SPE 63242 Use of Highly Acid-Soluble Chelating Agents in Well Stimulation Services

Wayne W. Frenier, SPE Schlumberger, and David Wilson, Druce Crump and Ladell Jones, The Dow Chemical Co.
Copyright 2000, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 2000 SPE Annual Technical Conference and Exhibition held in Dallas, Texas, 14 October 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.

Introduction Chelating agents have been used extensively in oil/gas field treatments. See Figure 1 for structures. Primary uses include stabilization of iron, scale removal and uses as stimulation agents. Iron Control. EDTA, in particular, is used to stabilize iron in spent HCl. Crowe1 reviewed the use of chelating agents and reducing agents for iron control. According to this author, EDTA will control precipitation of ferric and ferrous hydroxide up to 350 oF. Above 250 oF, its efficiency actually improves since it then acts as a reducing agent1. It works better than citric acid/acetic acid2,3 because CaEDTA is believed to be more soluble than calcium citrate. Mixtures of citric acid and levulinic acid4 and citric acid with 5sulfosalicylic acid5 have been developed to get around the shortcomings of citric acid, a biodegradable material. An alternate complexer is dihydroxymaleic acid6. Taylor7,8 also surveyed the use of iron control chemicals. He concluded that ferric iron would precipitate between pH 1.0-2.0, in spent acid, not between 2.2-3.3 as has been assumed from the solubility product calculations. He also teaches the use of citric/acetic acid mixtures as compared with EDTA or NTA. He claims that EDTA is not soluble (enough) in 15% HCl to control significant amounts of Fe3+. This assertion is contrary to our practice where > 3% tetrasodium EDTA (expressed as the 100% salt) is routinely used in acidizing formulations (though we agree that HCl formulations with >3% sodium EDTA are not stable if left for more than a few hours). Goughler9 advocates cleaning the tubulars prior to acidizing the formation to reduce the iron load introduced into the formation. Chelants also are used with erythorbic acid10 to stabilize iron and prevent precipitation of sulfur in sour acid and with aldehydes11 or ketones12 for the same purpose (the carbonyls react with the sulfide ions). However, Brezinski13 claims that EDTA and NTA are not stable as iron control agents in HCl/carbonate spending tests. He suggests using sulfide control chemicals.

Abstract Chelating agents are materials that are used to control undesirable reactions of metal ions. In oilfield chemical treatments, chelating agents are frequently added to stimulation acids to prevent precipitation of solids as the acid spends on the formation being treated. These precipitates include iron hydroxide and iron sulfide. In addition, chelating agents are used as components in many scale removal/prevention formulations. Two different types of chelating agents are in use: polycarboxylic acids (including polyaminopolycarboxylic acids) and phosphonates. Chelating formulations based on ethylenediaminetetraacetic acid (EDTA) have been used extensively to control iron precipitation and to remove scale. Formulations based on nitrilotriacetic acid (NTA) and diethylenetriaminepentaacetic acids (DTPA) also are in use. Each of these materials has problems: 1) EDTA has low solubility in hydrochloric acid and is not readily biodegradable in standard laboratory tests. 2) NTA is acid soluble and biodegradable, but has a lower stability constant for iron than EDTA (or DTPA) and is considered to be an animal carcinogen. This report describes the search for the "universal" or "ideal" chelating agent for use in oilfield services. The materials evaluated include hydroxyaminopolycarboxylic acids (HACA) such as hydroxyethylethylenediaminetriacetic acid (HEDTA) and hydroxyethyliminodiacetic acid (HEIDA) as well as other types of chelating agents.

W. W. FRENIER, D. A. WILSON, D. CRUMP AND L. L. JONES

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Scale Removal. Disodium EDTA has been used as a scaleremoval agent in the Prudhoe Bay field of Alaska14. In this application, CaCO3 scale had precipitated in the perforation treatments, but 17 wells treated with disodium EDTA maintained production after these treatments. Rhudy15reviewed the use of EDTA and DTPA formulations to remove Ca, Ba and Sr scales from reservoir cores. There has been considerable interest in improving the removal of BaSO4 scales from the tubulars and the near wellbore region, due to the slow reaction rates of these scales with conventional chelant based solvents. An additional concern with the barium sulfate deposits is the occurrence of Naturally Occurring Radioactive Material (NORM) in conjunction with the sulfate scales. J. M. Paul16,17,18 has proposed several solvents for the sulfate scales that are based on the use of a scale "converter" or a dissolution catalyst, with a chelating agent. The chelate can be EDTA based, but DTPA is more effective in this formulation. Oxalic acid, fluoride and dithionate are described as being catalysts. Stimulation Agents. A different application for EDTA-type chelating agents has been proposed by Fredd and Fogler19,20. This application uses the chelating agents as the primary dissolution agent in matrix acidizing of carbonate formations (calcite: calcium carbonate and dolomite: calcium/magnesium carbonate). The purpose of the carbonate matrix acidizing treatment is to remove near wellbore damage and to produce "wormholes" that increase the permeability of the near wellbore region. Because HCl reacts so rapidly on most carbonate surfaces, diverting agents, ball sealers and foams21 are used to direct some of the acid flow away from large channels that may form initially and take all of the subsequent acid volume. By adjusting the flow rate and pH of the fluid, it may be possible to tailor the slower reacting EDTA solutions to the well conditions and achieve maximum wormhole formation with a minimum amount of solvent. Biodegradability. Though the chelating agents are not acutely toxic (LD50 oral rats = 5 g/kg), EDTA and DTPA are not considered to be biodegradable using any of the standard assays, and frequently cannot be discharged to the environment. Biodegradability is an especially important criterion in the North Sea areas. The subject of biodegradability of chelating agents is complex, because the results depend on the test method used in the evaluation. In addition, EDTA-type chelating agents can be degraded by chemical/photochemical methods, so the final fate of these materials in the environment is not clear. Lauff22,23 found that Agrobacterium is capable of degrading EDTA or 1,3propylenediaminetetraacetic acid (PDTA) complexes in waste water. Optimal Fe3+ EDTA degradation occurred below pH 7. This author also described a pure culture of Agrobacterium sp, which was isolated from a waste treatment facility. The isolate grew on ferric EDTA as the sole carbon source. The degradation produced carbon dioxide, ammonia and an unidentified metabolite. The rate of degradation was 24

tunnels and in the near-wellbore region of a sandstone formation. High decline rates followed conventional HCl mM/day. In a similar vein, Brunch24 studied settled sewage sludge that was used to inoculate BOD dilution water. After seven days, the test solutions were tested for the chelating agents. NTA and HEIDA lost their chelation ability, while EDTA, DTPA, HEDTA and cyclohexanediaminetetraacetic acid (CYDTA) were unchanged. It was concluded that chelants with single nitrogen are biodegradable, but those with two nitrogen atoms are not biodegradable. Microorganisms can be "trained" to degrade EDTA. Henneken25 described the use of a Gram-negative rod-shaped bacterium strain BNCI (isolated from industrial waste sludge) that uses EDTA as its sole nutrient. Using this bacterium, reaction kinetics were studied. The rate was similar to the degradation rate for NTA. Means26 described the degradation of NTA, EDTA, and DTPA in soil. Degradation of NTA, EDTA and DTPA increased in the presence of nutrients and decreased with decreasing oxidation potential. In the short term, the order of rate of degradation was DTPA>EDTA>NTA, but in the long term (180 days), NTA~DTPA>EDTA. Photodegradation was greater for DTPA than EDTA or NTA. Degradation of all three chelants was not rapid enough to preclude concern about their release into the environment. Recently, Athey27 has been issued a patent on some uses of HEIDA (claimed to be biodegradable) in scale removal services. This current paper describes the testing of chelating agents having a hydroxyethyl group. The goal was to find a "universal" or "ideal" chelating agent for use in oilfield services. The characteristics include high solubility in acid, ability to complex iron and calcium under oilfield conditions, and enhanced biodegradability. Materials with the hyroxyethyl group frequently have high water solubility. Chemicals of this class have been employed in industrial cleaning applications and also are powerful complexers for iron in the acid range.28,29,30 This paper explores some possible uses of these chemicals in oilfield acidizing and scale removal applications. Experimental Procedures The Dow Chemical Co., Freeport, TX, supplied the experimental and commercial chelating agents (except NTA). See Figure 1 for chemical structures, and Table 1 for chemical properties. Tests were conducted using 43% Na2HEIDA (Fw 221/0.43= 514), Na3HEDTA- 41% (Fw 344/0.41 = 839), Na3NTA.H2O, FW = 275), Na4EDTA, 38% (Fw 380/0.38 = 1000) and citric acid (FW 192). A major use for chelating agents in oilfield services consists of stabilizing iron during and after the acidizing treatments of carbonate formations. See literature cited above. Tests were run to simulate this application of chelating agent. A sample containing 100 g of hydrochloric acid was contaminated with various amounts of Fe(III) as FeCl3. Iron control agents were added at equimolar amounts, based on the amount of iron added. The solutions were neutralized to pH 3.5-3.8 using powdered CaCO3. The sample was split into two

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USE OF HIGHLY ACID-SOLUBLE CHELATING AGENTS IN WELL STIMULATION SERVICES

portions. One portion was put into a water bath (or oven) at 150 oF and the other sample was stored at lab temperature (about 70 oF). Tests at 190 oF were conducted by placing a sample of the neutralized solution into an oven. A final sample containing one chelant (Na3HEDTA) was put in a corrosion autoclave at 310 oF. After the test period (6 to 72 hours of exposure), a small sample was filtered and analyzed using Inductively Coupled Plasma Spectroscopy (ICP). Calcite (reagent grade CaCO3) and gypsum (field scale made up of cubes with about 5 mm sides) solubility tests were run in stirred flasks for 10-24 hours. An excess of the scale was added in each test. The metal concentrations were determined using ICP. Corrosion tests were run in highpressure autoclaves as described by Frenier.31 Inhibitor A is a mixture of acetylenic alcohols and phenylvinyl ketones and inhibitor B is a mixture of quats and unsaturated aldehydes. Results and Discussion Table 2 lists the solubility of the sodium salts of EDTA, HEDTA and HEIDA (in gallons of the liquid concentrates/1000 gallons of acid and as wt% of the active salt). The hydroxy chelating agents are much more soluble in the acid than EDTA. This is confirmed visually in Figure 2. A major use for chelating agents is to stabilize iron in solution during matrix acidizing treatments. A number of "recovery" tests were run. Solutions containing various amounts of ferric iron, and an equimolar amount of various chelating agents, were spent by adding calcium carbonate. The slurries were aged at various temperatures from ambient to 310 oF. At the end of the tests, the iron concentration was determined using ICP and the percentage of the expected iron concentration (% recovery) was calculated. Figures 3-8 show the trends for iron recovery for spent 15% HCl or calcium recovered. Iron recovery was most consistently high for the solutions containing the stronger complex formers, EDTA and HEDTA. The recovery values were usually > 80%, even at 150 oF. Calcium recovery values for most of the chelant tests were in the range of 70-90%. The recoveries for HEIDA, HEDTA and NTA were in the 80-90% range. The higher temperature stability tests (Figures 6, 7 and 8) show that HEDTA stabilized iron at least up to 310 oF (Figure 8). NTA was usable at least to 190 oF. HEIDA could be used up to at least 200 oF. In these tests (6 hours), there was excess HEIDA. Note that equimolar amounts of HEIDA did not adequately stabilize the iron in the severe 72 hour tests at 190 o F. The EDTA data requires clarification because the amount of EDTA added to control > 3000 ppm ferric iron would form a supersaturated solution (and probably a precipitate of EDTA acid) if this test was attempted in the field. However, it can be done in the lab by rapidly stirring the acid mixture with the calcite solids. In general, the chelation constants (Table 1) are good predictors of iron stability in the spent solution. However, HEDTA usually performs as good as (or better) than EDTA, but has a lower stability constant than EDTA (log K 19.8 vs. log K 25.0). In addition, HEIDA provided good

stabilization of iron under many conditions, despite a measured stability constant (for Fe(III)) of 11.6 It appears that the hydroxyethyl group in these compounds provides benefits not predicted from the published stability constant data. Table 3 shows corrosion rate data developed for typical acidizing solutions containing either EDTA or HEDTA as the iron control agent. The use of HEDTA (instead of EDTA) did not change the corrosion protection afforded by this acid corrosion inhibitor. Figure 9 shows calcite dissolution curves for sodium HEDTA solutions (for 20% trisodium HEDTA- a 50% dilution of the commercial solution) as a function of pH and temperature. The capacity increases as the pH decreases. This implies that the acid portion of the chelating agent is participating in the scale dissolution reaction. There also is some indication of inverse solubility of the calcium salts. This phenomenon is less pronounced at low pH than at high pH. Table 4 shows the calcite holding capacity of various calcite solvents. The acidic HEDTA solution has a capacity equivalent to diammonium EDTA. It also has a capacity equivalent to about 7.5% HCl, and they are more effective than NTA, citric acid and acetic acid. Citric acid and NTA have very low capacities for calcium in the acidic pH range. Figure 10 shows the dissolution curves for three alkaline chelating agent solutions (pH 11-12) with field gypsum deposits. The solvents were used at 50% (wt/wt) dilution based on the commercial concentrates. The sodium HEDTA solution had the largest capacity. This can be partially explained by the lower molecular weight compared with EDTA. HEIDA had a capacity equal to EDTA at 24 hours and dissolved considerably more calcium than EDTA at 6 hours. Table 5 shows results of biodegradation tests run on the sodium salts of the chelating agents, using several different protocols. HEIDA was found to be biodegradable in 8 of 8 standard laboratory tests performed, including an OECD 306 protocol run by the closed bottle method in North Sea water. HEIDA also passed in an OECD 306 test performed in Gulf of Mexico water using CO2 evolution for measuring degradation. NTA was included in the Gulf of Mexico water test, but did not reach a passsing level of degradation within the 28-day test period. As can be seen from the various test method results summarized in Table 5, HEIDA tends to show a more rapid rate of degradation than NTA. Figure 11 compares the measured North Sea Ecotox values of sodium HEDTA and sodium HEIDA. Neither material would be considered to have any acutely toxic characteristics. Conclusions 1. The tests demonstrated that HACAs are very effective complexers for iron (III) in hydrochloric acid. HEDTA will control iron precipitation to at least 310 oF, while HEIDA will control precipitation of iron to at least 200 oF for at least 6 hours. High capacity solvents for calcite and gypsum also can be produced from these chelating agents.

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SPE 63242

2. The major benefits of these materials flow from the high solubility of the salts in acids over a wide pH range. One of the materials (HEIDA) is also very biodegradable. While HEIDA will be adequate in many situations, it was not as effective as HEDTA in all conditions. So, while a "universal" chelating agent from a functional sense was identified, no "ideal" chemical exists at this time. 3. These new materials may be used in acidizing services as well as in scale removal formulations. Additional reports will consider in more detail the use of HACA materials in scale dissolution and other oilfield services. Acknowledgements We thank the management of Schlumberger, Ltd. and the Dow Chemical Co for support and permission to publish this report. References 1. Crowe, C. W., "Method of Preventing Precipitation of Ferrous Sulfide and Sulfur During Acidizing", US patent 4633949 (1987). 2. Ewing, B. C., et. al., "A Synergistic Chelation System for Acidizing in the Presence of High Iron Concentrations", SPE Paper 11795 (1983). 3. Smith, C. F., et. al., "Secondary Deposition of Iron Compounds following Acidizing," J Petro. Tech pp. 1121-1129 (1969) 4. Dill, W. and J. A. Knox, "Acidizing Subterranean Well Formations Containing Deposits of Metal Compounds", US Patent 4151098 (1979). 5. Street, Jr., E. H., "Process for Sequestering Iron while Acidizing a Reservoir", US Patent 4167214 (1979) 6. Dill, W. R., et. al., "Composition and Method of Stimulating Subterranean Formations", US Patent 4679631 (1987). 7. Taylor, K. C., et. al., "A Systematic Study of Iron Control Chemicals used During Well Stimulation", SPE paper 39419 (1998). 8. Taylor, K. C., et. al., "A Systematic Study of Iron Control Chemicals used During Well Stimulation- Part 2", SPE paper 50772 (1999). 9. Goughler, P. D., "Field Investigation Identifies Source and Magnitude of Iron Problems", SPE paper 13812 (1985) 10. Crowe, C., et. al., "Method for Preventing Precipitation of Ferric Compounds During Acid Treatment of Wells", US Patent 4574050 (1986).. 11. W. R. Dill and M. L. Walker, "Composition and Method for Controlling Precipitation When Acidizing Sour Wells", US Patent 4888121 (1989). 12. Williamson, C. D., "Precipitation Control", US Patent 5126059 (1992). 13. Brezinski, M. M., "Chelating Agents in Sour Well Acidizing: Methodology or Mythology," SPE 54721 (1999) 14. Shaughnessy, C. M. and W. E. Kline, "EDTA Removes Formation Damage at Prudhoe Bay", SPE Paper 11188 (1982).

15. Rhudy, J. S., "Removal of Mineral Scale from Reservoir Cores by Scale Dissolver", SPE Paper 25161 (1993) 16. Paul, J. M. and E. R. Fieler, "A New Solvent for Oilfield Scales", SPE Paper 24847 (1992). 17. Morris, R. L. and Paul, J., "Method for Removing Alkaline Sulfate Scale", US Patent 4980077 (1990). 18. Paul, J. M. and R. L Morris, "Composition for Removing an Alkaline Earth Sulfate Scale", US Patent 5282995 (1994). 19. Fredd, C. N., "The Influence of Transport and Reaction on Wormhole Formation in Carbonate Porous Media: A Study of Alternative Stimulation Fluids", Ph.D. Thesis, The Univ. of Michigan (1998). 20. Fredd, C. N., and H. S. Fogler, "The Influence of Chelating Agents on the Kinetics of Calcite Dissolution", J. Coll. & Interface. Sci., 204, 187-197 (1998). 21. Coulter, G. R. and A. R. Jennings, Jr., "A Contemporary Approach to Matrix Acidizing", SPE Paper 38594 (1997). 22. Lauff, J. J. et al., "Degradation of Ferric Chelates of Aminocarboxylic acids by Agrobacterium", Int. Patent AppI., WO 9115591 (1991). 23. Lauff, J. J., et al., "Degradation of Ferric Chelate of EDTA by a Pure Culture of an Agrobacterium sp", AppI. Environ. Microbiol., 56(11), pp. 3346-53 (1990). 24. Brunch, R. L., and Ettinger, M. B., "Biodegradability of Potential Organic Substitutes for Phosphates", Purdue Univ. Eng. Bull., Extn. Srs, Vol. 129 (Part 1), pp. 393396. (1967). 25. Henneken, L., et. al., J Chem. Technol Biotechnol, Vol 73, pp. 144-152 (1998) 26. Means, J. L. et aI., "Relative Degradation Rates of NTA, EDTA and DTPA and Environmental Implications", Environmental Pollution (Series B) 1, pp. 45-60 (1980). 27. Athey, P. S., et al, "Method for Controlling Alkaline Earth and Transition Metal Scaling with 2Hydroxyethyliminodiacetic acid," US Patent 5972868 (1999) 28. Frenier, W. W., and D. A. Wilson, "Aqueous Composition and Method of Use, US Patent 4430128 (1984). 29. Frenier, W. W., "Improved Solvent for Removing Iron Oxide Deposits", US Patent 4623399 (1986). 30. Frenier, W. W., and D. A. Wilson, "Aqueous Acid Composition and Method of Use, US Patent 4636327 (1987). 31. 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. 32. Martell, A. E. and Smith, R. "Critical Stability Constants," Plenum Publishing Co., N.Y., NY (1974).

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USE OF HIGHLY ACID-SOLUBLE CHELATING AGENTS IN WELL STIMULATION SERVICES

Ligand

Citric acid

TABLE 1- CHELATING AGENT STABILITY (EQUILIBRIUM) CONSTANTS 32 MW pKa Values Log of Stability Constant (K) 1:1 Complex Acid Na pK1 pK2 pK3 pK4 pK5 Fe(II) Fe(III) Cu(II) Ca(II) salt 192 258 5.7 4.4 2.9 4.4 11.5 5.9 3.5 191 278 257 344 9.7 9.8 2.5 5.4 1.8 2.6 8.3 12.2 15.9 19.8 12.9 17.4 6.4 8.4

NTA-Nitrilotriacetic acid HEDTAHydroxyethylethylenediamine-triacetic acid EDTAEthylenediaminetetraacetic acid DTPADiethylenetriaminepentaacetic acid HEIDAHydroxyethyliminodiacetic acid

292

380

10.2

6.1

2.7

2.0

14.2

25.0

18.8

10.7

393

503

10.5

8.5

4.3

2.6

1.8

16.5

28.0

21.1

10.9

177

221

8.7

2.2

6.8

11.6

11.7

4.8

TABLE 2- MAXIMUM SOLUBILITY OF CHELANTS IN HCl Chelant 15% HCl Tetrasodium EDTA 50 gal/1000 2.5% active 8 gal/1000 Trisodium HEDTA > 115* 5.8 22 Disodium HEIDA > 73* 3.7 15 * will dissolve at least this amount

28% HCl 0.4% active 1.1 0.8

TABLE 3- COMPARISON OF Na4EDTA and Na3HEDTA at 2.6% in HCl: Test: 300 oF, 6 HOURS Acid Inh. Aid Chelant Rate Lb/ft2 N80 13Cr 15% HCl 0.6% A 1.5% FORMIC ACID EDTA 0.023 0.055 15% HCl 0.6% A 1.5% FORMIC ACID HEDTA 0.023 0.055 15% HCl 0.6% B 1.5% FORMIC ACID EDTA 0.014 0.025 15% HCl 0.6% B 1.5% FORMIC ACID HEDTA 0.018 0.030 28% HCl 0.8% A 3% FORMIC ACID EDTA 0.045 0.075 28% HCl 0.8% A 3% FORMIC ACID HEDTA 0.045 0.075 12/3 Mud 0.6% A 2% FORMIC ACID EDTA 0.029 0.050 12/3 Mud 0.6% A 2% FORMIC ACID HEDTA 0.029 0.050

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TABLE 4 CALCITE DISSOLUTION CAPACITY OF VARIOUS DISSOLVERS Dissolver CaCO3 dissolved (lb/1000 gal) 20% Trisodium HEDTA, (pH 2.5) 738 20% Tetrasodium EDTA (pH 12) 520 21% Diammonium EDTA (pH 4.5) 735 20% Disodium HEIDA, (pH 2.5) 250 15% HCl 1833 10 % Formic acid 845 5% Citric acid 5 20% Trisodium NTA (pH 4) 5 10% Acetic acid 422

TABLE 5- TYPICAL BIODEGRADATION DATA IN STANDARD LAB TESTS using non-acclimated municipal seed, except for OECD 306, which uses no added innoculum (times required for listed degradation rates of < 28 days are found in parentheses)
OECD 301 B (281 day) OECD 301 D (282 day) OECD 301 E (283 day) OECD 301 F (282 day) OECD 302 A (284 day) OECD 302 B (284 day) OECD 306 (285 day) OECD 306 (286 day)

Chelant

EDTA

< 5%

< 5%

< 5%

Not tested

< 5%

< 5%

Not tested
7

Not tested

HEDTA

< 5% 80% (~3 wks) 90% (~ 2 wks)

< 5% 80% (~3 wks) 80% (~2 wks)

< 5% 80% (~3 wks) 90% (~1 wk)

Not tested

< 5% 85% (~12 wks) 90% (less than 1 week)

< 5% 85% (~1 2 wks) 90% (less than 1 week)

-8%

Not tested

NTA

Not tested 90% (~2 wks)

Not tested

54%

HEIDA

63%

89% (reached passing level within 20 days)

Pass level for ready biodegradability is 60% of theoretical CO2 production (from OECD Guidlelines for Testing of Chemicals, Section 301, page 3/62, and adopted 17.07.92) 2 Pass level for ready biodegradability is 60% of theoretical oxygen demand (from OECD Guidlelines for Testing of Chemicals, Section 301, page 3/62, and adopted 17.07.92) 3 Pass level for ready biodegradability is 70% removal of dissolved organic carbon (from OECD Guidlelines for Testing of Chemicals, Section 301, page 3/62, and adopted 17.07.92) 4 A figure of more than 20% biodegradation may be regarded as evidence for inherent, primary biodegradability. A figure of more than 70% mineralisation may be regarded as evidence for ultimate biodegradation. (from OECD Guidlelines for Testing of Chemicals, Summary Section, page 4) 5 Pass level for ready biodegradability is 60% of theoretical oxygen demand (from OECD Guidelines for Testing of Chemicals, Section 306, pages 1/27 and 2/27, adopted 17.07.92) This OECD 306 test was performed using North Sea water. 6 This OECD 306 test was performed using Gulf of Mexico water using CO2 evolution to measure degradation. 7 From a separate test.

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USE OF HIGHLY ACID-SOLUBLE CHELATING AGENTS IN WELL STIMULATION SERVICES

C O 2H HO2C HO2C N N C O2H HO HO2C N N

CO2H CO2H

Ethylenediaminetetraacetic Acid (EDTA)

Hydroxyethylethylenediaminetriacetic Acid (HEDTA)

C O2H

HO

C O2H C O2H

HO 2 C HO 2 C

C O 2H C O2H

Hydroxyethyliminodiacetic Acid (HEIDA)

Diethylenetriaminepentaacetic Acid (DTPA)

OH HO2C CO2H CO2H

HO2C HO 2 C

C O2H

Nitrilotriacetic Acid (NTA)

Fig. 1-Chelating Agent Structures

Citric Acid

Sodium HEDTA

Sodium NTA

Sodium EDTA

Sodium HEIDA

Fig. 2-15% HCl with equimolar amount of chelant for 10,000 ppm Fe(III)

W. W. FRENIER, D. A. WILSON, D. CRUMP AND L. L. JONES

SPE 63242

Iron at Room Temp, Spent HCl, pH 3.5

% Fe Recovered 100.0 80.0 60.0 40.0 20.0 0.0 0 2000 4000 6000 8000 10000 Initial [Fe], ppm

Na2HEIDA Na3HEDTA Na3NTA Na4EDTA

Fig. 3- Recovery of Ferric iron from 15% HCl, spent with CaCO3. Samples contained equimolar (based on iron o concentration) of the chelating agent. Solution aged at room temperature (68-70 F) for 72 hours.

Iron at 150 F Spent HCl, pH 3.5

% Fe Recovered 100.0 80.0 60.0 40.0 20.0 0.0 0 2000 4000 6000 8000 10000 Initial [Fe], ppm
Fig. 4- Recovery of Ferric iron from 15% HCl, spent with CaCO3. Samples contained equimolar o (based on iron concentration) of the chelating agent. Solution aged at 150 F for 72 hours.

Na2HEIDA Na3HEDTA Na3NTA Na4EDTA

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USE OF HIGHLY ACID-SOLUBLE CHELATING AGENTS IN WELL STIMULATION SERVICES

Calcium Recovery at 150 F

100.0

% Calcium Recovery

Na2HEIDA Na3HEDTA Na3NTA Na4EDTA

90.0 80.0 70.0 60.0 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

[Ca], ppm
Fig. 5- Recovery of calcium from 15% HCl, spent with CaCO3. Samples contained equimolar (based on iron o concentration) of the chelating agent. Solution aged (150 F) for 72 hours.

Iron Recovery in 15% HCl, 190 F Equimolar Chelant, 72 Hours

120.0 100.0 % Fe Recovered 80.0 60.0 40.0 20.0 0.0 0 2000 4000 6000 [Fe], ppm
Fig. 6- Recovery of Ferric iron from 15% HCl, spent with CaCO3. Samples contained equimolar (based on iron o concentration) of the chelating agent. Solution aged at 190 F for 72 hours.

Na2HEIDA Na3HEDTA Na3NTA

8000

10000

12000

10

W. W. FRENIER, D. A. WILSON, D. CRUMP AND L. L. JONES

SPE 63242

Six Hour Iron Recovery

110 %Fe Recovered 100 90 80 70 60 50 0 1000 2000 3000 4000 5000 6000 Fe(III), ppm
Fig. 7- Recovery of Ferric iron from 15% HCl, spent with CaCO3. Samples contained 50 gal sodium HEIDA o o solution/1000 gal of acid. Solution aged at 150 F or 200 F for 6 hours.

Spent with CaCO3, 50 gal/1000 Na2HEIDA

150 F 200 F

% Metals Recovered

Metals Recovery in 15% HCl at 310 F

120.0 100.0 80.0 60.0 40.0 20.0 0.0 0 2000 4000 [Fe], ppm 6000 8000

1.1 Mole ratio Na3HEDTA/Fe Fe Recovery Ca Recovery

Fig. 8- Recovery of Ferric iron from 15% HCl, spent with CaCO3. Samples contained 1.1 mole ratio of Na3HEDTA o solutions (based on iron concentration). Solution aged at 310 F for 24 hours.

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USE OF HIGHLY ACID-SOLUBLE CHELATING AGENTS IN WELL STIMULATION SERVICES

11

D issolution of C alcite at 190 F

35000 25000 20000 15000 10000 5000 0 0 1 2 3 4 5 6 7 8 9 10 pH 2.5 pH 4.0 pH 7.0 pH 11
T im e, hours
[Ca], ppm

Dissolution of C alcite at 150 F

35000 30000 25000 20000 15000 10000 5000 0 0 1 2 3 4 5 6 7 8 9 10

30000
[C a], ppm

pH 2.5 pH 4.0 pH 7.0 pH 11

Tim e, Hours

D is s o lu tio n o f C a lc ite a t 7 2 F

[C a ], p p m

20% Trisodium HEDTA

35000 30000 25000 20000 15000 10000 5000 0 0 1 2 3 4 5 6 7 8 9 10 pH 2.5 pH 4.0 pH 7.0 pH 11

T im e , H o u rs

Fig. 9 Dissolution of calcite in sodium HEDTA solutions. pH adjusted with HCl; three temperatures (72 F, o o 150 F, 190 F).

D isso lu tio n o f C aS O4 (F ield Gyp ), 170 F

25000 20000
[C a], ppm

15000 10000 5000 0 0 10 20 30

Sodium EDTA Sodium HEDTA Sodium HEIDA

T ime , H rs

Fig. 10- Solubility of Gypsum in 20% (active) Chelant Solutions at 170 F. The pH of the solutions was 11.5-12.0.

12

W. W. FRENIER, D. A. WILSON, D. CRUMP AND L. L. JONES

SPE 63242

! Na 3HEDTA (Com. soln)

! Na 2HEIDA (Com. soln.)

Turbot: LC

50-96 >1800

mg/L

Turbot: LC

50-96

>1800 mg/L

Acartia : LC 50-96 >5600 mg/L Skeltonema : EC 50-72 15.0 mg/L

Acartia : LC 50-96 2434 mg/L Skeltonema : EC 50-72 3828 mg/L

Active (purified)l
BOD 28 day -8% LogP -9

Active (Purified)
BOD 28 day 63% LogP -9

Fig. 11. Ecotox characteristics of HACA chelating agents using North Sea testing protocols. Tox. tests run on commercial solution and BOD/LogP run on purified chelating agent.