Analysis of Factors MT

in the Flow of Polymer

SHELL 0/L CO.
G. J. HIRASAKI
HOUSTON, ~EX,
G. A. POPE SHELL DEvELOPMENT CO,
MEMBERS SPE-AIME HOUSTON, TEX.

ABSTRACT are seldom complete data on all sjstems of interest.

A correlation thar represents these effects as a
l~isplucement 0/ oil by polymer solu!ion hos
several rinique characteristics thrrt ar~ ?:ot present function of the polymer, brine, rock properties, and
irr normal water ~)ooding. These in< l14de non- flow conditions would result in a more accurate
Neu,toniun effects, pe.rmecbility reduction, and evaluation of systems that may not have been
polymer adsorption. measured in the laboratory at the desired conditions.
\foreover, if the dependence of rhese effects on the
The rbeological bei)nvior o/ the flow o{ pofymer
solutio:l through porous nreaiii could be Neu tonian
system properties were known, it would aid rhe
at IOU /lou: rIItes, pseudoplnstic at intermcdiote search for an optimal system. A model is proposed
{louI rutes, and di[(itant at high flow rates. The for representing the effects as a function of the
pseudo plastic behuvior is modcIed uith the f3lake- system properties. The model is consistent with a
KOZPnY mocfel for power-[uw model /[uids, Tbe number of experimental observations but enough
dilatant bchuvior i.s modeled with Ibe viscoelastic data have not yet been acquired to determine the
properties 0/ the po[yrner solution. extent of applicability of a correlation. It is hoped
The reduction in permeability is postulated to be that the presentation of these models will encourage
due to an udsorbca Ioym of polymer molecular coils further research to verify or improve the models.
that reduces the e/fective size of the pores, A
dimensionless number bas been formulated to MODEL FOR PSEUDOPLASTIC FLOW
correlote the perm~abiIity reduction factor with the THROUGH POROUS MEDIA
polymrr, brine, rrnd rock properties. This din~rwsion- The Blake-Kozeny model represents the porous
Iess number represents the ratio O/ the size O/ the medium as a bur, dle of capillary tubes with a length
polymer mofr-cular r-oil to an t-//ective pore radius that is greater than the length of the porous medium
0/ the porous medium, by a tortuosity factor, r. The equivalent radius of
A model hos been developed to represent the capillary tubes can be related to the parricle
adsorption us u Iurrction 01 polymer, brine, and rock diameter of a packed bed from the hydraullc radius
properties. T!w model assumes that the polymer is
concept or to the permeability and porosity by
ud.sorbed on the sur/ace 0/ the porous medium as o comparison with Darcys law for Newtonian fluids.
monolayer G/ molec741ar coils that have a s~gmcnt The modified Blake-Kozeny models represents
density .grcuter than the molecular coil in dilute the flow of a power-law fluid in the capillaries. The
solr41ion, relationship between the pressure drop and flow
rate can be expressed as a product of the fricrion
LVTRODUCTION factor and Reynolds number.
Displacement of oil by polymer solutions has
several unique characteristics that are not present f Re =1.0()
in normal waterflooding.12 These include non-
Newtonian effects, permeability reduction, and This expression can be related to the apparent
polymer adsorption. In principle, the effects could viscosity and the rock permeability and porosity
be measured experimentally for each fluid-rock through the following relationships:
system of interest over the entire range of flow
conditions existing in the reservoir. However, there

Original manuscript received in Society of Petroleum Engineers where

office Aug. 4, 1972. Revised manuscript received Jan, 10, 1974.
Paper (SPE 4026) was presented at SP E-AIME 47th Annual Fall
Meeting, held in San Antonio, Tex., Oct. 8-11, 1972. @ Copyright
1974 American Institute of Mining, Metallurgical, and Petroleum
=58>...........(3)
Engineers, Inc. app up L
lReferece~ listed at end of pap~~.

At G[9T .197-t 337

 Kelzan-!d for the systems considered here. However,
with polymers such as partially hydrolyzed poly -
acrylamides, the permeability reduction due to the
. . . . . . . . . . . . . . . ..$ (4) adsorption of the polymer is significant and must
be considered. The permeability reduction with
The coefficient K, (cp sec -1) and exponent n, are polyacrylamide is discussed later,
the power-law parameters determined from viscom- Eq. 2 can be expressed in terms of an equivalerrt
etric data. shear rate in the core so that the viscosity can be
determined directly from the viscosity-shear rate
data from viscometric measurements.
D =K#l-l . . . . . . . . . . ...(5)

= K@-1 .(6)
A tortuosity of 25/12 has been assumed. app core
The modified Blake-Kozeny model was applied to
Lhe flow of Kelzan-\4 biopolymer solutions through where
cores with residual oil saturation. The core and
n
fluid data are summarized in Tables 1 and 2.4 The

()
viscometric data for the three polymer solutions are =3n+l n-1 12U
{
shown in Fig. 1. All three solutions showed core 4n
pszudop!astic behavior to a different extent. The (150$4/2
pewer-law coefficient, K, and exponent n, were . . . . ,., . . . . . . . . . .(7)
determined from the viscometric data (tire actual
}alues were determined from a log-log plot of shear The Blake-Kozeny model does not represent the
stress vs rate of strain). The coefficient H pore-size distribution. A model representing a
determined from Eq. 4, and the power-law exponent bundle of capillary tubes that reflecr the pore-size
n, were used to compute the apparent viscosity from distribution is
Eq. 2. The calculated app?-ent viscosity is

()
compared with the experimental values on Fig, 2, Kl+3nn
The maximum difference between the calculated and =~
experimental values was less than 10 percent, app h
n
The Blal<e-Kozeny model accurately reproduced
the apparent viscosity behavior of the biopolymer 03

10
10 - ---,----r--r~- ~~-T
7
10 J o
rs(R)R2 dR

hu
n-1

F
8 . f-l
-o-$vslfh! 7
1 . (8)
b -6-SYSTEM 2
-t-sYslfM 3
1

where o(R) is the pore-size frequency distribution

function. Thus, the apparent viscosity has the same
1 exponential dependence on the flow rate with an
5HFAR RAlf, Y[sec) arbitrary pore-size distribution.
FIG. 1 VISCOMETRIC BEHAVIOR OF KELZAN-M,
y(SEC-]). MODEL FOR VISCOELASTIC FLOW
THROUGH POROUS MEDIA

The modified Blake-Kozeny model does not

TABLE 1 CORE DATA

Core Number kw(md)

_j_
sor
1 17. 0.188 0T2
2 7.7 0.20 0.20
3 22.8 0.20 0.20

TABLE 2 KELZAN SOLUTION DATA

Core Concentration %rine

Number (ppm) (Cp) (cp s~cn-l) n
u (cmkec)
1 Kelzon.M 200 0.84 7.6 0%
FIG, 2 RHEOLOGICAL BJ2HAVIO~ OF KELZAN-M IN 2 Kelzon-M 300 0.45 2.25 0.85
CORES. 3 Kelzon.M 300 0.45 5.5 0.69

33rs SOCIETY OF YET ROLEIM KS GISEERS JO URX,\L

represent the dilatant behavior observed at high 3wr
flow rates, We would not expect to see viscoelastic = . . . . . (14)
effects with this model because the power-law fluid (1 + efr)(l - Zefr)
model does not have a characteristic relaxation time
and the flow field in a smooth-bore capillary tube where ~ is the rate of elongation. The normal stress
does not have a characteristic deformation time. difference is the difference in normal stress between
,Marshall and .Metzners suggested that the fluid the direction of elongation and normal to it. The
relaxation time, fli, and the rate of elongation or
numerator is the stress due to a simple viscous fluid
contraction that occurs as the fluid flows through a and the denominator is the influence of the
channel or pore with varying cross-sectional area viscoelasticity. The stress goes to infinity as the
should be used to represent viscoelastic behavior. product, 20,1, approaches unity. This implies that
Thus, a dimensionless group such as the Deborah the viscoelastic model should have a similar
number sho~ld be used to represent the viscoelastic limiting dependence on the Deborah number. A model
effect in porous media. The Deborah number for to add this viscoelastic dependence [o the modified
flow in a packed bed was expressed as Blake-Kozeny model is proposed as

= E3fv 1
Deb~..... . . (9) f Re = . . . . . . ,$. (15)
1- ND~b
P
This model of the pseudoplastic and viscoelastic
The dependence of the Deborah number on the
behavior is compared with the experimental data of
velocity can be expressed by (1) assuming that the Marshall and !vfetzner on Fig. 3, A similar model
fluid has a constant elastic modulus, G, and a has recently been introduced by Weisler8 as
power-law behavior, and (2) expressing the particle
diameter, ~Jp, in terms of the permeability and
porosity. fRe= l+ci N2 . (16)
Deb
w H
~n- 1 (lo) where a is an empirical parameter.
If=;=; Eq. 15 can be expressed in terms of the apparent
viscosity as

n-1
Dp = Hu
*G)
a app = efu

V=ulfi......... (]2) [
1-
( I-@w) J-w 1
. . . . . . . . . . . . . . . (17)
H
N n.. .(lj) where the fluid relaxation time, ()~, is a function of
Deb =
G(I - 0) dt-m-k~d u
100 I_ I I 1 , 11111 I I J JIllll 1 I I Illllj
Eq. 13 shows that because of the shear rate
dependence of the relaxation time, a wide range of 50- 0 ET-597
a POIYISOBUIVIENE
values of velocities is compressed into a narrower
range of values of the Deborah number. Eq. 13 o
implies that the viscoelastic effect will be greater 0

with decreasing permeability for the same velocity. 10z :

This has been observed in several experiments .167*g
35 0
It can be shown chat the fluid relaxation time is - z
~
proportional to the molecular weight raised to the A
=
1.5 power. This strong dependence of the visco- *
elastic effect on the moIecular weight has been A

observed in several experiments. 1$12 -.

The relationship between the fluid relaxation
0.5
time and the rate of elongation can be illustrated
with a simple example, If the fluid is modeled with F
a simple ,Maxwell model and the flow field is a
simpJe elongational fJow, the normal stress I I I 111111 I I I 1111[1 [ I I Ill
0.1
difference is 10-2 0.1 1 10
N D*b

~11 22 = / FIG. 3 CORRELATION OF VISCOELASTICITY WITH

T - T33 DEBORAH NUMBER.
ALIGIST.]97$ 339
the shear rate, and the permeability and porosity, reduction will apply to either the polymer or the
kw and @w, are evaluated at the appropriate brine following the polymer.
saturation. There are at least three mechanisms for
In Fig. 4 the theoretical curves based on the permeability reduction: adsorption, gel formation,
viscoelastic model and theological data are and plugging. We shall not consider plugging here.
compared with experimental data for 0,2 percent Gel formation has been observed and its thickness
Separan AP-30 in 2.0 percent NaCl solution. g The measured in both capillary tubes and packed beds.16
salinity was high enough that the apparent viscosity However, the polymer concentrations were much
did not show pseudoplastic behavior. The low- larger than could economically be used in reservoir
permeability core showed a higher apparent viscosity flooding processes, so we shall nor consider gel
than the viscometrically measured polymer solution formation either.
viscosity, probably on account of the effect of .4 model is postulated to represent the permea-
permeability reduction. The model predicted quite bility reduction due to the adsorption of polymer on
well the behavior in the high-permeability cores. the matrix material. The model includes the effects
The model predicted a limiting velocity for the of polymer molecular weight, water salinity, rock
low-permeability core that was greater by a factor permeability and porosity, and flow rate.
of 3 than the observed value. F.xperimental measurements have shown that
The model is compared with experimental data for polymers adsorb on the solid surface as a monolayer
the flow of 0.15 percent Polyox WSR-301 10 in Fig. with thickness approximately equal to the diameter
s. The power-law model is shown for comp~rison by of the molecular coil in that particular solvent. 17,18
the dashed curve. From this we see rhat the Thus the thickness of the adsorbed layer will be
viscoelastic behavior can cause the flattening of modeled as equal to the diameter of the molecular
the power-law curve to an apparent constant coil in solution. The diameter of the molecular coil
viscosity region, followed by a rising curve. is a function of the molecular weight end of the
Dependence of the viscoelastic effect on the intrinsic viscosity in a particular solvent at a given
formation permeability has been observed in several shear rate. The radius of the molecular coil in a
experimental7~g and is shown for Separan AP-30 on dilute solution can be estimated from Einsreins
Fig. 4. equation for the viscosity of an infinitely dilute
suspension of hard spheres. 19
MODEL FOR PERMEABILITY

()
REDUCTION WITIi POLYACRYLAMIDE 30M[p,] 13
. . . . . ., (18)
Polymers such as partiaily hydrolyzed poly - M =
!-rA
acrylamide adsorb on the porous media, reduce rhe
mobility beyond what could be expected from the An equivalent capillary radius of a porous medium
viscosity alone, and reduce the mobility of brine can be expressed as
following the polymer. These effects are a function
of both the fluid and the rock material. Parameters 87k 1/2
that influence these phenomena are the polymer R= . . . . . . . . . . (19)
molecular weight, water salinity, rock permeability eq
() o
and porosity, rock composition, and flow rate.
The reduction of permeability with polyacrylamide If a capillary tube with a radius of Re had a
reduces the mobility both of the polymer solution monolayer of molecular coils of radius T,Ma\ sorbed
and of the brine following the polymer. Hereafter on its surface, the capillary radius would be
unless specified otherwise, the term permeability reduced by

35 1 1 1 1 r 1 Ill I II
1
1 I
f-lrl
r
1?
l-rlrrrTl-T ! I I
1~~7T-T
30~
/ lo/-
25- I
)
/
/1 ~8k
! 20- .

s // / s; %.
z 26
15-

10- . ---- ------ m--- 4[ POWER LAW MOOfl

1
k1390md
0 k,womd, +:0 291
lHEOi[llCAl
4:024
2
$- b k,hlbornd, +$0 263
--- fXPf QIMINIAl
c k,3500md, +,0 350
i I I I I 1111 I I I I I !111 I I I . . ~~ I I I 1 [11
10 10 ,02
O,..s
101 ., 1o 10 I
, cmlsec ~ , ft/DAY
4 4
FIG. 4THEOLOGICAL BEHAVIOP OF 0.2 PERCENT FIG. 5 THEOLOGICAL BEHAVIOR OF 0,15 PERCENT
SEPARAN AP-30 IN 2.0 PERCENT NaCl, POLYOX WSR-301 IN GALLUP CORE.

MO SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 6R=2rM . . . . . . .. (20) cations with some surfactants added. The brines in
Solutions 3 and 4 are synthetic brines of NaCl
added to deionized water. It is assumed that the
Thus, a dimensionless group to represent the intrinsic viscosity, [p], is equal to (PP - ~wli(c~w)
reduction of the pore radius due to adsorption of at the measured concentration because the latter is
polymer will be defined as nearly constant at these concentrations. The core
22-M data and the results of the experiments are showri
6= on Table 4, The apparent viscosity was computed
R from Eq. 2 at I ft/day and the permeability
eq reduction was calculated as
1/3

()
30M[~] RflJw
z . . . . . .,OOO . . (25)
k
lTA
= 2 app
. . . . .. (21)
*Tk !1/2
The value of the pore reduction group, A~, was
calcldated from Eq. 22 using an assumed molecular
(-l@ weight of 5. x 106 for Pusher 700. The values of
the permeability reduction factor, R&, are plotted
Using practical units of millidarcy for k and a on Fig. 6 as a function of N~, The solid curve is
value for r of 25/12, the dimensionless pore radius the idealized theoretical curve based on Eq. 24.
reduction group can be expressed as The dashed curve represents the empirical curve
#3[w11/3 that fitted the experimental data by multiplying AJ~
-3 in Eq. 24 by a factor of 1.36. This deviation from
= 3,9 x 10 the theoretical model may be due to inaccuracies in
6 measurements or to factor: not considered in the
(k/@l/2 ~ (22)
model, such as plugging of the smaller pores, pore-
If it is assumed that all the pores are of the same size distribution, rock composition, and clay
radius and that the adsorbed layer is impermeable, content. The data shown on Fig. 6 represent the
the reduction in flow rate would be analogous to data that were available at the time of writing.
the reduction of the capillary radius irr the Hagen- Further experiments need to be conducted for a
Poiseui Ile law. wider range of permeabilities, different polymers,
and brines of a wider range of salinities to verify
R4~. . . . . . . .. (23) the correlation.
~ = Experimental measurements of the adsorbed layer
8W L have been made for the adsorption of polymers from
Thus, the permeability reduction factor for this
idealized case could be expressed as
TABLE 3 POLYACRYLAMIDE PUSHER 700
SOLUTION DATA
k
w (IWwy
= (1 -NJ-4. . . . . .(24) \,/&/
k=; K
Solution
Number Description cp(sec)n- 1 n (d f/gin)
P
1 500 ppm solution 5.2 0.875 100.
However, the distribution of pore sizes cannot be 2 400 ppm sOlution** 4.5 0,875 106.
neglected when N~ becomes significant compared 3 500 ppm in 1% NOCl 4.5 0.875 C4.6
4 700 ppm in 2% NoCI 5.1 0.875 70.0
with 1,0. In particular the smaller pores will
Viscosity measured at 95 F.
become plugged first and the polymer will continue *Evoluoted ot Y = 1. see-l.
flowing rhrough the larger pores. Thus, it would be .* Natu,o I brine with Surfacfont.

more appropriate to correlate the permeability

reduction factor with N~ and empirically determine
TABLE 4 MEASUREC PERMEABILITY REDUCTlON
the functional relationship. Such a correlation need FACTOR AND PORE REDUCTION NUMBER
not differentiate between plugging the smaller pores
Core Solution
and reducing the pore radius by adsorption. However, Number (m!) 4 Nutr,ber R(*
there may be a difference in behavior between rock
with and without residual oil.
1 ii 0.197 1 iii 5.6 1.9 0.068
2 201. 0.200 3 8.) 5.4 1.3 0.087
A sexies of experiments was conducted to 3 181. 0.200 1 11.8 5.3 1.7 0.096
correlate the permeability reduction with the pore 4 143. 0.200 4 10.4 5.2 1.9 0.108
reduction group, N~, The measurements were made 5 117. 0.204 1 12.9 5.2 2.1 0.120
6 97. 0.194 2 14.4 4.5 2.7 0.129
with Pusher 700 in sandstone cores at zero oil 1 21.5 5.1 3.6 0.144
7 80. 0.200
saturation. The polymer solution da:a are summar- 8 22. 0.193 1 27.0 4.7 5.0 0.271
ized in Table 3.The water of Solutions 1 and 2 is
a natural brine containing both NaCl and multivalent

AUGUST, 1974
dilute solution onto porous glass discs and glass molecular weights.
powder. l~ls The thickcess of the adsorbed layer The dependence of the permeability reduction on
was independent of the concentration for co~centra- the shear rate can be represented by the shear-rate
tions greater than a value of about 0.0~ percent. dependence of the intrinsic viscosity. However, the
Above a sufficiently large molecular weight, the dilatant behavior at high flow rates cannot be
dependence of the layer thickness on the molecular represented with this model,
weight was observed to be the same as the The dependence of the permeability reduction on
dependence of the equivalent radius in dilute tt,e rock properties is represented by the ratio (k/@)
solution on the molecular weight. An interesting in N~. The value of N6 is inversely proportional to
observation made by Rowland is that the layer the square root of the permeability. Thus, the
thickness is directly proportional to the intrinsic reduction in permeability can become very signifi-
1,11,12 rhe permeability
viscosity (to the firs: power). This may seem to be cailt at low permeabilities.

in contradiction with Eq. 18, but on examination of reduction for Eqs. 22 arid 24 is shown in Fig. 7.
his experimental conditions, the difference in An example will be considered to illustrate the
intrinsic viscosity is primarily due to Ilse of order of magnitude that can be expected with this
different molecular weight fractions. If it is assumed model. Suppose that
that the equivalent radius is proportional to the
square root of the molecular weight, as in the case
of a random coil model or a real polymer in a theta
1/11- 100. df/gm ,
solvent, 19 then the intrinsic viscosity can be
expressed as a function of the molecular weight as k = 100. md ,

$5 = 0.20.
[U]= KOM1/2 . . . . . . . . . .. @6)
The value of the group N~ is
Elimination of the molecular weight between Eqs.
N~ - 0.116.
18 and 26 and substitution into Eq. 20 results in
The permeability reduction factor expressed by Eq.
1/3 24 or read from Fig. 6 is Rk - 1.64.

&R=2

Thus, for different

() TTAK2

molecular
30

0
weights but the same
[wE . . . . .
The diameter of the polymer molecular coil for a
polymer with a molecular weight of 3. x 106 and an
intrinsic viscosity of 100. df/gm can be determined
from Eq. 18 as 0.34 microns. This is in agreement
with the pore diameter of 0.5 to 1.5 microns observed
solvent, the theoretical layer thickness is propor- Gogarty* 1 and pore diameter of 0.45 to 1.0 microns
tional to the intrinsic viscosity as observed by observed by Smith 12 that was required to bloc! the
Rowland, flow of the polymer.
The dependence on the molecular weight for the Gogarty 11 observed that small decrease in polymer
same solvent can also be expressed as size (due to salinity) can cause a large change in
viscosity. This can be understood by expressing
1 \ 1/3
Eq. 18 in terms of the intrinsic viscosity.

H
30K
o ~1/2 . . . . , (28)
L5R=2
ITA r;
nA
[w] =--; (29)
Thus, for the same solvent, Na is proportional to the
square root of the molecular weight. This also is
consistent with the observations made by Smith 12
for three polyacrylamide solutions of differing

~
:

F
I
.
z 50 (1-l 36 N~)LJ0 ~
o / 4
1=
u o /
2 ~ /
z 1
>r t (1- Na)_4
5 .$
:./6
:
,,,,/ o
w
z
= 10 I d
g 001 005 01 05 10
PoRE REDuCTION GROUP. NB

FIG, 6 CORRELATION OF PERMEABILITY REDUC- FIG. 7 DEPENDENCE OF THE PERMEABILITY

TION. REDUCTION FACTOR ON THE PERMEABILITY.

342 SOCIETY OF PETROLEUM EN GISEERS JoCR~AL

Thus, the intrinsic viscosity changes as the cube The area covered by a spherical molecule of
of the molecular coil radius. radius rm assuming that the spheres are close-
The effect of salinity or other solvents (e.g., packed, will be denoted by AM. Assume that the
a1cohol)20 on the permeability reduction is reflected radius of the molecule before compression on the
through the intrinsic viscosity. For example, the surface is equal to the radius of the molecular coil
intrirr~ic viscosity of a polyacrylamide, Pusher in the solvent at infinite dilution.
520,10 for shear rates from 0.2 to 1,0 see-l is
shown on Fig. 8. Reducing the salinity from 5,000 =3,5r~, . . . ..m . . ..o .(31)
ppm to zero will increase the intrinsic viscosity by M
more than a factor of 100. The effect on the 2/3

()
permeability reduction depends on how it changes 30M[~]
the value of N~ relative to 1.0. Generally, a = 3.5 . . . . . ,. (32)
reduction in salnity greatly increases the
TtA
permeability reducti!~n. 12 ~*o
Let Ad be the amount of polymer adsorbed per unit
MODEL FOR ADSORPTION mass of the rock.
OF POLYACRYLAMIDE
MO
The adsorption o! polyacrylamide will also be
Ad=:L - . . . . . .. (33)
modeled as a monolayer of polymer moJeculal coils.
However, the molecules in the layer may be laterally %4 A rtr
compressed such that the segment density is greater
than the density of the molecular coil in dilute Substituting Eqs. 30 and 32 into Eq. 33 and
solution .17~ 18 Denote this increase in segment expressing in common units (i. e., millidarcies)
density as u. The ir,crease in segment density is a results in
function of the affinity of the mineral surface for
the polymer molecule.
The surface area per unit volume of the porous .. . (34)
Ad = 118. -
medium assuming a tortuosity of 25/1 2 is 1/2
k 2/3 prb
~@3 1/2
[WI

a
v
=

() 25k

where in this case, the single-phase

. . . . . . . . . . . .

porosity
(30)

and
To illustrate
predicted
example.

~ ~ 0.25,
the magnitude
by the model,
of
consider
the adsorption
the following

permeability should be used.

k - 100. md ,

104
> I I I I d M . 3. x ltJ6 gm/mol ,
I
[p]= 100 d~/gm ,
r A 7 ().2 !ieC-l
o 7:1. Osec-l p - 2,0 gmlcc .

We then have

103z Ad - 4.940, pgm/gm .

z It has been observed 18 for a particular system

-m that o has values between 2 and 8, This will imply
G that the amount of polymer adsorbed in this example
is between 10, and 40. pgm/gm. This is within the
X* range of values observed experimentally.
Adsorption measurements were made on several
102=
of the cores shown on Table 4 to compare with the
theoretical values calculated from Eq. 34. The
values of the segment density, u, required for the
theoretical value of adsorption to equal the measured
value were determined. The results summarized on

,Lu_u_1
o 0.1 0.2 0.3 0.4 0.S 0.6
Table 5 indicate

the experimental
that segment

adsorption
density
between 2 and 3 are required for Eq. 34 to correlate
values

data. Further experi-

*/oNaCl ments are needed with other polymer-rock systems
FIG. 8 DEPENDENCE OF INTRINSIC VISCOSITY ON to determine the parameters that influence rJ.
SALINITY. Eq. 34 is consistent with the small molecular

A1; GL: ST, 1974 343

weight dependence observed in some experi- and the adsorption when it does occur is broueht -(7

ments. 17) 18 The intrinsic viscosity for a random about by hydrogen bonding. In these investigations
coil or in a theta solvent can be expressed as the effects on the adsorption of pH and density of
ionized groups were not differentiated between the
[p]= KotvII/2 . . . . . . . . .. (35) size of the molecular coil and the segment density
factor, U,

Substituting Eq, 35 into Eq. 34 results in

PERMEABILITY REDUCTION AND
ADSOF. PTION WITH KELZAN

Although the models for permeability reduction

and adsorption were developed for polyacrylamide,
they were applied to data that were recently
measured for Kelzan-,MF. A nonadsorbing tracer was
for polymers of different molecular weight (and used to correct for the inaccessible pore volume in
same degree of hydrolysis) in the same solvent. calculating the adsorption. The theoretical permea-
Thus, adsorption with the same solvent is not a bility reduction factor using Eq. 24 was 1.4; the
function of molecular weight. measured residual resistance factor was 1.2.
The model of the adsorption expressed by Eq. 34 Comparison of measured adsorption with Eq. 34
will explain the strong dependence of the adsorption resulted in a segment density factor of 3,1. The
on the salinity observed by Smith .12 As the salhity results are summarized in Table 6.
increased the intrinsic viscosity in the denominator
of Eq. 34 decreased, which results in an increased ESTIMATION OF FLLJID PROPERTIES
adsorption, The effect of calcium and magnesium
ions on adsorption can now be differentiated The viscosity of polyethylene oxide WSR-301 was
between its effect on the molecular coil size estimated by interpolation from the viscometric data
(through its effect on the intrinsic viscosity) and of Brmrnan and Claridge10 and of Dauben.6 The
the surface attraction of the polymer on the minera J relaxation time was estimated from the data of
surface. Williams2s~2Q by assuming no dependence on
Although the segment density factor of the concentration. The viscosity data for Separan AP- 30
adsorbed molecules may vary, the layer thickness were reported by Abrams. y The relaxation time of
is independent of the segment density above a Separan AP-30 was estimated from the data of
threshold value. If this is the case, then increasing h~eister and Biggs25 and corrected for salinity and
the segment density factor itself will not increase concentrations, The shear dependence was computed
the permeability reduction factor, but will only as
result in increased polymer loss due to adsorption.
Thus, a correlation
ability reduction
between adsorption
should not be expected. 1 Smith12
and perme-
Id Y) = W(Y = l.o)yn-l 37)
observed that calcium carbonate adsorbs above six
times as much partially hydrolyzed polyacrylamide
from a lo-percent sodium chloride solution as does ef(y) = ef(y = l.()) yn-l . . . . . . . (38)
silica for tile same surface area.
The effect that solvent pH and the density of
The values of the parameters estimated for the two
ionizable groups on the polymer molecules has on the
adsorption has been investigated for two systems. fluid systems are shown on Table 7.
The first system was a series of vinyl acetate-
crotonic acid copolymers on anastase (Ti02)21 and CONCLUSIONS
the second was sodium polyacrylate and hydrolyzed In summary, the following characteristics of the
polyacrylamide on kaolinite.22 It was observed that
the adsorption decreased with increasing pH and
density of ionizable groups. Above a critical pH, TABLE 6 KELZAN PERMEABILITY REDUCTION
AND ADSORPTION
there was very !ittle adsorption. In the investigation
of the adsorption on kaolinite, it was postulated 300
that the negative surface charge on the kaolinite
particle repells the negative ionized carboxyl group, Permeability (k), md 350
Porosity (+) 0.27
Rock bulk density (~rb ) 1.93
TABLE 5 MEASURED AND CALCULATED ADSORPTION Polymer molecular weight (M), gm/mol 1.4 X 106
FOR POLYACRYLAMIDE
Pore reduction number (N~), dimensionless 0.08
Core Number +W(exp) Ad (Eq. 39) Permeability reduction (Eq. 24) 1.4
(Table 5) (/J9m/9m) (,t.lgm/gm) u 1.2
Permeability reduction (measured)
1 6.0 2.0 u Xo Polymer adsorption (Ad (Eq, 24), ~~gm/gm 1.160
5 7.7 3,7 0 2.1 Polymer adsorption (Ad) (measured), ,Ugm/gm 3.6
6 8.1 3.8 u 2.1 Ratio of segment density of molecular coil on the
7 13.0 4.4 u 3.0 surface to that in dilute solution, o 3.1

344 SOCIETY OF PET ROLEI:M ES GI!$EERS JOt!RSAL

flow of polymer solution through porous media have DP = particle diameter, cm
been modeled. friction factor
1=
1. The pseudoplastic behavior is modeled with
G= modulus of elasticity, gin/cm
the Blake-Kozeny model for power-law model fluids
through packed beds. H = coeffici~nt in f31ake-Kozeny model, cp (cm/
2, The dilatant behavior is modeled with the sec)l-n
viscoelastic properties of the polymer solution. k= absolure permeability, cm2, md, darcy
This additional, viscoelastic resistance is modeled kw = ~ermeability to water, cm2
as a simpie elongational flow to represent the K= power-law coefficient, cp (sec)o-l
elongation and contraction that occurs as the fluid K. = coefficient for molecular weight dependence
flows through a pore with varying cross-sectionaI of the intrinsic viscosity, dp/gm (gin/
area. It is a function of the Deborah number, which mole)-?~
is a ratio of the relaxation time of the fluid ro a L= length, cm
characteristic deformation rime ot the flow field.
,\l ? polymer molecula~ weight, gm/mol
3. The reduction in permeability with polyacryl-
n. power-law exponent
amide is postulated to be due to an adsorbed layer
of polymer molecular coils that reduces the effec:ive N~ = dimensionless pore reduction number
size of the pores. A dimensionless pore reduction NDeb = Deborah number
group has been formulated to correlate the p. pressure, atm, dynelcm2
permeability reduction factor with the polymer, brine, q. flow rate, cc/see
and rock properties. This dimensionless number
represents the ratio of the size of the polymer l. pore radius, cm
moleculdr coil to an effective pore radius of the Re = Reynolds number
porous medium. R eq = an equivalent pore radius of rock, cm
4. The model for the adsorption of polymer R, . resistance factor
assumes that the polymer is adsorbed on the surface Rk . permeability reduction factor
of the porous medium as a monolayer of molecular
Rr, :- residual resistance fac:or
coils that have a segment density greater than the
molecular coil in dilute solution by a factor between ?L!f= radius of molecular coil in dilute solution,
2 and 8. This model represents adsorption as a cm
function of polymer, brine, and rock properties. u= superficial fluid velocity, cmlsec
A model to correlate these effects as a function u. interstitial velocity, cm/sec
of the polymer, brine, rock properties, and flow shear rate, sec -1
conditions would result in a more accurate evalua-
K rate of elongation, sec -1
tion of systems that may not have been measured in
the laboratory at the desired conditions. Moreover,
p. viscosity, cp
if the dependence of these effects on the system tlapp = apparent polymer solution viscosity, cp
properties were known, it would aid in the search [p]= polymer intrinsic viscosity, df/gm (Idf =
for an optimal system. Iim P - Ps
The model is consistent with a number of loomf) = =., O ~
experimental observations, but enough data have
not yet been acquired to determine the extent of Prb = rock bulk density, gin/cc
. . 0. ratio of segment density of molecular coil
appllcablllty of a correlation. It is hoped that the
presentation of these models will encourage further on the surface to that in dilute solution
research to verify or improve the models. r= tortuosity
~ij ~ stress, dynes/cm2
NOMENCLATURE porosity
4=
Avogadros number, 6.o23 x 1023 mole-
4. pore space occupied by water, q5w = +Sw
cules/mol (j, = fluid relaxation time, sec
polymer adsorption, pgm/gm
surface area per unit volume of porous
medium, cm2/cc REFERENCES

surface area covered by molecular coil, 1. Jennings, R. R., Roger, J. H., and West, T. J.:
cm2/molecule Factors Influencing Mobility Control by Polymer
Solutions, J. Pet. Tech, (March 1971) 391-401;
polymer concentration, gm/100 ml, approx-
Trans., AIME, Vol. 251.
imately weight percent
2. Savins, J. G.: Non-Newtonian Flow Through Porous
TABLE 7 ESTIMATED FLUID PROPERTIES Media, ltd. Eng. Chern. \1969) Vol. 61, 10-12,

Il({c; ;.o) ef(&Lo) 3. Christopher, R. H., and Middleman, S.: Power-Law

Fluid
Flow Through a Packed Tube, Ind, Eng. Cbetn,
0.2% Separan AP-30 in 11.0 0.029 1.0 Fundamentals (1965) Vol. 4, No. 4, 422.
2.0% NaCl 4. Herce, J. A., and Rivera, R. B.: Personal communi-
0.15% Po!yox wSR.301 10,0 0.316 0.88 cation (1971),

.\[GIST. ]9;4 34.5

 5. Marshall, R.
J., and Metzner, A. B.: F1ow of 16. Kozicki, W., Hsu, C. J., and Tiu, C.: Non-Newtonian
Viscoelastic Fluida Through Porous Media, Ind, F1OW Through Packed Beds and Porous Media,
Eng. Cbem. Fundamentals (1967) Vol. 6, No. 3, 393. Chem. Eng. Sci, (1967) Vol. 22, 487.

6. Dauben, D. L.: (( Non. Ne~tonian Flow Throu@ porous 17, Rowland, F. W.: Thickness and Structure of Layers
Media, PhD dissertation, U. of Oklahoma, Norman of High Polymer Adsorbed from Solution onto
(1966). Surfaces, PhD dissertation, Polytechnic Inst. of
Brooklyn, Brooklyn, N. Y. (1963).
7. Dauben, D. L., and Menzie, D. E.: F1ow of Polymer
Solutions Through Porous Media, j. Pef. Tech. 16. Rowland, F. W., and Eirich, F. R.: Flow Rates of
(Aug. 1967) 1065-1073; Tfans., AIME, Vol. 240, Polymer Solutions Through Porous Disks as a Func-
8, Weisler, E.: Viscoelaatic Effects in the Flow of tion of Solute, II Thickness and Structure of Adsorbed
Non-Newtonian Fluids Through a Porous Medinm, f Polymer Films, ]. Polymer Science, Part A-1 ( 1966)
/rid, Errg, Chem. Fundarnen~/s (1971) VO1. 10, No. 5, Vol. 4, 2401.
411. 19. Flory, P. J.: Principles o/ Polymer Chemistry, Cornell
9. ,4brams, A.: Personal communication (1966), U. Press, Ithaca, N. Y. (1953).

10. Brannon, J. R., and Claridge, E. L.: Personal 20. Burcik, E. J.: ,IA Note on the Flow Behavior of
PoIyacrylamide Solutions in Porous Media, Prod.
communication (1967).
Mon!hly (June 1965) 14.
11. Gogarty, ~Mobility Control with Polymer
Solutions,]! So~.: Pet, Eng, J. (June 1967) 161-173; 21. Schmidt, W., and Eirich, F. R.: Adsorption of a
Trans., AIME, Vol. 240. Copolymer Polyelectrolyte, ]. PbYs. Cbenr. (1962)
Vcl. 66, 1907,
12. Smith, F. W.: The Behavior of Partially Hydrolyzed
Polyacrylamide Solution in Porous Media, J, Pet, 22. .Michaels, A. S., and Morelos, O.: Polyelectrolyte
Adsorption by Kaolinite, /rid, Eng. Cbern. (1955)
Tech. (Feb. 1970) 148-156.
Vol. 47, No. 7, 1801.
13. Pye, D. J.: t(lmproved Secondary Recovery by COntrO1
of Water Mobility, ~. Pe/. Tech, (Aug. 1964) 911- 23. Williams, M. C,: Concentrated Polymer Solutions:
Part II, Dependence of Viscosity and Relaxation
916; Trans., AIME, Vol. 231.
Time on Concentration and Molecular Weight, A/ChE
14. Mungan, N., Smith, F. W., and Thompson, J. !..: -/OU,. (1967) Vol. 13, No. 3, 534.
Some .4spects of Polymer Floods, J. Pet. Tech.
24. Williams, M. C.: Normal Stresses and Related
(Sept. 1966) 1143-1 150; Trans., AIME, Vol. 237.
Viscoelastic Phenomena ir, Polymer Solutions, PhD
I 5. Mungan, N., Smith, F. W., and Thompson, J. L, :
dissertation, U. of Wisconsin, Madison (1964),
Rh:ology and Adsorption of Aqueous Polymer
paper presented at the 20th Annual 25. Miester, B, J., and Biggs, R. D.: Prediction of the
Solution s,
Technical Meeting, Pet. Sot. of CIM, Edmcnton, First Normal Stress Difference in Polymer Solutions,))
A/ChE Jour. (1969) Vol. 15, No, 5, 643.
Canada, May 7-9 (1969).
***

346 SOCIETY OF PET ROLE1:M EN CISEERS JOURNAL