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15
Microemulsion and Optimal
Formulation Occurrence in
pH-Dependent Systems as Found
in Alkaline-Enhanced Oil Recovery
HERCILIO RIVAS, XIOMARA GUTIRREZ, and JOS LUIS ZIRITT
INTEVEP, S.A., Research and Technological Support Center of Petrleos de
Venezuela, Caracas, Venezuela
RAQUEL E. ANTN and JEAN-LOUIS SALAGER Laboratorio FIRP,
Facultad de Ingeniera, Universidad de los Andes, Mrida, Venezuela
I.
Introduction
305
II.
306
III.
308
IV.
309
315
Field Application
320
References
324
V.
VI.
I. INTRODUCTION
Since the beginning of this century it has been well known that a relationship exists
between the interfacial tension at the crude oil-water interface in a given reservoir
and the percentage of oil recovered in a process of enhanced oil recovery (EOR).
The efficiency of the process increases as the interfacial tension decreases. A system
with an ultralow interfacial tension represents the ideal situation for achieving
maximum oil recovery.
305
306
Rivas et al.
Several studies have shown that it is possible to obtain very low interfacial
tensions in certain systems with crude oil/alkaline aqueous solutions [1-11]. The
values of interfacial tension depend very much on the pH and ionic strength of the
aqueous solution [12]. Riesberg and Doscher [7] suggested that the carboxylic acids
present in the crude oil can be neutralized by the addition of caustic solution,
producing carboxylate ions that have very high interfacial activity. This led to the
use of caustic solutions in enhanced oil recovery in a process known as alkaline
flooding.
In alkaline flooding, a caustic solution is injected into the reservoir to react with
the naturally occurring acids in the crude oil to produce an ionized form of the acid,
commonly called soap. Several mechanisms have been proposed to explain the
process of alkaline flooding; however, all of them include emulsification at the
reservoir and a change in the rock wettability.
In this work, we present the results of extensive research whose objectives are to
gain an understanding of the mechanism of reduction of the interfacial tension in oil
/acid/ alkaline solution systems, as well as the properties of the emulsions formed.
Therefore a series of phase behavior studies were conducted using model and real
systems. In some cases the results obtained are compared with those from the
literature.
II. ALKALINE FLOODING BASICS
Alkaline EOR processes are methods to be applied with crude oils containing acidic
substances, often carboxylic acids. When an alkaline aqueous solution is injected
into the reservoir, a surface-active mixture is produced in situ at the oil-water
interface by the saponification of the acids that are contained in the oil [1 - 11],
There is actually an equilibrium between the nondissociated acid and its (sodium)
salt, which will be referred to as a soap as a general term even though it is not
necessarily a fatty acid salt. This equilibrium is affected by the pH, the mass
inventory of acid in the different phases of the system, and the nature of the
substances.
In this situation the surface-active composition is a mixture of lipophilic species,
i.e., the nondissociated acids, and hydrophilic species, i.e., the ionized (sodium)
soaps. If the linear mixing rule of the hydrophilic lipophilic balance (HLB) is
assumed to hold (at least qualitatively), the characteristics of the surfactant mixture
depend not only on the acid/soap type but also on the relative amounts of acid and
soap, which, in turn, are directly linked to the pH.
A variation of pH may thus produce a variation of the HLB of the interfacial
surfactant mixture just as with the so-called formulation scans reported in the phase
307
308
Rivas et al.
The alkaline soaps can absorb on the rock surface [4] and result in a wettability
change (21, an effect that has been linked to a change in oil recovery, although not
necessarily an increase. In the present case the soap might probably turn an oil-wet
rock to a water-wet rock.
Interactions between the soaps and divalent cations can result in precipitation or
gel formation, which may also impair the recovery process.
Finally, it must be remembered that soaps are anionic surfactants, which are thus
sensitive to a change in salinity. As remarked by Antn and Salager [39], the
introduction of NaOH or alkaline salts produces an increase in metallic ions that can
affect the formation, whether or not the OH- ions play a role. On the other hand,
Qutubuddin et al. [40] were the first to bring evidence that adding NaOH to a
carboxylic acid/oil/water system first increased the hydrophilic tendency (because of
an increase in the proportion of soap with the pH), then turned back the tendency to
a less hydrophilic situation because of a dominant effect of the increase of ionic
strength on the anionic surfactant (soap).
As pointed by Rudin and Wasan [22], the current impression is that many studies
have been carried out by just adding some alkaline product, sometimes at a fixed
concentration, to see if the soap produced would lower the tension or facilitate the
emulsification, rather than exploring systematically the effect of the pH as a
formulation variable until an optimum formulation is reached at which the
concomitant occurrence of low tension plus rapid coalescence and low viscosity
converge to produce the desirable effect.
In the following this approach will be stressed, because it is believed to be the key
to the attainment of an efficient alkaline flooding process.
309
24
g (dyne/cm)
20
16
12
Aromatic Compounds
Saturated Compounds
8
4
Asphaltenes
Resins 1
Resins 2
pH
2
10
12
14
Alkaline EOR studies have been carried out with a variety of basic substances,
mainly sodium hydroxide, bicarbonate, carbonate, and silicate, as well as mixtures
[1-7, 22, 25-32, 35-38, 46-58].
Some reports focused on the attainment of low interfacial tension, whereas other
used the actual recovery as the goodness criterion. Some discussed different effects
able to faciitate the mobilization of trapped oil, such as spontaneous emulsification
or wettability change [2,36,37,59].
Because the change in pH is not in general a variable that can be manipulated up
to an optimum formulation (which is not sought after anyway in many cases), some
fine-tuning formulation adjustments can be carried out by adding pH-independent
surfactants (60) or by other means.
310
Rivas et al.
range; and the water phase contains NaOH. To increase the accuracy of the results,
the water phase also contains NaCl in such an amount that the total Na+ content, i.e.,
the salinity, can be kept constant when the pH is changed by changing the added
NaOH [44, 45, 61-64].
Because soaps are anionic surfactants, some alcohol is also added in systems with
high soap concentrations so that a microemulsion forms instead of a solid
mesophase, particularly in the high-solubilization cases near the optimum
formulation, In low-concentration systems alcohol is not necessary, but there is not
enough surfactant to form a three-phase system at the optimum formulation, the
occurrence of which is detected through the interfacial tension minimum.
The fundamentals concepts that are outlined here are discussed in detail in a
recent report [63], which makes use of the basic framework presented by Cratin [65]
some time ago.
Let AcH be the nondissociated acid and Ac-Na+ the corresponding soap species.
As may be remembered from the paper by Griffin [66] on HLB, carboxylic acids
(respectively soaps) have very low (respectively high) HLB numbers. Thus their
mixture can be hydrophilic or lipophilic (or indifferent, as at the optimum
formulation) depending on the relative amounts of each of them. Actually, it is more
correct to speak of surfactant affinity balance toward the oil and water, because the
nature of these phases, as well as the temperature, plays a role in the balance.
However, the discussion is based on the HLB for the sake of simplicity, and it is
assumed to deal with a given oil-brine pair at constant temperature.
In water, the acid is dissociated according to
AcH Ac- + H+
(1)
[Ac ][H ]
=
w
+
w
[AcH w ]
(2)
Keeping in mind that the relative amounts of acid and soap are linked with the
formulation, it is seen that the fraction
[Ac -w ] = K a
(3)
[ AcHw ] [H+ ]
depends on the pH. The higher the pH, the higher the ratio, and the more hydrophilic
the acid/ soap mixture, as seen from the HLB mixing rule written as a function of a,
the dissociated fraction:
HLBmixture = (1 a) HLBAcH + a HLBAc-
(4)
311
Note that since K. is typically 10-6-10-7, it is obvious that the soap exists in sizable
quantity only at high pH. The HLB that corresponds to the optimum formulation of
this particular system (oil/brine/temperature at unit water-to-oil ratio for the sake of
simplicity) is attained for some value of a, which depends of course on the acid
type, i.e., on HLBAcH and HLBAc- that can be estimated for instance from an
empirical relationship [63].
The previous reasoning is true only for the water phase; if there is an oil phase in
equilibrium with the water phase, some of the surfactant species can partition into
the oil phase. In the present case, it can be safety assumed that only the
nondissociated species AcH is able to do so [63,67], as indicated in Fig. 2.
The partition coefficient of the acid is defined [for a water-to-oil (WOR) ratio = 1
system] by
[AcH o ]
Pa =
(5)
[AcH w ]
As Pa is typically about 100, it is obvious that neglecting the nondissociated acid
that has partitioned into the oil phase can be a gross error of judgment.
Antn [63] demonstrated that for a pH scan produced by adding more and more
NaOH, the relationship between the pH and the overall acid dissociated fraction fi is
f
P
pH = -log10 [H + ] = log10 i + log10 a
1- fi
Ka
(6)
oil
water
fi =
[Ac ]
w
(7)
[AcH t ]
[AcH o ]
partitionning
[AcHw ]
dissociation
[Ac w ]
FIG. 2 Dual equilibria: partitioning of the nondissociated acid and acid dissociation
in the aqueous phase.
312
Rivas et al.
[AcHt] is the total acid originally in the system, supposed to be all in water or oil,
which is the same because it was assumed that WOR = 1.
If fn measures the amount of added NaOH with respect to the amount of acid
originally present in the system, that is,
[Na ]
+
fn =
(8)
[AcH t ]
[H ] - [OH ] = f
+
+
fi = fn
[AcH t ]
(9)
It is seen that they are essentially equal, except for very high or very low pH. A
straightforward calculation [63] from Eqs. 4 and 6 leads to the relationship between
the pH and the overall HLB of the system:
HLB - HLBAcH
1
1
= fi =
=
+
HLBAc- - HLBAcH
1+ (Pa /K a )[H ] 1+ 10 pH1/ 2 -pH
(10)
where pH1/2 is the pH at which half the original acid has been dissociated (fi = 0.5).
A pH-HLB plot of this relationship has a typical sigmoid shape with a buffered
(almost pH-independent) variation near pH1/2 Figure 3 shows that the intersection of
the HLB - pH curve and an horizontal line at optimum HLB (which is always near
C10
C8
C12
20
pH1/2
15
C14
C16
C18
pH*
HLB = 11
HLB
10
pH
10
11
12
FIG. 3 HLB-pH relationship in oil/water systems for different fatty acids. (From
Ref. 63.)
313
HLB = 10 - 11) makes it possible to define the optimum pH, symbolized pH*,
which occurs near pH1/2 located at the inflexion point.
This is true for different acids, each of them characterized by its pH* or pH1/2.
Note the linear variation of these characteristic pH values with the acid chain length
and the agreement between the two series of data.
Acid
pH1/2
pH*
C08
7.2
7.0
C10
8.0
7.9
C12
8.9
8.7
C14
9.5
9.6
C16
10.3
10.35
C18
11.0
11.15
When the system contains acid at a concentration exceeding the critical micelle
concentration (CMC) of the acid/soap, a three-phase system is exhibited at the
optimum formulation, provided that some alcohol, say 2% sec-butanol, is added to
dissolve the mesophases. It may be thought that the microemulsion middle phase
contains most of the surfactant species as in a typical anionic system [13]. This is
not the case, probably because the nondissociated acid fully behaves as an nonionic
surfactant that is able to fractionate into the oil phase [68]. Antn [63] has proposed
a very simple way to detect this partitioning without resorting to chemical analysis.
The volume of the microemulsion middle phase is plotted as a function of the
total amount of acid originally poured in the system. Because the water phase
concentration is roughly equal to the CMC, the surfactant inventory in the water
phase (QCMC) is essentially negligible. If it were the same with the oil phase the
microemulsion volume would be proportional to the total acid. Figure 4 shows that
the variation is linear but not proportional. However, it can be made proportional if
a certain amount (calculated by extrapolation at zero microemulsion volume) is
subtracted. This amount is AcHo, i.e., the acid that has partitioned into the oil phase,
which can be very important as in the data presented [67].
The influence of the formulation and the water/oil ratio on the phase behavior and
emulsion type and properties has been studied by plotting the result on a
bidimensional map, which has been found useful for comparison because it exhibits
the typical patterns of a very general phenomenon [69-73] whatever the formulation
variable [70,74]. Figure 5 shows the phase behavior and emulsion inversion line for
both a conventional surfactant [69] and an acid/soap system [64]. It is clear that the
phenomenology is identical, so that the pH can trigger exactly the same kind of
change for any formulation variable [61,62]. The high-pH region is associated with
314
Rivas et al.
(AcH t-ext ) =
(AcH) + QCMC
3
2
1
0
0
0,1
0,2
0,3
0,4
0,5
Amount of Acid (g) in the System (AcH t )
FIG. 4 Variation of the microemulsion middle-phase volume with the total amount
of acid originally introduced into the system. (From Ref. 67.)
2 wt.% MYRISTIC
ACID
4 wt % NaCl
2% n-PENTANOL
KEROSENE
+
B
2
3
3
A+
W/O
7
10
C+
2
A-
O/W
EMULSION pH
O/W
C
W/O
B-
2
2
O/W
2
O/W
0.4
0.6
0.8
315
phenomena found with hydrophilic surfactants, whereas in the low-pH region the
patterns exhibited by lipophilic surfactants occur. Note that the phenomenology
concerns not only the phase behavior but also the emulsified system type and
properties.
Acid/soap mixtures have also been associated with a conventional surfactant so
that the formulation adjustment can be shared. Similar results are attained
[22,45,60].
As a conclusion of this section, it must be stated that the general phenomenology
of these acid/soap-oil-water systems is qualitatively similar to that exhibited by
anionic surfactants, but with the extra fractionation feature found with low-ethylene
oxide number (EON) nonionic surfactant systems.
25
20
15
10
Spontaneous
Emulsification
3 4
9 10 11 12 13
pH
FIG. 6 Effect of pH on the interfacial tension for two Venezuelan heavy crude oils.
316
Rivas et al.
(11)
0.061
317
* 0 ppm NaCl
0.041
0.031
0.021
0.011
+ Spontaneous
* Emulsification
*
*
0.001
0.5 0.7 1 2
3 4
5 6
7 8
9 10 15
Sodium Carbonate Concentration (ppm) x (Thousands)
318
Rivas et al.
HAc
Interface HA + OH HAw
CO
OH -
H - + A+ (1)
H+ +
(aq) + H 2O
A - + Na
NaA
Precipitate (2)
A-
CO3 H
+ OH- (aq)
Aqueous Phase
phase more hydrophobic, promoting their diffusion and adsorption at the interface,
with a consequent decrease in the interfacial tension. A point is reached at which the
concentration of sodium carbonate (between 700 and 2000 ppm) is high enough to
give the optimum formulation for ultralow interfacial tensions. Under these
conditions, even when the pH remains constant, spontaneous emulsification is
observed. An increase in the sodium carbonate concentration causes a decrease in
number of carboxylate ions at the interface by shifting the equilibrium toward the
formation of an insoluble sodium carboxylate (ANa), and hence the interfacial
tension increases.
Figure 7 also shows the variation in the interfacial tension for the crude oil/water
system as a function of sodium carbonate concentration in the presence of 5000 ppm
NaCl. It can be seen that for any concentration of sodium carbonate, the interfacial
tension is higher in the presence than in the absence of NaCl. It is also demonstrated
that the region of spontaneous emulsification completely disappears in the presence
of NaCl. The same is shown in Fig. 9, where the sodium carbonate concentration is
kept constant while the NaCl concentration is increased. The increase in interfacial
tension with the NaCl concentration is evident.
It is therefore concluded that the optimum formulation in acids crude oil/alkaline
water systems, and in general the interfacial tension, is governed not only by the pH
319
0.06
1000
3000
5000
7000
10000
Sodium Chloride Concentration (ppm)
FIG. 9 Effect of sodium chloride concentration on the interfacial tension for the
heavy crude oil/water system containing 4000 ppm of sodium carbonate.
of the aqueous phase but also by the concentration of the cation of the alkalizing
agent (Na+ in this case), as both determine the fractions of ionized and unionized
acids, which are responsible for the HLB of the system [Eq. (4)].
Phase behavior studies carried out by increasing the concentration of sodium
carbonate in a system containing equal volumes of oil and water showed the
formation of a third phase (microemulsion) in a range of sodium carbonate
concentrations between 700 and 2000 ppm, which approximately coincides with the
zone of ultralow interfacial tension in Fig. 7. An increase in the stability of the
system and also in its viscosity is observed on either side of this concentration
range.
There is no doubt that by controlling the pH by using a buffer solution, a wide
range of electrolyte concentrations, for attaining ultralow interfacial tensions, can be
achieved.
It is also important to consider the effect of the cation present in the alkalizing
agent on the position of the optimum formulation. In Table 1 the ranges of
concentrations required to obtain spontaneous emulsification for the crude oil/water
system in the presence of different carbonates are shown. Lithium carbonate
requires the lowest concentration, followed by sodium carbonate, and the highest
one corresponds to potassium carbonate. This effect is associated with the cation
ionic radius and the solubility of the carboxylate ion formed. The smaller the ionic
radius, the lower the solubility of the carboxylate. Li+, with the smallest ionic radius,
320
Rivas et al.
500 - 600
900 - 1500
2000 - 4000
forms the most insoluble carboxylate, followed by Na+ and K+, respectively. This
property should be taken into consideration when selecting the conditions for an
alkaline flooding experiment.
It is evident from the results discussed and those in the literature [3,11,12] that the
chemical composition of both phases (crude oil and aqueous) has great important in
obtaining the low equilibrium interfacial tensions required for displacement in a
given reservoir. It is therefore important to study the effect of the alkaline agents in
the presence of different electrolyte solutions on the interfacial properties of crude
oil/water systems. We believe that this information is important for establishing the
correct conditions for the treatment of certain reservoirs by an alkaline flooding
process. Several experiments were conducted using different reagents, such as
sodium silicate, with results rather similar to those described above [75].
-4
10
10
A - {FOSTER}
B - {DU PREY}
-2
-3
10
10
-3
-2
CAPILARY NUMBER
10
10
-4
-1
10
10
-5
10
10
-6
10
10
-7
10
10
-8
10
10
-9
10
-1
321
10
20
30
40
10
50 60
reducing the interfacial tension on the order of 10-3 dyne/cm will yield capillary
numbers in the required range to achieve residual oil saturations near zero.
Figure 11 shows an example of how the residual oil saturation in a Berea
sandstone decreases when an alkaline solution of increased concentration is used to
displace Mene Grande crude oil contained in the porous medium. The Mene Grande
crude is a 16 API (American Petroleum Institute) oil with an acid number of 2.5 mg
KOH/g. Through phase behavior studies and interfacial tension measurements it was
determined that sodium silicate in this case promotes the ionization of the
carboxylic acids present in the crude oil, reducing the interfacial tension to ultralow
values.
The zone of spontaneous emulsification was found to be in the range of alkali
concentration in the aqueous phase between 1300 and 9000 ppm, in a 1:1
oil/alkaline solution system containing equal volumes of water and oil. Considering
the mixing, dispersion, and rock reaction effects in the porous medium, the low
322
Rivas et al.
60
50
40
Pressure: 3000 psi
Temperature: 70C
Average Porosity: 20%
Average Permeability: 143 mD
30
20
10
0
1000
2000
3000
4000
5000
6000
1.0
Pressure: 3000 psi
Temperature: 70 C
Porosity: 21.7%
Permeability: 138.9 mD
Swi: 15.0 %
Sor: 32.3 %
0.8
0.6
1.0
0.8
0.6
Kro
0.4
Kro -1-A
Krw -1-A
0.2
0.0
10
20
30
40
50
60
70
80
90
0.2
0.0
100
323
Berea sandstone. The residual oil saturation end point is 32.3%. The same
experiment was run using an 11,000 ppm sodium silicate solution as the imbition
fluid (Fig. 13). The sodium silicate solution, injected at a concentration high enough
to ensure interfacial tension values under 10-2 dyne/cm, changed the relative
permeability curves, moving the residual oil saturation end point to 6.2%. The
improvement in oil recovery or fluid displacement through porous media is caused
not only by the changes in the capillary number, as demonstrated before, but also by
the correction of heterogeneity of the porous medium.
Oil-in-water emulsions easily prepared from Midway Sunset crude oil and dilute
solutions of sodium hydroxide were used by McAuliffe [781 to study the flow of
emulsions through porous media. In experiments done with cores of different
permeabilities mounted in parallel, oil-in-water emulsions decreased the flow in the
higher permeability porous media and improved fluid distribution. Emulsion
systems are formed and are stable if sufficient emulsifying agent is present to orient
at the oil-water interface to form a film. During emulsion flow through porous
media, oil droplets tend to coalesce and grow due to surfactant loss. When the
droplets attain a size slightly larger than the pore throat, a higher pressure is required
to force the droplets through, creating a flow restriction.
In waterflooding processes in which water displaces oil, fingering develops
because of rock heterogeneity. When oil-in-water emulsions are injected or in situ
1.0
1.0
0.8
0.6
0.8
0.6
Kro
0.4
0.4
0.2
Kro
Krw
0.2
0.0
0
20
40
60
80
100
0.0
324
Rivas et al.
ACKNOWLEDGMENTS
The authors thank INTEVEP S.A. (Research and Technological Support, Center of
Petrleos de Venezuela) for allowing us to publish the information and Mr. Flix
Silva for his valuable collaboration in the preparation of the manuscript.
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326
Rivas et al.
327
328
Rivas et al.
329