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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
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.
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
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
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.
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