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

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 P110 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 Jones 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.

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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 hightemperature 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 highpressure/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 IC), 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/ft2 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 (N2) 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 N2 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.

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(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. 1 2 3 4 5 6 7 Time, hr 3 3 3 3 3 3 3 Emulsifier, gal/1,000 gal 10 10 10 10 10 10 10 Corrosion Inhibitor Nil I-G (10 gal/1,000 gal) I-C (10 gal/1,000 gal) I-N (10 gal/1,000 gal) I-C (20 gal/1,000 gal) I-N (20 gal/1,000 gal) Methanol (3.5 gal/1,000 gal) Emulsion Stability Stable Unstable Stable Stable Unstable Unstable 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.

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

Emulsion Stability Unstable Unstable Stable Unstable 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. 1 2 3 4 5 6 7 8 9 Temp., F 250 250 250 250 275 275 275 275 275 Time, hr 3 4 4 4 3 4 3 3 3 I-G, gal/1,000 gal 10 10 10 20 8 8 8 8 10 IN-H, lbm/1,000 gal 5 5 5 5 5 5 5 IN-O, gal/1,000 gal 40 40 40 40 40 40 40 Emulsifier, gal/1,000 gal 25 25 25 20 12 12 20 20 25 Corrosion Loss, 2 lbm/ft 0.037 0.23 0.11 0.1 0.406 0.5785 0.9 No coupon 0.321 Emulsion Stability Stable Unstable Unstable Unstable Unstable Unstable Unstable Unstable 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. 1 2 3 4 5 6 7 Temp., F 250 250 275 275 275 275 275 Time, hr 3 4 3 3 3 3 3 I-N, gal/1,000 gal 10 12 8 17 20 20 25 IN-H, lbm/1,000 gal 10 10 10 30 30 0 0 IN-O, gal/1,000 gal 40 40 40 40 40 40 40 Emulsifier, gal/1,000 gal 14 16 12 22 25 25 30 Corrosion Loss, 2 lbm/ft 0.0317 0.04424 0.2373 0.21 0.1 0.1685 0.0973 Emulsion Stability Stable Stable Unstable Unstable Unstable Unstable 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

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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. 1 2 3 4 5 6 7 8 9 10 11 12 Temp., F 250 275 275 275 275 275 275 275 275 275 300 300 Time, hr 6 3 3 4 3 3 3 4 6 6 2 2 I-C, gal/1,000 gal 8 8 8 8 8 8 20 8 12 12 8 8 IN-H, lbm/1,000 gal 10 10 0 0 0 0 30 60 15 15 40 0 IN-O, gal/1,000 gal 40 40 40 40 60 20 20 40 40 40 40 40 Emulsifier, gal/1,000 gal 12 12 12 12 12 12 25 12 20 25 12 12 Corrosion Loss, 2 lbm/ft 0.0238 0.0458 0.039 0.16 0.234 0.161 0.148 0.050 0.449 0.425 Without coupon Without coupon Emulsion Stability Stable Stable Stable Unstable Unstable Unstable Unstable Stable Unstable Unstable Stable 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. References
Buijse, M.A. and Van Domelen, M.S. 1998. Novel Application of Emulsified Acids to Matrix Stimulation of Heterogeneous Formation. Paper SPE 39583 presented at the SPE Formation Damage Control Conference, Lafayette, Louisiana, USA, 1819 February. doi: 10.2118/39583-MS. Hill, D. and Jones, A. 2003. An Engineered Approach to Corrosion Control During Matrix Acidizing of HTHP Sour Carbonate Reservoir. Paper NACE 03121 presented at Corrosion 2003, San Diego, California, USA, March. Navarrete, R.C., Holms, B.A., McConnell, S.B., and Linton, D.E. 2000. Laboratory, Theoretical and Field Studies of Emulsified Acid Treatment in High-Temperature Carbonate Formation. SPE Prod. & Fac. 15 (2): 96106. Pandya, N., Wadekar, S., and Cassidy, J. 2012. A Unique Emulsified Acid System with Three Intensifiers for Stimulation of Very High Temperature Carbonate Reservoirs. Paper SPE 163308 presented at Kuwait International Petroleum Conference and Exhibition, Kuwait, 1012 December. doi: 10.2118/163308-MS. Rostami, A. and Nasr-El-Din, H.A. 2009. Review and Evaluation of Corrosion Inhibitors Used in Well Stimulation. Paper SPE 121726 presented at SPE International Symposium on Oilfield Chemistry, The Woodlands. Texas, USA, 2022 April. doi: 10.2118/121726MS. Sabhapondit, A., Vielma Guillen, J.R., and Prakash, C. 2012. Laboratory Optimization of an Emulsified Acid Blend For Stimulation of High Temperature Carbonate Reservoir. Paper SPE 150337 presented at the North Africa Technical Conference and Exhibition, Cairo, Egypt, 2022 February. doi: 10.2118/150337-MS.

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Sayed, M.A., Nasr-El-Din, H.A., Zhou, J., Holt, S., and Al-Malki, H. 2012. A Novel Emulsified Acid System to Stimulate Carbonate Reservior. Paper SPE 151061 presented at the Formation Damage Control Conference, Lafayette, Louisiana, USA, 1517 February. doi:10.2118/151061-MS.