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Abstract

Because the world demand for energy is expected to continue growing, exploration is turning to deeper and high-temperature
reservoirs. Such reservoirs include fields with high bottomhole static temperatures (BHSTs), such as the Ursa (250F) and
Thunder Horse (280F) in Gulf of Mexico (GOM). Acid stimulation of such reservoirs at high temperature is a challenging
task. Emulsified acid systems are expected to perform better in reservoirs with BHSTs ranging from 275 to 375F compared to
nonretarded acids and gelled acid systems. However, fluid stability and the inhibition of corrosion are major challenges to
overcome for successful implementation of this technology. Emulsion instability and the corrosion rate are interrelated, and
both increase with higher temperature. Also, fluid stability decreases as a result of corrosion of the metal surfaces. At the same
time, an excessive addition of corrosion inhibitor destabilizes the fluid system. Hence, the proper selection and balance
between the corrosion inhibitor and emulsifiers are required. Three different types of corrosion inhibitors were evaluated, and
an emulsified system was designed with proper optimization of various ingredients, including corrosion inhibitor, an
intensifier, and a cationic emulsifier. The system was tested for stability and corrosion loss with static corrosion test using P-
110 coupons. After reviewing the literature, it is believed that this emulsified system is the only one to pass static corrosion
tests at 275F for 4 hr and remain stable at 300F for 2 hr with 28% acid strength. This enables the acid stimulation of
carbonate reservoirs having BHSTs up to 300F while reducing the corrosion rate. As per the study, the effect of the intensifier
was different to that found in plain acid, suggesting possible interactions of the additives with the emulsifier. Because fluid
stability and the rate of corrosion are interrelated, they should be evaluated together, especially for designing emulsified acid
systems for stimulation of very high-temperature carbonate reservoirs.

Introduction
Acid is predominantly used to remove damage near the wellbore and to stimulate the well, which in turn improves the rate of
hydrocarbon production (Sayed et al. 2012). In a carbonate reservoir, acid is mainly used to create linear flow for acid
fracturing and to create wormholes. An emulsified acid is mainly used for matrix acidizing because it lowers the diffusion rate
by two orders of magnitude. The first reduces the acid transfer rate, caused by an increase in the viscosity of the fluid. The
second disperses the acid phase into the oil, which results in a slow reaction when it contacts the carbonate reservoir (Buijse
and Vandolmen 1998). When using emulsified acid, the inhibitor components adsorb to the metal surface and can undergo
polymeric-type film forming on the metal surface because of reactions initiated by the hydrogen radicals (Navarrete et al.
2000). The corrosion inhibitor system is selected based on the metallurgy, acid type, acid concentration, temperature, and the
exposure time. Most corrosion inhibitors are organic compounds containing nitrogen, sulphur, and oxygen and are selected
based on the desired application temperature range (Rostami and Nasr-El-Din 2009). It is observed that a higher dosage of
corrosion inhibitor leads to destabilization of the emulsified acid system (Hill and J ones 2003). Even at high temperatures,
emulsified acid becomes destabilized because of the release of corrosion products (Fe
+2
, etc.). The unstable emulsion then
behaves as a plain acid (Sabhapondit et al. 2012). Hence, the proper corrosion inhibitor system should be selected carefully for
an emulsified acid system. The inhibition action is dependent on various factors, such as solubility in acid. If the solubility is
very low, then the acid phase cannot carry the corrosion inhibitor to the target location under downhole conditions. If the
solubility is too high, then adsorption of the corrosion inhibitor might not occur on the metal surface. Both of these conditions
lead to high corrosion losses. Mutual solvents, as well as the ionic nature of the surfactant used to provide chemical
compatibility, can also over-solubilize the corrosion inhibitor, which leads to excessive corrosion. As a result, corrosion tests
are conducted to identify any performance issues related to other chemicals added into the emulsified acids (Pandya et al.

IPTC 16452
A Novel Emulsified Acid System for Stimulation of Very High-Temperature
Carbonate Reservoirs
Nisha Pandya and Sushant Wadekar, Halliburton
Copyright 2013, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Beijing, China, 2628 March 2013.

This paper was selected for presentation by an IPTC Programme Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the International Petroleum Technology Conference and are subject to correction by the author(s). The material, as presented, does not necessarily
reflect any position of the International Petroleum Technology Conference, its officers, or members. Papers presented at IPTC are subject to publication review by Sponsor Society
Committees of IPTC. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the International Petroleum Technology
Conference is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous
acknowledgment of where and by whom the paper was presented. Write Librarian, IPTC, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax +1-972-952-9435


2 IPTC 16452
2012). The corrosion inhibitor and corrosion inhibitor intensifiers both can affect the stability of the emulsion. Hence, every
component present in the system should be selected on the basis of its effect on the stability of the emulsion.
In this paper, an emulsified acid was tested using three different corrosion inhibitors, along with an intensifier, for high-
temperature applications from 275 to 300F with 26 to 28% acid strength. It was observed that the optimum concentration of
corrosion inhibitor was required to pass the stability test as well as the corrosion test using P-110 alloy. High amounts of
corrosion inhibitor destabilize the emulsion, leading to high corrosion losses. Stability testing was performed in a high-
pressure/high-temperature (HP/HT) visual autoclave by varying the concentration of inhibitor and emulsifier. Each corrosion
inhibitor was investigated to find its temperature limit based on standard corrosion testing and the stability of the emulsion
after the testing.

Methods and Materials

Materials. HCl acid (35% acid strength) was used to make the acid blends. It was diluted with water as per the test
requirements. Diesel without any additives was used to make the emulsion. Three corrosion inhibitors (I-G, I-N, and I-C) were
used in this study. Corrosion inhibitor I-C was a formulated product based on a quaternary ammonium salt. A cationic blend of
emulsifiers was used for all tests. Various types of corrosion inhibitor intensifiers (IN-O and IN-H) were also used in the
study. These intensifiers are known to enhance the action of corrosion inhibitors.

Preparation of Emulsified Acid System. A total of 200 mL of emulsion with an acid-to-diesel phase ratio of 70:30 (v/v) was
prepared. The aqueous acid phase was prepared by mixing the required amount of water, corrosion inhibitors (I-G, I-N, and I-
C), and intensifiers (IN-O and IN-H), followed by the addition of HCl acid. The emulsifier was mixed separately with diesel in
a Waring

blender, which used a Variac transformer for speed control. The aqueous acid phase was added dropwise to this
mixture with continuous stirring. Once the addition was completed, the blend was mixed for 5 min, keeping the Variac
transformer at 70%, and then stored at room temperature. The emulsion was tested by pouring a few drops in water to see if it
spread or sank. Droplets that sank without spreading were considered an indication of an invert (water-in-oil) emulsion. The
stable invert emulsions were further tested using static HP/HT corrosion tests.

Static HP/HT Corrosion Test of Emulsified Acid System. The prepared emulsion was tested at high temperatures in an
HP/HT autoclave using P-110 or N-80 coupons. The coupons used were cut from oilfield pipe and had approximately 4.4-in.
2
surface areas. The metal coupon was prepared by degreasing it with acetone and bead-blasting and washing it with water and
acetone in sequence. The preweighed metal coupon was suspended in the glass cell using Teflon

tape. The glass cell was


filled with the test emulsion and covered with a glass cap. The glass cell was inserted into a small Hastelloy B-2 autoclave,
along with mineral oil as a heat-transfer medium. The autoclave was pressurized to 1,000 psi with nitrogen. The pressure was
maintained using a backpressure regulator assembly, which allowed for automatic bleed off of excess pressure that develops
during heating and release of corrosion products. The autoclave was heated in a heating jacket, and the temperature of the test
emulsion was regulated using Eurotherm controllers. The total test time included the 75 min of heat-up time and 15 min of
cool-down time.
After the test, the suspended coupon was removed and washed with a soft brush using mild abrasive cleaning powder and
then acetone. The dried coupon was weighed again; corrosion weight loss is expressed in lbm/ft
2
as ratio of weight loss to the
total surface area of the coupon. The emulsion was then carefully transferred to a graduated cylinder and allowed to settle for
10 to 15 min to test the fluid emulsion stability. Fig. 1 illustrates a stable emulsion (a) and two types of destabilized emulsions
(b and c).

Static HP/HT See-Through Autoclave (STA). An HP/HT STA was used for heating emulsified acid systems under a
nitrogen (N
2
) atmosphere. The test fluid was transferred to an HP/HT graduated cylinder, which was placed in the HP/HT
STA. The pressure was then increased to 1,000 psi with N
2
gas and the cell was heated with the surrounding electrical heating
tape. The heaters were switched off before 0.5 hr of the scheduled test duration and the test cell was cooled down to room
temperature. A flashlight was used from behind the quartz window to visually inspect for any separation of water at the
bottom. Once the test was over, the cell was cooled down, depressurized, and the graduated cylinder was taken out.
Appearances of the blends were recorded.

IPTC 16452 3


(a) (b) (c)

Fig. 1(a) Stable emulsion, (b) bottom water separation (destabilized emulsion), and (c) bottom water and top oil separation
(destabilized emulsion).

Results and Discussion

Comparative Study of I-G, I-N, and I-C. Emulsion stability testing was carried out in an HP/HT visual cell using three
different corrosion inhibitors (I-G, I-N, and I-C) at 275F for 3 hr. The effect the concentration of these corrosion inhibitors
had on the stability of the emulsified acid is shown in Table 1. The experimental data indicated that higher dosages (20
gal/1,000 gal and above) of corrosion inhibitors decrease the stability of the emulsified acid system for high-temperature
applications. The destabilization of the emulsion by I-N and I-C was found to be lower than I-G. These corrosion inhibitors
contain various solvents (e.g., methanol, isopropanol) as well as surfactants that solubilize the water-insoluble materials, such
as cinnamaldehyde, benzaldehyde, etc. The surfactants interfere with the emulsifier action by shifting the overall HLB value of
the system from the required set value.

TABLE 1CEA TEST RESULTS OF 28% HCl EMULSIFIED ACID IN STA AT 275F
AND 1,000 PSI (IN ABSENCE OF ALLOY SPECIMEN):
EFFECT OF DIFFERENT INHIBITORS
Sr.
No.
Time,
hr
Emulsifier,
gal/1,000 gal Corrosion Inhibitor Emulsion Stability
1 3 10 Nil Stable
2 3 10 I-G (10 gal/1,000 gal) Unstable
3 3 10 I-C (10 gal/1,000 gal) Stable
4 3 10 I-N (10 gal/1,000 gal) Stable
5 3 10 I-C (20 gal/1,000 gal) Unstable
6 3 10 I-N (20 gal/1,000 gal) Unstable
7 3 10 Methanol (3.5 gal/1,000 gal) Unstable


Effect of I-G on the Emulsified Acid System. The effect of the concentration of I-G on the stability of the emulsified acid
system at 275F is shown in Table 2. The test data indicated that higher concentration (25 gal/1,000 gal) of emulsifier is
required to stabilize the emulsified acid system containing 10 gal/1,000 gal of I-G. This indicates that the components present
in I-G also absorbed at the interface between diesel and acid. These components compete with the emulsifiers for absorption at
the interface. At lower concentrations of emulsifier, a weak interfacial film formed as a result of the increased proportion of
the components of I-G at the interface. At higher concentrations of emulsifier, a stable interfacial film formed as a result of a
sufficient amount of surfactants present at the interface. The stability of the emulsified acid system was also affected by the
use of additional corrosion inhibitor intensifiers IN-O and IN-H. These intensifiers are charged molecular species that interfere
in the action of cationic emulsifiers. I-G can be used up to 250F with acceptable corrosion loss (Table 3). The use of
additional corrosion inhibitor intensifier did not result in further improvement. I-G cannot be used at 275F because of
instability of the emulsion.

4 IPTC 16452
TABLE 2TESTS IN STA WITHOUT COUPON AT 275F WITH I-G
Sr.
No.
Time,
hr
I-G,
gal/1,000 gal
IN-H,
lbm/1,000 gal
IN-O,
gal/1,000 gal
Emulsifier,
gal/1,000 gal Emulsion Stability
1 3 10 0 0 10 Unstable
2 3 10 0 0 20 Unstable
3 3 10 0 0 25 Stable
4 6 10 0 0 25 Unstable
5 3 10 10 40 25 Unstable


TABLE 3EFFECT OF TEMPERATURE ON EMULSION STABILITY AND CORROSION LOSS FOR P110 ALLOY IN
PRESENCE OF I-G IN EMULSIFIED 28% HCl ACID
Sr.
No.
Temp.,
F
Time,
hr
I-G,
gal/1,000 gal
IN-H,
lbm/1,000 gal
IN-O,
gal/1,000 gal
Emulsifier,
gal/1,000 gal
Corrosion Loss,
lbm/ft
2

Emulsion
Stability
1 250 3 10 25 0.037 Stable
2 250 4 10 25 0.23 Unstable
3 250 4 10 5 40 25 0.11 Unstable
4 250 4 20 5 40 20 0.1 Unstable
5 275 3 8 5 40 12 0.406 Unstable
6 275 4 8 5 40 12 0.5785 Unstable
7 275 3 8 5 40 20 0.9 Unstable
8 275 3 8 5 40 20 No coupon Unstable
9 275 3 10 5 40 25 0.321 Unstable


Effect of I-N on the Emulsified Acid System. The stability of the emulsified acid system and corrosion are interrelated
phenomenon. As corrosion progresses, corrosion products, such as Fe
+2
, enter into the solution, which can cause emulsion
instability. If a corrosion inhibitor cannot provide enough of an inhibition effect, then the stability of the emulsion also
decreases. This reduces any additional inhibition effect of the emulsified acid system because of the barrier for direct contact
between the acid and metal surface. As a result, corrosion becomes faster and the emulsion becomes unstable, even though a
corrosion inhibitor is not directly interfering in the stability of the system. The same effect was shown by I-N (Table 4). I-N
can be used at 250F for 4 hr. For higher temperatures (275 and above), the inhibition effect of I-N becomes lower or lesser
because of a higher corrosion rate at higher temperatures. This results in breaking of the emulsion with higher corrosion loss.

TABLE 4EFFECT OF TEMPERATURE ON EMULSION STABILITY AND CORROSION LOSS FOR P110 ALLOY IN
PRESENCE OF I-N IN EMULSIFIED 28% HCl ACID
Sr.
No.
Temp.,
F
Time,
hr
I-N,
gal/1,000 gal
IN-H,
lbm/1,000 gal
IN-O,
gal/1,000 gal
Emulsifier,
gal/1,000 gal
Corrosion Loss,
lbm/ft
2

Emulsion
Stability
1 250 3 10 10 40 14 0.0317 Stable
2 250 4 12 10 40 16 0.04424 Stable
3 275 3 8 10 40 12 0.2373 Unstable
4 275 3 17 30 40 22 0.21 Unstable
5 275 3 20 30 40 25 0.1 Unstable
6 275 3 20 0 40 25 0.1685 Unstable
7 275 3 25 0 40 30 0.0973 Unstable

Effect of I-C on the Emulsified Acid System. The effect of I-C on the stability and corrosion loss of 28% emulsified acid is
shown in Table 5. It displayed a similar effect on the stability and corrosion loss as I-N. With an increase in temperature, both
the instability of the system and corrosion became faster, resulting in higher corrosion loss. The effectiveness of the corrosion
inhibitor is another factor that becomes critical in this case. A higher concentration of corrosion inhibitor normally destabilizes
the system. Hence, there is a limit to the maximum concentration of corrosion inhibitor, above which the emulsion becomes
unstable. The balance between corrosion inhibition and stability can be properly adjusted if the corrosion inhibitor shows
maximum inhibition at minimum concentration. Therefore, I-C is a more effective corrosion inhibitor than I-N because the
IPTC 16452 5
temperature limit of the emulsified acid can be increased to 275F using I-C as the corrosion inhibitor. As I-C is a cationic
corrosion inhibitor, its destabilizing effect on the emulsified acid system was reduced by using ionic intensifiers, such as IN-O
and IN-H. Corrosion inhibition was achieved up to 4 hr at 275F using I-C.
The system was stable at 300F for 2 hr. This enables the acidizing of carbonate reservoirs with BHSTs up to 275F using
an emulsified acid system.

TABLE 5EFFECT OF TEMPERATURE ON EMULSION STABILITY AND CORROSION LOSS FOR P110 ALLOY IN
PRESENCE OF I-C IN EMULSIFIED 28% HCl ACID
Sr.
No.
Temp.,
F
Time,
hr
I-C,
gal/1,000 gal
IN-H,
lbm/1,000 gal
IN-O,
gal/1,000 gal
Emulsifier,
gal/1,000 gal
Corrosion Loss,
lbm/ft
2

Emulsion
Stability
1 250 6 8 10 40 12 0.0238 Stable
2 275 3 8 10 40 12 0.0458 Stable
3 275 3 8 0 40 12 0.039 Stable
4 275 4 8 0 40 12 0.16 Unstable
5 275 3 8 0 60 12 0.234 Unstable
6 275 3 8 0 20 12 0.161 Unstable
7 275 3 20 30 20 25 0.148 Unstable
8 275 4 8 60 40 12 0.050 Stable
9 275 6 12 15 40 20 0.449 Unstable
10 275 6 12 15 40 25 0.425 Unstable
11 300 2 8 40 40 12 Without coupon Stable
12 300 2 8 0 40 12 Without coupon Stable


Conclusions
On the basis of the analysis presented, the following conclusions were drawn:
Three corrosion inhibitors, I-G, I-N, and I-C, were compared for their effect on the stability of an emulsified acid
system. I-G showed more destabilization effects than I-N and I-C.
I-G can provide corrosion protection up to 250F in an emulsified acid system without affecting the stability of the
system.
I-N showed corrosion inhibition up to 250F in an emulsified acid system.
I-C showed better corrosion inhibition than I-G and I-N in an emulsified acid system. I-C can be used up to 275F
without affecting the stability of the system.
A stable emulsified acid system was designed that passed the corrosion test at 275F for 4 hr and was also stable at
300F for 2 hr.
This system enables the stimulation of carbonate reservoirs with BHSTs in the range 250 to 275F. This study is very
useful for designing emulsified acid systems for high-temperature applications.

Acknowledgments
The authors thank Halliburton for permission to publish this research.

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