SPE 93000

Seawater as IOR Fluid in Fractured Chalk

T. Austad, S. Strand, E.J. Hgnesen, and P. Zhang, Stavanger U. College
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2005 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 2 4 February 2005.
This paper was selected for presentation by an SPE Program Committee following review of
information contained in a proposal submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers is
prohibited. Permission to reproduce in print is restricted to a proposal of not more than 300
words; illustrations may not be copied. The proposal must contain conspicuous
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

Abstract
The wetting nature of a carbonate reservoir determines the
potential of improved oil recovery by water injection,
especially if the formation is highly fractured, which often is
the case for chalk formations. The initial wetting state is
mostly governed by the properties of the crude oil, where the
acid number, AN, appeared to be a crucial parameter. The
reservoir temperature plays, however, a minor role as a
wetting parameter. Improved oil recovery by water injection
decreases as the water-wetness decreases due to decrease in
spontaneous imbibition. The relative high specific surface area
of chalk, about 2-3 m2/g, indicates that compositional
properties of injected fluid could influence the wetting
properties of the formation somewhat during the production
phase. The exceptional good response of seawater injection
into the Ekofisk formation is an indication of a special rockwater interaction, which improves the spontaneous
displacement of oil. In the present paper, we will summarize
the results from ongoing research to improve spontaneous
imbibition of water into oil-containing chalk samples at
various wetting states and temperatures. The chemical
composition of the imbibing fluid is discussed in relation to
the composition of initial brine and changes in the rock-fluid
(water and oil) equilibrium conditions. Major observations
are: (1) The presence of sulfate in seawater improved
spontaneous imbibition at all wetting conditions tested. (2)
Sulfate is a potential determinig ion towards chalk, which has
impact on the wetting state in a positive way. (3) The
adsorption of sulfate onto chalk increases as the temperature
increases, which implies that the efficiency of sulfate as an
active wettability modifier is improved as the temperature
increases. (4) The relative increase in sulfate adsorption onto
chalk increases at temperatures above 100 oC. (5) Injection of
produced water with a high Ca2+/SO42- ratio is recommended

to be used only as pressure support and not as an oil displacing

fluid.
Key words: Oil recovery; chalk; imbibition; seawater;
wettability; sulfate.
Introduction
Improved oil recovery by water flooding of fractured
carbonate reservoirs is usually not successful. The reason is
that 90% of the carbonate reservoirs are characterized as
neutral to slightly oil-wet, which prevents spontaneous
imbibition of water from the fractures into the oil-containing
matrix blocks1. The consequence is an early break through of
injected fluid, which follows the fracture network from
injector to producer. We have recently shown, that certain
surface active compounds of the cationic type, [R-N(CH3)3]+,
are able to modify the wetting condition to a more water-wet
state2. In laboratory experiments, the oil recovery by
spontaneous imbibition using such surface active material was
even higher than the recovery obtained from a strongly waterwet system3. It was, however, discovered that sulfate in the
injected fluid had a strong catalytic effect on the wettability
alteration process. Both the imbibition rate and ultimate oil
recovery increased, especially at low temperatures4. The
properties of the imbibition process was also scaled using a
scaling law containing both capillary and gravity forces
developed by Li and Horn5. All parameters scaled properly,
even the core dimension, when using just the core height as
the shape factor in the scaling group. This indicated that
gravity forces played an important role in the oil displacing
process6.
Recently, Hadhrami and Blunt7 observed wettability
alteration of carbonates by injecting hot water/steam (240 oC).
They explained the wetting alteration by desorption of
asphaltenic materials from the carbonate surface without any
experimental verifications. Nomally, desorption of large
molecules containing carboxylic groups from calcite surfaces
requires special solvents8. Tang and Kovscek9 have also
observed increased spontaneous imbibition into diatomic
material containing heavy crude oil by hot-water injection. It
was concluded from experimental observations that diatomic
fines were detached with increasing temperature, and the
authors suggested that fresh water-wet pore surfaces were
created.
It is also interesting to note that increased spontaneous
imbibition of water into preserved or extracted and restored
chalk cores from the Tor formation (Maastrichtian age) in the
Ekofisk field was observed when increasing the temperature

from ambient to reservoir (130 oC) conditions. It must also be

noticed that no temperature dependence on imbibition was
observed when the cores were extracted and restored without
aging10. The reason may be that the cores remained more
water-wet without performing the aging procedure, and
wettability modifying agents in the injected fluid will not
enhance the spontaneous imbibition of water, which is
discussed later in this paper.
The present work is motivated to understand the principles
behind the successful injection of seawater into the Ekofisk
chalk field in the North Sea, Tres=130 oC. Laboratory
experiments using cores from the Tor formation
(Maastrichtian age), which were characterized as water-wet,
produced about 60% of the initial oil in place in a spontaneous
imbibition process11. The Tor formation has been flooded with
seawater for a long time. Distinct differences concerning
imbibition behaviour have been observed between core
samples from the Tor formation and the Ekofisk formation
(Danian age)11,12. Neither Lower- nor Upper Ekofisk showed
any correlation between imbibition and porosity, and
furthermore, the spontaneous imbibition of water was much
lower then compared to the Tor formation, especially for the
Upper Ekofisk formation. From an imbibition point of view,
the water-wetness appeared to decrease as one moves upward
in the Ekofisk formation. It is also interesting to note that the
initial water saturation is usually less than 10%, which will
have impact on the wetting properties. Anyway, Phillips
planed water injection also in the Lower Ekofisk, and the pilot
test (1986) in the field appeared to perform even better than
expected based on laboratory experiments13. Since 1988, the
Lower Ekofisk field has been water-flooded with great
success.
In order to be able to improve or optimise the injection of
seawater into the Ekofisk chalk formation, we have to
understand the principles behind this successful IOR-process
in a fundamental way. Otherwise, it is difficult to suggest
improvements to enhance the oil recovery beyond the
expected recovery of about 43-44% with the technique
available today. The results and discussion presented in this
paper must be regarded as a state of the art review of the
different activities going on at our laboratory on the topic:
IOR from carbonates with a special focus on the Ekofisk
field.
Results and discussion.
Multiphase fluid flow in porous medium is governed by the
distribution of fluids in the porous medium. In a two-phase
system, oil and water, the distribution of fluids is related to the
wetting conditions of the rock surface, and also on the relative
saturation of the phases. The wetting conditions and the
relative fluid saturations then dictate the capillary pressure
relationship, which physically determines the potential of fluid
flow when no external viscous forces are active. Thus, the
capillary pressure is related to the spontaneous fluid flow, i. e.
in a secondary oil recovery process, this means the ability of
water to displace the oil spontaneously. In this section we
therefore start by summarizing some new and important
observations concerning wettability of chalk, and then

SPE 93000

continue to discuss how the injected water can be modified to

enhance spontaneous imbibition of water to improve oil
recovery for different wetting conditions of chalk. The
presentation is focused on seawater as the injecting fluid and
initial brine properties close to the Ekofisk brine.
Wettability Normally, the wetting conditions of carbonates
are dictated by the following parameters, which, of course, are
not independent of each other:
pH of the equilibrium brine
Temperature of the reservoir
Crude oil properties, e.g. acid-/base number (AN, BN)
Composition of the equilibrium brine, e.g. Potential
determining ions (Ca2+, CO32-, and SO42-)
pH of the equilibrium brine
Due to the great buffer
capacity of calcium carbonate from the formation, the pH in
carbonate reservoirs becomes quite constant, usually in the
range of 7-8. Thus, great changes in pH are not expected
provided that the system (oil/brine/carbonate) is in chemical
equilibrium. It is therefore expected that wettability alterations
due to changes in pH are only temporary. Usually, the calcite
surface is positively charged below a pH-value of about 9.5,
and the charge of the oil-water film is negative because of
dissociation of surface active carboxylic acids present in the
crude oil. The water-film between the rock and the oil then
becomes instable, and oil will contact the surface8,14. The
carboxylic group, which is usually present in large molecules
(resins and asphaltenes), adsorbs chemically strongly onto the
carbonate surface by displacement of water8,15-16. Thus, the
acid number, AN, of the crude oil has been shown to be a
crucial factor for the wetting state of carbonates, and it was
observed that the water wetness decreases as the AN increases
as illustrated by Fig. 12. The presence of silica in the chalk
materials, which is negatively charged, will have a stabilizing
effect of the water film.
Temperature and crude oil
properties
Opposite to
sandstone reservoirs, the water-wetting nature appeared to
increase as the temperature increases for carbonate
reservoirs17. It is, however, well known that the carboxylic
group, -COOH, decomposes as the temperature increases, and
therefore, the temperature and acid number are not
independent wetting parameters. Typical examples from fields
are:
Ekofisk: chalk, preferential water-wet
Tres=130 oC, AN=0.1 mgKOH/g
Valhall: chalk, weakly water-wet
Tres=90 oC, AN=0.3-0.5 mgKOH/g
Yates:
dolomite, preferential oil-wet
Tres=30 oC, AN=1.0 mgKOH/g
Various types of clay minerals apparently act as catalysts
in the decarboxylation process18-19. It is also of special interest
to note that CaCO3 also behaves as a catalyst in the
decomposition process19. Thus, during geological time, the
formation acts as a catalyst for decarboxylation, and the AN
will decrease as the temperature of the reservoir increases. As
far as the authors know, up to date, it has not been presented

SPE 93000

any experimental work in the literature trying to decouple the

effect of temperature and AN regarding the wettability
evaluation of carbonates. We have recently studied
experimentally the wetting properties of chalk using crude oils
of different ANs (0.17, 0.32, 0.49, 0.76, 2.07), and synthetic
Ekofisk brine20. The core samples were aged for 4 weeks at
three different temperatures (40, 80, and 120 oC). The wetting
conditions after aging were analysed at room temperature
using our newly developed chromatographic technique21. The
obtained correlations between AN and the new wetting index,
WI, are shown in Fig. 2, and the preliminary conclusions
could be listed as:
The wetting condition of the tested chalk was mainly
determined by the AN of the crude oil.
The water-wetness increased as the AN decreased in line
with previous qualitative studies22.
The temperature had a very minor effect on wetting
conditions, and no systematic trends were observed.
The wetting nature of pure carbonate reservoirs should
not be discussed in terms of reservoir temperature, but
rather related to the AN of the crude oil.
It should be noticed that the wetting tests were conducted
at room temperature, and the conclusions are based on the
assumption that wetting properties are maintained during the
wetting test. Later experiments have, however, confirmed this
assumption23.
The oil recovery from spontaneous imbibition of water is
related to the new wetting index (completely oil-wet WI=0,
neutral WI= 0.5, completely water-wet WI=1.0) as shown by
Fig. 3. In this figure, the imbibition data for all the aging
temperatures were included. It is interesting to note that the
correlations for the different aging temperatures are well
grouped together.
The impact of base number is not quite well understood,
but it is reasonable to believe that the ratio between AN and
BN will bee important because 1:1 acid/base complexes may
be formed in the crude oil, preventing acidic materials to
adsorb onto the carbonate surface. This is closely linked to the
proposed mechanism for wettability alteration using cationic
surfactant2. Thus, in cases where BN>>AN, the wetting
mechanism may be different.
Potential determining ions
Potential determining ions
in equilibrium solution with chalk, will influence the charge
type (positive or negative) and the charge density on the chalk
surfaces due to adsorption onto the surface. The initial
equilibrium brine present in Ekofisk, EF-brine, has an
artificial composition as described in Table 1. It is noticed that
the concentration of Ca2+ is high, and no potential determining
anions are present. The surface charge of the chalk is expected
to be strongly positive at a natural reservoir pH of 7-824. If
seawater is used as injection fluid, the composition is quite
different from the initial EF-brine, Table 1. In addition to
Ca2+, seawater contains SO42-, which also is regarded as a
strong potential determining ion towards calcium carbonate.
Even at a very low concentration, sulfate will influence the
charge density and sign of the chalk surface24. It is also worth
noting that the molar concentration of sulfate in seawater is

nearly twice the concentration of Ca2+. As a common ion for

CaCO3(s), Ca2+ is probably a stronger potential determining
ion compared to sulfate. Anyway, the chalk surface in
equilibrium with seawater will become less positively charged
compared to the chalk surface in equilibrium with EF-water.
Adsorbed negatively charged carboxylic components from the
crude oil will be more easily displaced from the surface by
seawater, and it is expected that the water-wetness will
increase somewhat. As a consequence, the injected seawater
will more easily imbibe spontaneously into the matrix blocks
of a fractured chalk reservoir and improve the oil recovery. As
noticed by Fig. 3, increase in water-wetness will increase oil
recovery by spontaneous imbibition.
Initially, the reservoir rock was saturated with water, and
then the oil invaded the rock and displaced water. It is also
argued that the stability of the waterfilm between the
oil/water- and the chalk/water interfaces is crucial for the
wetting properties14. In the pH range about 3-9, the oil-water
interface will be negatively charged for an acidic crude oil,
and the chalk water interface will be positively charged. Under
such conditions, the water film will become instable and polar
components from the crude oil will adsorb onto the chalk
surface and reduce the water-wetness, which often is the case
for carbonate reservoirs. If sulfate is present in the equilibrium
water at a concentration much higher than the concentration of
Ca2+, the stability of the water film will increase from an
electrostatic point of view due to adsorption of sulfate onto the
chalk. The question is: Is it possible to reverse the wetting
conditions by modifying the composition of the brine?
We have recently taken benefit of the potential
determining property of sulfate towards chalk by developing a
new wettability test for chalk21. The principle of the test is
based on the separation of a non-adsorbing tracer
thiocyanante, SCN-, and SO42- at water-wet sites in the porous
system. The area between the effluent curves for the two
components is directly proportional to the water-wet area in
the chalk sample. The flooding test is performed at residual oil
saturation, Sor, and typical effluent curves are shown in Fig. 4.
The new water wetting index, ranging from 0 to 1.0 for
completely oil-wet and completely water-wet conditions,
respectively, is calculated using heptane as the reference oil
for a completely water-wet system.
Using the same technique, the temperature effect of the
affinity of sulfate towards the chalk surface was studied by
flooding the tracer thiocyanate, SCN-, and sulfate, SO42-,
through a 100% water saturated chalk core, Fig. 5. Obviously,
the adsorption of sulfate onto the chalk surface increases as
the temperature increases because the area between the
respective effluent curves, SCN- and SO42-, increases with the
temperature. The area between the effluent curves at the
different temperatures is plotted relative to the area at 130 oC
versus the temperature, Fig 6. Between 40 and 100 oC, it
appeared to be a nearly linear correlation, but at temperatures
above 100 oC, the relative increase in the affinity of SO42- for
the chalk surface seemed to increase somewhat. It is important
to note that the affinity of sulfate towards chalk at 50 oC is
decreased by 60% compared to the affinity at 130 oC. Thus,
according to these findings, the potential of sulfate to act as a
wettability modifier of chalk increases drastically as the

temperature increases. This is also reflected in the solubility of

CaSO4(s) in seawater spiked with sulfate, SSW1 brine, Fig. 7.
The solubility data were calculated using the method
described by Carlberg and Matthews25, and a drastic decrease
in solubility is observed between 100 and 125 oC. Above 100
o
C, sulfate is more poorly solvated in water due to the break in
hydrogen bonding between water molecules and the sulfate
ion. Sulfate wants to leave the aqueous phase either by
adsorption onto chalk or precipitation of CaSO4(s).
Spontaneous imbibition
As noticed previously, sulfate appeared to act as a catalyst
regarding spontaneous imbibition with wettability alteration
using cationic surfactants, Fig. 84. Knowing that sulfate is a
strong potential determining ion towards CaCO3(s), we were
inspired to investigate if sulfate could act as a wettability
modifier itself. As a preliminary test, two chalk samples from
Stevens Klint were saturated with the Mixed-brine (Table 1)
and flooded to residual water saturation using an oil with
AN=1.7 mgKOH/g. The cores were aged in the crude oil at 90
o
C for 4 weeks to obtain correct wetting conditions and treated
as described previously22. Thereafter, imbibition tests were
conducted at 70 oC using the Mixed-brine with different
sulfate concentrations. The total salinity was kept constant by
adjusting the NaCl-concentration. The very fast oil production
of about 10% is related to some inhomogeneities in the
wetting conditions as discussed previously6, Fig 9. Thus, the
solution with low content of sulfate (0.4 g/l corresponding to
0.0042 mole/l) produced only about 3.6 % of the initial oil
within 45 days. The core with higher sulfate content (1.7 g/l
corresponding to 0.017 mole/l) produced about 18% of the oil
during the same time frame. At 50 days, the imbibiting fluid
was substituted by SSW with somewhat higher sulfate content
(0.024 mole/l), but no significant improvements in oil
production was detected. It must be noted that the initial brine
in this case did contain sulfate, which is not the case for the
Ekofisk chalk field.
In order to mimic the natural reservoir conditions, further
experiments were all performed using EF-brine as the initial
water. A lot of spontaneous imbibition studies in Stevens
Klint chalk using oils of different ANs (0.17, 0.32, 0.49, 0.76,
2.07) and aging temperatures (40, 80, 120 oC) were conducted
at 70 oC26. The cores were prepared in the same way as
described previously22 using EF-brine as the initial water.
Seawater with different content of sulfate, i.e. SSW-U (no
sulfate), SSW (artificial seawater), and SSW1 (sulfate content
of 4 times SSW), was used as the imbibing fluids. Due to the
great range in the AN of the crude oils used, the span in the
wetting conditions was from strongly water-wet to about
neutral conditions. Some of the imbibition tests are presented
in Fig. 10. The additional oil recovery from spontaneous
imbibition, when using water with gradually higher
concentration of sulfate, i. e. from SSW-U to SSW, and from
SSW to SSW1, is listed in Fig. 11 and 12, respectively. It
should be noticed, that for the cores first imbibed with SSW-U
were later on imbibed with SSW, and then finally with SSW1.
Therefore, in some cases, the additional increase in oil
recovery from SSW to SSW1 becomes very low, in fact close
to zero. At strongly water-wet conditions, i. e. at a high

SPE 93000

wetting index, the oil recovery from spontaneous imbibition is

generally high independent of the composition of the water.
Thus, additional oil recovery by modifying the water
composition is only marginal, as expected. This is
schematically illustrated by the suggested trend lines shown in
Fig. 11 and Fig. 12. Roughly estimated, the additional oil
recovered when going from SSW-U to SSW is in the range of
4-6% of initial oil in place, and when going from SSW to
SSW1, the additional oil amounts to about 6 % as the initial
water-wetness decreases. As expected and in line with
previous results2, the presence of cationic surfactant in SSW
improved the oil recovery significantly for the low water-wet
cases, Fig 10.
Effects of temperature As discussed above, the adsorption
of sulfate onto the carbonate surface increases as the
temperature increases, and improvements in spontaneous oil
recovery are therefore expected if the imbibition tests were
performed at higher temperatures. A double set of Stevens
Klint cores were prepared using EF-brine (no sulfate) as initial
water and a crude oil with high acid number, AN = 1.7
mgKOH/g. The aging conditions were the same as listed
previously, i. e. 90 oC for 4 weeks. No imbibition of water
took place at room temperature. The cores were then imbibed
at 90 and 130 oC using SSW as imbibing liquid, Fig. 1327. The
oil recovery after 25 days was about 23 and 43% of initial oil
in place for the imbibing temperature of 90 and 130 oC,
respectively. This is in line with the change in the chalk
affinity of sulfate at 90 and 130 oC, as shown by Fig.5.
Additional oil, about 60 % of IOIP, can be recovered by
adding the cationic surfactant to the imbibing fluid.
Effects of sulfate concentration at high tempeature
Imbibition tetsts conducted at high temperatrure, 130 oC, with
different concentration of sulfate in the imbibing fluid are
shown in Fig. 14. The double set of chalk cores were prepared
in the same way as described in section 3.1 (Fig. 13) using
EF-brine as the initial water present. Note that the oil recovery
is very low when using SSW-U (seawater without sulfate
present), in the range of 15%, which is probably mostly
related to fluid expansion and some inhomogenety in the
wetting conditions. After about 8 days, the imbibing fluid was
exchanged with SSW4, which contained 3 times the seawater
concentration of sulfate, and the salinity was kept constant by
adjusting the NaCl concentration. After a short time, 4-5 days,
the oil recovery was above 65%. The other two cores were
exposed to SSW, and the oil recovery amounted to about 5560% within 12 days27. Only marginal extra oil was produced
when SSW was exchanged with SSW4. As expected, it is
difficult to remobilise discontinuous capillary trapped oil by
increasing the sulfate concentration in a spontaneous
imbibition process, even though the temperature is quite high
and the sulfate concentration was increased 3 times. The
experiment demonstrates the great effect of sulfate to increase
the water-wetness at high temperatures. The oil recovery
jumps from 15% to 65% of OOIP by adding sulfate
corresponding to about 3 times the concentration in seawater
to an injection fluid without sulfate present. The effects are
dramatic. The optimal effect is achieved when the

SPE 93000

concentration of sulfate is increased up to the solubility limit

of CaSO4(s) at the actual test conditions.
Suggested mechanism for wettability modification using
sulfate
Enhanced spontaneous imbibition of water into
weakly water-wet chalk is obtained if the capillary forces are
increased. This can be done if the injected fluid can improve
the water-wetness of the chalk. A wettability alteration
mechanism, which is in line with the experimental data is
schematically visualised in Fig. 15. Sulfate, SO42-, will adsorb
onto the chalk surface and lower the positive charge density to
facilitate some desorption of negatively charged polar
components, i. e. carboxylic material. Knowing that both Ca2+
and SO42- are potential determining ions, recent experimental
data indicate that the concentration ratio [SO42-] / [Ca2+] is
important. Both of the ions are probably important in the
desorption process of carboxylic materials. Besides stronger
adsorption of sulfate onto the chalk as the temperature
increases, also increased diffusion rate of sulfate into the
porous network is expected as the temperature is increased. It
must also be noted, that due to adsorpten of sulfate onto chalk,
the concentration of sulfate at the water front will decrease,
which will lower the displacement efficiency of oil. Natural
stripping of sulfate during seawater flooding in chalk
reservoirs has recently also been discussed in relation to
scaling effects28.
Produced water
It is evident that the concentration ratio between sulfate and
calcium, [SO42-] / [Ca2+], is quite different in the produced
water compared to the injected seawater or seawater spiked
with sulfate. Seawater appeared to be an excellent injection
fluid in fractured chalk at weakly water-wet conditions
because [SO42-] 2[Ca2+]. The produced water is a mixture of
initial brine and injected fluid, which is strongly depleted in
sulfate partly due to adsorption onto the chalk surface.
Consequently, the concentration of Ca2+ is about 6 times
higher than the concentration of SO42- as shown in Table 1.
Under these conditions, it is hard to perform any change in the
wetting conditions because the chalk will probably remain
strongly positively charged. Thus, reinjection of produced
water should not be used to displace oil from the matrix
blocks, but rather be injected as pressure support in the already
water flooded area of the reservoir.
Preliminary concluding remarks
Based on the experimental results presented in this paper,
optimised oil recovery by injection of modified seawater into
neutral to moderate water-wet chalk can be very shortly
summarized as:
1. The ratio between sulfate and calcium concentration
should be as high as possible without causing
precipitation of CaSO4(s). Sulfate should be added to the
seawater.
2. The temperature at the waterfront should be as high as
possible. Displacement of oil after the reservoir is cooled
due to injection of cold water becomes less efficient. The

injection water should be heated to avoid cooling the

reservoir.
3. The concentration of sulfate at the waterfront should be
as high as possible. An injection strategy should be made
to prevent too low concentration of sulfate in the
waterfront because of adsorption onto the chalk surface.
4. Injection of produced water will probably have a
negative effect on the oil recovery process because of
unfavourable concentration ratio between the potential
determining ions Ca2+ and SO42-. Injection of produced
water should only be done for pressure support in the
already waterflooded area of the reservoir.
Acknowledgment
The authors acknowledge VISTA/Statoil, ConnocoPhillips,
and the Norwegian Research Council (NFR) for financial
support.
Nomenclature
AN
Acid number
BN
Base number
EF
Ekofisk formation water
OOIP
Original oil in place
PV
Pore volume
R
Spontaneous water imbibition recovery
R2
R2 statistic
(s)
Solid
SK
Stevns Klint
Sor
Residual oil saturation
SSW
Synthetic sea water
SSW1
Synthetic sea water with 4 times SO42SSW2
Synthetic sea water without SO42SSW4
Synthetic sea water with 3 times SO42SSW-M Synthetic sea water with SCN- and SO42SSW-U Synthetic sea water without SCN- and SO42Swi
Initial water saturation
Aging temperature
T-aging
Reservoir temperature
Tres
TDS
Total dissolved solid
WINew
New wettability index
References
1. Downs, H. H., Hoover, P. D., 1989. Enhanced oil recovery by
wettability alteration. In: Oil-Field Chemistry. Enhanced
Recovery and Production Simulation. Eds. Borchardt, J. K. and
Yen, T. F. ACS Symposium Series 396. Washington D. C.
2. Standnes, D. C., Austad, T., 2000b. Wettability alteration in
chalk. 2. Mechanism for wettability alteration from oil-wet to
water-wet using surfactants. J. Pet. Sci. Eng. 28, 123-143.
3. Standnes, D. C., Austad, T., 2003. Wettability alteration in
carbonates. Low-cost ammonoum surfactants based on bioderivatives from coconut palm as active chemicals to change the
wetting form from oil-wet to water-wet conditions. Colloids and
Surfaces A: Physicochem. Aspects 218, 161-173.
4. Strand, S., Standnes, D. C., Austad, T., 2003. Spontaneous
imbibition of aqueous surfactant solutuion into neutral to oil-wet
carbonate cores: Effects of brine salinity and composition.
Energy and Fuels, 17, 1133-1144.

SPE 93000

5. Li, K., Horn, R. N., 2002. A general scaling method for

spontaneous imbibition. Paper SPE 77544 presented at the SPE
Annual Techn. Conf. and Exib., San Antonio, TX, Sept 29 to
Oct. 2.
6. Hgnesen, E. J., Standnes, D. C., Austad, T., 2004. Scaling
spontaneous imbibition of aqueous surfactant solutions into
preferential oil-wet carbonates. Energy and Fuels 18, pp. 16651675.
7. Al-Hadhrami, H.S. and Blunt, M.J., 2000. Thermally Induced
Wettability Alteration to Improve Oil Recovery in Fractured.
SPE 59289 prepared for presentation at the 2000 SPE/DOE
Improved Oil Recovery Symposium held in Tulsa, Oklahoma,
April 2000, 35
8. Thomas, M. M., Clouse, J. A., Longo, J. M., 1993. Adsorption
of organic compounds on carbonate mainerals: 1. Model
compounds and their influence on mineral wettability. Chem.
Geol. 109, 201-213.
9. Tang, G., Q., Kovscek, A. R., 2002. Wettability ateration of
diatomice induced by hoy-fluid injection. Paper SPE 77461,
presented at the SPE Annual Tech. Conf. And Exhib., San
Antonio, TX, Sept 29 to Oct. 2.
10. Thomas, L. K., Dixon, T. N., Vienot, M. E., 1987. Ekofisk
waterflood pilot. J. Pet. Techn. 283, 221-232.
11. Torster, O., 1984. An experimental study of water imbibition
in chalk from the Ekofisk field. Paper SPE/DOE 12688
presented at the SOE/DOE Fourth Symp. on Enhanced Oil
Recovery, Tulsa, OK, April 15-18.
12. Dangerfield, J. A., Brown, D. A., 1987. 1. The Ekofisk field. In
North Sea Oil and Gas Reservoirs, ed. Kleppe, J. et al. The
Norwegian Institute of Technology, Graham & Trotman.pp. 322.
13. Hallenbeck, L. D.,Sylte, J. E., Ebbs, D. J., Thomas, L. K., 1989.
Implementation of the Ekofisk Waterflood. Paper SPE 19838
presented at the 64th Annual Techn. Conf. And Exhib. of SPE,
San Antonio, TX, October 8-11.
14. Hirasaki, G., Zhang, D. L., 2003. Surface chemistry of oil
recovery from fractured, oil-wet, carbonate formation. Paper
SPE- 80988 presented at the SPE International Symp. on
Oilfield Chemistry, Houston, TX, February 5-8.
15. Legens, C., Toulhoat, H., Cuiec, L., Villieras, F., Palermo, T.,
1998. Wettability change related to the adsorption of organic
acids on calcite: Experimental and Ab Initio computational
studies. Paper SPE 49319 presented at the Annual Technical
Conf. And Exhib., New Orleans, Louisiana, 27-30 Sept.

16. Madsen, L. and Lind, I., 1997. Adsorption of carboxylic acids

on reservoir minerals from organic and aqueous phase. SPE
37292 presenter at the 1997 SPE International Symposium on
Oilfield Chemistry held in Houston, Texas, February 18-21.
17. Rao, D. N., 1999. Wettability effects in thermal recovery
operations. SPE Reservoir Eval. And Eng., 2, pp. 420-430.
18. Jurg, J. W., Eisma, E., 1964. Petroleum hydrocarbons:
generation from fatty acids. Science 144, 1451-1452.
19. Shimoyama A., and Johns W.D., 1972. Formation of alkanes
from fatty acids in the presence of CaCO3. Geochimica et
Cosmochimica Acta (GCA), Vol. 36, pp 87-91.
20. Zhang, P. Austad, T., 2005b. The Relative Effects of Acid
Number and Temperature on Chalk Wettability. SPE 92999 to
be presented at the Oilfield Chemistry Symposium, Houston,
TX, February 2-5
21. Strand, S., Standnes, D. C., Austad, T., 2004. New wettability
test for chalk. Paper to be presented at the 8th International
Wettability Symposium Conference, Houston, TX, May 16-18.
22. Standnes, D. C., Austad, T., 2000a. Wettability alteration in
chalk. 1. Preparation of core material and oil properties. J. Pet.
Sci. Eng., 28, 111-121.
23. Strand, S. and Austad, T., 2004. Wettability tests on carbonates
at reservoir temperatures. Paper in preparation.
24. Pierre, A., Lamarche, J. M., Mercier, R., Foissy, A., and
Persello, J., 1990. Calcium as potential determing ion in aqueous
calcite suspensions. J. Dispersion Science and Technology, 11,
No. 6, pp. 611-635.
25. Carlberg, B. L., Mattews, R. R., 1973. Solubility of calcium
sulfate in brine. Paper SPE 4353 presented at the SPE Oilfield
Chemistry Symposium, Denver, Co, May 24-25.
26. Zhang, P., Austad, T., 2005a. Waterflooding of chalk:
Relationship between oil recovery, new wettability index, brine
composition, and cationic wettability modifier. Paper to be
presented at the SPE Europec/EAGE Symp. in Madrid, June 1316.
27. Hgnesen, E. J., Austad, T., 2005. Waterflooding of preferential
oil-wet carbonates: Oil recovery related to reservoir temperature
and brine composition. Paper to be presented at the SPE
Europec/EAGE Symp. in Madrid, June13-16.
28. Mackay, E. and Jordan, M.M., 2003. Natural sulphate ion
stripping during seawater flooding in chalk reservoirs. Paper
presented at the Chemicals in the Oil Industry VIII Symp.,
Royal Soc. Chem. and Eur. Oilfield Spec. Chem. Ass., Nov. 3-5,
Manchester, UK

SPE 93000

Table 1
Ions
Na
K

EF-brine
(mole/l)

SSW
(mole/l)

SSW1
(mole/l)

SSW4
(mole/l)

SSW-U
(mole/l)

Mixed-brine
(EF-brine/SSW)=1/3
(mole/l)

Prod. Water
(mole/l)

0.6849

0.450

0.419

0.402

0.642

0.5285

0.646

0.010

0.010

0.010

0.010

0.0160

0.007

2+

0.0246

0.045

0.045

0.045

0.045

0.0381

0.020

2+

0.2317

0.013

0.013

0.013

0.013

0.0857

0.039

1.1975

0.528

0.343

0.381

0.720

0.7491

0.752

0.002

0.002

0.002

0.002

0.0015

0.007

0.024

0.096

0.072

0.0160

0.007

68.009

33.39

33.39

33.39

35.72

44.94

Mg
Ca

Composition of the artificial waters used.

Cl

HCO

24

SO

TDS (g/l)

0.95
WINEW

Recovery, %OOIP

80

60

40

0.85

y = 0.605e0.081x

y = 0.5722e0.0925x

y = 0.5572e0.0888x

R2 = 0.9258

R2 = 0.9244

R2 = 0.8761

0.75

Oil A. AN=0, Test 1

Oil D. AN=0.055, Test 7

T,aging=40C

Oil B. AN=0.06, Test 5

Oil E. AN= 0.41, Test 8

20

T,aging=80C

0.65

Oil C. AN=0.52, Test 6

T,aging=120C

Oil F. AN=1.73, Test 9

0
1

10

100

1000

10000

100000

0.55

1000000

2.07

Time, min.

Fig. 2

0.32

0.17

Correlation between AN and new wettability index for cores

aged at different temperatures. Completely water-wet
WINew=1.0; Neutral WINew=0.5; Completely oil-wet WINew=0.

1.0
y = 0.001e

12.864x

y = 0.018e

R2 = 0.9446

9.3353x

y = 0.0005e

13.835x

C/Co

Recovery (OOIP%)

70
2

R = 0.9843

R = 0.8597

50
40

T-aging=40C

0.5

T-aging=80C

30

C/Co SCN Core 4/1 Crude 1 AN 0.1

A=0.123
C/Co SO4 Core 4/1 Crude 1 AN 0.1

T-aging=120C

20

C/Co SCN Core 5/1 Crude 1 AN 1.8

A=0.059
C/Co SO4 Core 5/1 Crude 1 AN 1.8

10
0
0.50

0.0

0.60

0.70

0.80

0.90

WInew
Fig. 3

0.49

AN (mg KOH/mg)

Fig. 1 Spontaneous imbibition (40C) of water into chalk containing oil

with different AN

60

0.76

Correlation between plateau oil recovery and the new wetting index.

0.5

1.0

PV

1.5

Fig. 4 Effluent profiles of SCN- and SO42- from SK-cores prepared without
initial water saturation using oils of different AN, 0.13 and 1.84 mgKOH/g.

SPE 93000

C/Co

1.0

0.8

C/Co SCN FL#7-1 SSW-M at 21C

A=0.174
C/Co SO4 FL#7-1 SSW-M at 21C
C/Co SCN FL#7-2 SSW-M at 40C
A=0.199
C/Co SO4 FL#7-2 SSW-M at 40C

0.5

C/Co SCN FL#7-3 at 70C

A=0.297
C/Co SO4 FL#7-3 at 70C
C/Co SCN FL#7-4 at 100C
A=0.402
C/Co SO4 FL#7-4 at 100C

0.3

C/Co SCN FL#7-5 at 130C

A=0.547*(Extrapolert 2.6PV)
C/Co SO4 FL#7-5 at 130C

0.0
0.6

Fig. 5

0.8

1.0

1.2

1.4

1.8

PV

2.0

2.2

Chromatographic separation between the effluent curves of SCN- and SO42- in chalk. The area between the respective
curves increases as temperature increase, documenting that the adsorption of SO42- increases with temperature.

1.2

0.025
Solubility, mole/l

Relative area, A(T)/A(130 C)

1.6

0.9

0.02

0.6

0.015
0.3

0.01
0

25

50

75

100

125

150

Fig. 6 The affinity of SO42- towards the chalk surface at different

emperatures relative to the the condition at 130 oC. The affinity of
sulfate towards chalk at 40 oC is decreased by 63% compared to the
affinity at 130 oC.

20

40

60

80

100

120

140

Temp. oC

Temp. oC

Fig. 7

Solubility of CaSO4(s) in SSW1 at different temperatures calculated

according to the method of Carlberg and Matthews (1973).

SPE 93000

30

80

Recovery, %OOIP

Recovery, %OOIP

100

Test 20. Brine A 1,7 g/l Sulfate

Test 19. Brine A 0.4 g/l Sulfate
Test 17. Brine A 0 g/l Sulfate

60

Brine A 1,7g/l Sulfate without C12TAB at 70C

20

Test 18. Brine A 0.07 g/l Sulfate

Brine A 0,4g/l Sulfate without C12TAB at 70C

40
10

20

0
0

50

100

150

200

250

10

20

30

40

Fig. 9

Catalytic effect of sulfate on spontaneous imbibition cationic

surfactant solution.

SSW

70
Oil recovery (%OOIP)

Fig. 8

50

60

50

WP#13 (AN=0.17, 40C)

40

WP#14 (AN=0.17, 80C)

SSW-U

30

SSW

WP#15 (AN=0.17, 120C)

WP#8 (AN=0.49, 80C)

20

WP#7' (AN=0.49, 40C)

WP#2 (AN=2.07, 80C)

10
WP#1 (AN=2.07, 40C)
0
0

15

30

45

60

75

90

Time (day)
Fig. 10

70

Preliminary study of the effects of sulfate in the imbibing fluid on the

ability to displace oil from chalk samples.

SSW+1wt%C12TAB

SSW1

60

Time (Day)

Time, Days

Some of the imbibition tests for crude oils with AN= 0.17, 0.49, and 2.07 mgKOH/g. At 30 days, the imbibing brine was substituted
with a solution of cationic surfactant dissolved in SSW.

10

SPE 93000

Recovery increment (OOIP%)

Recovery increment (OOIP%)

8
T-aging=40C
T-aging=80C

T-aging=120C

10
T-aging=40C

T-aging=80C
T-aging=120C

4
2

0
0.6

Fig. 11

0.7

0.8

WInew

0.9

0.5

0.7

0.8

0.9
WInew

Additional increase in oil recovery when going from SSW-U to

SSW, i. e. an increase in sulfate concentration of 0.024 mole/l.
Although the data are scattered, a schematic trend is suggested.

Fig. 12

80

Additional increase in oil recovery when going from SSW to SSW1,

i. e. an increase in sulfate concentration of about 4 times. Although
the data are scattered, a schematic trend is suggested.

80
Oil Production [%OOIP]

Recovery (9%OOIP)

0.6

Added
1wt%C12TA
B

60

40

60

40
Core#1 - 130C
Core#2 - 130C

20

20

Core#18 - SSW

Core#18 - SSW4

Core#17 - SSW

Core#17 - SSW4

Core#16 - SSW2

Core#16 - SSW4

Core#15 - SSW2

Core#15 - SSW4

Core#9 - 90C
Core#10 - 90C

0
0

Fig. 13

10

20

30

40

50

60
70
Time [Days]

80

10

15

20

25

30

Fig. 14

Effects of temperature on spontaneous imbibition of SSW into chalk

initial treated with EF-brine and crude oil with AN=1.7 mgKOH/g.

Effects of sulfate on spontaneous imbibition into preferential oilwet chalk at 130 oC. SSW4 contains 3 times the sulfate
concentration compared to SSW. SSW2 contains no sulfate.

+
SO42SO42-

+
+

Chalk surface
CaCO3(s)

+
SO42-

Fig. 15

35

Time [Days]

Schematic illustration of the mechanism for improving the water-wetness. Adsorbed polar negatively charged components from the crude oil is partly
displaced as sulfate adsorbs onto the positively charged chalk surface because the charge density is changed.