USING SYNTHETIC ACID COMPOSITIONS AS ALTERNATIVES TO CONVENTIONAL ACIDS IN THE OIL AND GAS INDUSTRY

Abstract

A synthetic acid composition for use in oil industry activities, said composition comprising: urea and hydrogen chloride in a molar ratio of not less than 0.1:1; a metal iodide or iodate; an alcohol or derivative thereof. Optionally, formic acid or a derivative thereof; propylene glycol or a derivative thereof, ethylene glycol glycerol or a mixture thereof; cinnamaldehyde or a derivative thereof; and a phosphonic acid derivative can be added to the composition.

Claims

1. A synthetic acid composition for use in oil industry activities, said composition comprising: urea and hydrogen chloride in a molar ratio of not less than 0.1:1; a metal iodide or iodate; an alcohol or derivative thereof; and optionally, a phosphonic acid derivative.

2. The synthetic acid composition according to claim 1, further comprising formic acid or derivative thereof.

3. The synthetic acid composition according to claim 1, further comprising propylene glycol or derivative thereof, ethylene glycol, glycerol or a mixture thereof.

4. The synthetic acid composition according to claim 1, further comprising cinnamaldehyde or a derivative thereof.

5. The synthetic acid composition according to claim 1, wherein the urea and hydrogen chloride are in a molar ratio of not less than 0.5:1.

6. The synthetic acid composition according to claim 5, wherein the urea and hydrogen chloride are in a molar ratio of not less than 1.0:1.

7. The synthetic acid composition according to claim 1, wherein the phosphonic acid derivative is aminoalkylphosphonic salt.

8. The synthetic acid composition according to claim 7, wherein the aminoalkylphosphonic salt is amino tris methylene phosphonic acid.

9. The synthetic acid composition according to claim 1, wherein the metal iodide or iodate is cuprous iodide.

10. The synthetic acid composition according to claim 1, wherein the metal iodide or iodate is potassium iodide.

11. The synthetic acid composition according to claim 1, wherein the metal iodide or iodate is sodium iodide.

12. The synthetic acid composition according to claim 1, wherein the metal iodide or iodate is lithium iodide.

13. The synthetic acid composition according to claim 1, wherein the alcohol or derivative thereof is an alkynyl alcohol or derivative thereof.

14. The synthetic acid composition according to claim 13, wherein the alkynyl alcohol or derivative thereof is propargyl alcohol or a derivative thereof.

15. The synthetic acid composition according to claim 7, wherein the aminoalkylphosphonic salt is present in a concentration ranging from 0.25 to 1.0% w/w.

16. The synthetic acid composition according to claim 15, wherein the aminoalkylphosphonic salt is present in a concentration of 0.5% w/w.

17. The synthetic acid composition according to claim 13, wherein the alkynyl alcohol or derivative thereof is present in a concentration ranging from 0.1 to 2.0% w/w.

18. The synthetic acid composition according to claim 17, wherein the alkynyl alcohol or derivative thereof is present in a concentration of 0.25% w/w.

19. The synthetic acid composition according to claim 1, wherein the metal iodide is present in a concentration ranging from 100 to 500 ppm.

20. The synthetic acid composition according to claim 2, wherein the formic acid or a derivative thereof is selected from the group consisting of: formic acid, acetic acid, ethylformate and butyl formate.

21. The synthetic acid composition according to claim 20, where the formic acid or derivative thereof is present in an amount ranging from 0.05-2.0% by weight of the composition.

22. The synthetic acid composition according to claim 21, where the formic acid or derivative thereof is present in an amount of approximately 0.1% by weight of the composition.

23. The synthetic acid composition according to claim 2, where the formic acid or derivative thereof is formic acid.

24. The synthetic acid composition according to claim 3, where the compound selected from the group consisting of: propylene glycol or derivative thereof, ethylene glycol, glycerol or a mixture thereof, is present in a range of 0.05-1.0% by weight of the composition.

25. The synthetic acid composition according to claim 24, where the compound selected from selected from the group consisting of: propylene glycol or derivative thereof, ethylene glycol, glycerol or a mixture thereof is present in an amount of approximately 0.05% by weight of the composition.

26. The synthetic acid composition according to claim 4, where cinnamaldehyde or derivative thereof is present in the range of 0.01-1.0% by weight of the composition.

27. The synthetic acid composition according to claim 26, where cinnamaldehyde or derivative thereof is present in an amount of approximately 0.03% by weight.

28. The use of a synthetic acid composition according to claim 1 in the oil industry to stimulate formations.

29. The use of a synthetic acid composition according to claim 1 in the oil industry to assist in reducing breakdown pressures during downhole pumping operations.

30. The use of a synthetic acid composition according to claim 1 in the oil industry to treat wellbore filter cake post drilling operations.

31. The use of a synthetic acid composition according to claim 1 in the oil industry to assist in freeing stuck pipe.

32. The use of a synthetic acid composition according to claim 1 in the oil industry to descale pipelines and/or production wells.

33. The use of a synthetic acid composition according to claim 1 in the oil industry to increase injectivity rate of injection wells.

34. The use of a synthetic acid composition according to claim 1 in the oil industry to lower the pH of fluids.

35. The use of a synthetic acid composition according to claim 1 in the oil industry to remove undesirable scale in surface equipment, wells and related equipment and/or facilities.

36. The use of a synthetic acid composition according to claim 1 in the oil industry to fracture wells.

37. The use of a synthetic acid composition according to claim 1 in the oil industry to perform matrix stimulations.

38. The use of a synthetic acid composition according to claim 1 in the oil industry to conduct annular and bullhead squeezes & soaks.

39. The use of a synthetic acid composition according to claim 1 in the oil industry to pickle tubing, pipe and/or coiled tubing.

40. The use of a synthetic acid composition according to claim 1 in the oil industry to increase effective permeability of formations.

41. The use of a synthetic acid composition according to claim 1 in the oil industry to reduce or remove wellbore damage.

42. The use of a synthetic acid composition according to claim 1 in the oil industry to clean perforations.

43. The use of a synthetic acid composition according to claim 1 in the oil industry to solubilize limestone, dolomite, calcite and combinations thereof.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0063] The description that follows, and the embodiments described therein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles of the present invention. These examples are provided for the purposes of explanation, and not limitation, of those principles and of the invention.

[0064] Urea-HCl is the main component in terms of volume and weight percent of the composition of the present invention, and consists basically of a carbonyl group connecting with nitrogen and hydrogen. When added to hydrochloric acid, there is a reaction that results in urea hydrochloride, which basically traps the chloride ion within the molecular structure. This reaction greatly reduces the hazardous effects of the hydrochloric acid on its own, such as the fuming effects, the hygroscopic effects, and the highly corrosive nature (the Cl.sup. ion will not readily bond with the Fe ion). The excess nitrogen can also act as a corrosion inhibitor at higher temperatures. Urea & Hydrogen chloride in a molar ratio of not less than 0.1:1; preferably in a molar ratio not less than 0.5:1, and more preferably in a molar ratio not less than 1.0:1. However, this ratio can be increased depending on the application.

[0065] It is preferable to add the urea at a molar ratio greater than 1 to the moles of HCl acid (or any acid). This is done in order to bind any available CI ions, thereby creating a safer, more inhibited product. Preferably, the composition according to the present invention comprises 1.05 moles of urea per 1.0 moles of HCl. The urea (hydrochloride) also allows for a reduced rate of reaction when in the presence of carbonate-based materials. This again due to the stronger molecular bonds associated over what hydrochloric acid traditionally displays. Further, since the composition according to the present invention is mainly comprised of urea (which is naturally biodegradable), the product testing has shown that the urea hydrochloride will maintain the same biodegradability function, something that hydrochloric acid will not on its own.

[0066] The use of formic acid as a corrosion inhibitor has been known for decades. However, the high concentrations in which its use has been reported along with the compounds it has been intermixed with have not made it a desirable compound in many applications. Prior art compositions containing formic acid require the presence of quinoline containing compounds or derivatives thereof, which render their use, in an increasingly environmentally conscious world, quite restricted.

[0067] In the present invention, formic acid or a derivative thereof such as formic acid, acetic acid, ethylformate and butyl formate can be added in an amount ranging from 0.05-2.0%, preferably in an amount of approximately 0.1%. Formic acid is the preferred compound, and is included on the PLONOR (Pose Little Or NO Risk to the environment) list for offshore oilfield use.

[0068] Alcohols and derivatives thereof, such as alkyne alcohols and derivatives and preferably propargyl alcohol and derivatives thereof can be used as corrosion inhibitors. Propargyl alcohol itself is traditionally used as a corrosion inhibitor which works extremely well at low concentrations. It is however a very toxic/flammable chemical to handle as a concentrate, so care must be taken when exposed to the concentrate. In the composition according to the present invention, it is preferred to use 2-Propyn-1-ol, complexed with methyloxirane, as this is a much safer derivative to handle. This is also a product that is approved for use offshore in the North Sea oilfield areas.

[0069] Metal iodides or iodates such as potassium iodide, sodium iodide, cuprous iodide and lithium iodide can potentially be used as corrosion inhibitor intensifier. In fact, potassium iodide is a metal iodide traditionally used as corrosion inhibitor intensifier, however it is expensive, but works extremely well. It is non-regulated and friendly to handle, and is included on the PLONOR (Pose Little Or NO Risk to the environment) list for offshore oilfield use.

[0070] Phosphonic acids and derivatives such as amino tris methylene phosphonic acid (ATMP) have some value as scale inhibitors. In fact, ATMP is a chemical traditionally used as an oilfield scale inhibitor, it has been found, when used in combination with urea/HCl, to increase the corrosion inhibition or protection. It has a good environmental profile, is readily available and reasonably priced.

[0071] Amino tris (methylenephosphonic acid) (ATMP) and its sodium salts are typically used in water treatment operations as scale inhibitors. They also find use as detergents and in cleaning applications, in paper, textile and photographic industries and in off-shore oil applications. Pure ATMP presents itself as a solid but it is generally obtained through process steps leading to a solution ranging from being colourless to having a pale yellow colour. ATMP acid and some of its sodium salts may cause corrosion to metals and may cause serious eye irritation to a varying degree dependent upon the pH/degree of neutralization.

[0072] ATMP must be handled with care when in its pure form or not in combination with certain other products. Typically, ATMP present in products intended for industrial use must be maintained in appropriate conditions in order to limit the exposure at a safe level to ensure human health and environment.

[0073] Amino tris (methylenephosphonic acid) and its sodium salts belong to the ATMP category in that all category members are various ionized forms of the acid. This category includes potassium and ammonium salts of that acid. The properties of the members of a category are usually consistent. Moreover, certain properties for a salt, in ecotoxicity studies, for example, can be directly appreciated by analogy to the properties of the parent acid. Amino tris (methylenephosphonic acid) may specifically be used as an intermediate for producing the phosphonates salts. The salt is used in situ (usually the case) or stored separately for further neutralization. One of the common uses of phosphonates is as scale inhibitors in the treatment of cooling and boiler water systems. In particular, for ATMP and its sodium salts are used in to prevent the formation of calcium carbonate scale.

[0074] In preferred embodiments of the present invention, 2-Propyn-1-ol, complexed with methyloxirane can be present in a range of 0.1-2.0%, preferably it is present in an amount of approximately 0.25%. Potassium Iodide can be present in a range of 0.01-0.5%, preferably it is present in an amount of approximately 0.022%. Formic Acid can be present in a range of 0.05-2.0%, preferably it is present in an amount of approximately 0.1%.

[0075] As a substitute for traditional propargyl alcohol, a preferred embodiment of the present invention uses 2-Propyn-1-ol, complexed with methyloxirane. As a substitute for potassium iodide one could use sodium iodide, copper iodide and lithium iodide. However, potassium iodide is the most preferred. As a substitute for formic acid one could use acetic acid. However, formic acid is most preferred. As a substitute for propylene glycol one could use ethylene glycol, glycerol or a mixture thereof. Propylene glycol being the most preferred. As a substitute for cinnamaldehyde one could use cinnamaldehyde derivatives and aromatic aldehydes selected from the group consisting of dicinnamaldehyde p-hydroxycinnamaldehyde; p-methylcinnamaldehyde; p-ethylcinnamaldehyde; p-methoxycinnamaldehyde; p-dimethylaminocinnamaldehyde; p-diethylaminocinnamaldehyde; p-nitrocinnamaldehyde; o-nitrocinnamaldehyde; 4-(3-propenal)cinnamaldehyde; p-sodium sulfocinnamaldehyde n-trimethylammoniumcinnamaldehyde sulfate; p-trimethylammoniumcinnamaldehyde o-methylsulfate; p-thiocyanocinnamaldehyde; p-(S-acetyl)thiocinnamaldehyde; p-(SN,N-dimethylcarbannoylthio)cinnamaldehyde; p-chorocinnamaldehyde; -methylcinnamaldehyde; P-methylcinnamaldehyde; -chlorocinnamaldehyde -bromocinnamaldehyde; -butylcinnamaldehyde; -amylcinnamaldehyde; -hexylcinnamaldehyde; -bromo-p-cyanocinnamaldehyde; -ethyl-p-methylcinnamaldehyde and p-methyl--pentylcinnamaldehyde. The most preferred is cinnamaldehyde.

Example 1Process to Prepare a Composition According to a Preferred Embodiment of the Invention

[0076] Start with a 50% by weight solution of pure urea liquor. Add a 36% by weight solution of hydrogen chloride while circulating until all reactions have completely ceased. The ATMP is then added followed by propargyl alcohol (or derivative), and potassium iodide. Circulation is maintained until, all products have been solubilized. Additional products are added now as required (iron control, demulsifier, etc.).

[0077] Table 1 lists the components of the composition of Example 1, including their weight percentage as compared to the total weight of the composition and the CAS numbers of each component.

TABLE-US-00001 TABLE 1 Composition of a certain embodiment of the present invention Chemical % Wt Composition CAS# Water 60.315 7732-18-5 Urea Hydrochloride 39.0% 506-89-8 Amino tris methylene phosphonic acid 0.576% 6419-19-8 Propargyl Alcohol 0.087% 107-19-7 Potassium Iodide 0.022% 7681-11-0

[0078] The resulting composition of Example 1 is a clear, odourless liquid having shelf-life of greater than 1 year. It has a freezing point temperature of approximately minus 30 C. and a boiling point temperature of approximately 1.00 C. It has a specific gravity of 1.150.02. It is completely soluble in water and its pH is less than 1.

[0079] The composition is biodegradable and is classified as a non-irritant according to the classifications for skin tests. The composition is non-fuming and has no volatile organic compounds nor does it have any BTEX levels above the drinking water quality levels. BTEX refers to the chemicals benzene, toluene, ethylbenzene and xylene. Toxicity testing was calculated using surrogate information and the LD.sub.50 was determined to be greater than 2000 mg/kg.

[0080] With respect to the corrosion impact of the composition on typical oilfield grade steel, it was established that it was clearly well below the acceptable corrosion limits set by industry for certain applications, such as spearhead applications or lower temperature scaling.

Example 2

[0081] Table 2 lists the components of the composition of Example 2 including their weight percentage as compared to the total weight of the composition and the CAS numbers of each component

TABLE-US-00002 TABLE 2 Composition according to an embodiment of the present invention Chemical % Wt Composition CAS# Water 58.92% 7732-18-5 Urea Hydrochloride 40.6% 506-89-8 2-Propyn-1-ol, complexed with 0.2% 38172-91-7 methyloxirane Potassium Iodide 0.05% 7681-11-0 Formic Acid 0.15% 64-18-6 Propylene Glycol 0.05% 57-55-6 Cinnamaldehyde 0.03% 14371-10-9

Corrosion Testing

[0082] The composition of Example 2 according to the present invention was exposed to corrosion testing. The results of the corrosion tests are reported in Table 3.

[0083] Samples of J55 grade steel were exposed to various synthetic acid solutions for periods of time ranging up to 24 hours at 90 C. temperatures. All of the tested compositions contained HCl and urea in a 1:1.05 ratio,

TABLE-US-00003 TABLE 3 Corrosion testing comparison between HCl-Urea and the composition of Example 2 at a 100% concentration Initial Final Loss Surface Run Inhibitor wt. wt. wt. area Density time (%) (g) (g) (g) (cm2) (g/cc) (hours) Mils/yr mm/year lb/ft.sup.2 HCl-Urea 37.616 34.324 3.092 28.922 7.86 6 7818.20 198.582 0.222 HCl-Urea 37.616 31.066 6.550 28.922 7.86 24 4140.46 105.168 0.470 Example #2 37.524 37.313 0.211 28.922 7.86 6 533.519 13.551 0.015 Example #2 37.524 35.540 1.984 28.922 7.86 24 1254.149 31.855 0.142

[0084] This type of corrosion testing helps to determine the impact of the use of such synthetic replacement acid composition according to the present invention compared to the industry standard HCl blends or any other mineral or organic acid blends). The results obtained for the composition containing only HCl and urea were used as a baseline to compare the other compositions.

[0085] Additionally, the compositions according to the present invention will allow the end user to utilize an alternative to conventional acids that has transportation and storage advantages as well as health, safety and environmental advantages. Enhancement in short/long term corrosion control is one of the key advantages of the present invention. The reduction in skin corrosiveness, the elimination of corrosive fumes, the controlled spending nature, and the high salt tolerance are some other advantages of compositions according to the present invention.

Aquatic Toxicity Testing

[0086] The biological test method that was employed was the Reference Method for Determining acute lethality using rainbow trout (1990Environment Canada, EPS 1/RM/9with the May 1996 and May 2007 amendments).

[0087] The Trout 96 hour Acute Test (WTR-ME-041) was performed at 5 different concentrations of compositions (62.5, 125, 250, 500 and 1000 ppm) one replicate per treatment, ten fish per replicate.

[0088] The test results indicate that at concentrations of the composition of Example 2 of up to and including 500 ppm there was a 100% survival rate in the fish sample studied. This is an indicator that the composition of Example 2 demonstrates an acceptable environmental safety profile.

Dermal Testing

[0089] The objective of this study was to evaluate the dermal irritancy and corrosiveness of the composition of Example 2, following a single application to the skin of New Zealand White rabbits. The undiluted test substance was placed on the shaved back of each of the three rabbits used in the study. The treated site was then covered by a gauze patch and secured with porous tape. The entire midsection of each rabbit was wrapped in lint-free cloth secured by an elastic adhesive bandage. The untreated skin site of each rabbit served as a control for comparison purposes. All wrapping materials were removed from each rabbit 4 hours following application of the test substance. The application site was then rinsed with water and wiped with gauze to remove any residual test substance. The skin of each rabbit was examined at 30-GO minutes and 24, 48 and 72 hours following removal of the wrappings. Descriptions of skin reactions were recorded for each animal. Dermal irritation scores were calculated for each time point, and a Primary Dermal Irritation Score was calculated according to the Draize descriptive ratings for skin irritancy.

[0090] Tables 4 and 5 report the results of the dermal testing. The scores for edema and erythema/eschar formation were 0 at all scoring intervals for all three rabbits. According to the Draize descriptive ratings for skin irritancy, the Primary Dermal Irritation Score (based on the 24- and 72-hour scoring intervals) for the test substance under the conditions employed in this study was 0.00. Thus, the composition of Example 2 was determined to be a non-irritant to the skin of New Zealand White rabbits. However, this conclusion was drawn without characterization of the test substance.

TABLE-US-00004 TABLE 4 Description of Individual Skin Reactions upon exposure to composition of Example 2 Scoring Interval (Time Following Removal of Wrappings) Animal 30-60 24 48 72 Number Minutes Hours Hours Hours (sex) Skin Reactions Scores 819 (F) Edema.sup.b 0 0 0 0 Erythema/eschar.sup.c 0 0 0 0 820 (F) Edema 0 0 0 0 Erythema/eschar 0 0 0 0 821 (F) Edema 0 0 0 0 Erythema/eschar 0 0 0 0 .sup.asee protocol Table 1 (Appendix A) for a detailed description of the Draize scoring scale (Draize, J. H., Appraisal of the Safety of Chemicals in Foods, Drugs, and Cosmetics, Assoc. Food & Drug Officials of the U.S., Austin, TX, 1959) .sup.bedema: 0 = none, 1 = very slight, 2 = slight, 3 = moderate, 4 (maximum possible) = severe .sup.cerythema/eschar: 0 = none, 1 = very slight, 2 = well-defined, 3 = moderate to severe, 4 (maximum possible) = severe erythema to slight eschar formation

TABLE-US-00005 TABLE 5 Primary Dermal Irritation Score of Individual Skin Reactions upon exposure to composition of Example 2 Scoring Interval (Time Following Removal of Wrappings) 30-60 30-60 30-60 30-60 Minutes Minutes Minutes Minutes Edema Score Skin Reactions Scores Summary.sup.b 0 3/3 3/3 3/3 3/3 1 0/3 0/3 0/3 0/3 2 0/3 0/3 0/3 0/3 3 0/3 0/3 0/3 0/3 4 0/3 0/3 0/3 0/3 Positive Score Mean 0.00 0.00 0.00 0.00 Erythema and/or Eschar Formation Score Skin Reactions Scores Summary.sup.b 0 3/3 3/3 3/3 3/3 1 0/3 0/3 0/3 0/3 2 0/3 0/3 0/3 0/3 3 0/3 0/3 0/3 0/3 4 0/3 0/3 0/3 0/3 Positive Score Mean 0.00 0.00 0.00 0.00 Irritation Score 0.00 0.00 0.00 0.00 Subtotal.sup.c PRIMARY DERMAL 0.00 (24-hour subtotal) + 0.00 (72-hour subtotal) = 0.00 (total score) IRRITATION 0.00 (total score)/2 = 0.00 (Primary Dermal Irritation Score) SCORE (DRAIZE): .sup.asee protocol Table 1 (Appendix A) for a detailed description of the Draize scoring scale (Draize, J.H., Appraisal of the Safety of Chemicals in Foods, Drugs, and Cosmetics, Assoc. Food & Drug Officials of the U.S., Austin, Tx, 1959) .sup.bNumber or animals with score/number of animals dosed .sup.cIrritation score subtotal = mean erythema score + mean edema score

Corrosion Testing

[0091] Corrosion testing using the composition of Example 2 was carried out under various conditions of temperature and on different steels to show the breadth of the applications for which compositions according to the present invention can be used. Table 6 sets out the test results of corrosion test that were carried out on N-80 steel (density of 7.86 g/ee) using the composition of Example 2 at a 50% concentration. Table 7 reports the test results of corrosion tests that were carried out on J-55 steel (density of 7.86 g/cc) using the composition of Example 2 at a 50% concentration. Table 8 reports the test results of corrosion tests that were carried out on various metal samples using the composition of Example 2 at a 100% concentration. These test results show that the composition of Example 2 meets the regulatory standards for the transportation industry on mild steel, and provides a strong level of protection with respect to aluminum.

TABLE-US-00006 TABLE 6 Corrosion tests carried out on N-80 steel (density of 7.86 g/cc) using the composition of Example 2 at a 50% concentration Initial Final Loss Surface Run Temp Wt. wt. wt. Area Time C. (g) (g) (g) (cm2) (hours) Mils/yr mm/year lb/ft.sup.2 70 C. 40.898 40.863 0.035 27.11 6 94.41353 2.398 0.003 70 C. 40.898 40.816 0.082 27.11 24 55.29936 1.405 0.006 90 C. 40.896 40.838 0.058 27.11 6 156.4567 3.974 0.004 90 C. 40.896 40.740 0.156 27.11 24 105.2037 2.672 0.011

TABLE-US-00007 TABLE 7 Corrosion tests carried out on J-55 steel (density of 7.86 g/cc) using the composition of Example 2 at a 50% concentration Initial Final Loss Surface Run Temp Wt. wt. wt. Area Time C. (g) (g) (g) (cm2) (hours) Mils/yr mm/year lb/ft.sup.2 30 C. 37.705 37.700 0.005 28.922 6 12.64263 0.321 0.000 30 C. 37.705 37.692 0.013 28.922 24 8.217709 0.209 0.001 30 C. 37.705 37.676 0.029 28.922 72 6.110604 0.155 0.002 50 C. 37.513 37.502 0.011 28.922 6 27.81378 0.706 0.001 50 C. 37.513 37.485 0.028 28.922 24 17.69968 0.450 0.002 70 C. 37.435 37.396 0.039 28.922 6 98.61251 2.505 0.003 70 C. 37.435 37.350 0.085 28.922 24 53.73117 1.365 0.006 90 C. 37.514 37.430 0.084 28.922 6 212.3962 5.395 0.006 90 C. 37.514 37.255 0.259 28.922 24 163.7221 4.159 0.018

TABLE-US-00008 TABLE 8 Corrosion tests carried out on various metal samples using the composition of Example 2 at a 100% concentration Initial Final Loss Surface Run Temp Wt. wt. wt. Area Density Time Coupon C. (g) (g) (g) (cm2) g/cc (hours) Mils/yr mm/year lb/ft.sup.2 1018 steel 55 C. 13.994 13.955 0.039 28.503 7.82 72 8.381163 0.213 0.003 7075 25 C. 6.196 6.185 0.011 29.471 2.81 6 76.35013 1.939 0.001 aluminum 7075 25 C. 6.196 6.080 0.116 29.471 2.81 24 201.2867 5.113 0.008 aluminum 7075 25 C. 6.196 1.344 4.852 29.471 2.81 48 4209.668 106.926 0.344 aluminum

Example 3

[0092] Table 9 lists the components of the composition of Example 3 including their weight percentage as compared to the total weight of the composition and the CAS numbers of each component.

TABLE-US-00009 TABLE 9 Composition of a preferred embodiment of the present invention Chemical % Wt Composition CAS# Water 59.028% 7732-18-5 Urea Hydrochloride 40.6% 506-89-8 2-Propyn-1-ol, complexed with 0.25% 38172-91-7 methyloxirane Potassium Iodide 0.022% 7681-11-0 Formic Acid 0.1% 64-18-6

Corrosion Testing

[0093] The compositions of Example 2 and 3 according to the present invention were exposed to corrosion testing. The results of the corrosion tests are reported in Table 10.

[0094] Samples of J55 grade steel were exposed to various synthetic acid solutions for periods of time ranging up to 24 hours at 90 C. temperatures. All of the tested compositions contained HCl and urea in a 1:1.05 ratio.

TABLE-US-00010 TABLE 10 Corrosion testing comparison between HCl-Urea and the compositions of Example 2 and 3 at a 100% concentration Initial Final Loss Surface Run Inhibitor Wt. wt. wt. Area Density Time (%) (g) (g) (g) (cm2) g/cc (hours) Mils/yr mm/year lb/ft.sup.2 HCl-Urea 37.616 34.524 3.092 28.922 7.86 6 7818.20 198.582 0.222 HCl-Urea 37.616 31.066 6.550 28.922 7.86 24 4140.46 105.168 0.470 Example #2 37.524 37.313 0.211 28.922 7.86 6 533.519 13.551 0.015 Example #2 37.524 35.540 1.984 28.922 7.86 24 1254.149 31.855 0.142 Example #3 37.714 37.520 0.194 28.922 7.86 6 490.534 12.460 0.014 Example #3 37.714 37.329 0.385 28.922 7.86 24 243.371 6.182 0.027

[0095] This type of corrosion testing helps to determine the impact of the use of such synthetic replacement acid composition according to the present invention compared to the industry standard (MCI blends or any other mineral or organic acid blends). The results obtained for the composition containing only HCl and urea were used as a baseline to compare the other compositions. Additionally, the compositions according to the present invention will allow the end user to utilize an alternative to conventional acids that has the down-hole performance advantages, transportation and storage advantages as well as the health, safety and environmental advantages. Enhancement in short/long term corrosion control is one of the key advantages of the present invention. The reduction in skin corrosiveness, the elimination of corrosive fumes, the controlled spending nature, and the high salt tolerance are some other advantages of compositions according to the present invention.

Aquatic Toxicity Testing

[0096] The biological test method that was employed was the Reference Method for Determining acute lethality using rainbow trout (1990Environment Canada, EPS 1/RM/9with the May 1996 and May 2007 amendments).

[0097] The Trout 96 hour Acute Test (WTR-ME-041) was performed at 5 different concentrations of compositions (62.5, 125, 250, 500 and 1000 ppm) one replicate per treatment, ten fish per replicate.

[0098] The test results indicate that at concentrations of the composition of Example 3 of up to and including 500 ppm there was a 100% survival rate in the fish sample studied. This is an indicator that the composition of Example 3 demonstrates a highly acceptable environmental safety profile.

[0099] Additional testing was carried out to assess the inhibition of marine algal growth, acute toxicity and biodegradability establish the safety for the environment.

Elastomer Testing

[0100] When common sealing elements used in the oil and gas industry come in contact with acid compositions they tend to degrade or at least show sign of damage. A number of sealing elements common to the industry were exposed to a composition according to a preferred embodiment of the present invention to evaluate the impact of the latter on their integrity. More specifically, the hardening and drying and the loss of mechanical integrity of sealing elements can have substantial consequences to the operations of wells and result in undesirable shut downs to replace defective sealing elements. Testing was carried out to assess the impact of the exposure of composition of Example 3 to various elastomers. Long term (72 hour exposure) elastomer testing on the concentrated product of Example 3 at 70 C. and 28,000 kPa showed little to no degradation of various elastomers, including Nitrile 70, Viton 75, Atlas 80, and EPDM 70 style sealing elements.

Corrosion Testing

[0101] Corrosion testing using the composition of Example 3 was carried out under various conditions of temperature and on different steels to show the breadth of the applications for which compositions according to the present invention can be used. Table 11 sets out the test results of corrosion test that were carried out on N-80 steel (density of 7.86 g/cc) using the composition of Example 3 at a 50% concentration. Table 12 reports the test results of corrosion tests that were carried out on J-55 steel (density of 7.86 Wee) using the composition of Example 3 at a 50% concentration. Table 13 reports the test results of corrosion tests that were carried out on various metal samples using the composition of Example 3 at a 100% concentration. These test results show that the composition of Example 3 meets the regulatory standards for the transportation industry on mild steel, and provide a strong level of protection with respect to aluminum. Table 14 lists a number of applications for which compositions according to the present invention can be used as well as proposed dilution ranges.

TABLE-US-00011 TABLE 11 Corrosion tests carried out on N-80 steel (density of 7.86 g/cc) using the composition of Example 3 at a 50% concentration Initial Final Loss Surface Run Temp Wt. wt. wt. Area Density Time C. (g) (g) (g) (cm2) g/cc (hours) Mils/yr mm/year lb/ft.sup.2 70 C. 40.757 40.708 0.049 27.11 7.86 6 132.1789 3.357 0.003 90 C. 40.757 40.609 0.148 27.11 7.86 24 99.80859 2.535 0.010 90 C. 40.712 40.617 0.095 27.11 7.86 6 256.2653 6.509 0.007 90 C. 40.712 40.475 0.237 27.11 7.86 24 159.8286 4.060 0.017

TABLE-US-00012 TABLE12 Corrosion tests carried out on J-55 steel (density of 7.86 g/cc) using the composition of Example 3 at a 50% concentration Initial Final Loss Surface Run Temp Wt. wt. wt. Area Density Time C. (g) (g) (g) (cm2) g/cc (hours) Mils/yr mm/year lb/ft.sup.2 50 C. 38.366 38.342 0.024 28.922 7.86 6 60.68462 1.541 0.002 50 C. 38.366 38.323 0.043 28.922 7.86 24 27.18165 0.690 0.003 70 C. 38.728 38.596 0.132 28.922 7.86 6 333.7654 8.478 0.009 70 C. 38.728 38.448 0.280 28.922 7.86 24 176.9968 4.496 0.020 90 C. 37.543 37.463 0.080 28.922 7.86 6 202.2821 5.138 0.006 90 C. 37.543 37.106 0.437 28.922 7.86 24 276.2415 7.017 0.031

TABLE-US-00013 TABLE 13 Corrosion tests carried out on various metal samples using the composition of Example 3 at a 100% concentration Initial Final Loss Surface Run Temp Wt. wt. wt. Area Density Time Coupon C. (g) (g) (g) (cm2) g/cc (hours) Mils/yr mm/year lb/ft.sup.2 1018 steel 55 C. 13.994 13.955 0.039 28.503 7.82 72 8.381163 0.213 0.003 7075 25 C. 6.196 6.080 0.116 29.471 2.81 24 201.2867 5.113 0.008 aluminum 7075 25 C. 6.196 1.344 4.852 29.471 2.81 48 4209.668 106.926 0.344 aluminum

[0102] The uses (or applications) of the compositions according to the present invention upon dilution thereof ranging from approximately 1 to 75% dilution, include, but are not limited to: injection/disposal treatments; matrix acid squeezes, soaks or bullheads; acid fracturing, acid washes; fracturing spearheads (breakdowns); pipeline scale treatments, cement breakdowns or perforation cleaning; pH control; and de-scaling applications.

TABLE-US-00014 TABLE 14 Applications for which compositions according to the present invention can be used as well as proposed dilution ranges Application: Suggested Dilution: Benefits: Injection/Disposal 50% Compatible with mutual solvents and solvent Wells blends, very cost effective. Squeezes & Soaks 33%-50% Ease of storage & handling, cost effective Bullhead compared to conventional acid stimulations. Annular Ability to leave pump equipment in wellbore. Acid Fracs 50%-75% Decreased shipping and storage compared to conventional acid, no blend separation issues, comprehensive spend rate encourages deeper formation penetration. Frac Spearheads 33%-66% Able to adjust concentrations on the fly. (Break-downs) Decreased shipping and storage on location. Cement Break-downs 50% Higher concentrations recommended due to lower temperatures, and reduced solubility of aged cement. pH Control 0.1%-1.0% Used in a variety of applications to adjust pH level of water based systems. Liner De-Scaling, 1%-5% Continuous injection/de-scaling of slotted Heavy Oil liners, typically at very high temperatures.

Use of a Composition According to the Present Spearhead on Multi-Well Pad

[0103] An operator in Western Canada was performing horizontal multi-stage fracturing completions on a multiple well pad, using plug and perforate technology. Traditional methods of formation breakdown required the use of 6-10 m.sup.3 of 15% HCl acid to be pumped down the casing prior to each fracturing stage.

[0104] Prior to testing, multiple samples of the high salinity fracturing water (recycled fracturing fluid) were tested for compatibility, as this was proposed to be used as the diluents for the concentrated synthetic acid. By storing the concentrated synthetic acid composition in a tank and diluting it with the fracturing water on site, only two storage tanks were required for the treatments (360 m.sup.3 of spearhead acid). These are intended on being refilled periodically.

[0105] For each treatment, the tank of concentrated synthetic acid composition was blended on site through the fracturing blender with the fracturing water down to reach a concentration of 33% of the initial composition. 6-10 in.sup.3 of the synthetic acid composition was pumped for each spearhead stage, all other operational components and procedures remained the same as traditional methods using HCl acid (15% HCl acid was on location for a comparison well).

[0106] A total of 18 stages per well were treated on more than 8 wells, with 100% breakdown success on every stage. Breakdown pressure differentials in the range of 10-15 MPa were observed, and were found to be very comparable to HCl acid.

[0107] The main advantages of the use of the synthetic acid composition included: the reduction of the total loads of acid, and the required number of tanks by delivering concentrated product to location and diluting with fluids available on location (high salinity production water). Other advantages of the composition according to the present invention include: operational efficiencies which led to the elimination of having to periodically circulate tanks of HCl acid due to chemical separation; reduced potential corrosion to downhole tuhulars; and reduced HCl acid exposure to personnel by having a non-hazardous, non-fuming acid on location.

While the foregoing invention has been described in some detail for purposes of clarity and understanding, it will be appreciated by those skilled in the relevant arts, once they have been made familiar with this disclosure, that various changes in form and detail can be made without departing from the true scope of the invention in the appended claims.