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Wettability and oil recovery from carbonates:


Effects of temperature and potential
determining ions

ARTICLE in COLLOIDS AND SURFACES A PHYSICOCHEMICAL AND ENGINEERING ASPECTS · MAY 2006
Impact Factor: 2.75 · DOI: 10.1016/j.colsurfa.2006.01.009

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Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187

Wettability and oil recovery from carbonates: Effects of


temperature and potential determining ions
Peimao Zhang, Tor Austad ∗
University of Stavanger, 4036 Stavanger, Norway
Received 22 August 2005; received in revised form 19 December 2005; accepted 3 January 2006
Available online 13 February 2006

Abstract
The success of oil recovery from fractured low permeable carbonates by water injection is dictated by the wetting properties of the rock surface.
Potential determining ions like Ca2+ and SO4 2− have influence on the surface charge of the carbonate rock and are thereby linked to its wetting
properties. In the present study, zeta potentials of chalk surfaces were measured by changing the sulfate and calcium concentrations in aqueous
chalk suspensions. Series of long-term spontaneous imbibition tests were conducted at 70, 100 and 130 ◦ C using oil containing chalk cores which
were close to neutral wetting conditions. The concentration of SO4 2− in the imbibing fluids varied above and below the seawater concentration,
while the Ca2+ concentration was kept constant. Sulfate acted as a wettability modifying agent by improving the water wetting nature of the chalk.
The major experimental observations were: (1) the zeta potential on chalk was determined by the relative concentration of Ca2+ and SO4 2− present.
(2) The oil recovery was tremendously improved by increasing the sulfate concentration in the imbibing fluid. (3) The wettability modifying
property of sulfate increased as the temperature increased. (4) The chemical nature of the wettability modifying imbibition process was discussed.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Sulfate; Zeta potential; Oil recovery; Wettability alteration; Chalk

1. Introduction and wettability alteration in carbonates using surfactants have


also been discussed in the literature [8,12,13]. The large quan-
Improved oil recovery from fractured and low permeable car- tities of rather expensive chemicals needed in field conditions,
bonates is a great challenge. Because the wettability of most however, frighten the oil companies to start field projects due
carbonate reservoirs worldwide is characterized as neutral to to economical reasons. Therefore, cheap chemical additives are
preferential oil-wet, normal water flooding is usually not suc- welcome and of great importance.
cessful as an EOR technique [1–4]. The degree of success is The surface chemistry of oil recovery from fractured, oil-
generally determined by the extent of spontaneous imbibition wet carbonate formations has recently been discussed in detail
of water from the fractures into the matrix blocks, which is [8,13]. The stability of the water film between the rock and the
dominated by the capillary forces, and also linked to the wet- oil, often discussed in terms of disjoining pressure, is determined
ting conditions of the rock surface [2,5–8]. Expensive chemical by the zeta potential of the rock–water interface and the charge of
additives to the injection water, i.e. cationic surfactants of the the oil–water interface. The zeta potential of the carbonate–water
quaternary ammonium type, R-N(CH3 )3 Br, are able to change interface is determined by the pH and potential determining ions,
the wettability towards more water-wet conditions [3,9]. It was Ca2+ and CO3 2− , which are part of the carbonate structure. The
also documented that sulfate appeared to act as a catalyst in the brine present in a typical carbonate reservoir has a slightly basic
wettability alteration process induced by this cationic surfactant pH, typically about 7–8, a very high concentration of Ca2+ , and
[10,11]. The combined effects of low interfacial tension (IFT) a very small amount of CO3 2− , often negligible. As a conse-
quence, the rock–water interface becomes positively charged.
The carboxylic materials present in the crude oil will act as sur-
∗ Corresponding author. Tel.: +47 5183 2296; fax: +47 5183 1750.
face active materials, and due to partly dissociation of the acidic
E-mail addresses: peimao.zhang@uis.no (P. Zhang), tor.austad@uis.no group, the oil–water interface becomes negatively charged. The
(T. Austad). initial water film between the oil and the rock then becomes

0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.01.009
180 P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187

bility alteration, a deeper insight into the chemical process is


Nomenclature needed.
In the present paper, the relative strength of Ca2+ and SO4 2−
AN acid number, mgKOH/g of oil
as potential determining ions will be studied. Spontaneous imbi-
ASTM American Society for Testing and Materials
bition of water into chalk cores are performed at different tem-
BN base number, mgKOH/g of oil
peratures by using fluids with different content of sulfate, both
D core diameter
below and above the seawater concentration.
EF Ekofisk formation water
EOR enhanced oil recovery
ESA electrokinetic sonic amplitude effects 2. Experimental
h(s) hour(s)
IFT interfacial tension 2.1. Materials
L core length
OOIP original oil in place 2.1.1. Porous media
PV pore volume The porous material used is outcrop chalk from Stevns Klint
SK Stevns Klint (SK) nearby Copenhagen, Denmark, which is a soft and highly
SSW synthetic sea water porous chalk of Maastrichtian age. This chalk is very homoge-
Swi initial water saturation neous and composed of ≥96% fine-graded coccolithic matrix
taging aging time with porosity and permeability in the range of 45–50% and
Taging aging temperature 2–5 mD, respectively [19]. It has a specific surface area about
Timb imbibition temperature 2 m2 /g as determined by the Braunauer-Emmett-Teller (BET)
TDS total dissolved solid adsorption isotherm. All the chalk cores were drilled from one
wt.% weight percentage outcrop chalk block and prepared to the similar dimensions,
ZP bulk aqueous chalk suspension for zeta potential L ≈ 70 mm and D ≈ 37.5 mm.
measurements For zeta potential measurements, the SK chalk materials were
φ core porosity, fraction or % of pore volume milled for 48 h using a ball mill (type 400 VL manufactured by
Tecon AS, Norway) before use.

2.1.2. Oil
instable. Oil will come in direct contact with the rock, and the Two crude oils of different acid number, AN, termed
system becomes mixed-wet. It is well documented that the water Oils A and B were used. The high AN crude Oil A (AN =
wetness decreases as the acid content, as determined by the acid 2.07 mgKOH/g) was treated with silica gel to obtain a crude
number, AN (mgKOH/g), increases [14,15]. oil with very low AN (AN = 0.17 mgKOH/g), and crude Oil B
An interesting chemical question to be asked is: “Is it possi- (AN = 0.55 mgKOH/g) was obtained by mixing the two oils in
ble during the production time to reverse the wetting conditions a proper ratio as described previously [15]. The two crude oils
of chalk by composing an injection fluid with the appropriate were filtrated through a 5 ␮m Millipore filter before use in order
potential determining ions?” In that sense, the injection fluid to improve the flow through the low permeable chalk cores.
should contain strong negatively charged potential determining Some of the important parameters of the oils are listed in Table 1.
ions to make the carbonate surface negatively charged, which
will facilitate the desorption of negatively charged carboxylic
2.1.3. Brine
material. Carbonate, CO3 2− , is surely a potential determining
Artificial Ekofisk brine, termed EF-brine, and a modified
ion, which can make the surface negatively charged [8], but
Ekofisk brine, termed EF-mod, were used as initial waters
direct injection of carbonate into a formation containing large
present in the cores. The concentration of Ca2+ in EF-mod was
concentration of Ca2+ in the formation water will cause precip-
decreased to the same level as that in synthetic seawater (SSW).
itation of CaCO3 (s) with the possibility of blocking the pores.
The ionic strength was kept constant and equal to the EF-brine
It was confirmed by Pierre et al. [16], that sulfate was a
by adjusting the amount of NaCl (Table 2). Synthetic seawater,
strong potential determining ion towards CaCO3 . At slightly
SSW, and modified seawater were used as imbibing fluids. The
basic pH-values, sulfate is able to change the zeta potential of
the carbonate surface from positive to negative. Knowing that
the concentration of SO4 2− in seawater is about twice the con- Table 1
Properties of the oils used
centration of Ca2+ , seawater can be looked upon as a reference
fluid regarding the ability to reverse the wetting conditions in Oil ANa BNb Asphaltene Density Viscosity
carbonates. Very recent studies have documented that seawater (mgKOH/g) (mgKOH/g) content at 25 ◦ C at 25 ◦ C
(wt.%) (g/cm3 ) (cp)
appeared to be an excellent fluid for oil displacement by sponta-
neous imbibition [13,17,18]. The efficiency appeared to depend A 2.07 0.50 0.23 0.806 3.05
on the temperature conditions. In order to adjust the content of B 0.55 0.13 0.803 2.56
potential determining ions in the injection fluid for maximum a The AN was determined by West Lab Services according to ASTM D-664.
b The BN was determined according to modified ASTM D-2289.
oil displacement by spontaneous imbibition based on wetta-
P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187 181

Table 2
Composition of brines used
Ion SSW × 4S SSW × 3S SSW × 2S SSW SSW-1/2S SSW-1/4S SSW-US EF EF-mod ZP

Na+ 0.378 0.402 0.426 0.450 0.462 0.468 0.474 0.684 1.339 0.573
K+ 0.010 0.010 0.010 0.010 0.010 0.010 0.010 – – –
Mg2+ 0.045 0.045 0.045 0.045 0.045 0.045 0.045 0.025 0.025 –
Ca2+ 0.013 0.013 0.013 0.013 0.013 0.013 0.013 0.231 0.013 –
Cl− 0.309 0.381 0.453 0.528 0.561 0.579 0.597 1.196 1.414 0.573
HCO3 − 0.002 0.002 0.002 0.002 0.002 0.002 0.002 – – –
SO4 2− 0.096 0.072 0.048 0.024 0.012 0.006 – – – –
[SO4 2− /Ca2+ ] 7.39 5.54 3.70 1.85 0.92 0.46 0.00 – – –
Ionic strength 0.657 0.657 0.657 0.657 0.657 0.657 0.657 1.452 1.452 0.573
TDS (g/l) 30.99 31.79 32.59 33.39 31.79 34.19 34.19 68.01 82.05 33.39

content of SO4 2− in the modified seawaters varied between 0 to ductivity range specified for the instrument (0–5 S/m). Totally
4 times the concentration present in SSW. Also in this case, the four series of experiments were performed:
ionic strength was kept constant by adjusting the concentration
of NaCl. (1) Increasing concentration of Ca2+ was added to the aqueous
The basic solution for the zeta potential measurements was suspension.
0.573 mol/l NaCl, termed brine ZP. Small volumes of a concen- (2) Increasing concentration of SO4 2− was added to the aqueous
trated solution of CaCl2 were added when keeping the sulfate suspension.
concentration constant, or small volumes of a concentrated solu- (3) The concentration of calcium was kept constant which is
tion of NaSO4 were added when keeping the calcium concen- equal to the concentration in SSW, [Ca2+ ] = 0.013 mol/l,
tration constant. The pH was kept equal to 8.4 by adding small while small amount of sulfate was gradually added.
amounts of HCl or NaOH. (4) The concentration of sulfate was kept constant
[SO4 2− ] = 0.012 mol/l, while small amount of calcium was
2.2. Zeta potential measurements gradually added.

The zeta potential measurements were performed with milled 2.3. IFT measurement
Stevns Clint (SK) chalk suspended in the NaCl solution (brine
ZP), by using an AcoustoSizer from Matec applied Sciences, The IFT measurements between oil and brine were performed
USA. The AcoustoSizer technology involves the measurement at room temperature (18.5–20.2 ◦ C) by using a ring tensiometer.
of acoustic waves (known as electrokinetic sonic amplitude The measurements were performed to justify that the IFT values
effects, ESA) generated by an electric field applied across the between Oils A and B and the two brines were comparable as
slurry of the chalk. The alternating electrical field causes the listed in Table 3.
colloidal particles to oscillate, and an acoustic wave is gener-
ated. The ESA measurements determine the particle velocity 2.4. Core handling
over a range of excitation frequencies, i.e. a dynamic mobility
spectrum of the material. Particle size distribution and the zeta In order to obtain homogeneous wetting conditions, the cores
potential can then be determined from this dynamic mobility were handled according to the procedures described by Standnes
spectrum [20,21]. and Austad [14]. Spontaneous imbibition experiments were per-
The chalk material was milled for 48 h using a ball mill and formed on cores with and without initial water saturation. In the
sieved through a fine metal screen before use. A suspension of case without initial water, the dry cores were evacuated and sat-
4.0 wt.% chalk in the brine ZP was stirred at room temperature urated with oil under vacuum. They were then rested in the oil
for 2 days and used as a stock solution. Representative solutions for 2 h, and their porosities were calculated by the weight differ-
were added to the cell for zeta potential measurements at 25 ◦ C. ence, bulk volume, and oil density. Then the cores were placed
Series of tests were performed by gradually adding small portion in Hassler core holders and flooded with 1.5 PV of oil in each
of concentrated CaCl2 or NaSO4 into the suspension to reach
Table 3
a new equilibrium, and meanwhile the pH was kept constant, IFT between brine and oil interfaces (mN/m)
equal to 8.4, by adjusting with small amounts of HCl or NaOH.
The Acoustosizer is in principle capable of working at elevated Oil Brine
salt concentrations [21], the salinity of the ZP brine was close EF SSW
to the upper limit for electrophoretic studies. The conductivities Oil A (AN = 2.07) 16.5 12.5
measured for the whole experimental series were in the range of Oil B (AN = 0.55) 16.6 12.8
4.2–5.3 S/m, which are, for a few measurements, beyond the con-
182 P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187

Table 4
Experimental details
Core ID Physical properties Saturation fluids Aging process Spontaneous imbibition

Da (cm) La (cm) φ (%) PVa (cm3 ) Initial water Oil Swi (%) Taging (◦ C) taging (day) Timb (◦ C) Oil Imbibing Recovery
phase fluids (% OOIP)

CS70-1 3.50 5.80 48.7 27.1 EF mod Oil B 26.3 90 30 70 Oil B SSW × 4S 54.6
CS70-2 3.54 5.72 47.9 26.9 EF mod Oil B 25.9 90 30 70 Oil B SSW × 2S 42.3
CS70-3 3.55 6.40 48.5 30.6 EF mod Oil B 25.4 90 30 70 Oil B SSW 28.3
CS70-4 3.51 5.80 48.6 27.2 EF mod Oil B 23.2 90 30 70 Oil B SSW-1/4S 17.5
CS70-5 3.53 6.05 48.9 28.9 EF mod Oil B 25.0 90 30 70 Oil B SSW-US 14.1
CS100-1 3.54 5.96 47.3 27.8 EF mod Oil A 23.3 90 28 100 Oil A SSW 49.8
CS100-2 3.54 5.91 49.4 28.7 EF mod Oil A 22.9 90 28 100 Oil A SSW × 3S 44.0
CS100-3 3.54 5.70 48.5 27.2 EF mod Oil A 22.9 90 28 100 Oil A SSW-1/2S 33.0
CS100-4 3.54 5.77 48.9 27.8 EF mod Oil A 22.6 90 28 100 Oil A SSW × 2S 26.8
CS100-5 3.54 5.52 48.6 26.4 EF mod Oil A 23.1 90 28 100 Oil A SSW × 4S 17.7
CS100-6 3.54 4.83 49.9 23.7 EF mod Oil A 24.6 90 28 100 Oil A SSW-US 9.2
CS3-1 3.48 6.34 48.3 29.1 EF mod Oil A 21.4 90 57 130 Oil A SSW × 4S 65.8
CS3-2 3.48 5.93 48.7 27.5 EF mod Oil A 22.9 90 57 130 Oil A SSW × 2S 64.1
CS3-3 3.48 5.95 47.8 27.1 EF mod Oil A 22.8 90 57 130 Oil A SSW 59.8
CS3-4 3.48 5.98 48.4 27.5 EF mod Oil A 23.0 90 57 130 Oil A SSW-1/2S 59.8
CS3-5 3.48 5.88 48.0 26.8 EF mod Oil A 23.1 90 57 130 Oil A SSW-US 44.4
CS3-8 3.48 4.87 49.2 22.8 EF mod Oil A 22.7 90 57 130 Oil A SSW × 2S 20.6
a Measured after the core was shaved and both ends were cut.

direction with a confining pressure of 25 bars outside the rub- outermost layer. The main core parameters are summarized in
ber sleeve. Then the cores were aged in a closed container at Table 4.
50 ◦ C for 5 days surrounded by the same oil. For cores with
initial water, EF or EF-mod, the dry cores were evacuated and 2.5. Spontaneous imbibition
saturated with brine under vacuum, and their porosities were
similarly calculated after the cores were rested in the brine for The spontaneous imbibition tests were performed at three
2 h. The cores were then placed in a Hassler core holder and different temperatures, i.e. at 70 ◦ C by using standard Amott
flooded with 1.5 PV of oil in each direction with a confining cells, at 100 and 130 ◦ C by using steel imbibition cells, Fig. 1.
pressure of 25 bars outside the rubber sleeve to obtain residual When the steel imbibition cells were used at 100 and 130 ◦ C, a
water saturation. Then the cores were aged in a closed container back-pressure of 10 bars was maintained during the test period
at 90 ◦ C for at least 4 weeks using the same oil. Prior to the imbi- in order to keep the fluids below the bubble points. Different
bition tests, the cores were shaved off about 2 mm for all surfaces brines with different sulfate content were used as imbibing fluids,
using a lathe in order to remove the adsorbed material on the Table 2.

Fig. 1. Schematic diagram of the high temperature imbibition test unit (1) heating oven, (2) steel imbibition cell (with a coning top and marble balls beneath the
core), (3) piston cell (imbibing fluid top and compressed nitrogen gas bottom) and (4) burette.
P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187 183

3. Results and discussion

The Ca2+ ion is a species belonging to the lattice system of the


chalk, and in that sense it is described as a potential determining
ion for the solid phase. Sulfate is, however, not part of the chalk
structure, but it has a strong tendency to adsorb onto the surface
in the Stern layer to modify the surface charge of chalk. The
wettability modification of chalk during a spontaneous imbi-
bition process is strongly linked to the nature of the surface
charge of chalk. Therefore, in the first part of this section, the
results from the zeta potential measurements will be presented,
and then spontaneous imbibition studies into chalk of various
wetting conditions are discussed in terms of sulfate concentra-
tion, temperature, and concentration ratio of the calcium/sulfate Fig. 3. Zeta potential measurements on a aqueous chalk suspension system
present in the imbibing fluids. At the end of the section, some (pH 8.4) by varying [SO4 2− ] (keeping [Ca2+ ] = 0.013 mol/l) or varying [Ca2+ ]
comments concerning the mechanism of the imbibition process (keeping [SO4 2− ] = 0.012 mol/l). Initially 4 wt.% milled chalk powders were
mixed with brine ZP at room temperature.
will be made accordingly.

3.1. Zeta potential measurements


initial water present in the reservoir, which usually has a very
In a colloid system, the zeta potential measures the difference high concentration of Ca2+ . It was therefore of interest to study
in the electrical charge between the dense layer of ions surround- the relative effect of the two ions on the zeta potential when
ing the particle and the charge of the bulk of the suspended fluid they are competing for the chalk surface in the same mixture. In
surrounding the particles. In line with the results by Pierre et al. Fig. 3, the zeta potential is plotted versus the concentration ratio
[16], both Ca2+ and SO4 2− are able to modify the surface charge [SO4 2− ]/[Ca2+ ] in a semi logarithmic way. The test was per-
of chalk particles when they were added to the chalk suspension, formed by keeping the concentration of one of the ions constant
Fig. 2. NaCl has been verified to act as an indifferent salt towards while varying the concentration of the other ion. It is noticed
CaCO3(s) [16], and the zeta potential of chalk becomes slightly that the zeta potential is close to 0 when the concentration ratio
negative, probably due to the basic nature of the solution, pH between SO4 2− and Ca2+ is about 1, and it is positive when Ca2+
8.4. Small amounts of Ca2+ increased the zeta potential dras- is in excess of SO4 2− and negative when SO4 2− is in excess of
tically, but later on, the positive charge of the chalk particles Ca2+ . Thus, the average charge on the chalk surface appeared
appeared to increase quite linearly with increase of the concen- to be dictated by the relative concentration of the two potential
tration of Ca2+ . The zeta potential appeared to decrease linearly determining ions. It is, however, not correct to conclude that the
with increase in sulfate concentration in the concentration range affinity of the two ions toward the chalk surface is equal. In order
of 0–0.1 mol/l. to evaluate the relative affinity of the Ca2+ and SO4 2− towards
In an actual reservoir flooding process using seawater, the two the chalk surface, the amount of chalk particles should be much
major potential determining ions present are Ca2+ and SO4 2− . lower to allow a stronger competition between the ions.
Even though, the concentration of SO4 2− in seawater is about Previously, we have studied the dynamics of the mutual
twice the concentration of Ca2+ , the injected fluid may mix with adsorption of SO4 2− and Ca2+ onto chalk cores by a chromato-
graphic method. A solution containing the two ions and SCN− as
tracer was flooded through a chalk core, and it was documented
that the adsorption of Ca2+ created stronger adsorption of SO4 2−
and vice versa [17,23]. Also at a given concentration of Ca2+ , it
was experimentally verified that the affinity of sulfate towards
the chalk surface increased as the temperature increased [23].
Thus, the potential of using sulfate as a wettability modifying
agent increases as the temperature increases.

3.2. Spontaneous imbibition studies

In order to get a reasonable variation in the oil displace-


ment at the selected temperatures, 70, 100 and 130 ◦ C, using
different concentrations of sulfate in the imbibing fluid, it was
decided to use two oils with different acid numbers, Oil A
Fig. 2. Zeta potential measurements on an aqueous chalk suspension system (AN = 2.07 mgKOH/g) and Oil B (AN = 0.55 mgKOH/g). It is
by adding SO4 2− or Ca2+ (pH 8.4). Initially 4 wt.% milled chalk powders were also known that the water wetness decreases as the AN of the
mixed with brine ZP. crude oil increases, and by experience, the imbibition of water
184 P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187

Fig. 5. Imbibition tests on chalk cores performed at 100 ◦ C using Oil A


Fig. 4. Imbibition tests on chalk cores at 70 ◦ C using Oil B (AN = 2.07 mgKOH/g) at various SO4 2− concentrations in the imbibing fluids
(AN = 0.55 mgKOH/g) at various SO4 2− concentrations in the imbibing ([Ca2+ ] = 0.013 mol/l) EF-mod was used as initial brine.
fluids. EF-mod was used as initial brine. ([Ca2+ ] = 0.013 mol/l).

with Oil B. The effect of increasing the temperature from 70 to


into chalk cores prepared with these oils is nearly negligible at 100 ◦ C did not compensate for the decrease in the water-wetting
room temperature without any sulfate present [15]. nature of the cores. It is also interesting to note that at 100 ◦ C, the
To avoid uncontrolled concentration effects for both of the oil recovery plateau after 30 days was only reached for the test
potential determining ions on the imbibition process, it was without sulfate present in the imbibing fluid. In fact, the plateau
decided to keep the concentration of Ca2+ constant. The ordi- slightly below 10% was reached within only 5 days.
nary Ekofisk formation water was modified by decreasing the At 130 ◦ C, Oil A was displaced much faster from the cores
concentration of Ca2+ to the level of that presented in the SSW, exposed to different imbibing fluids with different concentra-
i.e. [Ca2+ ] = 0.013 mol/l, termed EF-mod, Table 2. The ionic tion of sulfate compared to the corresponding tests performed
strength of the EF-mod was, however, maintained by adjust- at 100 ◦ C. Also the oil recovery was much higher. About 65%
ing the concentration of NaCl. The maximum concentration of of the oil was recovered using 4× and 2× SO4 2− compared
SO4 2− in the imbibing fluid was increased up to four times of to synthetic seawater, which is even somewhat higher than the
the concentration present in ordinary SSW, which is close to recovery obtained in previous studies using a cationic surfac-
the saturation limit of CaSO4 at 130 ◦ C, as calculated by the tant dissolved in SSW as wettability modifier [3,9]. It should be
method by Carlberg and Mattews [24]. Furthermore, there will noticed that capillary forced imbibition into a completely water-
be no concentration gradient of calcium between the initial brine wet chalk core using heptane as model oil usually resulted in
and the imbibing fluids. an oil recovery of 60–70% [14]. For the core imbibed by a fluid
The spontaneous imbibition results at 70 ◦ C using Oil B containing 1/2 × SO4 2− the plateau recovery was not reached
(AN = 0.55 mgKOH/g) are presented in Fig. 4. The imbibition within 10 days. In the other cases, the plateau oil recoveries
was followed for a period of 30 days, and the impact of sulfate were reached within 5 days or even earlier.
present in the imbibing fluid is obvious. Relative to SSW, the Since the cores used in the tests performed at 100 and 130 ◦ C
content of sulfate in the imbibing fluid varied 4×, 2×, 1/4× and were treated in the same way, i.e. the same Oil A and the same
0×. Without sulfate present, the oil recovery reached only 14%
after 30 days. The very fast oil recovery of about 7% at the start
has previously been explained to be due to some inhomogeneity
in the wetting conditions close to the core surface, which could
be related to the core preparation method [14]. Thus, taking also
into account the fluid expansion by increasing the temperature
from ambient to 70 ◦ C, the actual oil recovery from the core is
small. The oil recovery using 4× SO4 2− in the imbibing fluid
reached more than 50% after 30 days. Thus, both the ultimate
oil recovery and oil expulsion rate increased tremendously as
the concentration of sulfate increased.
Similar results were obtained for the imbibition tests per-
formed at 100 and 130 ◦ C using Oil A (AN = 2.07 mgKOH/g)
as illustrated by Figs. 5 and 6 respectively. It is noticed that the
oil recovery at 100 ◦ C, Fig. 5, for the respective imbibing flu-
ids is somewhat lower than the recovery at 70 ◦ C using Oil B. Fig. 6. Imbibition tests on chalk cores performed at 130 ◦ C using Oil A
The reason is that the AN of Oil A is much higher than the AN (AN = 2.07 mgKOH/g) at various SO4 2− concentrations in the imbibing fluids
of Oil B, and the cores become less oil-wet in the latter case ([Ca2+ ] = 0.013 mol/l) EF-mod was used as initial brine.
P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187 185

Fig. 8. Correlation between the oil recovery, SO4 2− /Ca2+ in imbibing fluids,
Fig. 7. Comparison of the effects of temperature on maximum imbibi- and temperature effects.
tion recovery for chalk cores when different imbibing fluids were used
([Ca2+ ] = 0.013 mol/l). Oil A (AN = 2.07 mgKOH/g) was used as oil phase.

Initially, carboxylic materials present in the crude oil adsorb


initial water were used, the initial wetting conditions should be onto the positively charged chalk surface because the initial
quite similar. The impact of oil recovery related to amount of brine contains high concentration of Ca2+ as the only potential
sulfate present in the imbibing fluid and the increase in temper- determining ion. The imbibing fluid, which was seawater, also
ature from 100 to 130 ◦ C is then compared. As illustrated by contained SO4 2− as potential determining ion at a concentra-
Fig. 7, it appears that the smaller ultimate oil recovery at 100 ◦ C tion about twice the concentration of Ca2+ . Due to adsorption of
compared to 130 ◦ C can partly be compensated by increasing sulfate onto the water-wet sites of the chalk surface, the surface
the amount of sulfate in the imbibing fluid. The ultimate recov- charge will be less positive or even negative, which will facili-
ery at 100 and 130 ◦ C, using an imbibing fluid with 4× SO4 2− , tate desorption of negatively charged carboxylic materials. The
became more identical compared to the other imbibing fluids. rock surface then becomes more water-wet, and positive capil-
It is, however, important to note that the oil recovery data were lary forces are created. Water is then imbibed spontaneously into
determined after 30 and 10 days for the tests performed at 100 the porous system, and oil is displaced in a so-called counter-
and 130 ◦ C, respectively. current fluid flow process. Initial brine will also be displaced
So far, it is well documented that sulfate present in the imbib- together with the oil [22].
ing fluid has a very positive effect to enhance oil recovery by The chemical mechanism for the suggested process is not
spontaneous imbibition of water into chalk cores which are close fully understood at this stage, but it is obvious that the effi-
to neutral wetting conditions. The concentration of calcium was ciency of the process is strongly related to the temperature. From
kept constant during the tests, [Ca2+ ] = 0.013 mol/l, both in the previous work, it was observed that the adsorption of SO4 2−
imbibing fluid and initial brine. According to the zeta potential onto chalk increased as the temperature increased [23]. The
measurements, the observed surface charge on chalk is related adsorption of SO4 2− increased more drastically as the temper-
to the concentration ratio between the two potential determining ature increased beyond 100 ◦ C, probably because of decrease
ions, i.e. SO4 2− /Ca2+ . The oil recoveries after 30 and 10 days in hydrogen bonding between sulfate and water. The sudden
for the tests at 100 and 130 ◦ C, respectively, were plotted against decrease in the solubility of CaSO4 as the temperature increases
the [SO4 2− ]/[Ca2+ ] ratio (Fig. 8). For the test at 100 ◦ C, the oil beyond 100 ◦ C is also reflected in the solubility properties of
recovery appeared to increase in a linear way as the concentra- SO4 2− [18]. At a given temperature, it was observed that the
tion ratio [SO4 2− ]/[Ca2+ ] increases. It also seems to be true for adsorption of SO4 2− increased as the concentration of Ca2+
the tests performed at 130 ◦ C when the recovery was below the increased [23]. Also at a given temperature, the observations
maximum plateau value of about 65%. It is interesting to note showed that the oil recovery increased as the SO4 2− /Ca2+ ratio
that the linear relationship is also valid at concentration ratios increased, which indicated that Ca2+ was also involved in the
[SO4 2− ]/[Ca2+ ] < 1, which indicates that Ca2+ may also be active wettability alteration process, Fig. 8. Further studies on the influ-
in the wettability alteration process. This will be studied in more ence of calcium and magnesium, which are both strong potential
detail in a later paper. determining ions, are in progress at our laboratory.
Important information about the fluid flow inside the core
3.3. Wettability alteration and fluid flow mechanism during a spontaneous imbibition process using surfactants has
previously been successfully obtained by just cleaving the core
The present study is part of a project with the objective to vertically [9]. In order to obtain good contrasts between con-
increase the chemical knowledge of wettability alteration in car- tacted and non-contacted areas, the core was prepared without
bonates. Based on the results from this study and previously initial water present. With reference to Fig. 9, the core was ini-
published work in this series, some statements can be suggested. tially saturated with Oil B and imbibed with SSW × 4S at 70 ◦ C.
186 P. Zhang, T. Austad / Colloids and Surfaces A: Physicochem. Eng. Aspects 279 (2006) 179–187

Acknowledgements

The authors acknowledge ConocoPhillips and the Ekofisk


Coventurers, including TOTAL, ENI, Hydro, Statoil and Petoro,
for financing the work and for the permission to publish this
paper from the research center COREC. Thanks also to the Nor-
wegian Research Council, NFR, for financial support, Statoil
for delivering the oil, and Senior Researcher D. Olsen at GEUS,
Copenhagen Denmark, for providing the chalk material.

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