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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