Journal of Petroleum Science and Engineering 20 Ž1998.

267–276

Prospects of improved oil recovery related to wettability and

brine composition
Norman R. Morrow ) , Guo-qing Tang, Marc Valat, Xina Xie
Department of Chemical and Petroleum Engineering, UniÕersity of Wyoming, Laramie, WY 82071, USA
Accepted 21 January 1998

Abstract

Although attention is given to the composition of the injected brine in a waterflood with respect to compatibility with the
formation, tests are not usually made to determine its effect on oil recovery. This study shows that the wettability and
laboratory waterflood recoveries of crude oilrbrinerrock ŽCOBR. ensembles can be strongly dependent on brine
composition and on related COBR interactions. The sensitivity of these interactions to temperature and crude oil composition
is also demonstrated. q 1998 Published by Elsevier Science B.V. All rights reserved.

Keywords: contact angles; imbibition; waterflooding; adsorption; crude oil; brine composition; oil recovery

1. Introduction Spontaneous imbibition and waterflood recovery

The need for informed operating decisions is a
major incentive for investigation of reservoir wetta-
bility and its effect on oil recovery. The complexity
of wetting phenomena within reservoirs is widely
recognized. It is now well established that oil recov-
eries at strongly water-wet and strongly oil-wet con-
ditions do not bound results for all other possible
wetting conditions. Reservoir wettability is generally
treated as an essentially fixed property. This paper
addresses the possibility that rock–fluid interactions
can be changed in ways that increase production.
)
Corresponding author. Fax: q1-307-766-6777; e-mail:
morrownr@uwyo.edu.
curves that have bearing on this problem will be
presented.
2. The effect of brine composition on contact
angles
Contact angle measurements are sometimes used
as a measure of reservoir wettability ŽTreiber et al.,
1972.. They also provide a useful approach to identi-
fying changes in the wettability of minerals under
simplified conditions. For example, contact angle
measurements show that the wettability of crude
oilrbrinersolid systems can be significantly affected
by brine composition and pH ŽBuckley and Morrow,
1991.. In the present work, the effect of cation type
and concentration is reported for single component
brines.
In studying the effect of cation type on wetting,

0920-4105r98r$19.00 q 1998 Published by Elsevier Science B.V. All rights reserved.

PII S 0 9 2 0 - 4 1 0 5 Ž 9 8 . 0 0 0 3 0 - 8
268 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276
clean quartz plates were prewetted at 258C for 10
days with various brines ŽFig. 1.. The plates were
drained, but not dried, then aged in Prudhoe Bay
ŽA’95. crude oil for 10 days at temperatures of 25,
75 and 888C. Bulk crude oil was removed by gentle
rinsing with distilled toluene. After air drying, the
plates were immersed in the test brine. Clean decane
was used as the oil phase in measuring receding and
advancing contact angles by the dynamic Wilhelmy
plate method at measurement temperature Tm s 258C
ŽMennella et al., 1995.. The rationale for this ap-
proach to the study of wetting changes induced by
adsorption from crude oil has been discussed else-
where ŽBuckley et al., 1997; Liu and Buckley, 1997..
Advancing and receding contact angles were usually
well defined and independent of plate position for
individual plates. The reproducibility of contact an-
gles measured for separate plate treatments was usu-
ally ; "58 for aging at ambient temperature with
crude oil and ; "108 for high temperature aging,
with occasionally higher scatter ŽXie, 1996..
For plates aged at 258C ŽFig. 1a., receding angles
for monovalent ions increase as the thickness of the
hydration shell Ž r h y r i . decreases, where r h and r i
are the hydrated radius and bare ion radius, respec-
tively ŽIsraelachvili, 1994.. Advancing angles follow
the same trend within the limits of reproducibility.
The hydration shell may contribute to the stability of
water films which present a barrier to penetration
and adsorption of polar components of crude oil.
Fig. 1. The effect of cation type on contact angles for Ža. low and Žb. high aging temperatures. ŽQuartz plates were aged in A’95 crude oil
Ž ta s 10 days., washed with toluene, then immersed in chloride brine. Decane was the test oil. Values of bare ion radius ri and hydrated
radius r h are from Israelachvili Ž1994...
For plates aged at 258C with Ca2q and Al 3q
brines, although r h y r i is high, advancing and re-
ceding contact angles were generally higher than for
the monovalent-cations, but were still below 908.
Adsorption by ion binding is the most likely explana-
tion of the decreased water-wetness observed for
multivalent-cations ŽBuckley and Liu, 1996..
For plates aged at 758C ŽFig. 1b., the advancing
and receding contact angles were much higher than
for 258C aging. There were no monotonic trends
with hydrated radius, shell thickness, or valency.
Apart from the lowest contact angle being given by
lithium chloride, the trend observed for low tempera-
ture aging was not followed for the monovalent-ca-
tions. Advancing contact angles for Al 3q ŽpH s 3.5.
were much higher than for Ca2q.
The effect of concentration Žranging from 0.01 to
1 M. for different cation types Žvalency, z . on
contact angles is shown in Fig. 2 for aging at 888C.
There were always distinct differences between ad-
vancing and receding contact angles, but no consis-
tent trends were obtained. Similarities were observed
in the results for Kq and Mg 2q, with both giving
minima in advancing contact angles at intermediate
concentrations Ž0.4 and 0.6 M, respectively.. Ad-
vancing angles for Naq and Al 3q all fell within a
range of about 1308 to 1708. Results for Ca2q showed
the largest variation with relatively lower receding
and advancing contact angles and a minimum of 908
at 0.6 M.
 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276
Fig. 2. The effect of concentration and cation type on contact angles ŽTa s 888C, ta s 10 days..
Because of the variability of wettability for sin-
gle-salt brines, and the specificity of the results to
the A’95 crude oil and plate treatment conditions, it
is concluded that these results will be of limited
value in predicting trends in contact angles for multi-
component brines.
3. Oil recovery by spontaneous imbibition and
waterflooding
Spontaneous displacement of oil by water can be
used as a diagnostic test of wettability if imbibition
time is scaled to compensate for other factors which
affect imbibition rate. Ma et al. Ž1997. presented a
modified scaling group to obtain a dimensionless
time, t D , which compensates for differences in rock
and fluid properties:
k s 1
(
td s t
f (m w mo L2c
where k is permeability, f porosity, s interfacial
tension, m w and mo viscosity to water and oil,
respectively, and Lc is the characteristic length Žall
quantities in consistent units.. Change in wettability
is judged from decrease in imbibition rate relative to
the correlation for very strongly water-wet condi-
tions. In some cases, waterfloods, run on duplicate
core plugs, are presented as companion data sets to
the imbibition results. All results are for Berea sand-
stone.
The wettability of Berea sandstone cores was
changed by adsorption from crude oil. Variables that
269
affect wettability are the selected crude oil, brine,
and rock, as well as initial water saturation Ž S wi .,
aging time Ž ta ., aging temperature ŽTa ., and tempera-
ture of measurement ŽTm . ŽJadhunandan and Mor-
row, 1995; Zhou et al., 1996; Tang and Morrow,
1997.. Imbibition and waterflood results are pre-
sented in Fig. 3a and b for A’92 and A’95 crude oils,
respectively. Light ends were removed from the
crudes by evaporation as a precaution against evolu-
tion of gas during displacement tests. The crude oils
were from different parts of the Prudhoe Bay reser-
voir and are not expected to produce identical changes
in wettability. Because the supply of A’92 crude oil
had been exhausted, A’95 crude oil was used for the
remaining tests.
3.1. NaCl concentration
Rate and extent of spontaneous imbibition ŽFig.
3a., breakthrough and final waterflood recoveries
ŽFig. 3b. all increased with decrease in NaCl concen-
tration.
3.2. Cation Õalency, high temperature aging
There is systematic decrease in rate and extent of
imbibition with increase in cation valency ŽFig. 4.
Žwe expect the imbibition rate for KCl would be
even higher if the KCl were run at 5000 ppm..
Values of molarity and ionic strength for the tested
concentrations Žppm. are included in Fig. 4. Specific
270 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276

Fig. 3. Effect of NaCl concentration on oil recovery ŽBerea sandstone..

interactions between negatively charged sites on the

solid and on aggregates in the oil phase probably
result in specific adsorption by ion binding ŽBuckley
and Liu, 1996.. Multivalent ions will also cause
compression of a double layer ŽIsraelachvili, 1994.
but this is not a likely explanation of the variations
in imbibition rates at the prevailing brine concentra-
tions. The low pH Ž; 3.5. resulting from hydrolysis
in the presence of Al 3q ions will also contribute to
decreased water-wetness through acid–base interac-
tions ŽBuckley et al., 1998..

3.3. Brine composition, low temperature aging

Scaled imbibition results are shown in Fig. 5 for

Fig. 4. Effect of cation valency on imbibition ŽBerea sandstone..
Naq, Kq, Ca2q and Al 3q brines Žall 0.09 M.. For
the monovalent-cations, the imbibition was relatively
fast with potassium giving the highest recovery. For
multivalent-cations, the imbibition recovery curves
fell close together. Initial imbibition was slow, but
the final recoveries exceeded those for brines with
monovalent-cations and that given by the correlation
for very strongly water-wet conditions. Oil recovery
 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276 271

by spontaneous imbibition has been previously re-

ported to pass through a maximum with decrease in
water-wetness ŽMa et al., 1994..

3.4. Brine composition, high temperature aging

For aging at 808C with A’95 crude oil ŽFig. 6., as

for low temperature aging ŽFig. 5., brines containing
monovalent-cations gave higher imbibition rates than
multivalent-cation brines. Wettability alteration in-
creased with the valency of the cations. For multiva-
lent-cations, high temperature aging caused a large
decrease in water-wetness for Al 3q and a similar but
smaller effect for Ca2q for early time imbibition.
The effect of cation valency on imbibition shown in
Fig. 6 is qualitatively similar to the results obtained
by aging with A’92 crude of oil at 808C, but with
other conditions different in several respects Žsee
Fig. 4.. For monovalent-cations, the initial imbibi- Fig. 6. Spontaneous imbibition and brine composition—high tem-
tion rates overlie the VSWW correlation. The differ- perature aging, equal molar concentration.
ence between low and high temperature aging imbi-
bition results for monovalent-cations Žcf. Figs. 5 and to the difference in aging times for the imbibition
6. was less than indicated by the contact angle tests Ž10 vs. 2 days..
results Žcf. Fig. 1a and b.; this may be related in part
3.5. Aging time

Results for the effect of aging time on imbibition

and waterflood recoveries are presented in Fig. 7 for
Dagang crude oil. The brine composition used in
these tests is given in Table 1. The crude oil was
solid at room temperature; aging and displacement
steps were both run at reservoir temperature ŽTa s Tm
s Tres s 758C..
With increase in aging time, imbibition was de-
pressed ŽFig. 7a. and waterflood recovery increased
ŽFig. 7b.. This behavior is qualitatively consistent
with the effect of aging time on recovery of a
Prudhoe Bay crude oil by imbibition for Ta at reser-
voir temperature and Tm at ambient temperature,
Tamb ŽZhou et al., 1996.. However, for Tm s Tres
Žhigh temperature measurements., the variation in
imbibition rates is much less than that observed by
Zhou et al. Ž1996. for Tm s Tamb .

3.6. Dilution of synthetic reserÕoir brine

Fig. 5. Effect of cation type on spontaneous imbibition for equal The effect of reservoir brine and diluted reservoir
molar concentrations and low temperature aging. brine on imbibition and waterflooding Žsee Fig. 8a
272 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276

Fig. 7. Change in oil recovery with aging time for displacements run at elevated temperature for Dagang crude oil and Dagang brine Žafter
the work of Tang and Morrow Ž1997...

and b, respectively. was determined for CS reservoir
brine ŽTable 1. and CS crude oil. The synthetic
reservoir brine was diluted to 1r10 and 1r100 of its
original concentration. The extent of imbibition and
the breakthrough and final waterflood recoveries in-
creased with dilution of the brine. Although these
results appear to contradict a trend of increased
recovery with decreased water-wetness, ŽJadhunan-
dan and Morrow, 1995; Zhou et al., 1996. they are
consistent with trends for NaCl brines ŽFig. 3. and a
comparable data set on the effect of change in
reservoir brine concentration for Dagang crude oil
and Dagang brine ŽTang and Morrow, 1997..
3.7. Agingr displacement temperature
Imbibition results shown in Fig. 9a for A’95
crude oil and Dagang brine show that both rate and
extent of imbibition increase with temperature ŽTa s
Tm .. This trend was unexpected because increase in
aging temperature tends to decrease water-wetness
when wettability is measured under ambient condi-
tions ŽJadhunandan and Morrow, 1995.. Increase in
temperature tends to decrease aggregate size and
increase the solvency of asphaltenes in crude oil
ŽBuckley et al., 1997.. However, higher temperature
may still enhance the adsorption process because of

Table 1
Composition of synthetic reservoir brines Žppm.
Brine Kq Naq Ca2q Mg 2q Cly HCOy
3 SO42y pH Ionic strength
PB 52 8374 110 24 13,100 y y 6.8 0.375
DG 7237) 4267 218 32 13,414 y y 7.0 0.388
CS 56 5626 58 24 8249 1119 18 7.8 0.253

)KCl originates from clay stabilization treatment for injected brine.

 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276 273

Fig. 8. Change in oil recovery with dilution of reservoir brine ŽCS crude oil..

Fig. 9. Effect of aging temperature ŽTa . and displacement temperature ŽTm . for Ta s Tm Žafter the work of Tang and Morrow Ž1997...
274 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276
Fig. 10. Effect of removal of light ends on the rate of spontaneous imbibition and oil recovery by waterflooding.
kinetic effects. The trend in imbibition recovery with
temperature of measurement indicates that some form
of desorption or reorientation of functional groups in
the adsorbate can accompany advance of the
waterroil interface during imbibition. Other evi-
dence of changes toward water-wetness with time
andror increase in water saturation has been re-
ported ŽZhou et al., 1996; Tang and Morrow, 1997..
Desorption of organic structures overlain by brine
phase has been inferred from reduction in contact
angles at elevated temperatures ŽLiu and Buckley,
1997..
3.8. Crude oil composition
Removal of light ends from crude oil increased
water-wetness and decreased oil recovery by water-
flooding ŽFig. 10.. Opposite changes in wetting
properties and waterflood recoveries were obtained
by addition of alkanes ŽTang and Morrow, 1997..
The changes in oil composition are not sufficient to
cause precipitation of asphaltenes, but it appears that
the decrease in solvency of the oil with decrease in
molecular weight affects the tendency for heavy
polar components to adsorb at the solid surface
ŽBuckley et al., 1998.. The general trend of increase
in water flood recovery with decrease in water-wet-
ness resulting from change in oil composition is
opposite to the effect of dilution but is qualitatively
consistent with the trends observed for the effect of
aging time ŽZhou et al., 1996. and aging temperature
ŽJadhunandan and Morrow, 1995..
4. Summary
Contact angle measurements at smooth quartz
surfaces provide a useful basic guide to how crude
oils can induce wettability changes by adsorption.
However, from experience to date, they do not pro-
vide a reliable indication of how wettability affects
displacement of crude oil from a sandstone by spon-
taneous imbibition of brine. Contact angles measured
at smooth quartz are often much higher than those
indicated by spontaneous imbibition. There are nu-
merous possible reasons for this, ranging from the
adopted protocol for investigating wetting changes at
smooth mineral surfaces to the complex surface min-
 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276
Table 2
Summary of observed relationships between extent andror rate of
oil recovery by imbibition Ž R im . and oil recovery by waterflood-
ing Ž R wf .
R im R wf
Aging conditions
Aging time, ta Žincrease. o p
Aging temperature, Ta Žincrease. o p
Brine composition
Valency Žincrease. o p
Brine concentration Ždecrease. p p
Displacement conditions
Increase in displacement temperature, Tm p) p
Crude oil composition
Light ends Ždecrease. p) o toil, EORI of the University of Wyoming, and US
Light ends Žincrease. o p
)Early time imbibition data sometimes show crossover.
eralogy and topology of rocks, the fluid distribution
therein, and related interactions.
Relationships between oil recovery by imbibition
and waterflooding show trends ŽTable 2. which point
to possible approaches to improved oil recovery.
Provided due consideration is given to avoidance of
formation damage, results to date indicate that injec-
tion of dilute brine is preferable. The effect of modi-
fying injection brine compositions should always be
tested with respect to specific reservoir conditions.
Increase in recovery with temperature suggests that it
is better to inject water at above-reservoir tempera-
ture rather than below. The latter is usually the case
with injection of sea water. Displacement of oil by
condensed water resulting from steam injection may
be beneficial through the combined effect of temper-
ature and brine composition on wettability.
The change in wettability with removal of light
ends or addition of alkanes suggests that reservoir
wettability will change with reservoir pressure. If the
pressure is lowered for a reservoir above the bubble
point, the solvency of the crude oil with respect to
asphaltenes will decrease to a minimum at the bub-
ble point. Below the bubble point, the solvency of
the oil increases with reduction in content of light
ends in the oil. At present, many waterfloods are run
at close to the bubble point. The changes in labora-
tory waterflood efficiency that accompany change in
wettability with crude oil composition, temperature
275
and brine composition, all indicate possible ap-
proaches to improved reservoir recovery factors.
However, because of the complexity and specificity
of crude oilrbrinerrock ŽCOBR. interactions and
the present level of understanding, the need to test
specific circumstances, rather than rely on general-
izations, cannot be overemphasized.
Acknowledgements
Support for this project was provided by Arco,
B.P., Chevron, Conoco, Dagang, Elf, Exxon,
Marathon, Mobil, NorskHydro, Phillips, Shell, Sta-
DOErWRI Jointly Sponsored Research Program.
Marc Valat was jointly supported as a visiting scien-
tist by Elf Aquitaine and a Lavoisier Scholarship
provided by the government of France.
References
Buckley, J.S., Liu, Y., 1996. Some mechanisms of crude
oilrbrinersolid interactions. Presented at the 4th Int. Symp.
on Evaluation of Reservoir Wettability and Its Effect on Oil
Recovery, Montpellier, France, Sept. 11–13, 1996.
Buckley, J.S., Morrow, N.R., 1991. An overview of crude oil
adhesion phenomena. In: Toulhoat, H., Lecourtier, J. ŽEds..,
Physical Chemistry of Colloids and Interfaces in Oil Produc-
tion. Editions Technip, Paris.
Buckley, J.S., Liu, Y., Xie, X., Morrow, N.R., 1997. Asphaltenes
and crude oil wetting—the effect of oil composition. SPEJ, 2,
June Ž1998. 107–119.
Buckley, J.S., Liu, Y., Monsterleet, S., 1998. Mechanisms of
wetting alteration by crude oils. SPEJ, 3, March, 53–60.
Israelachvili, J., 1994. Intermolecular and Surface Forces, 2nd
edn. Academic Press, New York, 1991.
Jadhunandan, P., Morrow, N.R., 1995. Effect of wettability on
waterflood recovery for crude oilrbrinerrock systems. SPE
Reservoir Engineering, Feb. 1995, pp. 40–46.
Liu, Y., Buckley, J.S., 1997. Evolution of wetting alteration by
adsorption from crude oil. SPEFE, March 1997, pp. 5–11.
Ma, S., Morrow, N.R., Zhou, X., Zhang, X., 1994. Characteriza-
tion of wettability from spontaneous imbibition measurements.
Proceedings of the Petroleum Society of CIM 45th Annual
Technical Meeting and AOSTRA 1994 Annual Technical
Conference, June 12–15, 1994, Calgary, Canada, CIM 94-47.
Ma, S., Morrow, N.R., Zhang, X., 1997. Generalized scaling of
spontaneous imbibition data for strongly water-wet systems.
JPSE 18, 165–178.
Mennella, A., Morrow, N.R., Xie, X., 1995. Application of the
276 N.R. Morrow et al.r Journal of Petroleum Science and Engineering 20 (1998) 267–276
dynamic Wilhelmy plate to identification of slippage at a
liquid–liquid–solid three-phase line of contact. JPSE 13 Ž3r4.,
179–192.
Tang, G.Q., Morrow, N.R., 1997. Salinity, temperature, oil com-
position, and oil recovery by waterflooding. SPE Reservoir
Engineering, November, 269–276.
Treiber, L.E., Archer, D.L., Owens, W.W., 1972. A laboratory
evaluation of the wettability of 50 oil-producing reservoirs.
Soc. Petrol. Eng. J. 12, 531–540.
Xie, X., 1996. Application of the dynamic Wilhelmy plate tech-
nique to investigation of oilrbrinerquartz wetting alteration
by adsorption from crude oil. PhD Thesis, University of
Wyoming, Laramie, WY.
Zhou, X., Morrow, N.R. and Ma, S., 1996. Interrelationship of
wettability, initial water saturation, aging time and oil recov-
ery by spontaneous imbibition and waterflooding. Presented at
the SPErDOE 10th Symposium on Improved Oil Recovery,
Tulsa, OK, April 1996, SPE paper 35436.