer presented at Joint SPR.AtChE Sytrponhn held
Aug, 26.29, .1962, in Denver, COIO. ceH is approximately 1 particle diameter long in
heferencee given at end of pspert random sphere packs, On the other hand, the data
. . . . . .. .
...-

of other “investigators 3*5 indicate that this limiting tailing and asymmetry for pulsed systems. However,
situation is reached in liquids only at Re > 103 if cettqin basic advantages of the cell model should
at “all. be noted.
Fig, 1 is a replot of dispersion data from several 1. Serial solution of ordinary differential equations
sources, reduced via the diffusion model, Of partic- is required, rather than solution of a boundary-value
ular interest is the aImost linear dependence of partial differential equation.
~ . Re on velocity for liquids in the range 10-3 < 2. Complications such as additional transport
Re < K?. 315$10Effotw.2*4 to explain this behavior phenomena, chemical reactions, or flow ptofiles
in terms of the capillary diffusion effect of Taylorg can be added to the cell model without changing
are otd y qua] itative, since # . Re is predicted to its mathematical form or markedly increasing the
vary with the square of velocity. difficulty of obtaining solutions to the equations
for a single cell.
ALTERNATE MATHEMATICAL MODELS The addition of parameters to account for asym-
Several authors l-8’6 have pointed out the equiv- merry, etc., can make use of these advantages
alence between the diffusion model and the series only if the basic form of the cell model is retained.
of perfectly mixed cells in limiting cases. In the The procedure used here to add parameters is
latter model, the ith cell in the series is governed based on the concept of capacitance 3 in a porous
by the simple material balance medium, which implies the presence of a nonflowing
volume in the medium. If it is to have an effect on
Cf-1 -c, = + . . . . . . . . . . (1) the flowing stream, this stagnant volume must be
tonne cted to the flowing voIume by some sort of
i = 1, 2, . . . . fi resistance to material transport. Hence, at least
two new parameters are introduce~ a ‘stagnant
voIume fraction, and a mass-transfer factor, For
where Ci is the concentration of a trace component this simpIest modification of the celI model, the
in the flowing stream and ~is dimensionless time equations for cell t’ Me
based on the mean residence time in the mixing
ceJ1. If a mathematical pulse ~ (O+)& introduced dCj *
c~–1 -cf=(I -#&+/T “ “ . . (3)
into the first cell at F = O+. the Nth cell will
produce a concentration vs. time curve which is
closely approximated. by dCi *
f.~ = E(Cj-C~) . . . . ..# (4)
- (fi-z12

c(K3=&e‘q’ ““””’ :(2)


* r’ = 1, 2, .. . N

where f is the fraction of cell volume which is


if ~ is chosen properly, and ~ is not too small. nonflowing, Cf* is the tracer concentration in this
E q. 2 is the anaIytical solution_of_the d~fusion fraction, ~is a dimensiortlesa atass-transfer modulus
eq~tion for ‘pulse forcing, with N, r and x being and F is again dimensionless time based on the
the dittiensionles’s total Iength, of medium, time and mean residence time in the entire ‘cell .volunie.
dispersion modulus, respectively (based on the
~..
cell length). This equation is commonly. used to LIMITING BEHAVIOR OF THE
obtain dispersion coefficients from experimental
THREE-PARAMETER MODEL
pulse - response curves.
The simple cell model also cents’ins one parameter, If Z becomes very large, or / approaches zero,
which is the lengtlf of the mixing cell. Like the Eqs, 3 and 4 will reduce to Eq. 1, whose limiting
diffusion model, it does not predict the observed behavior is’ known. Gases at low pressure are
probabIy characterized by large ~ as will be dis-
cussed Iater.
The limit of large N for fixed path length L is

fry/
102

also interesting. This corresponds to a small value


la

*.Re,
I
I
+.=,:;
,/’
‘ ‘ ./
/
. -?WS LAO, C*,-U2, SAND
of 1, the length of the mixing cell; in this case
Eqs. ”3 and 4 may be approximated b y

+- RW.2 , H.-A, 5A!I0


-==(w)~+/~ ......
18

Ioa /’,
7/,-4
i.
,,6’ p-

—--
REF. 6, OASES, SPHtRtS

REF.S, LIQUIDS,SPKRW$,

------W.S,UQIJW, iwrntt
ETC.
ax
. (5)

,/’ ---- REF.10, Uaulos. Wm ac*


/ ; f— =a (C- C*), . . . . . . . . ..(6)”.
# , I I I dr
d @ d R* 1 19 $ lot ,.3

FIG. 1 OSXAN
. . . . .
f sOCIETY OF PETROI. EIJ.M ENGINEERS JOIiRNAL
.. . .-
.- ---- . ...!.-- ._
,,
., .’.’ ..”
.

where the longitudinal variable x, the total length includes the latter author’s fit using Eq. 2.
N, a and r are now dimensionless based on the
characteristic length d. ANALYSIS OF MODEL PARAMETERS
The solution of Eqs. 5 and 6 for the pulse experi- The velocity and mass transport in. an average
ment conditions C(X,O) = C*(z, O) = (), O < x < N; void in a porous medium are complicated functions
C(O, r) = 8(0+) is of position as well as Re and fluid properties. The
division of celI volume into flowing and stagnant
C(N, r) = e-d a(r-N(l -/)) + 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 dimen-
sional cons ideations.
1. The velocity distribution, hence R and ~/,
should depend on Re m-tly.
. . . . . . . . ...”... . . . . . . (7) 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,
where ~(r - N( 1 -f) ) ia the unit impuhe function so that the capacitance effect will be more significant
located at r = Af(l -/). Ii(z) = ]1 (iz) is the first- for systems with large values of SC, -
order Bessel function of the first kind of imaginary For gases (Sc on the order of unity), the capac-
argument. For large argument z, itance effect is apparently insignificant, The
limiting behavior at high’ Re c= be realized in the
11(22) . e2z cell model (Eq. 1) by letting N equal the ratio of
—=
flow-path length to mixing-cell length. The latter
z
7=”””””’””’””(8) has been obkerveds to be approximately 1 part’ic~e
diameter in random sphere packs (i.e., Z = d, N = N,
Under conditions such that I T-N I <<~N and ctN >> I,
etc. ),
tk square roots in Eq. 7 can be expsnded in the
Although the diffusion model is physically the
form
correct one at low R e, the cell model can be used
if ~ is allowed to vary with fluid properties. Agree-
ment is obtain~d between the two models for “long”
flow paths if N = ~ PeL.
. ., .,... . . . . . . . ... ,, For liquids (Schmidr number on the order of 103),
(9)

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
case, I
Eq. 10 also predicts that the dispersing pulse r——
will move through the model with a dimensionless FIG. 2
ve]ocity of unity, rather than 1/(1-/), which is in
agreement with experimental observation. This
paradoxical behavior of the nonflowing volume is
encountered in a number of simiIar situations. ~
NUMERICAL
.. SOLUTION FOR “SMALL” N

,’ Eqs, 3 and 4 have been integrated numerically


on the Rice U. computer for a number of combinations
I
of the parameters ~ tt’ and h? Figs. 2 and 3 indicate
i“ the variety of b~eakthrough-curve shapes avail abIe.
!
, ‘ The curve for N = cu in Fig; 2 was computed from
1 Eq. 7.
I
Figs. 4 and 5 give “best fits” of experimen~al
curves publ i shed by Canberry and Brecton. 3 Fig. 4
.
MARCH, 196S

“.. ..- ““- ”.; 1 “----- ~~,= ‘“.


. .
f“”
. -.

I
RWERCNCE
3
RUN 13, .aml. snhsr,,
—— . ._ —
R,- 100
_ L- 6La cm.
L- 91.8 cm.
---+ ~
----- lHIS WORti ,
f., tc,, R..oel , -\
‘. ———
CL, . -. . . .—.
Cfi —N-294 I
\ ~
R-106—! I

t’ “’ 1)$-( “
,,’
‘.
.. —. -— -- .— ~.. —— —— -. -~
‘k <i - -4--
1.
/

t—
t.
FIG. 5
FIG, 4
capacitance is apparently the dominarit effect over the system of interest if dispersion is to be accounted
a wide range of I/e, The effective dispersion co- for accurately.
efficient increases linearly with Re, beginning at
the lower limit of the molekular diffusivity at Re NOMENCLATURE ~
on the order of 10-3, Z% seen in Fig. 1, # for liquids Re = Reynold’s number, i7d/v where U = mean
remains significantly higher than the limiting value interstitial velocity, d = a length parameter
for gases even at Re = 5 x 102. character sti c of the porous matrix, and
Fig. 4 shows the extent to which experimental v = kinematic viscosity of the fIowing fluid
cwves may depart from the cliffus ion model, ,In Sc = Schmidt number, v/Din where Dm = a cherac-
this case, the “best fit” using the three-parameter teriatic molecuhr diffusivity
cell model gives (~2fla) = 4,3, which is more than
Peclet number, ZL/Dm where L =’total length
twice the value of @quoted by the authors? Attempts
of flow path
to fit the curves in Fig. 5 with Eq. 2 leads to
different values of ~ for the two fIow-path lengths. dispersion moduli, DE/Cd, or DE/ii, where
DE = effective long itudin al dispersion
DETERMINATION OF PARAMETERS AND coefficient, and 2 = length of a mixing cell
USE OF THE MODEL in the cell model
dimensionless time, ti7d or tZ’[
T&e necessary data for ,a general determination
of N, ~ and E are not presently available. Data on’ dimensionless flow” path Iength, L/c! or L/l
gas systems can give little information, since the dimensionless mass-t&nsfer parameter, based
capacit ante effect is small. Much of the liquid ondorl
data was taken under conditions such that the one- f . fraction of cell volume which ii nonflowing
dimensional flow assumptions are invalid; the,
information obtained is characteristic of the indi- REFERENCES
vidual systems rather than porous media in general,
For a specific system, the model may be useful L Aris, R.and Amundsonz N. R.: AfChE Jorm. (1957)
Vol. 3, 280,
even if the fIow is” not one-dimensional. The experi-
2. Blackwell, R. J.; Rayne, J. R, end “Terry, W, M., Jr.:
mental curve in Fig. 4 is for a system with tube-to- ~~Factor~ ~fluenc~g the Efficiency of Miscible
particle diameter ratio of about 10. Lateral mixing, Displacement)’, Trans., AIME (1959) Vol. 216, L
coupled with gross velocity profile, probably con- 3. Carberry, J. J. and Bretton, R, H.: AICbE Jour.
tributed significantly to the measured dispersion, (195S) Vol. 4, 367.
In many flow problems, dispersion may be safely 4. Coltina, R. E; Flow of Fluids Though Porous
disregarded. Some instances where it must be’ Materials, Reinhold Publishing Cozp., N. Y. (1961).
included in reasonably accurate manner are in: 5.’ Ebach, R. A. tid White, R., R.: A1CM3 jour. (1958)
vol. 4, 16L
(I) miscible-displacement calculations; (z) certain
6, Deana, H. A. end ‘Lapidus, L.: AICbE Jorw, (1960),
chemical-reactor design problems; end (3) chromato- VOL 6, 663.
graphic techniques for measuring other trenspok
7. Klinkenberg, A. and Sjenitzer, F.: Cbem, Eng, Sci.
phenomena. (1956) vol. 5, 25S.
“Most of the specific probIems in these categories 8, McHmry, K. W. and Wilhelm, R. H.:’ AIChE Jour.
must be attacked by numerical methods in any case. (1957) vol. 3, 33.
The three-parameter cell model can be used in place 9. Taylor,”’ G, L: Proc., Roy. Sec. London (1953) VOL
of the basic. continuity equations in these calcula- 151A, 42 L
tions, since it is quite amenabIe to generalization. 6 10. von Rosenberg, D. U.: AICZIE ~osr. (1956) VOL 2,

The model parameters must be predetermined for 55. ***

2,
.. ,,

. . . . . . ..-. .’.
sOCti TY OF P8TROLEUM ENGINEERS JO UR-NA:I. ‘“ . ‘“ “ -

,, .
.* .-.
,, .$
.-

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