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SPE 39631 “
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Two-Phase Flow Property Modifications by Polymer Adsorption
A. Zaitoun, SPE, Institut Fran~ais du PMrole
H. Berth, SPE and D. Lasseux, Lept-Ensam

,.
.— .—
Cq@ght 1%%, %cbMy M Petroleum E-, kc
is formed on pore walls. Comprehensive pictures of end point
for presentafio~=lhe 1998 SPE/OOE Improved Oil Remveiy
%%WSJ’$SZ=T%M?JW Ky2mi f=.
pore situations are provided.
J, ,-.
Introduction
Water-soluble polymers or gels are known to reduce the
relative permeability to water more than the relative
permeability to oil or to gas. 1-10 Liang et al. plotted on a
single graph literature data of permeability reductions for oil
and for water induced by different polymer or gel systems in
different core materiak (see Fig. 1).3, Most resuIts show
“disproportionate permeability reduction” (DPR). This unique
Abstract
property is the basis for the use of polymers and gels as water
The ability for polymers or weak gels to reduce selectively the
control agents in near-wellbore treatments of production wells,
relative permeability to water with respect to the relative
especially when polymer injection has to be bullheaded
permeability to oil or to gas is a unique property well
without mechanical zone isolation to protect the oil zones.
documented but voorIv understood. To better understand two-
Although DPR is well documented in the literature, its
phase flow prop&-ty c~anges induced by polymer adsorption,
origin is still unclear and not consensual. The different scenarii
an original experimental set-up was designed that enabled
proposed can be classified in three main features: (1)
profiIe saturation check insid”e the core by gamma rays,
swelling/shrinking with water/oil, (2) fluid partitioning and
material baIance, pressure drop and direct measurement of the
(3) wall effects.
capiIlary pressure during displacement of oiI by water.
ReIative permeability curves were computed with the measured
(1) Swelling/shrinking with water/oiI. It was
data as input into a specially designed software (FISOLE).
commonly thought in the past years that DPR was due to gel
Experiments were run fiirit with a naturally water-wet
swelling in the presence of water (because of gel affinity
sandstone (Vosges sandstone), then with the same type of core
towards water) and gel shrinking in the presence of oil
previously treated with sikme to make it oil-wet. Main results
(because of gel repulsion with respect to oil). As demonstrated
obtained after polyacrylamide adsorption are:
1- Disprop&tionate relative permeability modification is by Liang et al,,5$6 this explanation cannot hold because gel
observed both in water-wet and in ofl-wet cores. hydration water has no affinity towards oil, and thus cannot be
2- The polymer induces an increase in water irreducible expelIed by osmotic forces.
saturation. However, the gel shrink by physical compression, when
3- The polymer induces an increase in the capillary pressure. oil is forced to flow through a geI which fills the pore space.
4- After adsomtion in the oiI-wet core, the core becomes Dawe and Zhang show in micromodel experiments that, after
water-wet & attested by the inversion of the capillary filling the pore space with gel, injection of oil occurred into
pressure sign and the strong reduction in residual oiI the center of the pore channels, the oil droplets breaking the
saturation. gel in the process. 11 To explain this behaviour, Liang et al.
All these results can be interpreted in terms of “wail proposed the picture of Fig. 2, where an oil droplet breaks
effects”, i.e. an adsorbed polymer layer of significant thickness through a geI when capihy forces overcome elastic forces.6

285
2 A. ZAITOUN, H. BERTIN, D. LASSEUX SPE 3963 i

-: .- .
To summariz.g ‘this first scenario, we can say that the probability that all the bonds break down simultaneoudy is
sweI@j7slrinking behavior is not possible by osmotic very Iow.
process, but by mechanical forces. The gel can shrink and The macromolecule behaves like an octopus stickkg on a
expel hydration water. under the action of hydrodynamic forces rock. The animal is solidly attached on the rock by numerous
exerted by the oil phase, suction cups, each one representing a weak sticking point.” A
man cannot remove the octopus from the rock at onc~;_the
(2) Fluid partitioning. This hypothesis was proposed force required is too high. The only way to do it is to proceed
recentIy by several authors such as Seright et al.3-6 These step by step, i.e. to remove progressively each tentacle from
authors assume that oil and water flow through different the rock while avoiding another one taking its pIace.
channels inside the porous network and that, because of its Polymer adsorption on pore walls induces three’effects-(l~
hydrophilic character, the gel invades preferentially the water steric, (ii) lubrication and (iii) nettability modification. The
paths. Therefore water mobility is preferentially reduced. steric effect is due to the reduction of flow cross-section by the
We may assume that, when water and oil flow presence of the polymer layer adsorbed on the pore walls,,
simultaneously through a water-wet porous medium, the oiI whose thickness is significant compared to pore size- and
will flow preferentially through the largest pore channels which is aImost unpenetrable to fluid flow. The same
whereas the water, because. of the presence of oil in the large polyacrylamide macromolecule of 107 daIton behaves in
pore channels, wilI flow preferentially through the smallest solution like a flexible coil with a sphere diameter of 0.4 pm.
nore channeIs. At intermediate fractional flow values, fluid A monolayer of polyacryhunide macromolecule covering pore
&u-titioning should naturally occur. The symetric situation walls is thus expected to reduce the average pore diameter by
would occur in oil-wet media, with water taking the place of 0,8 pm. If we take into account that the average pore diameter
oil. of a 100 mD sandstone is around 3 ~m, we can easily predict
However, at the end point situations, only one phase flows that the presence of this adsorbed polymer Iayer at the pore
effectively, whereas the otkkx phase is quasi-immobile. When wall reduces significant] y core permeability.
a gelant is injected into a core at a given saturation Sw, due to (ii) The lubrication effect induced by the polymer layer
a tiscositygermmlly one order of magnitude greater than covering the pore waIIs makes” the flow of the nonwetting
water, this gelant will sweep away all the fluids, including oil, fluid (oil) easier because it attenuates rock surface roughness
and render the invaded zones at residual oil saturation Ser. and forms a water film which helps the oil slip through the
Therefore, most pore channels and especially the largest ones, center of the pore channels.
wiIl be invaded by the gelant. After gelation, the gel will be (iii) The adsorption of hydrophilic polymer may occur on
present in large channels where oil is supposed to flow. The oil-wet parts of the surface of the rock thus rendering these
oil should thus “see” the gel. water-wet. Adsorption of hydrophilic polymers on oil or on
The weakness of the ilyid partitioning scenario to explain oil-wet minerals has been reported in the literature. 12 It may
DPR Lies on the fact that DPR occurs (and is often maximum) be due to the coverage of submicronic oil-wet zones by the
at end points and not onIy at intermediate fractional flow micronic polymer macromolecule that is attached to w;ter-wet
values. We have thus to conclude that, even if fluid parts of the surface of the solid. Enhancing water nettability is
partitioning exists, the oil shouId “see” the gel in its natural a factor that improves oil mobility and reduces water
pathways. Other effects shouId thus contribute to DPR. The mobility. 13 It should thus contribute to the DPR.
cases where gelant penetration of oil pathways is prevented DPR effects have been frequently investigated with geIs
have to be considered as very particular and certainly not as a (and not with single polymers) . A gel is a compIex fluid,
common situation (geIant penetration of oiI zones could be whose properties may change during the expe%-rnents
prevented for example by highly-viscous oil saturation or in (crosslinking reaction, syneresis, polymer leaching, etc. J-
fi-actured formations). The complexity of the geIling reaction and t%e “lack of
Since in normaI situations DPR is observed at end points stability of the gel are factors that complitaie ‘DFR
with often a maximum of intensity, the hypothesis of fluid’ investigation. For reason of simplicity and ‘to avo’icf gel
partitioning has to be rejected, at least as the single complications, the experimental work descrl%ed ‘b”e~ow has
explanation. been performed with a single high-moIecular-weight polymer,
and the DPR investigation was performed after” ”po~y-rner
(3) Wall effects. High-molecular-.weight polymers are adsorption in the core. A special experimental set-up was
known to adsorb irreversibly on minerals. This property is due designed that enabled oil/water reIative permea~ility
to the number of attachment points that a macromolecule can determination on the whole saturation range as’ weIl as
have on the surface of a solid. For example, we examine the capillary pressure modifications.
case of a polyacryku-nide polymer with a molecular weight of Unlike geIs, adsorbed polymers do not fill up ‘thti pore
107 daItom.The monomer moIecuhr weight is 71. Therefore, space. Therefore, especially in the range of permeability
the number of latmal groups carried by the polymer chain is investigated (200-700 mD), we expect that waII effects should
around 150,000. If only one group on 1,000 is linked to the be”dominant.
.—
surface, then the macromolecule is attached by 150 bonds.
This implies that (1) even if each bond is weak, the sum of
bonds can Iead to a strong bonding force, and (2) the

286
 f

SPE 39-637 TWO-PHASE FLOW PROPERTY MODIFICATIONS BY POLYMER ADSORPTION ,3

Experimental Water-wet core. Saturation profiles are steeeper after

DetaiIs on the experimental procedure are given in Reference polymer adsorption (Fig.4), thus showing that viscous” forces
7. The experimental program aimed at determining the are markedly enhanced. Polymer adsorption increases Sw-i from
changes in two-phase flow properties of a natural sandstone 0.33 to 0.49, whereas Sor is little affected. This increase in
.
induced by polymer adsorption. Swi is due to adsorbed polymer hydration water in addition to
The polymer (in powder form) was a nonionic a probable increase in inaccessible pore volume to oil due to
polyacrylamide (PAM) with a molecular weight of 107 dalton. the plugging of fine pore channels by the polymer layer. This
PAM was dissolved in a 50 g/L KI brine. This brine was increase in Swi has been already reported in the literature. 2
chosen to have a good contrast in y-ray saturation check. 0.4
DPR is shown by the change in the relative permeability
glL of NaN3 was added as a bactericide.
curves (Fig.6). After polymer adsorption, the relative
The cores were Vosges sandstones with a water
permeability to water drops strongly ori the whole saturation
permeability in the range 200-700 mD. Each core had square
range whereas the relative permeability to oil is little affected.
sections of 5 x 5 cm and with length around 25 cm. The
We notice that kro is even slightly increased in the remaining
porosity was around 0.20 and the total pore volume around
saturation range although absolute end point kro value is
125 cm3. The core was coated with epoxy resin and holes were
lower because of the higher Swi. This increase in kro may be
drilled on both side at different Ievels along the core to fix
pressure taps, The core was put horizontal in the experimental attributed to what we caIled the “lubrication effect”. which is a
set-up. Upper side pressure taps were fitted with oil-wet semi- combination of surface roughness attenuation and slipping
permeable membranes, whereas Iower side ones were fitted effect at pore wall.
with water-wet membranes. By this procedure we cotdd Another surprising effect, which has not been frequently
measure simultaneously the pressure in the oil and the reported in the literature, is the increase in the capillary
pressure in the water at different IeveIs in the core, thus the pressure (Fig.5). In fact, this result is expected from the
capillary pressure. reduction in pore throat radius by the adsorbed-unpenetrable-
Fig.3 shows the experimental set-up. The saturation polymer layer. Capillary pressure is given by
inside the core was determined by y-ray attenuation during the ~=~
c
displacement of oil by brine (imbibition). This displacement
was performed at low-rate (5 cm3/h) in order to be able to It was shown that the interfaci;l tension a was unchanged
check changes in the capiIlary pressure. The unsteady-state by the poIymer.7 A reduction in the average pore radius r
procedure was chosen in all our experiments during imbibition should thus increase Pc. Although our result is qualitatively
cycles. Before each imbibit~,on step, the core was put at Swi consistent with this hypothesis, the magnitude in the Pc
by high-rate .oiI injection (1”00 cm3/h). change is higher than expected.
We used a mineraI oiI (MarcoI 52 ‘) with a viscosity of
10.5 mPa.s at 20%’. All the set-up was placed in a room at Oil-wet core. Adsorption of PAM on the silane~~re;ted oil-
20”C. wet sandstone induced strong modifications of two-p%aie’flow
Relative permeability curves were determined from’ properties.
saturation, pressure drop, material balance and capillary The first unexpected result lies on the fact that hydrophilic
pressure me asm-ements by a minimization computer program polymers can adsorb on hydrophobic silane-treated siwfaces and
@E30LE~). are not washed-out by oil and water flushes. One can object to
The experimental coreflood procedure included the the representativity of silane-treated rocks with respect to
following steps reservoir naturally oil-wet rocks. We plan, in the future, to
1- Brin; inj;ction - Determination of k repeat our experiments with naturally oil- wet or mixed-wet
2- Oil injection + Swi rock materials.
3- Brine + kr Pc curves before polymer In the oil-wet core, we observed, as in the water-wet core,
4- Polymer low-rate injection/adsorption an increase in Swi and a DPR for relative permeabi~ities
5- Brine to remove alI free polymer (Table 1). In addition to these effects, polymer adsorption
6- OiI * S wi induced a dramatic drop in Sor (from 0.54 to O.17). A dramatic
7- Brine + kr Pc after polymer change in “Pc occurred, with a shift from negative to positive
For oiI-wet experiments, the sandstone core was treated values (Fig.7). All results seem to indicate that “core
with time by a procedure detailed elsewhere. 12*14 nettability was strongly modified by PAM adsorption. From a
typical oil-wet situation, we moved to a water-wet or at Ieast
Results and discussion mixed-wet one.
.&
Table 1 summarizes end point data. Water-wet core
experhne~I results are given in Figs.4 to 6 whereas End point situations. Fig.S demonstrates possible end
Fig.7 concerns oiI-wet core restdts. point situations for a water-wet material with an adsorbed
-.
poIymer Iayer at the pore walls. In this example, we focus on
large pore channels accessible to both water and oiI.
At residual oil saturation, the presence of oiI droplets
trapped by capillary forces in front of pore throats induces a

287
4 A. ZAITOUN, H. BERTIN, D. LASSEUX SPE 39631

dramatic decrease in the size of the pore throat accessible to 7. The changes in saturation profile induced by adsorbed
water (thus a low krw value), The adsorbed polymer layer, polymer indicate a strong increase in viscous forces, which
with a thickness of around 0.4 ~m induces a dramatic drop in dominate capillary forces.
water permeability, much Iower than at 100Yc water 8. DPR has obvious applications in water shutoff and
satur*. polymer flood technology.
On the contrary, at irreducible water saturation, the
polymer Iayer does not reduce dramatically the size of the pore Nomenclature
throat accessible to oil (as it does for water at Sor). The h adsorbed layer thickness (~)
poIymer layer can also be compressed by the flow of oil in the k permeability (~m2)
n~ throats. Moreover, both lubrication and water kr relative permeability
wettability improvement help the oil to flow through the kro relative permeability to oil
center oflhe pore channels. km relative permeability to water
Pc capiIkuy pressure (Pa)
Pore-sc~e modeIling. ~n a recent paper,8 we presented r average pore radius (~m)
resuIts “of pore scale modeIIing of the effect of an adsorbed Sw water saturation
polymer Iayer on two-phase flOW. The pore model was made Sor residual oil saturation
of a succession of regular pore constrictions as given by Sw water irreducible saturation
Fig.9. The nonwetting fluid was supposed to flow through 0 oi/water interracial tension (N/m)
the center of the pore channel whereas the wetting fluid was
supposed to flow in the pore space between the pore walI and Acknowledgements
the nonwetting “fluid. In this model, the adsorbed po~ymer This study was supported by the Groupement scientifique
layer was introduced as an unpenetrable Iayer with a constant ARTEP-CNRS. The authors wish to acknowledge P. Barreau
thickness, fiui~ysaturated by the wetting fluid, and L. Rousseau who performed laboratory experiments.
Resolution of such a two-phase flow pore model leads to
both relative permeability and capillary pressure curves before References
and after polymer adsorption. Surprisingly, we found that 1. Schneider, F.N. and Owens, W. W.: “Steady-State
when we enter the polymer in the model with only this steric Measurements of Relative Permeability for Polymer/Oil
effect, without any sIipping assumption, we can qualitatively Systems,” SPE./(February 1982)79.
predict both the DPR and the increase in capillary pressure 2. Zaitoun, A. and KohIer, N.: “Two-Phase Flow Through Porous
observed experimentally. Resolution of such a simple pore Media: Effect of an Adsorbed Polymer Layer,” paper SPE
model highlights the importance of wall effects in DPR. 18085 presented at the 1988 SPE Annual Technical
Conference abd Exhibition, Houston, 2-5 October.
3. Liang, J., Sun, H, and Seright, R. S,: “Reduction of C)J and
Conclusions
Water Permeabilities Using Gels, ” paper SPE 24195
1. Two-phase flow property modifications induced by presented at the 1992 SPE/DOE Symposium on Enhanced Oil
polyacrylamide adsorption in sandstone cores can be Recovery, Tulsa, 22-24 April.
interpreted in terms of waII effects i.e., by the presence of 4. Seright, R. S.: “Reduction of Gas and water Permeabilities
a polymer layer adsorbed on pore walls. Using Gels,” SPEPF (November 1995)103-108.
2. Wall effects include (1) steric effects, (2) lubrication effects 5. Liang, J., Sun, H. and Seright, R.S.: “Why Do Gels Reduce
and[3) nettability changes. (1) Steric effects are due to the Water Permeability More Than Oil Permeability?” SPERE
fact that adsorbed polymer is unpenetrable to all fluids and (November 1995) 282-286.
occupies a significant fraction of the pore volume. (2) This 6, Liang, J. and Seright, R. S.: “Further Investigations of Why
polymer layer makes the flow of the non-wetting fluid Gels Reduce Water Permeability More Than Oil
Permeability,” SPEPF (November 1997) 225-230.
(oil) easier by rendering the surface of the solid smoother
7. Bameau, P., Bertin, H,, Lasseux, D., Gh%at, P. and Zaitoun,
and imhcing slipping effect at pore wall. (3) The polymer A.: “Water Control in Producing Wells: Influence of an
is aIso shown to adsorb on oil-wet materials ?nd thus to Adsorbed-Polymer Layer on Relative Permeabilities and
change the wettabilily to water-wet. Capillary Pressure,” SPERE (November 1997) 234-239,
3. The increase in irreducible water saturation. Swi is 8. Barreau, P., Lasseux, D., Bertin, H., Gh%at, P, and Zaitcxrn, ,
attributed to stenc effects. A.: “Polymer Adsorption Effect on Relative Permeability and
4. The increase in the capih-y pressure is attributed to steric Capillary Pressure: Investigation of a Pore ScaIe Scenario,”
effects atid, for the oil-wet core, to nettability change. paper SPE 37303 presented at the 1997 Int. Symposium on
5. Disproportionate permeability reduction (DPR) is probably Oilfield Chemistry, Houston, 18-21 February.
9. Zaitoun, A. and Kohler, N,: “Thin Polyacrylamide Gels for
due to a combination of steric, lubrication and nettability
Water Control in High-Permeability Production Wells,”
effeck paper SPE 22785 presented at the 1991 SPE Annual Technical
6. The strong reduction in-residual oil saturation induced by Conference and Exhibition, Dallas, 6-9 October.
polymer adsorption in the oil-wet core is attributed to 10. Thompson, K.E. and Fogler, H.S.: “Pore-Level Mechanisms
nettability change, for Altering Multiphase Permeability with Gels,” SPEJ
(September 1997) 350-362.

.-

288
SPE 39631 TWO-PHASE FLOW PROPERTY MODIFICATIONS BY POLYMER ADSORPTION _.5”

11. Dawe, R.A. and Zhang, Y.: “Mechanistic Study of the

Selective Action of Oil and Water Penetrating into a GeI
Emplaced in a Porous Medium,” 1 Pet. Sci. & Eng. (December
1994) 12, 113.
12. Broseta, D. et al.: “Polymer Adsorption/Retention in Porous ..0
Media: Effect of Core Nettability and ResiduaI Oil,” SPE
Advanced Technology Series (March 1995) 103.
13. Anderson, W. G.: WettabiIity Literature Survey - Part 6: The ,..
Effects of Nettability on Waterflooding,” JPT (December ,.. .
1987) 1605-1622.
14. Lombard, J.M., Lenormtid, R. and Robin, M.: “Intermediate
Nettability: Capillary Pressure in Mixtures of OiI-Wet and
Water-Wet Sand Grains,” Physical Chemistry of Colloids abd
inte~aces in Oil Production;, H. Tordhoat &s~ J. Lecourtier .-
(eds.), Technip, Paris (1992).

TABLE 1 - End point results in Vosges sandstone

Nature of core S~i kro Sor krw

Water-wet Before Polymer 0.33 0.89 0.34 0.062

After Polymer 0.49 0.55 0.33 0.0028

Oil-wet Before Polymer 0.32 1.0 0.54 0.47

After Polymer 0.49 0.42 0.17 0.11

..

,—

289
6 A. ZAITOUN, H. BERTIN. D. LASSEUX SPE 39631

1 ~ s 10 20 so 1(M
Permeabilityreductionfor water

““-—“~.l . Disproportionate permeability reduction by polymers and gel

!,
J

.. ..-. ...—

:..

Fig.2 - BaIance between capillary forces and gel elasticity when forcing oil or water
through an aqueous gel
.

pressure transducer
......................................... .
r I

pump app*tm-----------------------------T-----=------------;
I

---”----”””-””-~

water oil polymer

Fig.3 - Experimental set-up

290
SPE 39631 TWO-PHASE FLOW PROPERTY MODIFICATIONS BY POLYMER ADSORPTION ‘? ‘“’
_~G ..

1.2 1.2
Expnmmld
1 1

11.R .
.
II R

/ \ .‘,

.,
‘!
11.6 ().6

‘“,
: 4 )
‘., -
\ . ‘, , ..

‘“\
L
()4 1),4
“’,~ “,,,\\ ‘i
().2
0.2
..,:, ..~., ,.% .
()
b“.
0
[ r 1 I 1 ‘.
2 4 6 8 10 12 14 o ~ 4 6 8 10 l.1 16
,-
Before polymer adsorption After polymer adsorption

E“lg.4 . Modification of saturation profile during imbibition

after polymer adsorption in water-wet sandstone

P=(Pa)
A ..
mxlo ,
— beforepoymel
.- afer pd ymer
. . . . . . .. . . . .. . .
“...,,
500C0 -
......
...
4csxxl - .....
..,.
KKsXl - ,\.
,--
20300-
~
+-:-- IOWJ - \

o-
\ ‘: s. ..
0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0 70

Fig.5 - Modification of capillary pressure after

polymer adsorption in water-wet sandstone

- before pohmer

k, Q--4 uflrr pohmer

1
.,..
(). 1

(1,01

rl.cuI

O.csxll _.
0.30 0.35 0.40 0.45 0s0 0.55 0 cm ().65 070

_—
l?lg.6 - Modification of relative permeability after polymer
adsorption in water-wet sandstone
,-—

.
.—.
,-..
..

—,-

291
8 A. ZAITOUN, H. BERTIN, D. LASSEUX SPE 39631

PJrw * P.(Pa)
am ‘,?ocm ,
I Y f
I xx) –
18(hm -

10CO -
lmm -
m- 14(nn -
Sw
0
I 12mm -
-ml – ().30 03s (1. 050 Iomm -
-Itmxl - 8om -
.1s00 - 6ols3-

-Zmx) -
+ 4cQo - ●✌
=23XI – 2m30.
●

0.4 0.5 0.6 0:7 6.8

Bi@ore po~mer adwrption Afterpo/ymer adsorption

Fig.7 - Modification of capillary pressure after

polymer adsorption in oil-wet sandstone

Uoitcdl

--
-—
OIL .—
———
—.—— ——— __—__
--”* -— — _ —_ —_———
——— _—_—_-
. Fig.9 - pore scale modeIIing of absorbed - -‘
L—— — —
———
._—_—
— poIymer layer
==

Fig.8 - Pore scale end point situations

.- /