Otc 24470 MS
Otc 24470 MS
Abstract
Most rocks of carbonate reservoirs is preferably lipophilic, this feature of rock-fluid interaction, also known
as wettability and is closely linked at low oil recovery rates. The application of surface modifying agents is a way to
changing the wettability of carbonates, making them preferentially hydrophilic and thereby favoring the reduction of
residual oil saturation (Ros).
Actually reservoirs with heterogeneous permeability, which have regions of low permeability and presence
of fractures and high permeability channels, there is a tendency that the injection water to flow preferentially
through these channels with high permeability. This type of reservoir, the oil recovery process is improved by
capillary forces, spontaneous process known as imbibition, where water tends to soak the smaller pores, expelling
the oil to the larger pores. This phenomenon retard breakthrough and reducing the residual oil saturation (Ros).
However, spontaneous imbibition only occurs appreciably in water wet reservoir. In the oil wet formations, the
water has less affinity for the wall of the pores and the capillary forces are small and in many cases could be
negative.
The paper presents results of Enhanced Oil Recovery (EOR) Group from Cenpes/ Petrobras, evaluating
two anionics and one cationic surfactants, with different interfacial tension (IFT) and their ability to increase
hydrophilicity of carbonates. The results showed that the anionic surfactant with higher IFT values was responsible
for increased to make the carbonate preferably hydrophilic, keeping in high values the capillary pressure.
The results were demonstrated by the core flow tests, which showed higher oil relative permeability and
Ros reduction; spontaneous imbibition test, presents higher oil recovery and contact angle evaluated, which
showed lower adhesion of the oil phase on the surface of carbonate.
The agent wettability modifying can be applied as a chemical method of EOR, as well as around the
producing well. In this last one, could be created convergence zones for oil and be increased the effective oil
permeability near the oil production well.
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Introduction
The oil reservoir carbonates, due to its complex diagenesis, exhibit peculiar characteristics when
compared to the sandstone reservoirs. The intense lithological transformations suffered by the carbonates are
inherent to their high reactivity, which results in atypical petrophysical features, this features may be caused by the
water originated from the formation and/or meteorical waters (underground water originated by rain), which
solubilize and recrystallizes in new carbonates, in order to keep the chemical equilibrium of the ions in the
reservoir. These mechanisms can create high permeability channels (super K) or cementing in the porous spaces.
Another component which alters the morphology of reservoirs is the stress caused by continuous overlaying of
land during your diagenesis, commonly seen in ultra deep reservoirs such as the Pre-Salt reservoir, which is
capable of significantly altering the porous medium of the reservoir through the reduction of the porosity or
fracturing.
Wettability is notoriously know as yet another factor which influences the behavior of reservoir fluids
(water/oil/gas) and is closely linked to the recovery rates of an oil reservoir, due to the influence of wettability in the
distribution and in the flow of fluids presents. Wettability is defined in petroleum industry as the tendency of a fluid
of adhering to the surface of a solid material when in the presence of another immiscible fluid (AGBALAKA et al.,
c2008). In oil-wet (OW) reservoirs, generally, it is observed a reduction of the relative permeability and leads to
higher values of residual oil saturation (Ros), when compared to preferably water-wet (WW) reservoirs
(STANDNES and AUSTAD, c2000). This phenomenon occurs because the arrangement of the fluids in lipophilic
rocks is organized with the oil phase occupying the smaller pores and covering the walls of the bigger pores,
resulting in negative capillary pressures
The capillary forces is very important for to the oil recovery process in matrixes which have preferential
channels or fractures, seeing that the injection water can only recover oil through those high permeability regions.
However, in cases in which a rock is WW, as soon as the capillary pressure in the pores becomes positive, water
can penetrate the small pores, thereby expelling the oil to the bigger pores and afterwards towards preferable
channels to the production well.
The lipophilic or hydrophilic feature of a reservoir depends upon a series of factors, some of them being
the composition of the rock (sandstone or carbonates) (CHILINGAR and YEN, c1983), the presence of
heteroatoms in the composition of the oil, such as oxygen, sulfur and nitrogen (asphaltenes, resins and
thiophenes) (Mc GEE et al, c1985), the pH of the reservoir, as well as the composition of water in the formation
(TREIBER et al, c1972).
The injection of surfactants with the intention of making the rock in the reservoir preferably hydrophilic is a
widely studied chemical EOR method. The modification of the wettability by surfactants can be differentiated by
some types of mechanisms, including the adsorption of the surfactant in the surface of the rock. In this case, the
modification of the wettability depends not only on the capability of the surfactant of being adsorbed in the surface
but also on the molecular structure (hydrophilic lipophilic balance) and the orientation in which it processes the
adsorption, i.e., whether from the polar or nonpolar part of the surfactant (SOMASUNDARAM, c2006). Another
hydrofilization mechanism is the formation of ionic pairs from the oil surfactant agents, which has be responsible
for increasing the lipophilic feature of the reservoir rock (STANDNES and AUSTAD, c2000).
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Experiments
In all tests were used carbonate outcrop sample, the plugs were previously cleaned in a toluene and
methanol flow, after dried in a laboratory oven. The products tested were diluted with synthetic sea water (Table 1).
Table 1. Chemical composition of the synthetic seawater used in this work.
Ion
Sodium
Potassium
(Na )
11000
(K )
395
2+
670
2+
255
2+
0.2
2+
2+
(Fe )
0.15
Chloride
(Cl-)
19600
Bromide
(Br-)
64
Magnesium
(Mg )
Calcium
(Ca )
Barium
(Ba )
Strontium
(Sr )
Iron
2-
Sulfate
(SO4 )
Bicarbonate
(HCO3 )
Acetate
106
42
-
(CH3COO )
6.65
32297
The spinning drop method consists in the insertion of a drop of a liquid on another immiscible liquid, which
is located in a capillary. The capillary spins around its axis at a constant speed, deforming the drop under the effect
of centrifugal acceleration. This deformation results from the IFT between the fluids, which is related to the density
of the liquids present, temperature and rotation of the system. (Equation 1) (COUPER et al., c1983).
The interfacial tension is expressed in the International System of Units, in mN/m. This unit indicates that
the interfacial tension of water, for example, is equivalent to the free energy per area unit in the frontier between
water and the other fluid.
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EWM-11 anionic surfactant, developed at Cenpes/ Petrobras by the EOR and the Elevation and
CARBONATE
WETTABILITY INVERSION
ROCK
WETTED
BY OIL /
ROCK
WETTED
BY WATER
Figure 1. Imbibition cell (Amott). Adapted from the Petrobras, COMEP 2010 institutional video.
The products were diluted in sea water at 0.5 wt% (5000ppm). The imbibition cells were stored in an oven
at 60C for 35 days, and the volume of oil produced was periodically recorded. The choice of the commercial
surfactants for this study was based on the studies of Standnes and Austad (c2000), and the cationic and anionic
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products were selected due to its features, which presented the best performance in imbibition tests. The studies
showed a direct relationship between the efficiency of the anionic surfactant during imbibition and its degree of
ethoxylation (STANDNES and AUSTAD, c2000). The surfactants were compared with an EWM-11 surfactant,
which has a relatively low capability of reducing the interfacial tension (IFT), as seen further below.
Contact angle
The measurement of the contact angle is a quantitative method used to determine the wettability degree
according to the contact angle (), is resulting from the balance between the interfacial tensions of the fluids
involved (oil and water) and the solid surface (GOLABI, c2009) (KSHITIJ, c2009). The contact angle can be easily
interpreted when the surface is smooth, but a very rough surface may lead to a misinterpretation of the contact
angle, also known as the apparent contact angle, which can be different from the actual contact angle (ABDALLAH
et al., c2007). However, this type of deviation is only relevant when the compared contact angles are very similar.
During the imbibition process, some differences in the contact angle between the decane and the
carbonate surface in the cells A0 and A1, both immersed in sea water and A3 immersed in at EWM-11, could be
observed (Table 3).
This contact angle variation was influenced by the pre-treatment intended for enhancing the lipophilicity of
the carbonate, as well as for the contact with the products evaluated in the spontaneous imbibition tests.
The effects of wettability on relative permeability
The aim of the test is to evaluate the capacity of the EWM-11 product in modifying the wettability of the
carbonate through the values of the terminal saturation points (Swi and Sor) and the oil and water relative
permeability.
In summary, ion oil-wet rocks, expected the higher permeability to water in the residual oil saturation
(Krw@Sor) than in water wet rocks. In a preferably hydrophilic porous medium, water will also permeate through
the smaller and consequently less permeable pores, the inverse behavior occurs when the relative permeability to
oil is measured in WW rocks, thereby the oil flowed through the bigger pores, showing better permeabilities
(GOLABI et al, c2009) (ANDERSON, c1987b).
In this assays were compared three carbonate outcrop plugs with similar petrophysical properties. These
properties were previously measured in the basic petrophysical parameters for reservoir characterization (porosity,
absolute permeability and porous volume) (Table 3). After that, two of these plugs (M11 and M12) did not contact
any surface agent and the M13 plug was pre-treated in flow, recirculating 4 porous volumes (VPs) of the EWM-11
product in solution at a 3000ppm concentration for 3 days at a 0.025cc/min flow rate. This way, about 5 porous
volumes were recycled by the sample every 24h. The system was placed in an oven at 70C during the test (Figure
2).
After this stage the same procedure below was used for the relative permeability evaluation for all 3 plugs.
This procedure consisted of: saturating the plugs with synthetic seawater; confining the plugs in a holder at 2000
psi; water flow and measure absolute water permeability (Kw); injection of white mineral oil ( = 4,5cP) to take the
sample to Swi, to obtain the oil relative permeability (Kro@Swi) and finally the injection of water to obtain Ros and
Krw@Ros.
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The absolute permeability to water must show values close to the absolute permeability to gas, thereby
ratifying the efficiency in the saturation. Discrepancies between these permeability values may help detect the
presence of internal air within the pores.
2 cos
The IFT of different products was measured with the use of decane as an oil phase. The EWM-11 cause a
small reduction in the IFT (26mN/m), when compared to the tension between the pure seawater and the decane
(32mN/m).
The IFT value presented by the EWM-11 surfactant was significantly high when compared to
commercial surfactants L(10EO)P and DTAB, which reduced the interfacial tension to 3 and 4 mN/m respectively
(Table 2) (Figure 3).
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25 C
30 C
40 C
50 C
60 C
Brine
35.0
35.0
35.0
33.0
32.0
29.0
29.0
29.0
27.0
26.0
4.5
4.5
3.0
3.0
3.0
5.2
5.5
4.0
4.0
4.0
and 2.2% respectively, both immersed in pure seawater, it is observed a discrepancy in the recovery factors due to
such distinct wettabilities (Figure 4). As expected, the imbibition occurred much less intensely in plug A1, treated
with NA, thereby ratifying the efficiency of the treatment in increasing the lipophilicity of rocks.
Plug A0, benchmark sample, was not in contact with NA, and represented the degree of oil wettability
equivalent to the original of the studied samples. Therefore, one may assumed that the pre-treated rocks with NA
(A1, A2, A3 and A4), when attaining an imbibition value close to 34.5% after being immersed in surfactants, it
would be as if the rock had returned to its original wettability.
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The anionic surfactants can act as wettability modifier through the adsorption of the lipophilic grouping
(nonpolar) at the surface of the MO rock (lipophilic), exposing the hydrophilic part (polar) of the surfactant, thereby
reducing the interaction between the oil (nonpolar) and the surface of the rock (CHEN et al., c2000) (VARADARAJ
et al, c1994). The adsorption may occur too with the formation of more than double-layer at the surface.
Furthermore, the anionic surfactants act by strongly reducing the IFT and favoring the formation of smaller oil
droplets, thereby increasing the mobility of oil in the reservoir (SEETHEPALLI et al, c2004).
Saturation index
Saturated weigth
9.73
174.99
9.29
95.45
A1
3.801
6.786
170.84
4.15
9.58
177.43
9.03
94.21
A2
3.787
6.554
172.62
4.05
10.30
179.46
9.37
91.00
A3
3.797
6.466
168.16
3.97
10.36
175.20
9.64
93.11
A4
3.792
6.378
168.19
4.50
9.66
174.75
8.99
93.03
(%)
3.83
PV W* (cm)
168.21
(g)
Weight (g)
6.480
(cm)
Length (cm)
3.802
Pore volume
Diameter (cm)
A0
Absolute
Core
permeability (mD)
Table 3. Basic petrophysical properties: Samples A0, A1, A2, A3 and A4.
* PVW, pore volume by weight, difference between the saturated weight and the dry plug weight, divided by the density of the fluid used in the
saturation.
A negative aspect of this mechanism would be the formation of more stable emulsions between water and
oil, which would demand the insertion of specific demulsifying in the water/oil separation basins. Besides, the
formation of emulsions are generally very viscous and undesirable in the vicinities of the injector well (FAROUQ
and COLOMONT, c1977).
When comparing the oil recovery between the anionic surfactants EWM-11 (IFT= 26mN/m) and L(10EO)P
(IFT= 3mN/m), 22.8% and 5.3%, respectively, one may assume that the low IFT value of the product L(10EO)P
was a factor which hindered the imbibing process, since a low IFT causes a reduction in the capillary pressure of
the porous medium. Such effect is especially stronger for the low permeabilities plugs, whose absolute
permeability to gas are close to 4 mD (Table 3), a low permeability is a scenario in which prevails the oil recovery
mechanism through capillary forces over gravitational forces (GRUPTA et al, c2008).
For a cationic surfactant such as DTAB, the inversion mechanism is processed through the desorption of
the surface agents present in the oil which make the carbonate oil wet, followed by the formation an elestrostatic
bond (ion-pair) between the surface agent in the oil and the cationic surfactant. Carboxylates (RCOO-) are the
examples of surface agent composites present in oil and often present in the molecular structures of asphaltenes
and resins.(STANDNES and AUSTAD et. al c2000).
Among the products evaluated, the surfactants DTAB and L(10EO)P showed the major decrease of IFT,
but presented different values of imbibitions. This behavior reveals that only the reduction of IFT is not enough to
increase the imbibitions process and reveals the importance in the kind of mechanism wettability inversion in oil
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recovery, this mechanism is the predominant factor for enhanced oil recovery, when capillary forces are reduced
by reducing the IFT.
With the comparison of the imbibitions process of the cationic product DTAB (IFT= 4mN/m) and the anionic
product EWM-11 (IFT= 26mN/m), with IFT distinct, similar recovery values at the end of the 35
observed. However, up to the 22
nd
th
day can be
day, the chart presents higher imbibed volume for product EWM-11. This
behavior suggests that the different mechanisms between anionics and cationics surfactants result in a higher
imbibing velocity for EWM-11 and consequently a higher wettability inversion time rate for the carbonate, this
behavior it was noticed by Milter and Austad (c1996a).
10
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Figure 5. Decane droplets in the surface of plug A0 (original wettability), immerse in synthetic seawater.
Figure 6. Decane drop on the surface of plug A1 (pre-treated with naphtenic acid), immersed in synthetic seawater.
Figure 7. Decane droplets on the surface of plug A3 (pre-treated with naphtenic acid) and immersed in EWM-11
solution (0.5%).
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11
Saturation Index
Weight (VPP) cm
Saturated weight
4.97
8.78
128.55
8.44
96.13
M12
3.79
4.68
122.03
2.56
8.11
129.59
7.38
91.03
M13
3.79
4.75
121.15
4.44
8.08
129.10
7.79
96.41
(%)
119.94
(g)
4.71
(cm)
Sample Weight
Porous Volume
Length (cm)
3.78
Absolute
Diameter (cm)
M11
(g)
Core
Permeability (mD)
The modification of the wettability in plug M13, caused by the treatment with EWM-11, reflected in the
values of the terminal saturation points (Swi and Ros) (Table 5). Plugs M11 and M12 presented 28.4% and 38.2% of
Swi respectively. An M13 sample presented a higher Swi value (48.6%). The explanation for that can the increase in
water wettability after the treatment with the EWM-11 product. This WW feature increased the capillary pressure of
the system, as the water, as a wetting fluid, started to imbibe the smaller pores which were, until then,
inaccessible, thereby increasing the Swi value.
Table 5. Relative permeability results and terminal points of saturation (Swi and Ros) of samples M11, M12 and M13.
M11
K (mD)
Kr %
Kg
4.5
100.0
Kw
3.0
66.7
2.6
56.7
0.7
15.6
M12
K (mD)
Kr %
Kg
2.56
100.0
Kw
1.90
74.2
1.56
61.1
0.25
9.7
M13
K (mD)
Kr %
Kg
4.44
100.0
Kw - 1
2.70
60.81
1.7
38.3
3.8
85.1
0.3
7.1
The reduction in the residual oil saturation (Ros) value was another consequence of the increase of
hydrophilicity of plug M13. When compared to plugs M11 and M12, which obtained Ros s similar to 35.5% and
37.95% respectively, plug M13 presented an Ros of 16.7%, a reduction of nearly 50% in the rocks capability of
retaining oil during the injection of water (Table 5).
12
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Conclusions
Evaluation of outcrop carbonates with low permeability:
The anionic surfactant EWM-11 was effective in increasing the hydrophilicity of the carbonate and
enhanced oil recovery without significantly reducing the IFT.
Evaluating the anionics surfactant EWM-11 and L(10EO)P, the product EWM-11 has higher IFT, keeping
capillary pressure high of the porous medium, had enhanced recovery of oil.
The DTAB (cationic) and L(10EO)P (anionic) show similar behavior in relation to IFT change, but showed
different results for oil recovery. Notes that only reduced IFT (for values presented), does not explain the high
levels of oil recovery.
Products EWM-11 and DTAB, both were efficient in reversing the wettability of carbonate, however acting
through distinct mechanisms. The EWM-11 has higher IFT and showed higher velocity for oil recovery by
spontaneous imbibitions process.
The contact with product EWM-11 increases the hydrophilicity of the carbonate surface, reflecting in
increment of the Swi and Ros, as well the relative permeability to oil.
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