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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
fry/
102
*.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
Ioa /’,
7/,-4
i.
,,6’ p-
—
—--
REF. 6, OASES, SPHtRtS
REF.S, LIQUIDS,SPKRW$,
------W.S,UQIJW, iwrntt
ETC.
ax
. (5)
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)
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,
2,
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. . . . . . ..-. .’.
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