SPE 150337

Laboratory Optimization of an Emulsified Acid Blend for Stimulation of

High-Temperature Carbonate Reservoirs
Anupom Sabhapondit, Jose R. Vielma Guillen, SPE, and Chetan Prakash, Halliburton

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the North Africa Technical Conference and Exhibition held in Cairo, Egypt, 20–22 February 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract
Emulsified hydrochloric (HCl) acid has been used in both fracture and matrix acidizing of carbonate reservoirs to help
penetrate deeper into the reservoir before spending. The emulsion stability and adequate corrosion inhibition are critical
requirements of this blend, which are challenging to accomplish using emulsified acids of high HCl acid concentration
(>26%) at high temperatures (>250°F) because many corrosion inhibitors used in the industry can severely affect emulsion
stability by interacting with the emulsifier. The requirement of other additives, such as iron-control additives, surfactants
other than the emulsifier, H2S scavengers, etc., can further add to the challenges.
This work presents the laboratory optimization of 26% emulsified HCl-acid blends for use at temperature ranges between
250 and 300°F. Quaternary ammonium salt based Inhibitor I-C and a propargyl alcohol based Inhibitor I-N were used in this
study. One inorganic halide based (IN-H) and one organic acid based (IN-O) intensifier were used to achieve adequate
corrosion inhibition. A single commercial blend of surfactants was used for all the tests.
Based on the high-pressure high-temperature (HPHT) static corrosion tests, Inhibitor I-C performed better than Inhibitor
I-N at 275°F. However, Inhibitor I-C was found more damaging to emulsion stability than Inhibitor I-N. At 250°F, the
performances of both inhibitors were comparable.
A common misconception that prevails in the industry is that a stable emulsified acid can ensure a successful acid job
without (or with a very little amount of) corrosion inhibitor. It was clearly evidenced during this study that the emulsion
stability alone does not ensure the protection of alloys from corrosion. Using a suitable corrosion inhibitor in appropriate
concentration is as equally important as emulsion stability for successful completion of an emulsified acid job without
encountering severe corrosion problems.

Introduction
Stimulating high-temperature carbonate reservoirs by acidizing treatments has always been a challenge to oilfield
technologists because of the high reaction rate between carbonates and HCl acid. A common way is the use of an emulsified
acid. This allows the dispersed aqueous phase containing the acid to react at a much slower rate with the carbonate formation,
resulting in better conductivity in fracture acidizing and deeper penetration in matrix-acidizing treatments. An emulsified acid
blend does not use a polymeric gelling agent; unlike gelled acid blends, no residual polymer is left in the formation after the
treatment, leaving the formation clean. Emulsified acids were traditionally used in acid fracturing. More recently, they were
considered and applied in matrix-acidizing treatments of carbonate formations (Navarrete et al. 2000; Hill and Jones 2003;
Buijse and van Domelen 1998). Several research studies have been published on the reactivity of emulsified acid, suitable
emulsifiers for high-temperature applications, rheology of emulsified acid, and effects of various physical parameters on
emulsion stability, etc. (Navarrete et al. 2000; Bazin and Abdulahad 1999; Sarma et al. 2007; Xu et al. 2007; Al-Mutairi et al.
2007; Nasr-El-Din 2008). However, only a few studies are available in the literature about the effect of corrosion inhibitors
on the stability of an emulsified acid system (Hill and Jones 2003).
The most important component of an emulsified acid system is the emulsifier. A well-chosen emulsifier can provide good
stability to the emulsified acid, even at higher temperatures. However, the stability of an emulsion, and therefore its
effectiveness as a retarded acid system, depends on several other parameters. They include the type and quantity of other
additives present in the acid blend, temperature of application, treatment duration, etc. Corrosion inhibitors, used for the
protection of metal pipes and parts, are the most important chemical additive present in any acid blend. Their interaction with
the emulsifier is an important factor affecting the stability of an emulsified acid system. Higher loading of inhibitors
2 SPE 150337

generally reduces the stability of the emulsion (Hill and Jones 2003). On the other hand, addition of a suitable corrosion
inhibitor at the prescribed concentration in an acid blend is a must for performing any acid job. Therefore, the effect of the
corrosion inhibitor on emulsion stability is far more important than the effect of other additives. A perception exists that, in
an emulsified acid system, the aqueous acid phase is completely encapsulated and hence cannot come in contact with the
metal tubular, eliminating the need for a corrosion inhibitor. In reality, the emulsion reduces the diffusion rate of H+ ions in
the acid significantly, thus slowing down its reaction with the metal, which is exactly the same effect it shows in carbonate
formations (Navarrete et al. 2000). It cannot stop the interaction between the H+ ions and the metal surface. Therefore,
addition of corrosion inhibitor is necessary even in emulsified acids. It also helps make the system safer in case of an
unexpected emulsion break in the tubing or casing. Moreover, there is a greater chance of corrosion from an emulsified acid
under static conditions compared to dynamic conditions. Therefore, a suitable corrosion inhibitor must be present in the
emulsified acid blend to keep the metals safe during shut-in conditions.
Recently, several emulsified acid blends using 26% HCl acid were designed and tested in the laboratory for screening
suitable emulsified acid blends for use in wells with bottomhole static temperatures (BHSTs) varying between 200 to 275°F
and treatment times up to six hours. Two different corrosion inhibitors were used at various concentrations, depending on the
application temperature and time to achieve corrosion loss below the acceptable limit of 0.05 lbm/ft2, as well as maintaining a
stable emulsion. Inhibitor I-N was a propargyl-alcohol-based formulation, while Inhibitor I-C was a quaternary ammonium
salt based formulation. An inorganic halide based (IN-H) and an organic acid based (IN-O) intensifier were also used with
the corrosion inhibitors to achieve adequate corrosion inhibition. A commercial cationic-emulsifier blend was used in all
cases, in various concentrations. This paper presents the laboratory corrosion-loss and emulsion-stability results while
optimizing the emulsified acid blends for application at different temperatures for different treatment times.

Experimental

Laboratory Preparation of Emulsified Acid. All of the acid blends prepared contained the same quantity of an iron-control
agent and a sulfide-cracking inhibitor. The oil-aqueous-phase ratio was 30:70 in all cases. The corrosion-inhibitor type and
concentrations and the emulsifier concentrations were varied to obtain a stable emulsion with permissible corrosion loss. An
organic-acid-based inhibitor intensifier (IN-O) and an inorganic halide-based inhibitor intensifier (IN-H) were used at various
concentrations to achieve low corrosion loss. Diesel was used as the oil phase. A total of 200 mL of emulsified acid was
prepared for each recipe studied. The diesel and the emulsifier were mixed thoroughly in a Waring® blender. In a separate
beaker, the aqueous phase was prepared by first mixing the corrosion inhibitor and intensifiers with water, followed by 35%
HCl acid, the iron-control agents, and the sulfide-cracking inhibitor. The aqueous phase was added slowly to the oil phase
with continuous stirring at 20% of the blender’s maximum speed using the lower speed option. On completion of addition,
the emulsion was mixed at 70% of the maximum speed for five minutes. The formation of water-in-oil emulsion was
confirmed by pouring a drop of the blend into water in a beaker. If the drop sank without any dispersion of oil, the blend was
considered as water-in-oil emulsion (Fig. 1). If dispersion of oil was observed, the blend was discarded and a new blend was
prepared to ensure the emulsion had oil as the outer phase.

Fig. 1—Drops of oil-external phase emulsion in water.

SPE 150337 3

Checking Stability of the Emulsion. Stability of the emulsions at high temperatures was determined based on aqueous-
phase separation after the corrosion test. The emulsion after the static HPHT corrosion test was transferred to and kept in a
graduated cylinder, and any separation was recorded within 15 minutes (Fig. 2). An emulsion was considered unstable if any
aqueous-layer separation at the bottom of the cylinder was observed (Fig. 3). An emulsion is expected to be the most unstable
under static conditions inside the metal tubulars (Hill and Jones 2003). Hence, the stability was checked only after a static-
corrosion test to evaluate the emulsions under the worst conditions.

Fig. 2—A stable emulsion. Fig. 3—An unstable emulsion.

Static HPHT Corrosion Test. Curved rectangular coupons of N80 alloy were used for the corrosion tests. The total surface
area of each coupon was ≈ 4.4 square inches.
Acid-corrosion testing was conducted using small Hastelloy B-2 autoclaves, which test only one specimen at a time (Fig.
4). 125-mL glass cells were used for the tests, and the volume of the acid blend used for each test was 100 mL. The coupons
were initially degreased with acetone and then bead blasted. The initial weight of the coupon was recorded. The coupon was
suspended in the glass cell with the help of Teflon® tape. 100 mL of the acid blend was poured into the glass cell. After
capping the glass cell, the autoclave was filled with mineral oil until it was 1 in. below the glass cell mouth, which acts as a
heat-transfer medium. The cell contents were pressurized to 1,000 psi with nitrogen. Pressure was maintained using a
backpressure regulator assembly, which allows for automatic bleed off of excess pressure developed during heating and
release of corrosion products. The autoclaves were heated using Eurotherm controllers. The contact times included heat-up
time of 75 minutes and cool-down time of 15 minutes.

Fig. 4—Hastelloy autoclave.

After completion of the heating period, the autoclave was first allowed to cool slowly at room temperature and later
cooled in water. The pressure was released and the glass cell was carefully removed. The coupon was cleaned with a soft
4 SPE 150337

brush using a mild abrasive cleaning powder, washed with water, and rinsed with acetone. The coupon was dried and the
final weight was recorded; weight loss was expressed in lbm/ft2. The emulsion was carefully transferred to a graduated
cylinder to check the stability.

Results and Discussion

Effect of Corrosion Inhibitor on Emulsion Stability. A misconception sometimes exists that a stable emulsion itself is
enough to protect metal pipes from corrosion without the addition of any corrosion inhibitor. However, the data in Table 1
shows that the formation of an oil-external-phase emulsion and its stability at high temperatures are not the only criteria for a
successful emulsified acid job. As evident from Table 1, the blend in Test 1 formed a stable emulsion, which should result in
good acidizing of a carbonate reservoir. However, in spite of the emulsion being stable, the corrosion loss was >0.05 lbm/ft2;
metal tubular would be expected to corrode during this job, and hence this blend was not acceptable. On the other hand, with
the introduction of Inhibitor I-C and Intensifier IN-O to the same blend, the corrosion loss was reduced to a lower value of
0.035 lbm/ft2 without affecting the emulsion stability. Thus, the blend in Test 2 was expected to show good performance
without much corroding of the tubular.
Test No. 3 shows that the corrosion loss increased to a high extent when the temperature was increased to 250°F without
an inhibitor present in the blend. The emulsion was also found unstable after the test. On the other hand, in Test 4, addition of
5 gal/1,000 gal Inhibitor I-N and 40 gal/1,000 gal Intensifier IN-O reduced the corrosion loss to 0.042 lbm/ft2 and also kept
the emulsion stable until the test was complete, despite using a lower concentration of emulsifier than that in Test 3. The high
corrosion rate possibly destabilized the emulsion in Test 3. The fact that a higher corrosion rate itself can cause
destabilization of an emulsion will be evident from the results discussed in a later stage (Table 3, tests at 250°F). However,
as evident from Test 5, the emulsion can remain stable even after high corrosion loss if a sufficient amount of emulsifier is
present. This test also showed that the presence of an inhibitor and intensifiers and formation of a stable emulsion alone
might not fulfill the criteria for a suitable emulsified acid for carbonate stimulation. To achieve acceptable corrosion loss, it is
necessary to use the correct inhibitor and intensifier in the proper concentration, apart from getting a stable emulsion.

TABLE 1—EFFECT OF CORROSION INHIBITOR ON N80 STEEL IN EMULSIFIED 26% HCl ACID

Test Test Corrosion

Test Temp. Time Inhibitor I-C Inhibitor I-N Emulsifier Other Emulsion Loss
2
No. (°F) (hr) (gal/1,000 gal) (gal/1,000 gal) (gal/1,000 gal) Additives Stability (lbm/ft )
1 200 6 — — 8 — Stable 0.056
Intensifier IN-O:
2 200 6 6 — 8 Stable 0.035
20 gal/1,000 gal
3 250 4 — — 8 — Unstable 0.17
Intensifier IN-O:
4 250 4 — 5 6 Stable 0.042
40 gal/1,000 gal
Intensifier IN-O:
40 gal/1,000 gal;
5 275 3 — 8 12 Stable 0.123
Intensifier IN-H:
5 ppt

Presence of a corrosion inhibitor can also protect the metal tubular in case of an unexpected emulsion break, even at low
temperatures. A corrosion-inhibitor system, thus, is a necessary component of an emulsified-acid blend. Considering the
severe effect of many corrosion inhibitors on emulsion stability, this study was conducted to optimize an emulsion of 26%
HCl acid in diesel for N80 alloy at various temperatures ranging from 200 to 275°F.

Optimization of Acid Recipe. It was observed that, even at a higher concentration of HCl acid, such as 26%, emulsified-acid
systems were stable with an acceptable amount of corrosion loss (<0.05 lbm/ft2) at comparatively lower temperatures. Table
2 shows the experimental data at 200 and 225°F.
It is clear from Tests 1 and 2 that either of the inhibitors could be used in conjunction with 20 gal/1,000 gal Intensifier IN-
O at 200°F for six-hour acid jobs. However, Inhibitor I-C showed a better corrosion-inhibition performance compared to
Intensifier I-N at the same temperature and test duration.
Test 3 shows that the corrosion loss was low when the test duration was reduced to two hours, despite increasing the test
temperature and reducing the inhibitor and surfactant concentrations.
SPE 150337 5

TABLE 2—CORROSION LOSS AND EMULSION STABILITY IN EMULSIFIED 26% HCl ACID, N80 ALLOY

Test Test Corrosion

Test Temp. Time Inhibitor I-C Inhibitor I-N Emulsifier Emulsion Loss
2
No. (°F) (hr) (gal/1,000 gal) (gal/1,000 gal) (gal/1,000 gal) Intensifier Stability (lbm/ft )
Intensifier IN-O:
1 200 6 6 — 8 Stable 0.035
20 gal/1,000 gal
Intensifier IN-O:
2 200 6 — 6 8 Stable 0.049
20 gal/1,000 gal
3 225 2 4 — 6 — Stable 0.002

Optimization of the inhibitor and emulsifier quantities was found more challenging at the higher temperature ranges.
Table 3 shows the corrosion-loss and emulsion-stability results of various emulsified acid blends of 26% HCl acid at 250°F.
Tests 1, 2, and 3 showed that neither 4 or 5 gal/1,000 gal of Inhibitor I-C nor 5 gal/1,000 gal of Inhibitor I-N with 6
gal/1,000 gal emulsifier could result in an acceptable corrosion loss, nor would the emulsion remain stable for three hours at
250°F. A comparatively high amount of Inhibitor I-C, without increasing the emulsifier content, did not allow the emulsion
to form (Test 4). Another combination using a high concentration of inhibitor with a higher concentration of emulsifier
resulted in an oil-outer-phase emulsion at room temperature; but it was found unstable after a four-hour test at 250°F (Test 5).
The low corrosion loss was a result of the high concentration of inhibitor and intensifiers used in that blend.
Finally, the introduction of 40 gal/1,000 gal Intensifier IN-O to the recipe of Test 2 resulted in an emulsified acid blend,
which remained stable after a four-hour test at 250°F, with corrosion loss within the acceptable limit (Tests 6 through 8).
Replacing Inhibitor I-C with Inhibitor I-N also resulted in a stable emulsion with slightly lower corrosion loss (Test 9). Thus,
Intensifier IN-O helped in creating the successful blend, possibly by reducing the corrosion loss to a level that did not
destabilize the emulsion. Being an organic-acid-based material, Intensifier IN-O might not play a direct role in stabilizing an
emulsion.

TABLE 3—CORROSION LOSS AND EMULSION STABILITY AT 250°F FOR EMULSIFIED 26% HCl ACID, N80 ALLOY

Test Corrosion
Test Time Inhibitor I-C Inhibitor I-N Emulsifier Emulsion Loss
2
No. (hr) (gal/1,000 gal) (gal/1,000 gal) (gal/1,000 gal) Intensifier Stability (lbm/ft )
1 3 4 — 6 — Unstable 0.122
2 3 5 — 6 — Unstable 0.1
3 3 — 5 6 — Unstable 0.196
Intensifier IN-H: Emulsion not
4 — 25 — 6 —
30 gal/1,000 gal formed
Intensifier IN-O:
40 gal/1,000 gal;
5 4 15 — 20 Unstable 0.026
Intensifier IN-H:
30 ppt
Intensifier IN-O:
6 2 5 — 6 Stable 0.015
40 gal/1,000 gal
Intensifier IN-O:
7 3 5 — 6 Stable 0.027
40 gal/1,000 gal
Intensifier IN-O:
8 4 5 — 6 Stable 0.049
40 gal/1,000 gal
Intensifier IN-O:
9 4 — 5 6 Stable 0.042
40 gal/1,000 gal

Table 4 summarizes the results at 275°F. Because the temperature was higher, the inhibitor as well as the emulsifier
concentration was increased to 8 and 12 gal/1,000 gal, respectively. It resulted in a near-pass corrosion loss. However, the
emulsion did not remain stable after the three-hour test. In Test 2, 5 ppt of Intensifier IN-H was added to the blend of Test 1.
As evident from the results of Test 2, the corrosion loss was reduced to 0.038 lbm/ft2. The emulsion after the test was stable.
Replacement of Inhibitor I-C with Inhibitor I-N did not work at this temperature. Despite the presence of a stable
emulsion, the corrosion loss was high in this test (Test 3). Further increments of Inhibitor I-C and Intensifier IN-H (Test 4)
increased the corrosion loss, though no change in the emulsion stability was observed compared to Test 3. It clearly indicated
that, although the emulsion was visually stable after the test, the aqueous phase contacted the metal surface to a higher extent
in Test 4 compared to Test 2. This could be an indication that this emulsion would have broken earlier than the one in Test 3,
had they been kept under the test conditions for a longer time.
6 SPE 150337

TABLE 4—CORROSION LOSS AND EMULSION STABILITY AT 275°F FOR EMULSIFIED 26% HCl ACID, N80 ALLOY

Test
Test Time Inhibitor I-C Inhibitor I-N Emulsifier Emulsion Corrosion Loss
2
No. (hr) (gal/1,000 gal) (gal/1,000 gal) (gal/1,000 gal) Other Additives Stability (lbm/ft )
Intensifier IN-O:
1 3 8 — 12 Unstable 0.056
40 gal/1,000 gal
Intensifier IN-O:
0.038
2 3 8 — 12 40 gal/1,000 gal; Stable
Intensifier IN-H: 5 ppt
Intensifier IN-O:
3 3 — 8 12 40 gal/1,000 gal; Stable 0.123
Intensifier IN-H: 5 ppt
Intensifier IN-O:
4 3 10 — 15 40 gal/1,000 gal; Stable 0.048
Intensifier IN-H: 30 ppt
Intensifier IN-O: Emulsion
5 — 15 — 20 40 gal/1,000 gal; not —
Intensifier IN-H: 30 ppt formed
Intensifier IN-O:
6 3 — 15 20 40 gal/1,000 gal; Stable 0.053
Intensifier IN-H: 30 ppt
Intensifier IN-O:
7 3 — 15 20 40 gal/1,000 gal; Stable 0.063
Intensifier IN-H: 5 ppt
Intensifier IN-O:
8 3 — 20 20 40 gal/1,000 gal; Unstable 0.06
Intensifier IN-H: 20 ppt

A further increase of Inhibitor I-C did not allow the emulsion to form despite a substantial increase in emulsifier quantity
(Test 5). Interestingly, the same amount of Inhibitor I-N resulted in a stable blend under similar conditions. The corrosion
loss in this blend was also a near-pass 0.053 lbm/ft2 (Test 6). Thus, Inhibitor I-N, being nonionic in nature, was possibly less
damaging to the emulsion stability. When Intensifier IN-H was reduced to 5 ppt in the next blend (Test 7), the corrosion loss
was increased to 0.063 lbm/ft2. An increment of Inhibitor I-N to 20 gal/1,000 gal left the emulsion broken after the three-hour
test at 275°F (Test 8). The corrosion loss remained 0.06 lbm/ft2 because of the high concentration of inhibitor used. Thus, in
comparison to Inhibitor I-C, Inhibitor I-N worked only at a higher concentration at higher temperatures, but became
detrimental to the emulsion stability at that high concentration.

Conclusion
The following conclusions are a result of this work.
• Corrosion inhibitor is a necessary component of an emulsified-acid blend.
• The stability of an emulsified-acid blend does not ensure the protection of metal tubular from corrosion. It is
necessary to optimize the concentrations of suitable corrosion inhibitor and intensifiers to achieve acceptable
corrosion loss along with a stable emulsion.
• It is a challenging job to optimize the acid recipe for emulsified 26% HCl acid, especially for applications at 250°F
and higher.
• Two corrosion inhibitors were tested under different conditions of temperature and duration. Inhibitor I-C was
quaternary ammonium salt based while Inhibitor I-N was propargyl alcohol based materials. A cationic blend of
emulsifier was used for all the tests. Optimizing the balanced concentrations of inhibitor and emulsifier was found to
be critical for designing a good emulsified-acid blend.
• Corrosion-inhibition performance of Inhibitor I-C was better compared to Inhibitor I-N at 275°F. However, Inhibitor
I-C was found more damaging to emulsion stability compared to Inhibitor I-N. At lower temperatures, Inhibitor I-N
might be a better option.

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SPE 150337 7

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