SPE 87563 Application of pH Buffer as Corrosion Inhibitor in NaBr Brine Packer Fluids at High Temperatures

Mingjie Ke, SPE, Paul H. Javora, SPE and Qi Qu, SPE, BJ Services Company

Copyright 2004, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 1st International Symposium on Oilfield Corrosion held in Aberdeen, UK, 28 May 2004. 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, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers 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, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

temperature, and economic requirements. However, brine corrosivity is a major concern --- especially when the brines are used as packer fluids (which remain in contact with tubing and casing for an extended period of time). In general, brine corrosivity increases with increases in temperature, brine density and zinc content. Also, single-salt brines have lower corrosion rates than multiple-salt brines. Some single-salt brines have lower corrosion rates than others. In recent years, failures of high-strength, corrosion-resistant alloy (CRA) tubular materials such as super 13Cr stainless steel, 22Cr and 25Cr duplex stainless steels have been reported by the industry 1-3. These failures were investigated and determined to be caused by stress corrosion cracking (SCC) of steel materials after exposure to inhibited CaCl2 brines under high-temperature conditions. Due to the potential of chloride-induced SCC, some operators in the Gulf of Mexico have decided to use chloride-free brine fluids (such as NaBr, CaBr2 and formate brines) for well completions. Among these chloride-free brines, NaBr has lower corrosion rates than CaBr24, and formate brines decompose at high temperatures5. The decomposition of formate brines will produce hydrogen, methane, and carbon monoxide over longterm exposure to high temperatures. Furthermore, formate brines are more expensive than NaBr. Therefore, sodium bromide has gained more and more attention for hightemperature packer fluid applications. Sodium bromide brine can be prepared up to a density of 12.7 ppg (S.G.=1.525) which is equivalent to 47% NaBr by weight of solution. Depending on their densities, NaBr brines normally have a pH range of 7.0-8.5. Although NaBr brines exhibit low weight loss corrosion even at temperatures4, some oilfield tubular materials are susceptible to pitting and localized corrosion. Generally, most brine service companies use low molecular weight inorganic sulfur (SCN-) or filmforming amine chemicals in brine packer fluids as corrosion control measures. However, when these are applied at high temperature, thermal decomposition has become a critical issue. Burke et al.6 reported that SCN- decomposes at 150oC and yields hydrogen sulfide (H2S). The H2S will induce hydrogen sulfide SCC of steel materials. Potter7 has reported the formation damage potential of film-forming amine corrosion inhibtiors at temperatures of 150-300oF (66-149oC). In addition, Silverman et al.8 have reported that amine corrosion inhibitors attacked Nitrile and Viton elastomer seals

Abstract Sodium bromide brine (NaBr) has been widely used as a packer fluid in well completions for more than 20 years. While NaBr brines exhibit low corrosion even at high temperatures, some oilfield tubular materials are susceptible to pitting and localized corrosion. Traditionally, film-forming amine and low molecular weight inorganic sulfur (SCN-) chemicals have been added as corrosion inhibitors. However, when applied at high temperature, thermal decomposition has become a critical issue. Furthermore, adverse effects on tubular materials, downhole elastomers and formation rock have been documented. Alternatively, corrosion may be controlled by increasing the pH of the brines. While pH can be raised by the addition of sodium hydroxide (NaOH), lime (CaO), hydrated lime (Ca(OH)2), and the magnesium analogues, these chemicals provide less control and less protection for tubular materials, especially when the influx of an acid gas is possible. This paper describes laboratory results of a pH buffer applied as a corrosion inhibitor in NaBr brines and field case histories for buffered NaBr packer fluids in high-temperature highpressure wells. Results from buffer capacity, general corrosion, galvanic corrosion, and stress corrosion cracking (SCC) tests are presented. Field case histories are presented to demonstrate the successful use of the pH buffer in NaBr brines. Introduction The oil and gas industry has used sodium, calcium and zinc bromide and chloride brines for well completions for more than 20 years. More recently, sodium, potassium and cesium formate brines are being explored for use as completion and packer fluids. These brines can be applied as single-, two- or three-salt mixtures based on density, crystallization

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SPE 87563

at elevated temperatures. Attacks resulted in rapid embrittlement of both elastomer seals. Due to these drawbacks, using these chemical additives in packer fluids is not considered by some operators in the Gulf of Mexico. To provide corrosion control, one alternative method is to increase the pH of brine fluids and thus reduce their corrosivity. Hudson4 states that adjusting the pH of zinc bromide (ZnBr2) brines to less acidity will help reduce corrosivity. Houchin et al.9 evaluated the use of potassium carbonate as a non-corrosive chloride-free completion fluid. The non-corrosive characteristics of potassium carbonate are primarily attributed to the high pH of potassium carbonate fluids. Depending on the natures of brines, most brine services companies normally use sodium hydroxide (NaOH), lime (CaO), hydrated lime (Ca(OH)2), and the magnesium analogues to adjust or increase the pH of brines. However, these chemicals provide less control and less protection for tubular materials, especially when the influx of an acid gas is possible. This study applied a buffer to raise the pH of NaBr brines and thus reduce their corrosivity. The buffer proposed has strong alkaline properties and a good solubility in NaBr brines. Over a wide concentration range, it can maintain the pH of NaBr brines at a level of 9.0-11.0, which is considered less corrosive for downhole tubular materials. Buffer capacity evaluation and laboratory corrosion testing along with field case histories demonstrate its effectiveness as a corrosion inhibitor in NaBr brines even in acid gases of CO2/H2S at high temperatures. The buffer applied is cost-effective and readily available. Furthermore, it can be easily handled and monitored during well completions. Experimental pH Buffer Capacity pH buffer capacity was evaluated in two NaBr brines. One had a density of 9.0 ppg (S.G.=1.080) and the other had a density of 12.4 ppg (S.G.=1.489). Both were prepared by diluting 12.5 ppg (S.G.=1.501) NaBr stock brine with tap water. After the brines were prepared, the pH buffer was added to each brine under agitation. A pH electrode was used to directly measure the brines pH at room temperature of 70oF (21oC). Results in Figure 1 present the pH values of NaBr brines vs. buffer loadings. Weight Loss Corrosion Testing Two types of weight loss corrosion tests were performed in NaBr brines. One was single-coupon weight loss testing, and the other was bi-metallic (galvanic) corrosion testing. Singlecoupon corrosion testing was conducted on P110, Q125 carbon steels, 13Cr and HP1 13Cr stainless steels and 22Cr duplex stainless steel. Bi-metallic corrosion testing was carried out by coupling P110 and 22Cr coupons together. All these steel coupons were cut from oilfield-grade tubulars obtained from operators or tubular suppliers. The NaBr brines evaluated had densities of 9.0 ppg, 12.4 ppg and 12.5 ppg, respectively. Most tests were conducted at 400oF (204oC) under a 400 psig nitrogen (N2) headspace

pressure. For CO2 environments, testing was carried out at 350oF (177oC) under a 400 psig N2 containing 30 psig CO2. Coupons were weighed before and after testing to determine corrosion rates. The corrosion tests were performed by exposing the metal coupons to brines under pressure. Testing time ranged from 7-to-30 days. After testing, coupons were examined for pitting and localized corrosion and the pH values of the brines were measured. Test results are presented in Tables 1-6. Stress Corrosion Cracking Tests Standard C-ring coupons were tested in 9.5 ppg (S.G.=1.140), 12.0 ppg (S.G.=1.441) and 12.4 ppg (S.G.=1.489) NaBr brines, respectively. C-ring coupons were cut from tubular samples of 22Cr (140 ksi) duplex stainless steels, modified 13Cr (95 ksi) and HP1 13Cr (95 ksi) stainless steels. Each Cring coupon was first stressed to the 90% or 100% yield strength. The deflection necessary to obtain the desired stress was calculated based on Equation (5) found on the NACE standards of the C-ring test (TM0177). Immediately after being stressed, each C-ring coupon was immersed in the NaBr brine, and testing was conducted at required temperatures of 212 to 400oF (100-204oC) under N2 or CO2/H2S pressure. After testing, each C-ring coupon was examined for SCC under a microscope. Also, pH values of the brines were measured. Results obtained are presented in Tables 7 and 8. Results and Discussion Buffer Capacity As shown in Figure 1, the 9.0 ppg NaBr and 12.4 ppg NaBr brines had initial pH values of 7.8 and 7.4, respectively. With 1 ppb (pound per barrel) buffer addition, the pH of 9.0 ppg NaBr was raised to 9.8 and that of 12.4 ppg NaBr, increased to 9.3. As the buffer concentrations increased, pH values of both brines increased less than one pH unit. This indicates that over a wide concentration range the buffer can maintain pH of brines in a range of 9.0-11.0, which is considered as a less corrosive environment for downhole tubular materials. This is a unique characteristic of the buffer; that is, it will not overtreat the brine to a pH which may cause an adverse effect on downhole tubulars (such as caustic cracking). Based on the buffer capacity evaluation and corrosion testing below, it is recommended to apply 1 to 10 ppb (pound per barrel) buffer as a corrosion inhibitor in NaBr brines, depending upon density. The higher the brine density, the greater amount of buffer added. If an acid gas such as CO2 and/or H2S may be present, a higher buffer loading is required. The more buffer added, the higher buffer capacity of the brine and the less corrosive environment the brine will produce, especially under CO2 and H2S environments. Weight Loss Corrosion Testing at 400oF (204oC) Result in Table 1 indicate that without treatment the 9.0 ppg NaBr brine produced a very low corrosion rate of 1.4 mpy on P110 coupons over a 7-day exposure. With increased brine density, corrosion rate increased. For example, the 12.4 ppg NaBr produced a higher corrosion rate of 4.8 mpy under identical test conditions. In both cases, localized corrosion was found on the surfaces of P110 coupons. When the brines were buffered, both 9.0 ppg and 12.4 ppg NaBr brines

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SPE 87563

produced very low corrosion rates (below 1 mpy) with general corrosion on the coupon surfaces. This indicates that the buffer reduced the corrosion rate and prevented localized corrosion. After testing, the pH of buffered NaBr brines remained almost unchanged. For comparison purposes, the 12.4 ppg NaBr was also treated with NaOH and tested on a P110 coupon for its corrosion control capacity. Although its initial pH was 9.1, the 12.4 ppg NaBr produced a corrosion rate of 4.3 mpy, which is similar to that without treatment. Furthermore, localized corrosion was observed on coupon surfaces. Therefore, NaOH was ineffective in preventing weight loss corrosion and localized attack of NaBr brine on P110 carbon steel. Table 2 presents corrosion rates for P110 in the NaBr brines over a 30-day exposure. Without treatment, P110 corrosion rates in both 9.0 ppg and 12.4 ppg NaBr brines were much lower than those from 7-day tests. In general, corrosion rates of metals in brines decrease with increased exposure time in an enclosed environment4. Although the corrosion rates were very low, localized corrosion was identified on both coupons. But with the buffer treatment, the 9.0 ppg and 12.4 ppg NaBr brines produced very low corrosion rates along with general corrosion on the surfaces of P110. Furthermore, the pH of brines remained at a high level. This demonstrates that the pH buffer can effectively protect downhole tubulars over a long period of time. Table 3 presents results of corrosion tests on 22Cr duplex coupons in the 9.0 ppg and the 12.4 ppg NaBr brines over 30 days. As shown, 22Cr was completely immune in both brines with and without the buffer treatment at 400oF (204oC). Results in Table 4 indicate that without treatment a 12.5 ppg NaBr brine produced low corrosion rates on 13Cr over 7 days. However, pitting and localized corrosion were identified on the cut sides and near cut edges of coupons. When the buffer was applied, the corrosion rates were reduced and no pitting or localized corrosion was found on coupon surfaces. It appears that the buffer can also protect 13Cr at 400oF (204oC). Weight Loss Corrosion Testing at 350oF (177oC) under 400 psig N2 Pressure Containing 30 psig CO2 Table 5 presents results of corrosion tests on Q125 and HP1 13Cr in 12.4 ppg NaBr brines under 400 psig N2 containing 30 psig CO2 environment. Without treatment the NaBr brine produced a corrosion rate of 5.7 mpy on the Q125 and 2.4 mpy on the HP1 13Cr over a 7-day exposure. In both cases, neither pitting and nor localized corrosion were identified on Q125 and HP1 13Cr. Due to dissolved CO2, the pH values of brines dropped to 4.8, which is considered as a more corrosive environment. With the buffer addition, the 12.4 ppg NaBr brine produced much lower corrosion rates on both metals, especially on Q125, where the rate fell below 1 mpy. On HP1 13Cr, it was reduced to 1.2 mpy, which is considered low over a 7-day test. Due to the pH buffer, the brine maintained a higher pH of about 8.0. Based on the results, the buffer was very effective in preventing weight loss corrosion of Q125 carbon steel under CO2 environments.

Bi-Metallic (Galvanic) Corrosion Testing at 400oF (204oC) As shown in Table 6, bi-metallic coupling did not affect the corrosion rates of P110 and 22Cr materials over 30 days. Without treatment, both 9.0 ppg and 12.4 ppg NaBr brines produced corrosion rates identical to the single-coupon tests. Similarly, localized corrosion was observed on the P110 coupon surfaces. With the buffer treatment, much lower corrosion rates were obtained on P110 and no localized corrosion was identified. Therefore, the pH buffer can protect P110 carbon steel from localized attack even under the galvanic conditions. Stress Corrosion Cracking Testing Under 400 psig N2 Pressure Results in Table 7 indicate that in both un-treated and buffertreated 12.4 ppg NaBr brines, no SCC occurred on the surfaces of 22Cr (140 ksi) duplex stainless steel C-rings over a 30-day exposure at 400oF (204oC). Therefore, the pH buffer did not affect SSC behavior of 22Cr in NaBr brines. Table 7 also presents results of C-ring testing on a modified 13Cr (95 ksi) tubular. As shown, no SCC occurred on the modified 13Cr C-ring exposed to a buffered 12.0 ppg NaBr brine over 21 days at 212oF (100oC). For all the tests with buffer, the pH of buffered brines remained almost identical to pre-test levels. Stress Corrosion Cracking Tests in CO2/H2S Environments Table 8 presents results of C-ring testing in a buffered 9.5 ppg NaBr brine under a 225 psig CO2 containing 5 ppm H2S. The C-ring material was HP1 13Cr (95 ksi) tubular. The 9.5 ppg NaBr was treated with buffer, oxygen scavenger and hydrogen sulfide scavenger. Due to the presence of the acid gases CO2 and H2S, a higher buffer loading was applied. Testing was conducted at 300oF (149oC) and 350oF (177oC), respectively. After a 15-day test, no SCC occurred on the 13Cr C-rings with 90% and 100% stress levels. However, the pH values of brines were reduced from 10.4 to 7.5, due to the presence of CO2 and H2S. Case Histories Case History #1 This was the first application of the buffer in a NaBr brine packer fluid in a high-temperature, high-pressure gas well. The well was located in the Gulf of Mexico and had a bottomhole temperature above 380oF (193oC). The reservoir contained 4%-5% (mol.) CO2 and 10-20 ppm H2S. Due to the concern of chloride-induced stress corrosion cracking, the packer fluid proposed was a 9.0 ppg NaBr brine. The casing tubular was carbon steel and the production tubing was 25Cr duplex stainless steel. Due to the drawbacks of amine or inorganic sulfur (SCN-) chemicals, neither was considered as a corrosion inhibitor. The pH buffer studied was selected as a corrosion control alternative. After extensive laboratory corrosion testing and buffer capacity evaluation, it was determined that the pH buffer could be applied as a corrosion inhibitor for the NaBr packer fluid. With the support of laboratory personal and appropriate testing and monitoring of fluids performed by trained engineers in the field, the NaBr brine, which was only treated with the buffer, was successfully used as the packer fluid. The operator was satisfied with the results of buffered NaBr brine after well completion. The well

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was completed in March 2002, and no tubular failure has been reported. Case History #2 The well was located in the Gulf of Mexico, and had a bottomhole temperature of 245oF (118oC). Produced gas contained 3%5% (mol.) CO2 and trace H2S. The packer fluid proposed was a 9.5 ppg NaBr. With only buffer treatment, the NaBr was used as a packer fluid. The well was completed in August 2003. Case History #3 The well, located in the Gulf of Mexico, had a bottomhole temperature of 325oF (163oC). Produced gas contained 3% 5% (mol.) CO2 and trace H2S. The packer fluid proposed was a 12.5 ppg NaBr brine. To combat CO2 and H2S corrosion at the high temperature, extensive laboratory stress corrosion cracking tests were conducted on HP1 13Cr (95 ksi) production tubulars with buffer and chemical additives (such as oxygen scavenger, H2S scavenger and corrosion inhibitor). Based on the laboratory data and as requested by the operator, the 12.5 ppg NaBr brine was treated with buffer, oxygen scavenger, H2S scavenger and corrosion inhibitor, and left in the annulus as a packer fluid. The well was completed in January 2004. Conclusions 1. A pH buffer has been developed and successfully applied as a corrosion inhibitor in NaBr brine packer fluids. 2. The pH buffer effectively controls weight loss corrosion of carbon steel and 13Cr as well as localized corrosion and pitting at high temperatures. 3. It also can control corrosion in CO2/H2S environments. 4. It is cost-effective, readily available, and easily handled and monitored in the field. 5. Field case histories demonstrate its effectiveness in hightemperature and high-pressure environments. Acknowledgement The authors wish to thank the management of BJ Services Company for the permission to publish this paper. References 1. Ibrahim, M.Z. et al.: Corrosion Behavior of Super 13Cr Martensitic Stainless Steels in Completion Fluids, NACE Corrosion/03 Paper No. 03097.

2.

3.

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5.

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7.

8.

9.

Mack, R. et al.: Stress Corrosion Cracking of A Cold Worked 22Cr Duplex Stainless Steel Production Tubing in A High Density Clear Brine CaCl2 Packer Fluid, NACE Corrosion/02 Paper No. 02067. Mowat, D.E. et al.: Erskine Field HPHT Workover and Tubing Corrosion Failure Investigation, SPE/IADC 67779, presented at the 2001 SPE/IADC Drilling Conference in Amsterdam, The Netherlands, February 27-March 1, 2001. Hudson, T.E.: Corrosivity of Heavy Brines Understanding it and Techniques Operators Can Use to Control It, OTC 5266, presented at the 18th Annual OTC in Houston, Texas, May 5-8, 1986. Javora, P.H. et al.: The Chemistry of Formate Brines at Downhole Conditions, SPE 80211, presented at the SPE International Symposium on Oilfield Chemistry in Houston, Texas, February 5-8, 2003. Burke, P.A. et al.: CO2 Corrosion Behavior of Carbon and Alloy Steels in High Concentration Brine Solution, NACE Corrosion/88 Paper No. 212, St. Louis, Missouri, March 21-25, 1988. Potter G.F.: Formation Damage of Brine Corrosion Inhibitors, SPE 12495, presented at the Formation Damage Control Symposium in Bakersfield, California, February 13-14, 1984. Silverman, S.A. et al.: Use of High-Strength Alloys and Elastomers in Heavy Completion Brines, SPE 84515, presented at the SPE Annual Technical Conference and Exhibition in Denver, Colorado, October 5-8, 2003. Houchin, L.R. et al.: Evaluation of Potassium Carbonate as a Non-Corrosive, Chloride-Free Completion Fluid, SPE 27392, presented at the SPE International Symposium on Formation Damage Control in Lafayette, Louisiana, February 7-10, 1994.

Metric Conversion Factors (oF-32) 0.5556 = oC in 2.54 = cm lb 0.4536 = kg gal 3785 = cc ppg 119.8264 = kg/m3 bbl 0.159 = m3 psi 6.895 = kPa

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SPE 87563

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 0 1 2 3 4 5 6

pH

9.0 ppg NaBr 12.4 ppg NaBr

10

11

12

13

14

15

Buffer Loading (ppb)

Figure 1.

pH of NaBr Brine vs. Buffer Loading

Table 1. NaBr System 9.0 ppg without treatment 9.0 ppg with buffer 12.4 ppg without treatment 12.4 ppg with buffer 12.4 ppg with adjusted pH by NaOH

Corrosion Rates of P110 over 7 Days at 400oF (204oC) pH 1 pH 2 Corrosion Rate, mpy Comments 8.2 10.4 8.1 9.8 9.1 7.8 10.1 8.4 9.6 8.4 1.4 0.3 4.8 0.2 4.3 Localized corrosion General corrosion Localized corrosion General corrosion Localized corrosion

Table 2. NaBr System 9.0 ppg without treatment 9.0 ppg with buffer 12.4 ppg without treatment 12.4 ppg with buffer

Corrosion Rates of P110 over 30 Days at 400oF (204oC) pH 1 pH 2 Corrosion Rate, mpy Comments 7.7 10.3 7.3 9.8 6.8 9.4 7.3 9.6 0.6 0.3 1.1 0.1 Localized corrosion. General corrosion Localized corrosion. General corrosion

Table 3. NaBr System 9.0 ppg without treatment 9.0 ppg with buffer 12.4 ppg without treatment 12.4 ppg with buffer

Corrosion Rates of 22Cr over 30 Days at 400oF (204oC) pH 1 pH 2 Corrosion Rate, mpy 8.1 6.9 0.0 10.5 10.1 0.0 8.0 7.9 0.0 9.5 9.4 0.0

Table 4. Corrosion Rates of 13Cr over 7 Days at 400oF (204oC) NaBr System pH 1 pH 2 Corrosion Comments Rate, mpy 12.5 ppg 7.3 8.5 1.3 Pitting on cut side and localized corrosion without treatment near cut edge 12.5 ppg with buffer 10.1 9.6 0.2 General corrosion

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SPE 87563

NaBr System 12.4 ppg without treatment 12.4 ppg with buffer 12.4 ppg without treatment 12.4 ppg with buffer

Table 5. Corrosion Rates of Q125 and HP1 13Cr under 400 psig N2 Containing 30 psig CO2 over 7 Days at 350oF (177oC) Coupons pH 1 pH 2 Corrosion Rate Comments mpy Q125 7.2 4.8 5.7 General corrosion Q125 HP1 13Cr HP1 13Cr 10.0 7.2 10.0 7.9 4.8 8.3 0.2 2.4 1.2 General corrosion General corrosion General corrosion

Table 6. NaBr System 9.0 ppg without treatment 9.0 ppg with buffer 12.4 ppg without treatment 12.4 ppg with buffer

Bi-Metallic (Galvanic) Tests of P110 and Cr22 over 30 Days at 400oF (204oC) Coupons pH 1 pH 2 Corrosion Rate Comments (galvanic) mpy P110 8.1 7.3 0.4 Localized corrosion 22Cr 8.1 7.3 0.0 P110 10.5 10.3 0.2 General corrosion 22Cr 10.5 10.3 0.0 P110 7.1 7.2 1.4 Localized corrosion 22Cr 7.1 7.2 0.0 P110 9.4 9.4 0.0 22Cr 9.4 9.4 0.0

Table 7. C-Ring Stress Corrosion Cracking Tests at 90% Stress Level under 400 psig N2 Exposure NaBr System Metal Tubulars Temperature o F Time (Day) 12.4 ppg NaBr 22Cr 400 (204oC) 30 12.4 ppg NaBr with buffer 22Cr 400 30 12.0 ppg NaBr with buffer Modified 13Cr 212 (100oC) 21

Comments No crack No crack No crack

C-Ring Stress Corrosion Cracking Tests of HP1 13Cr Over 15 Days in 225 psig CO2 containing 5 ppm H2S Environments Brine System Stress Level, % Temperature, oF Comments 9.5 ppg NaBr with buffer, oxygen 90 300 (149oC) No crack scavenger and H2S scavenger 100 300 No crack 90 350 (177oC) No crack 100 350 No crack

Table 8.

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