SPE 58712 Investigation of Sulfide Scavengers in Well Acidizing Fluids

H.A. Nasr-El-Din, SPE, A.Y. Al-Humaidan, SPE, B.A. Fadhel, Saudi Aramco, W.W. Frenier, SPE and D. Hill, SPE, Schlumberger

Copyright 2000, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 2000 SPE International Symposium on Formation Damage Control held in Lafayette, Louisiana, 2324 February 2000. 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.

Abstract This paper describes the development of acidizing systems that use several different aldehyde-based sulfide suppression chemicals in conjunction with new acid corrosion inhibitors. Specific combinations of these chemicals have allowed the acid to dissolve FeS, suppress H2S and still enable the acid to be inhibited to industry corrosion standards. Laboratory tests include dissolution of FeS, measurement of H2S evolved, measurement of acid concentration and chloride ion concentrations. We also determined the effect of FeS and H2S on the corrosion of oilfield steels with these additives. Laboratory measurements covered the temperature range from 75 to 275 oF (reservoir temperature). Experimental results were compared with that previously published data.1 The new system enabled the acid to dissolve more FeS than fluids containing previously tested suppressors, while controlling H2S evolution and corrosion. During field testing, samples of the spent acid were captured and were analyzed for [Fe], [S2-] and [HCl]. The data will contribute to an understanding of the corrosion processes and sulfide control during acid treatments. The field acid treatments were accomplished successfully without significant changes in procedures and resulted in large increase in gas production. This system is designed primarily for "tube cleaning" operations prior to acid stimulation (matrix and fracture acidizing), but the control chemicals have also been tested for use in the actual stimulation fluid stages. The new chemicals and procedures will allow the operators to safely remove large amounts of fouling deposits, while controlling the toxic and corrosive effects of H2S much more effectively than previously used products.

Introduction In many wells, pipelines, or in the hydrocarbon processing units of refineries, iron-based surfaces may come into contact with sulfur-containing fluids. At the temperatures present in the various sections or reactors, and during long periods of contact, iron sulfide deposits (generally FeS, but sometimes, FeS2) will form. The reduced sulfur minerals with approximately 1:1 Fe/S mol ratios (makinawite, troilite, pyrrhotite) can be dissolved using mineral acids, while pyrite and marcasite (FeS2) have low acid solubility. 2 While scale removal using mineral acids is a very effective procedure, it produces large amounts of hydrogen sulfide. FeS + 2H+ = Fe2+ + H2S (1).

Hydrogen sulfide causes severe safety and operational problems once the acid leaves the system being treated, and H2S stimulates corrosion of the base metal. For pipelines or in refinery operations, surface cleaning is the major goal of the operation. Lawson et al.3 reviewed the major procedures for safely removing iron sulfide deposits: 1) mineral acids with an acid-gas scrubber; 2) mineral acids with hydrogen sulfide suppression chemicals; 3) multiple stages of oxidizing agents with acids; and 4) alkaline cleaners. Several different suppression technologies have been developed for surface cleaning operations. Frenier and coworkers4-6 and Buske7 developed suppression chemicals that contain aldehydes. The most efficient agent is formaldehyde, which reacts stoichiometrically with hydrogen sulfide to produce trithiane, a very insoluble material.8 In treating sour oil and gas wells, as compared with treating surface equipment, corrosion suppression (not elimination of sulfide gas) and dissolution of FeS are of major concern. The inhibitor package must protect several types of steel at high temperatures in the presence of concentrated acid containing numerous additives. The various additives are required since the purpose of the treatment may include removal of inorganic and organic damage from producing formations (matrix treatments). Tubular cleaning prior to acidizing the formation is commonly performed and is strongly recommended.9,10 During acidizing treatments, the control of iron and sulfur precipitation is an important requirement. The control is

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necessary to prevent formation damage due to precipitation of iron compounds and elemental sulfur. As the acid spends on carbonate surfaces, ferric iron precipitates at pH > 1.5,10 and ferrous iron precipitates at pH values > about 6.0. Elemental sulfur can precipitate if ferric iron is present:9 Fe3+ + S2= Fe2+ + So (2).

As the pH rises above 1.9, any residual iron can react with sulfide ions to re-precipitate FeS.11 Fe2+ + S2= FeS (3).

sour water injectors. A 7.5 wt% HCl solution was effective in removing FeS and biomass. A sulfide scavenger tested (but not named) did not damage the cores. Al-Humaidan and Nasr-El-Din1 examined a number of sulfide scavengers at ambient conditions. None of the commercial formulations were as effective as formaldehyde. In addition, they found that most of these scavengers adversely affected acid reactions with iron sulfide scale, especially at high scavenger concentrations. Therefore, the objective of this work is to identify a scavenger or a mixture of scavengers to improve suppression of H2S evolution while preserving the high dissolution of FeS as well as controlling corrosion up to 275 oF. Experimental Procedures Three sets of experiments were conducted. The first set was done at atmospheric pressure and temperature of 25 C. The second set was also done at atmospheric pressure, however, the test temperature was 150 F. The third set was done at a temperature of 275 F and a pressure of 3000 psi. The experimental set-ups and procedures used are explained in the following sections. Experimental set-up and test procedure used at ambient conditions. The first set of experiments was performed at ambient conditions. The set-up consisted of a reactor and two absorbers.1 The reactor initially contained a known amount of iron sulfide. Then, hydrochloric acid with various chemicals was added to the reactor. The absorbers are connected in series and contained a cadmium sulfate solution at a concentration of 10 wt%. Iron sulfide particles with a diameter less than 75 microns (200 mesh) were used. A predetermined amount of iron sulfide particles (typically 1 g) was placed in the reactor. Then, five g of 7.5 wt% hydrochloric acid with additives were poured on the solids. In all experimental runs, a hydrogen sulfide scavenger was added to the acid just prior to the experiment. The effectiveness of various hydrogen sulfide scavengers was studied over a wide range of concentrations. The reactants were continuously mixed using a magnetic stirrer. The reaction was allowed to proceed for two hours then the liquid and solids phases present in the reactor were separated and analyzed. To determine the amount of H2S gas produced from the reaction between iron sulfide and hydrochloric acid, the gas passes through the cadmium sulfate solution, which is present in the absorbers. Hydrogen sulfide reacts with cadmium sulfate and produces a yellow precipitate of cadmium sulfide. The amount of hydrogen sulfide released was determined from the weight of cadmium sulfide. The concentrations of key ions in the aqueous phase in the reactor (supernatant) were measured. Chloride was measured by titration with a 0.1N silver nitrate solution. Iron concentration was measured by Inductively Coupled PlasmaEmission Spectroscopy (ICP-ES). Acid concentration was measured by titration with a 0.1 N NaOH solution. Sulfide ion

Iron sulfide and elemental sulfur have been implicated in production declines following acid treatments. For these reasons, acid treatments of sour wells have a number of goals and requirements for success: 1. Dissolution of any FeS (or other sulfides) already present, 2. Elimination of reprecipitation of solids after completion of the acidizing procedures, 3. Suppression of formation of H2S during acid dissolution of FeS, and 4. Control of corrosion to well tubulars during the acidizing process. Iron control during acidizing treatments can be achieved by adding chelating agents (citric acid, NTA, etc.) or by using reducing agents (sodium erythorbate). Crowe12 patented a combination of chelating and reducing agents to simultaneously prevent iron and sulfur precipitation in spent acids. This technology may control the reactions in Equations 2 and 3. The combination of reduction and chelation should control all of the solids as the pH rises to > 1.9. Hall and Dill13 reviewed a number of precipitation control methods for sour and sweet wells. They acknowledged that chelating agents are effective in controlling iron precipitation, but advocated the use of a sulfide modifier, NTA and ethyleneglycol monobutylether (EGMBE) to treat sour wells containing iron. Dill and Walker14 claimed a combination of a chelating agent (NTA) and an aldehyde (aldol) for controlling iron and sulfur precipitation. Walker et al.9 expanded on this concept and noted that iron control agents are not required during tube clean-out procedures. However, they advocated the use of a "sulfide scavenger". This material apparently is the "sulfide modifier" endorsed previously by Hall and Dill.13 Walker et al. also claimed that the reducing agents described by Crowe12 are not effective in 15 wt% HCl. Ford et al.2 advocated well clean-out procedures using only the acid and the sulfide scavenger. However, in the case histories described, the acid formulation was injected directly into the formation. Williamson 15 claimed the use of a chelating agent and a ketone for the same types of treatments for which the Walker et al.9 acid formulations are used. Kasnick and Engen 16 advocated acid washing of the tubing prior to formation acidizing treatment of a deep gas well in Saudi Arabia. No mention of sulfide control was made. Nasr-El-Din et al.17,18 studied various additives for stimulating sandstone through

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INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

was measured using the iodometric method. Experimental set-up and test procedure used at 150 F. The second set of tests was conducted at 150 F and atmospheric pressure. The experimental set-up consisted of a three neck reaction flask equipped with a dropping funnel, heating mantle/temperature controller and a mechanical stirrer, Fig. 1. The dropping funnel was used for efficient addition of all acid solutions containing all additives. The mechanical stirrer was used for efficient mixing of the acid with the powdered iron sulfide. The acid gases produced by the reaction were swept to a scrubber containing 300 cm3 of a 3 wt% NaOH solution. Two ratios of acid to FeS were used: 200 g acid to 3 g FeS, 108 g acid to 10 g FeS. Two grades of FeS were used: 1) a technical grade with a particle size of about 40 mesh; and 2) a purified (99.9 wt%) grade with a particle size of 100-200 mesh. The acid was heated to the test temperature, and the FeS particles were added and the solution was stirred with a mechanical blade stirrer. In selected tests, an L-80 coupon was inserted to measure the corrosion of the test fluid. The designations of the additives are given in Table 1. Experimental set-up and test procedure used at 275 F. the third set of tests was performed at 275 F and 3,000 psi in a small, high temperature corrosion autoclave at Stim-Lab, Duncan, OK. Iron sulfide scale (1.2 g) was added to 100 mL of 7.5 wt% HCl inhibited with 1% Acid Corrosion Inhibitor B + 2% Inhibitor Aid (formic acid). At the conclusion of the test, the pressure was cautiously bled and the produced gases were bubbled through 300 cm3 of a 3 wt% NaOH solution. The concentrations of iron and sulfur were determined in the residual acid (supernatant) and the sodium hydroxide solution, respectively, and the scavenging efficiency was determined. Corrosion Inhibition. Additional corrosion tests were completed with L-80 steel coupons exposed to 7.5 wt% HCl inhibited with Inhibitor B and Inhibitor Aid as described for the above tests. Corrosion tests were completed at 275 F and 5,000 psi for four hours contact time at temperature. Standard corrosion autoclave test procedures were employed.19 The maximum allowable corrosion rate recommended for these test conditions is 0.05 lb/ft2 with no unacceptable pitting. Acceptable pitting is represented by a pitting index of 3 or less. Results and Discussion Performance of the scavengers at ambient conditions. AlHumaidan and Nasr-El-Din1 examined several hydrogen sulfide scavengers that can be used during acidizing treatments. They found that formaldehyde was very effective in their experiments. Formaldehyde, however, has limited use in the oil industry because it is carcinogen. One way to overcome this problem is to use hexamethlyenetetraamine (HMTA) which reacts with HCl to produce formaldehyde.5

N N N N + 4H +6 H2 O 6 CH2O + 4 NH4

Hexamethylenetetraamine

(4)

The performance of HMTA was evaluated by adding 5 g of 7.5 wt% HCl to 1 g of FeS particles. The efficiencies of capturing hydrogen sulfide and dissolving FeS were determined as described in Reference 1. It is worth mentioning that 43.2 wt% of FeS should be dissolved by the amount of the acid used. Fig. 2 shows the efficiencies of capturing hydrogen sulfide and dissolving FeS as a function of the initial HMTA concentration. The efficiency of capturing hydrogen sulfide was relatively high. However, the efficiency of dissolving FeS was 19% at 0.2 wt% HMTA. It decreased and reached 12.6% at 8 wt% HMTA. These results indicate that most of the acid did not react with the FeS. As a result, the amount of H2S released was low. The concentration of the acid in the supernatant was measured. Fig. 3 shows the variation of HCl concentration as a function of the initial HMTA concentration. Acid concentration was 3.6 w/v% at 0.2 wt% HMTA and decreased to 0.5 at HMTA concentration of 8 wt%. At low HMTA concentrations, the amount of formaldehyde available is small. As a result, hydrogen sulfide accumulates and the rate of reaction of the acid and FeS diminishes. At high HMTA concentrations, a large portion of the acid reacts with HMTA, and, as a result, the concentration of HCl in the supernatant diminishes. Several important points should be noted in Figs. 2 and 3. First, the efficiency of capturing hydrogen sulfide can be misleading. The efficiency of dissolving iron sulfide should be considered simultaneously. HMTA consumes a portion of the acid used. This amount should be considered when designing a formula for field application. Finally, HMTA is not as effective as formaldehyde. This point will be further discussed in the following sections. Other aldehyde-based chemicals were also examined. The efficiencies of capturing hydrogen sulfide and dissolving FeS in the presence of Aldehyde B, Table 1, are shown in Fig. 4 as a function of the initial scavenger concentration. The efficiency of capturing hydrogen sulfide increased with the scavenger concentration up to 5 wt% Aldehyde B, then remained constant. The efficiency of dissolving FeS slightly decreased with the scavenger concentration, then remained constant. A comparison of the results shown in Figs. 2 and 4 clearly indicate that the performance of Aldehyde B is significantly better than HMTA. This conclusion is further confirmed by examining acid concentration in the supernatant in the presence of Aldehyde B, Fig. 5. Acid concentration was 0.3 w/v% at 0.25 wt% Aldehyde B. It increased to 1.4 w/v% at Aldehyde B concentration of 8 wt%. These values are

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significantly less than those obtained in the presence of low concentrations of HMTA. At high scavenger concentrations, acid concentration in the supernatant of HMTA solutions was lower. This is because of the acid reaction with HMTA. Previous studies have indicated that formaldehyde is the most effective scavenger. It is of interest to compare the performance of several aldehydes examined in the present study with that of formaldehyde. Fig. 6 compares the efficiency of capturing hydrogen sulfide obtained with Aldehyde A, B and HMTA with that obtained with formaldehyde. The efficiency of capturing hydrogen sulfide is highest when HMTA was used. However, this trend is misleading as mentioned before. The efficiency of formaldehyde to capture hydrogen sulfide is higher than that obtained with Aldehyde A or B, especially at high initial scavenger concentrations. The efficiency of capturing H2S using Aldehyde A is nearly similar to that obtained with Aldehyde B. Fig. 7 compares the efficiency of dissolving FeS in the presence of various scavengers. HMTA has the lowest efficiency, whereas formaldehyde has the highest efficiency. Aldehyde B has a slightly better efficiency than Aldehyde A. The results shown in Figs. 6 and 7 indicate that formaldehyde is the most effective aldehyde. HMTA is not as efficient as formaldehyde. Aldehydes A and B have nearly similar performances. Performance of the scavengers at 150 F. The results discussed so far were obtained at room temperature. It is of interest to examine the performance of various scavengers at elevated temperatures. Figs. 8 and 9 show the percentage of FeS dissolved and H2S evolved (as measured by the amount of sulfide in the NaOH solution) for a set of tests conducted at 150 oF, which used 10 g of 200 mesh FeS and 108 g of 7.5 wt% HCl. There was just enough acid to dissolve the entire iron sulfide sample. The control acid (no additives) dissolved almost 95 wt% of the sample and there was 0.31 wt% S (total S by X-ray diffraction) in solution. This value was used as the saturation value for the supernatant and compared favorably with the literature value of 0.4 wt% H2S in HCl.20 Values > 0.31 wt% indicate that the scavenger is holding some sulfur in solution. The weight used of each aldehyde is the theoretical amount needed to scavenge all H2S that could be produced from acid reaction with iron sulfide. All of the aldehydes examined maintained more sulfur in solution than the control, Fig. 9. They also reduced total FeS dissolution to some extent, especially Aldehydes C and D. The formaldehyde test deserves more explanation. In the presence of hydrogen sulfide, trithiane is formed:

This material is insoluble in acid and thus takes some of the sulfur out of the solution (supernatant). Aldehyde A also produced some solids after the acid cooled, but not as much as formed with formaldehyde. Aldehyde B did not produce any solids, even when the acid cooled to room temperature. Aldehydes A and B were the most effective scavengers tested. Similar to the results obtained at room temperature, HMTA was not as effective as predicted from literature.5 However, even when an equivalent amount of additional HCl was added, it was not as effective as Aldehydes A or B. We also see that Aldehydes A and B interfered with the dissolution of FeS. More FeS dissolved in the presence of Aldehyde B. This is similar to the results obtained at room temperature. A mixture of 15 g Aldehyde A and 1 g Aldehyde D allowed much more FeS to dissolve than the 2 vol% Aldehyde D test. It is worth noting that Corrosion Inhibitor B did inhibit the dissolution of FeS to some extent. This is in agreement with recent studies conducted by Nasr-El-Din et al.21 on the effect of acid additives on acid reaction with iron sulfide scales. The second type of tests employed 200 cm3 of 7.5 wt% HCl as a solvent for 3 g of the technical grade (40 mesh max) FeS. This amount of FeS should yield about 1 wt% Fe in solution, and is considered to be a good model for the amount of iron expected in most tube cleaning operations (if the entire volume of acid in the tubing is used as the mount used in the calculation). All tests were run at 150 oF and lasted for four hours. In some tests, a weighed L-80 corrosion coupon was placed in the flask so that a corrosion rate could be determined. The results are displayed in Fig. 10. Corrosion rates for these tests are given in Table 2. All of the solvent combinations dissolved at least 83 wt% of the scale. Many formulations dissolved 100 wt% of the deposit. All of them scrubbed essentially all of the H2S produced. The Aldehyde Bbased solutions were more corrosive than the Aldehyde Abased solutions. Addition of Aldehyde D reduced the corrosion rate in the presence of Aldehyde B. The formulation with Aldehydes B and D and Inhibitor B looks like an excellent compromise. Aldehyde scavengers react with H2S to produce complex sulfides (Eq. 5 is a special example). It is our observation that "oils" of undefined compositions, frequently form. The Aldehyde B solutions always had less black oil than the Aldehyde A or C solutions. Some of the test solutions had a wetting agent (Surfactant A) and an iron control agent (NTA) to simulate some field formulations. Evaluation of corrosion inhibition at 275 F. Acceptable corrosion inhibition for L-80 steel coupons was achieved using 0.6% Inhibitor B and 2.0% Inhibitor Aid. The test was conducted using 7.5 wt% HCl and the coupons were exposed to the acid for four hours at 275 F in an H2S environment containing an equivalent concentration of 0.5 mol% H2S. Corrosion data are shown for Aldehyde B and Aldehyde A in combination with Aldehyde D at a 10/1 volume ratio Table 3. The addition of Aldehyde D is necessary for achieving acceptable corrosion protection at this temperature.

H 3 CH2O + 3 H2S

S S

S + 3 H 2O

Formaldehyde Hydrogen Sulfide

Trithiane

(5)

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INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

Performance of the scavengers at 275 F. At the conclusion of the corrosion tests completed at 275 F, selected samples were submitted for total iron and sulfur analyses. Results of these analyses are shown in Tables 4 and 5 for Aldehyde B and Aldehyde A with varied surfactants, respectively. Results show high FeS dissolution. These results clearly show that greater than 80 wt% dissolution of the FeS is observed with the use of Aldehyde B or Aldehyde A. The iron and sulfur analyses are frequently observed to be higher than 100%, based on the quantity of FeS added to the test. These observations are attributed to the high temperature test and some of the water may have evaporated during the test and ions may have been concentrated, resulting in values greater than 100%. A closer evaluation of the test procedure and analyses are planned. Please note that high iron and sulfur content is desirable for this test procedure. A high [Fe] content signifies high FeS dissolution. On the other hand, high [S] content indicates good scavenging of the aldehyde used. This is a direct analysis of the acid following the corrosion tests and illustrates the high solubility of the scavenged sulfur products. One conclusion is clear: Aldehyde B and Aldehyde A are both effective in controlling H2S and high solubility of FeS is achieved for these test conditions. Field application. Based on extensive lab studies, it was decided to use HCl to pickle the tubing of a deep gas well in a sour carbonate reservoir in Saudi Arabia. Acid additives included Corrosion Inhibitor B, Inhibitor Aid (formic acid), and a mixture of Aldehyde B and Aldehyde D, Table 6. The acid volume was 5000 gals and acid concentration was 20 wt%. The acid was pumped in the well tubing and displaced using low sulfate water. Once the acid reaches the bottom of the tubing, the well was allowed to flow back. Samples of the return fluids were collected each two minutes. Hydrogen sulfide content was determined on site using the iodometric method, and the concentration of ferrous iron was determined using the method described by Taylor et al.22 The concentration of key ions were also determined and the results are given in Table 7. Initial samples contained low concentrations of sodium, calcium and magnesium. These samples represent the low salinity water that was used to displace the pickle acid down the well tubing. Samples collected after one hour contained live acid. The concentrations of Fe+2 and Fe+3 were relatively high in these samples. Hydrogen sulfide concentration values increased somewhat with the arrival of the acidic samples. It is interesting to note that the concentration of Fe+2 in the last sample reached 4800 mg/L. This amount corresponds to nearly 2750 mg/L of sulfide ion. Field measurements indicate that the concentration of sulfide is only a fraction of this value. These results confirmed that the acid system used in this well was capable of scavenging a large amount of hydrogen sulfide produced. In addition, iron concentrations in the flowback samples collected after the main acid treatment were low, which confirmed that the pickling acid did dissolve most of the corrosion products present in the well tubing. The acid

formula given in Table 6 was also used in three more wells. And similar trends were obtained. In addition, the main acid treatment has resulted in significant increases in gas production. Conclusions 1. The preponderance of the above data supports our recommendation that use of Aldehyde B with Aldehyde D is the overall best choice, considering FeS dissolution, corrosion and production of organic oil. 2. Aldehyde A is also effective in scavenging H2S; however, visual observations of experiments completed at temperatures 150 F reveal more oil residue formed during the test than observed for tests completed with Aldehyde B. Field results confirmed that the mixture of Aldehyde B and Aldehyde D was effective in reducing the amount of hydrogen sulfide released. Meanwhile they did not significantly affect acid reactions with iron compounds present in the well tubing.

3.

Acknowledgments The authors wish to acknowledge the Saudi Arabian Ministry of Petroleum and Mineral Resources, the Saudi Arabian Oil Company (Saudi Aramco) and Schlumberger, LTD for granting permission to present and publish this paper. The authors would like to thank Mr. R.M. Saleh for performing some of the experimental work. ULU and SALD of Saudi Aramco conducted chemical analysis of the acid return samples. References 1. Al-Humaidan, A.Y. and Nasr-El-Din, H.A.:"Optimization of Hydrogen Sulfide Scavengers Used During Well Stimulation," paper SPE 50765 presented at the 1999 SPE Oilfield Chemistry held in Houston, TX, February 16-19. 2. Ford, W.G.F., Walker, M.L., Halterman, M.P., Parker, D.L., Brawley, D.G., and Fulton, R.G.: Removing a Typical Iron Sulfide Scale: The Scientific Approach, paper SPE 24327 presented at the 1992 SPE Rocky Mountain Regional Meeting held in Casper, WY, May 18-21. 3. Lawson, M.B., Martin, L.D. and Arnold, G.D.:Chemical Cleaning of FeS Scales, Paper 219, Corrosion/80, NACE held in Houston, TX, March 1980. 4. Frenier, W.W. et al.: Composition and Method for Removing Sulfide-Containing Scale from Surfaces, US Patent 4,220,550, 1980. 5. Frenier, W.W.:Method and Composition for Removing Sulfide-Containing Scale from Metal Surfaces, US Patent 4,310,435, 1982. 6. Ball, C.L. and Frenier, W.W.: An Improved Solvent for Iron Sulfide Deposits, Paper 2, Corrosion/84, NACE, Houston, TX, April, 1984. 7. Buske, G.R.: Method and Composition for Removing Sulfide-Containing Scale from Metal Surfaces, US

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8.

9.

10.

11.

12.

13.

14.

15. 16.

17.

18.

Patent 4,289,639, 1981. Van Dijk, J. and Bos, A.: An Experimental Study of the Reactivity and Selectivity of Novel Polymeric TriazineType H2S Scavengers, Presented at the Chemistry in Industry Conference, Royal Society of Chemistry, 1998. Walker, M.L., Dill, W.R., Besler, M.R., and McFatridge, D.G.: Iron Control in West Texas Sour-Gas Wells Provides Sustained Production Increases, JPT (May 1991) 603. Taylor, K.C., Nasr-El-Din, H.A. and Al-Alawi, M.: Systematic Study of Iron Control Chemicals Used During Well Stimulation, SPEJ, 4, 19-24, 1999. Crowe, C.W.: Evaluation of Agents for Preventing Precipitation of Ferric Hydroxide from Spent Treating Acid, JPT (April 1985) 691. Crowe, C.W.: "Method of Preventing Precipitation of Ferrous Sulfide and Sulfur During Acidizing," US patent 4,633,949, 1987. Hall, B.E. and Dill, W.R.: Iron Control Additives for Limestone and Sandstone Acidizing of Sweet and Sour Wells, paper SPE 17157 presented at the 1988 SPE Formation Damage Control Symposium held in Bakersfield, CA, February 8-9. Dill, W.R. and Walker, M.L.: "Composition and method for Controlling Precipitation When Acidizing Sour Wells", US Patent 4,888,121, 1989. Williamson, C.D.:"Precipitation Control", US patent 5,126,059, 1992. Kasnick, M.A. and Engen, R.J.: Iron Sulfide Scaling and Associated Corrosion in Saudi Arabian Khuff Gas Wells, paper SPE 17933 presented at the 1989 SPE Middle East Oil Technical Conference and Exhibition held in Manama, Bahrain, March 11-14. Nasr-El-Din, H.A., Al-Anazi, H.A. and Hopkins, J.A.: "Acid/rock Interactions During Stimulation of Sour Water Injectors in a Sandstone Reservoir," paper SPE 37215 presented at the 1997 SPE Int. Symposium on Oilfield Chemistry held in Houston, TX, February 18-21. Nasr-El-Din, H.A., Rosser, H.R. and Hopkins, J.A.:Stimulation of Injection Water Supply Wells in

19.

20.

21.

22.

Central Arabia, paper SPE 36181 presented at the 1996 ADIPEC held in Abu Dhabi, October 13-16. Frenier, W.W.:"Acidizing Fluids used to Stimulate High Temperature Wells Can be inhibited with Organic Chemicals," paper SPE 18468 presented at the 1989 SPE Int. Symposium on Oilfield Chemistry, Houston, TX, February 8-10. Linke, W.F.: Solubilities of Inorganic and Metal Organic Compounds, Ed. A. Seidell, 4th Edition, American Chemical Society, Washington, DC, 1958, 1154. Nasr-El-Din, H.A, Al-Humaidan, A.Y., Fadhel, B.A. and Saleh, R.M.: "Effect of Acid Additives on the Efficiency of Dissolving Iron Sulfide Scale, Paper # 439, to be presented in NACE Conference, 2000. Taylor, K.C., Nasr-El-Din, H.A. and Al-Alawi, M.: Field Test Measures Amount and Type of Iron in Spent Acids, paper SPE 50780 presented at the 1999 SPE International Symposium on Oilfield Chemistry held in Houston, TX, February 16-19.

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INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

Table 1: List of Additives Additive Designation

Aldehyde A Aldehyde B Aldehyde C Aldehyde D Formaldehyde Inhibitor A Inhibitor B Inhibitor C Formic acid Surfactant A Surfactant B

Chemical Type
Aliphatic aldehyde solution Aliphatic aldehyde solution Aliphatic aldehyde solution Aromatic aldehyde solution 37 wt% formaldehyde Acetylenic alcohol/phenyl vinyl ketone Acetylenic alcohol/aromatic quat Aromatic quat /aromatic aldehyde Aqueous formic acid Nonionic Surfactant A Nonionic Surfactant B

Table 2: Corrosion Inhibition of L-80 Steels in 7.5 wt% HCl Acid Systems
Test: 150 F - 4 hr - FeS (tech):HCl ratio: 3:200
Pit

Inhibitor Loading
Inh-B

H2S Control
Ald-A or B Ald-D

Additives
--0.25% --0.5% Surf-A + 1.0% NTA 0.5% Surf-A + 1.0% NTA 0.5% Surf-A + 1.0% NTA

Corrosion Rate
(lb/ft2) 0.002 0.005 0.001

(PI)* 0 0 0

0.2% 0.2% 0.2%

Ald. A 3.0% Ald. B 3.0% Ald. A 2.75%

0.2%

Ald. B 2.75%

0.25%

0.004

0.2%

Ald. B 3.0%

--

0.02

* PI = pitting index. PI 3 is acceptable

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Table 3: Corrosion Inhibition of L-80 Steels in 7.5 wt% HCl Acid Systems
Test: 275 F - 4 hr - 5,000 psi FeS (tech):HCl ratio: 1.2:100

Inhibitor Loading
Inh-B Formic Acid

H2S Control
Ald-A/B Ald-D

Additives
0.2% Surf- A (0.5%) + NTA (35 ppt) Surf-B (0.5%) + NTA (35 ppt) Surf-A (0.3%) + NTA (35 ppt) Surf-A (0.5%) + NTA (35 ppt) Surf-A (0.3%) NTA (35 ppt) Surf-A (0.3%) NTA (35 ppt) Surf-A (0.3%) + NTA (35 ppt)

Pit Corrosion Rate (PI)* (lb/ft2)

1.0%

2.0%

2.0% A

0.019

1.0%

2.0%

2.0% A

0.2%

0.028

0.6%

2.0%

2.0% A

0.2%

0.009

1.0%

2.0%

2.0% B

0.2%

0.035

0.6% 0.6% 0.6%

2.0% 2.0% 2.0%

2.0% A 2.0% B 2.0% B

none 0.2% none

1 2 1

0.083 0.028 0.054

* PI = pitting index. PI 3 is acceptable ppt: lbs additive per thousand gallons of acid

Table 4: FeS Dissolution in 7.5 wt% HCl Inhibited with 1.0% Inh. B + 2.0% Formic Acid
Test: 275 F- 4 hr - FeS (tech):HCl ratio: 1.2:100
Additives
Total [Fe] Scavenger Ald-D Others ppm (g Fe) (g Fe) (g FeS) (% theo.) (% S) (g FeS) (% FeS)

Iron Analyses
[Fe] due Corrosion Equiv. FeS dissolved(1)

Sulfur Analysis
[S] conc. In acid Equiv. FeS dissolved(2)

Ald-B (2.0%) Ald-B (2.0%) Ald-A (2.0%) Ald-B (2.0%)

0.2% Surf-A (0.5%) NTA (35 ppt) 0.2% Surf-A (0.3%) NTA (35 ppt) 0.2% Surf-A (0.3%) NTA (35 ppt) 0.2% Surf-B (0.5%) NTA (35 ppt)

9600 1.51 8700 1.37 5590 0.88 13080 2.06

0.438 0.3786 0.2072 0.6663

1.07 0.99 0.67 1.39

89.4% 82.6% 56.1% 116.0%

0.426 0.398 0.342 0.483

1.16811 108.9% 1.09133 110.1% 0.93778 139.4% 1.32441 95.1%

(1) Equivalent FeS dissolved based on iron analyses. (2) Equivalent FeS dissolved based on H2S generated and determined by sulfur analyses

SPE 58712

INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

Table 5: FeS Dissolution in 7.5% HCl Inhibited with 0.6% Inh-B + 2.0% Formic Acid
Test: 275F- 4 hr - FeS (tech):HCl ratio: 1.2:100
Additives
Total [Fe] Scavenger Ald-D Others ppm (g Fe)

Iron Analyses
[Fe] due Corrosion (g Fe) Equiv. FeS dissolved (1) (g FeS) (% theo.)

Sulfur Analysis
[S] conc in acid (% S) Equiv. FeS dissolved (2) (g FeS) (% FeS)

Ald-B (2.0%) None Ald-A (2.0%) None Ald-A (2.0%) None

Surf-A (0.3%) Surf-A (0.3%) Surf-A (0.3%)

16900 2.66 12440 1.96 12400 1.95

1.0945 0.6587 0.6587

1.57 1.30 1.29

130.5% 108.3% 107.8%

0.498 0.346 0.342

1.36554 0.94875 0.93778

87.2% 73.0% 72.5%

(1) Equivalent FeS dissolved based on iron analyses. (2) Equivalent FeS dissolved based on H2S generated and determined by sulfur analyses.

Table 6: Formula of the acid used in the pickle treatment.

Material
Low sulfate content water Raw acid (31 wt%) Corrosion Inhibitor B Corrosion Inhibitor Aid Surfactant Aldehyde B Aldehyde D

Concentration, gals/1000 gals of acid

349 612 6 20 3 20 2

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H.A. NASR-EL-DIN ET AL.

SPE 58712

Table 7: Chemical analysis a of well return samples after the pickle treatment
Time, Minutes pH HCl, % wt/v Sulfide Na Ca Mg Cl SO4 Fe (III Fe (II

0 8 16 24 32 40 48 56 64 72 80 88 96 102 106

2.2 2.2 2.3 2.1 2 1.8 1.7 1.4 1 0.6 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1

0.03 0.03 0.03 0.121 0.07 0.11 0.14 0.29 0.69 1.58 11.4 NA 19.33 18.72 18.69
b

130 110 140 190 110 140 160 140 160 190 210 210 190 190 190

217 218 212 214 209 210 213 210 221 215 164 119 111 117 115

142 140 140 143 138 141 142 140 145 155 99 65 58 68 64

48 48 47 47 46 47 48 47 49 55 34 22 20 21 21

808 789 734 976 1130 14900 1740 3140 6690 145000 106000 183000 186000 NA 183000

305 301 306 300 293 296 292 294 278 428 258 171 148 168 181

28.2 23.2 20.9 28.5 29.8 37.7 41 48.7 73.3 104 532 682 972 2160 3910

40 53 35 43 55 45 48 50 58 120 580 750 1060 2490 4800

a. All ion concentrations are expressed in mg/L. b. Not available.

SPE 58712

INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

11

Figure 1: Sulfide Reaction Tester at 150 oF

Stirrer Dropping Funnel

Gas Trap

Reaction Flask

Heating Mantel with Controller

Figure 2: Efficiency of Capturing H2S and Dissolving of FeS Using HMTA.

100 Efficiency, % 80 60 40 20 0 0.0 2.0 4.0 6.0 8.0 10.0 Initial Scavenger Concentration, wt%
Dissolution of FeS Capturing of H2S

12

H.A. NASR-EL-DIN ET AL.

SPE 58712

Figure 3: Acid Concentration in the Supernatant - HMTA.

HCl Concentration, % wt/v

8 6 4 2 0 0 2 4 6 8 10 In i t i a l S c a v e n g e r C o n c e n t r a t i o n , w t %

Figure 4: Efficiency of Capturing H2S and Dissolving FeS - Aldehyde-B.

100

Efficiency, %

80 60 40 20 0 0 2 4 6 8 10 Dissolution of FeS Capturing of H2S

Initial Scavenger Concentration, wt%

SPE 58712

INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

13

Figure 5: Acid Concentration in the Supernatant - Aldehyde-B.

HCl Concentration, % wt/v

8 6 4 2 0 0.0 2.0 4.0 6.0 8.0 10.0

I n i t i a l S c a v e n g e r C o n c e n t r a t i o n , w t%

Figure 6: Efficiency of Capturing H2S in the Presence of Formaldehyde, Aldehyde-B, HMTA, Aldehyde-A. 100 80 60 40 20 0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
Formaldehyde Aldehyde-B HMTA Aldehyde-A

Efficiency of Capturing H2S, %

Initial Scavenger Concentration, wt%

14

H.A. NASR-EL-DIN ET AL.

SPE 58712

Figure 7: Efficiency of Dissolving Iron Sulfide in the Presence of Formaldehyde, Aldehyde-B, HMTA, Aldehyde-A.

60 FeS Dissolved, % 50 40 30 20 10 0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 Initial Scavenger Concentration, wt%
Formaldehyde Aldehyde-B HMTA Aldehyde-A

SPE 58712

INVESTIGATION OF SULFIDE SCAVENGERS IN WELL ACIDIZING FLUIDS

15

Figure 8: Dissolution of FeS in HCl at 150 F

10 g FeS, 108 g HCl

100.00 90.00 80.00 70.00 60.00 FeS Dissolved, % H2S Evolved, %

Wt.%

50.00 40.00 30.00 20.00 10.00 0.00

l B TA ld. D d. C yde ro ld. A h. B ld. D d. B h M nt In A A A Al % In Al deh H Co L g g g al 2% /1 g 16 g 0.2 0 m 5 16 1 m 0. / 6 A B or .1 f . d. 2 l d % A Al g 37 g g 6 15 1 9

Additive

Figure 9: Dissolution of FeS in 7.5 wt% HCl at 150 F

10 g FeS, 108 g Acid

100.00

10.00

Wt.%
1.00

FeS Dissolved, % [S] in Acid, %

0.10

g A A ld ld .B .B /0 .2 % In h B

TA

.A

.D

ol

ld

2. 16

15

16

Additive

37 %

10 g A ld fo .C rm al de hy de

0. 2%

16

/1

16

.A

m L

A ld .D

In h. B

tr

ld

ld

on

16

H.A. NASR-EL-DIN ET AL.

SPE 58712

Figure 10: Dissolution of FeS in 7.5 wt% HCl at 150 F

3 g FeS, 200 g Acid

100.00

10.00

1.00

Wt. %

0.10

0.01

0.00

0.00

In h. A

A ld .B

5. 5

1 g A ld Al .A d. /In D. 5. h. 5 A D ld /A .B ld .B /In h. B /A 5. ld 5 .D A ld .B /In 5. 5 h. A B ld .B /In h. C .

A ld .A

6g

A ld .A

A ld .B

5 Al d. A

6g

A ld .A

In h

Additive

% Dissolved H2S Evolved, %