Evaluation of Some Stainless Steel and Nickel Alloys in Acidizing Environments

Summary
The present study involved the evaluation of selected stainless and nickel base alloys in the following acidizing media: (1) 15 percent HCl, (2) 28 percent HCl, (3) 12 percent formic acid and (4) 13 percent HCl/2 percent HF. Tests were conducted both with H2S and with CO2 at 200 F and 400 F. Two different inhibitors were used in each acidizing media. Acidizing media were generally found to be very aggressive to stainless and nickel base alloys. In most cases, the 22 Cr and 25 Cr duplex stainless steels exhibited selective attack of the ferrite phase by the acid solutions. However, under most conditions, corrosive attack was of a general nature with pitting occurring in only a few cases. Isolated occurrences of intergranular corrosion and end grain attack were noted. A method of determining compatibility of high alloy materials with acidizing media is presented based on the following guidelines: (1) general weight loss corrosion rate of <2000 mpy, (2) low tendency for localized corrosion, and (3) no stress corrosion cracking.

Introduction
In recent years, the use of highly alloyed, stainless and nickel base alloys in corrosive oilfield production environments has become increasingly prevalent. These materials offer great potential in revolutionizing well completion design by increasing allowable stress levels, removing inhibitor systems, and basically making it possible to do some operations not possible using conventional technology. Most importantly, these "high alloy" completions have been shown to offer substantial economic advantage in many cases over conventional completions particularly in offshore operations.

Extensive laboratory testing has identified specific stainless steels and nickel alloys that can be utilized under conditions of H2S, CO2, and brine. These studies have been the basis for many current projects involving actual field use of these materials. Arising from this experience are concerns over the performance of the more commonly accepted high alloy materials in acid environments. Acids have been used to stimulate well production for decades by adding corrosion inhibitors to reduce the extent of the corrosive attack on the steels and nickel alloys center around the following areas: 1. What is the limit of corrosion resistance for stainless steels and nickel alloys in acidizing environments? 2. Are there synergistic effects of acids and H2S on corrosion and environmental cracking? 3. How effective are conventional acid inhibitors on high alloy materials? However, to date, there has been only limited published information on the behavior of these high performance materials in acidizing environments.

The Present Study

Presented herein is the final report summarizing the findings of a testing program in which information was generated on the corrosion and environmental cracking behavior of commonly used stainless steels and nickel base alloys in simulated acidizing environments. This information will aid in the selection of high alloy materials for oilfield service. Most importantly, the new data obtained should provide a basis for the development of better guidelines and practices for acidizing when stainless steels and nickel base alloys are utilized.

Experimental Approach
Four acidizing media are common in oilfield operations. They are inhibited formulations of the following: 1. 2. 3. 4. 15% Hydrochloric Acid 28% Hydrochloric Acid 12% Formic Acid 13% Hydrochloric Acid + 2% Hydrofluoric Acid

Two important considerations in acidizing are that stainless and nickel alloy materials used in high alloy completions must (1) not sustain severe localized corrosive attack and , (2) not be susceptible to environmental cracking when contacted with these fluids. Of utmost concern is that exposure to acidizing media may destroy the passivity on the metal surface and eventually lead to corrosion and/or cracking. In the present study, tests were conducted on selected high alloy materials under simulated acidizing conditions. This involved a three step exposure sequence over a period of two weeks (14 days). The three step procedure is shown below: Step 1 - Full strength acid + inhibitor (duration - 6 hours) Step 2 - Reacted Acid and full strength inhibitor (duration - 6 days) Step 3 - Reacted/ Diluted Acid and no inhibitor (duration - 7 days) The rationale for this approach is that during acidizing, the materials will be contacted with full strength acid and inhibitor (Step 1). This environment is the most severe from the standpoint of acid strength. However, the inhibitor will also be at full strength. As the acidizing media is circulated out of the well and for a period of time after acidizing, the acid and inhibitor are being diluted with formation fluids (Step 2 and 3). Test were conducted with and without H2S gas to simulate acidizing under both sweet and sour conditions and at two different temperatures.

Experimental Program Materials and Procedures

Four series of autoclave exposure tests were conducted on selected high alloy materials in acidizing media. These autoclave exposures were divided into tasks designated 1 through 4 as shown below: Task 1 - 15% HCl Task 2 - 28% HCl Task 3 - 12% Formic Acid Task 4 - 12% HCl + 3% HF

Materials
Weight loss corrosion tests and stress corrosion cracking (SCC) tests were conducted on ten stainless and nickel base alloys. The materials strengthened by cold working, and used primarily as tubing were. 22 Cr - duplex stainless steel 25 Cr - duplex stainless steel 28 Cr - austenitic stainless steel 42 Ni - nickel base alloy 52 Ni - nickel base alloy C-276 - nickel base alloy Allcorr - nickel base alloy The materials strengthened by heat treatment, and used for tubulars and ancillary equipment were: 13 Cr - martensitic stainless steel Incoloy 925 - nickel base alloy Inconel 718 - nickel base alloy

Specimens
Weight loss corrosion coupons were used with the nominal dimensions of 1.0inch x 0.5-inch x 0.063-inch. A 0.25-inch hole was in the middle of the coupon. The coupons were isolated from each other with TFE shoulder washers. Susceptibility to SCC was determined with the use of C-ring specimens stressed to 100 percent of the 0.2 percent offset yield strength.

Inhibitors
All inhibitors are based on aromatic heterocyclic nitrogen compounds and formulated for use in oilfield acidizing environments. Inhibitors EWS-480 and EWS-557 were used for all HCl and HCl/HF acid formulations. For the formic acid media, EWS-482 and EWS-483 were used.

Environments
Task 1 through 4 involved exposure to each of the four acidizing media. Two formulations of each acid type were conducted. The primary difference in the formulations was the inhibitor. Two temperatures were used for each task: 200 F and 400 F. In addition, tests were conducted without H2S (PCO = 200 psi added at 75 F) and with H2S (PHS =100 psi added at 75F). Both C-ring specimens and corrosion coupons were exposed simultaneously to the test media. The procedure was to put the samples and acidizing media into TFE containers in Hastelloy C-276 lined autoclaves with CO2 or H2S gas. The autoclaves were run in a sequence of three steps simulating the acidizing processes as given in the Experimental Approach section.

Task 1 -15 percent HCl Tests

Autoclave exposure tests were conducted in a 15 percent HCl acidizing media. A total of eight tests were performed which were designated 1-1 through 1-4 and 1B-1 through 1B-4. Tests 1-1 through 1-4 were conducted with inhibitor EWS 480 and tests 1B-1 through 1B-4 were conducted with inhibitor EWS-557. Tests at 200F and 400F had 0.6 and 3.0 volume percent inhibitor, respectively. In all cases, each test involved a three step sequence of exposures as given in these tables. The reactant was CaCO3 which was added to reduce the acidity of the environment. Dilution were made with distilled water.

Task 2 - 28 Percent HCl Tests.

Autoclave exposure tests were conducted in a 28 percent HCl acidizing media. A total of eight test were performed which were designated 2-1 through 2-4 and 2B1 through 2B-4. Tests 2-1 through 2-4 were conducted with inhibitor EWS-480 and Tests 2B-1 through 2B-4 were conducted with inhibitor EWS-557. Tests at 200F and 400F had 1.2 and 6.0 volume percent inhibitor, respectively. As in the previous set of tests, CaCO3 was used as the reactant. Dilutions were made with distilled water. The tests conducted at 400F had to be reduced in duration to 7 days by deletion of the final steps in the sequence because of sever corrosion and/or cracking.

Task 3 - 12 Percent Formic Acid Tests.

Autoclave exposure tests were conducted in a 12 percent Formic Acid acidizing media. A total of eight tests were performed which were designated 3-1 through 3-4 and 3B-1 through 3B-4. Tests 3-1 through 3-4 were conducted with inhibitor EWS 482 and Tests 3B-1 through 3B-4 were conducted with inhibitor EWS 483. Tests at 200F and 400F had 0.6 and 3.0 volume percent inhibitor, respectively. The reactant, in this case, was CaCO3. Dilutions were made with 5 percent NaCl solutions.

Task 4 - 13 Percent HCl/2 Percent HF Tests.

Autoclave exposure tests were conducted in a 13 percent HC1/2 Percent HF acidizing media. A total of eight tests were performed which were designated 4-1 through 4.4 and 4B-1 through 4B-4. Tests 4-1 through 4.4 were conducted with inhibitor EWS 480 and Tests 4B-1 through 4B-4 were conducted with inhibitor EWS 557. Tests at 200 F and 400 F had 0.6 and 3.0 volume percent inhibitor, respectively. The reaction of the acid was obtained by addition of silica flour and bentonite. This reaction was conducted at 150 F. Dilutions were made with distilled water. Tests conducted at 400 F had to be terminated after the second step (7 days total duration) because of severe corrosion and/or cracking.

Evaluation of Specimens
Upon completion of each step of the autoclave tests the specimens were examined for susceptibility to cracking, weight loss corrosion rate and nature of corrosion. Susceptibility to cracking was made by visual observation at up to 100X. Weight loss corrosion rates were calculated from weight loss determination after 6 hours and the total 14 day exposure. These were based on weight measurements made to the nearest 0.1 mg before and after exposure.

Results and Discussion Task 1 -15 Percent HCl Tests Weight Loss Corrosion Results
For tests conducted with EWS-480 corrosion rates after both 6 hours and 14 days were greatest for alloys through 25 Cr duplex stainless steel. Maximum corrosion rates were found to be for the duplex stainless steels at both 200 F and 400 F. Corrosion rates of the duplex stainless steels are typically 7 to 30 times that of carbon steel. The type of corrosive attack exhibited by the duplex stainless steels was that of selective attack of the ferrite grains. The predominate mode of attack in the other materials was general corrosion during the initial 6 hour exposure and after the 14 day exposure. Pitting was observed in some materials after the 14 day exposure with H2S at 200 F (13 Cr, 28 Cr, 42 Ni and 925) and with CO2 at 400 F (52 Ni and Allcorr). Similar trends were noted for the Task 1B tests in 15 percent HCl with EWS-557 except that: 1. Lower general corrosion rates were observed at 200 F relative to the Task 1 tests with EWS-480 2. Lower tendency for pitting At 400 F, weight loss corrosion was severe with both inhibitors.

SCC Results
The SCC found in the 28 percent HCl acidizing media was only slightly more severe that that exhibited in the 15 percent HCl tests discussed previously (See Table). SCC was only observed during the first 6 hour step in the exposure sequence in one instance (28 Cr; 400 F with CO2) with both inhibitors. At 400 F, all specimen failed by SCC by the end of the second step of the sequence.

Task 3 - 12 Percent Formic Acid Test Weight Loss Corrosion Results

The formic acid environment was by far the least aggressive of the acidizing media examined in this study. Weight loss corrosion rates in all cases except the 22 Cr duplex stainless steel (at 400 F) were less than or equal to 1200 mpy at 400 F. The corrosive attack was general in nature except for the 22 Cr material. As in the case of the HCl systems, the duplex stainless steels exhibited high weight loss corrosion rates (5,000 mpy) with a selective attack of the ferrite phase. However, this attack was not as severe in formic acid as that found in HCl solutions. In general, inhibitor EWS 557 provided for lower general corrosion rates than did EWS 480 in most of the higher alloy materials. However, performance of the inhibitor is very alloy specific. Widely varying behavior was quite commonly observed with the same inhibitor in two or more closely related alloys.

SCC Results
SCC was not a major occurrence in the formic acid media. With both inhibitors EWS 480 and 557 in steps 1 and 2, no SCC was observed. However, in step three, where the dilution of the acid was made with 5 percent NaCl solution, SCC occurred in both 22 Cr and 25 Cr duplex stainless steels.

Task 4 - 13 Percent HCl/2 Percent HF Tests Weight Loss Corrosion Results

As anticipated, the HCl/HF acidizing media was the most severe of those examined in this study. Corrosion rates of 13 Cr and duplex stainless steels were from 370 mpy to over 47,000 mpy, respectively. This behavior in the duplex stainless steels was related to the same type of selective attack of the ferrite phase experienced in the other environments. The other materials exhibited sever general corrosion. Other forms of corrosion, however, were also noted. Allcorr specimens exhibited intergranular attack in the HCl/HF media at 400 F. In addition, the Inconel 718 and 42 Ni were found to have end grain attack in this environment.

SCC Results
With inhibitor EWS-480, SCC was not observed at 200 F. However, at 400 F, SCC was noted in all materials not removed from this test due to excessive corrosion after the end of the second step in the exposure sequence. With inhibitor EWS-557, SCC was found to be more severe with failures occurring at 200 F after steps 2 and 3 and at 400 F after step 1 (6 hours).

Compatibility of Stainless Alloys with Acidizing Media

Currently, there are no guidelines for determining the compatibility of acidizing environments and high alloy materials. It is, however, documented in the literature that corrosion rates on the order of 2000 mpy can be experienced on carbon steel in inhibited HCl at 250 F. These seemingly high corrosion rates are more or less acceptable due to the relatively short duration of the acidizing treatment. It is, therefore, rational to assume that a similar guideline can be extended to high alloy materials if other necessary criteria can be added. Specifically, such guidelines for compatibility of acidizing media and high alloy materials must include the following: 1. Weight Loss Corrosion rate 2,000 mpy 2. Low tendency for localized corrosion and selective attack 3. No SCC 15 and 28 percent HCl and the HCl/HF environments are very severe particularly at 400 F. In only a few cases were materials found which would give acceptable performance under these conditions. At 200 F, the number of materials exhibiting acceptable performance is greater than at 400 F. Note, however, that there are some differences in performance between the performance of these alloys depending on the inhibitor compound employed. In the formic acid tests, acceptable performance was observed under nearly all conditions examined. However, conditional acceptability was called out for some conditions because of cracking that occurred during Step 3. Such conditions would only occur due to prolonged exposure to spent acid and formation brine with no inhibitor. Consequently, the need for good "clean up" of the well after acidizing can be seen.

In summary, the behavior of stainless and nickel base alloys can vary greatly depending on the (1) acidizing media, (2), inhibitor, (3) duration of treatment, (4) downhole temperature, (5) gas concentration of formation, and (6) procedure used to "clean-up" the well following acidizing. However, performance can be predicted based on laboratory tests which simulate field procedures and conditions. The performance, as indicated in this study, is very alloy and environment specific. Consequently, the use of the information presented should be done carefully. Recommendations for selection of materials, acidizing media, and procedures should be made based on information relevant to the specific situation at hand.

Conclusions
Based on the results of the program presented in this report the following conclusions were made: 1. Oilfield acidizing media are aggressive to stainless and nickel base alloys with severity of attack by corrosion and SCC increasing dramatically over the range 200 F to 400 F. 2. The ranking of environment in decreasing order of severity are: (1) 13% HCl/12% HF (2) 28% HCl (3) 15% HCl (4) 12% formic acid 3. Behavior of the stainless and nickel base alloys is very alloy and environment specific. 4. Corrosive attack was characterized by general corrosion in most cases. However, specific cases were found where selective attack, pitting, intergranular corrosion and end grain attack were observed. 5. Duplex stainless steels typically exhibited selective attack of the ferrite phase in acidizing media.