Corrosion inhibition package

Abstract

An inhibition corrosion package for use with an acidic composition, where the package comprises a dialdehyde-containing hydrocarbon component; at least one surfactant; optionally, a propargyl alcohol or derivative thereof; and a solvent. Also disclosed are acidic compositions combining the corrosion inhibition package according to a preferred embodiment of the present invention for use in various industrial operations including but not limited to oil and gas operations. Also disclosed are methods of use of such compositions.

Claims

1. A corrosion inhibition package for use with an aqueous acid composition, said corrosion inhibition package consisting of: a dialdehyde-containing hydrocarbon component selected from the group consisting of: glutaraldehyde; succinaldehyde; malondialdehyde; adipaldehyde; heptanedial; nonanedial; undecanedial; 2,9-diethyldecanedial; and dodecanedial; a solvent selected from the group consisting of: isopropanol; methanol; ethanol; 2-butoxyethanol; diethylene glycol; di-n-hexyl-ether; and combinations thereof; an amphoteric surfactant selected from the group consisting of: a sultaine surfactant; a betaine surfactant; and combinations thereof, an anionic surfactant; and a propargyl alcohol.

2. The corrosion inhibition package as claimed in claim 1, wherein the sultaine surfactant is an amino sultaine surfactant, the betaine surfactant is an amino betaine surfactant, or a combination thereof.

3. The corrosion inhibition package as claimed in claim 1, wherein the betaine surfactant is an amido betaine surfactant comprising a hydrophobic tail from C.sub.8 to C.sub.16.

4. The corrosion inhibition package as claimed in claim 1, wherein the betaine surfactant is cocamidobetaine.

5. The corrosion inhibition package as claimed in claim 1, wherein the anionic surfactant is a carboxylic surfactant.

6. The corrosion inhibition package as claimed in claim 1, wherein the anionic surfactant is an iminodicarboxylate.

7. The corrosion inhibition package as claimed in claim 1, wherein the anionic surfactant is sodium lauriminodipropionate.

8. The corrosion inhibition package as claimed in claim 1, wherein the betaine surfactant is cocamidopropyl betaine, the anionic surfactant is β alanine, N-(2-carboxyethyl)-N-dodecyl-, sodium salt (1:1), or a combination thereof.

9. The corrosion inhibition package as claimed in claim 1, wherein the dialdehyde-containing hydrocarbon is present in an amount ranging from 2% to 25% by volume of the total volume of the corrosion inhibition package.

10. The corrosion inhibition package as claimed in claim 1, wherein the amphoteric surfactant and the anionic surfactant are present in a total amount ranging from 2% to 20% by volume of the total volume of the corrosion inhibition package.

11. An aqueous liquid acidic composition consisting of: an acidic solution; and a corrosion package consisting of: a dialdehyde-containing hydrocarbon component selected from the group consisting of: glutaraldehyde; succinaldehyde; malondialdehyde; adipaldehyde; heptanedial; nonanedial; undecanedial; and dodecanedial; a solvent selected from the group consisting of: isopropanol; methanol; ethanol; 2-butoxyethanol; diethylene glycol; di-n-hexyl-ether; and combinations thereof; an amphoteric surfactant is selected from the group consisting of: a sultaine surfactant; a betaine surfactant; and combinations thereof; an anionic surfactant; and a propargyl alcohol; wherein the volume % of the corrosion package in the acidic composition ranges from 0.1 to 10%.

12. The composition according to claim 11, wherein said acidic solution comprises an acid selected from the group consisting of: mineral acids; organic acids, synthetic acids; modified acids; complexed acids and combinations thereof.

13. The composition according to claim 11, wherein the acidic solution comprises an acid selected from the group consisting of: HCl; amino acid-HCl; urea-HCl; alkanolamine-HCl; hydrofluoric acid; sulfuric acid; toluenesulfonic acid; methanesulfonic acid; and phosphoric acid.

14. The composition according to claim 13, wherein the amino acid-HCl is lysine-HCl.

15. The composition according to claim 13, wherein the alkanolamine-HCl is MEA-HCl.

16. A method of minimizing pitting corrosion at temperatures above 130° C., wherein said method comprises: providing an acidic fluid; providing a composition consisting of: a dialdehyde-containing hydrocarbon component selected from the group consisting of: glutaraldehyde; succinaldehyde; malondialdehyde; adipaldehyde; heptanedial; nonanedial; undecanedial; and dodecanedial, a solvent selected from the group consisting of: isopropanol; methanol; ethanol; 2-butoxyethanol; diethylene glycol; di-n-hexyl-ether, and combinations thereof; an amphoteric surfactant is selected from the group consisting of: a sultaine surfactant; a betaine surfactant; and combinations thereof, and an anionic surfactant; combining said acidic fluid with said composition to obtain a mixed fluid; exposing said mixed fluid to a metallic surface at a temperature of at least 130° C.; and allowing said mixed fluid sufficient time of exposure to the metallic surface of a metal to minimize the pitting corrosion.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) The invention may be more completely understood in consideration of the following description of various embodiments of the invention in connection with the accompanying figures, in which:

(2) FIG. 1 is a schematic depiction of the various type of damage generated by pitting corrosion;

(3) FIG. 2 contains a picture of the surface of 6 metal coupons (identified as B900, A745, A929, A744, A933, and B883) after exposure to acidic fluids as described in the description;

(4) FIG. 3 contains a picture of the surface of 6 metal coupons (identified as B889, B890, A829, A827, A910, and A911) after exposure to acidic fluids as described in the description;

(5) FIG. 4 contains a picture of the surface of 6 metal coupons (identified as A743, A934, B882, A953, A954, and A952) after exposure to acidic fluids as described in the description; and

(6) FIG. 5 contains a picture of the surface of 4 metal coupons (identified as A839, C045, A962 and A963) after exposure to acidic fluids as described in the description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(7) 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.

(8) According to an aspect of the invention, there is provided a corrosion inhibition package for use with an acidic composition, said corrosion inhibition package comprising: a dialdehyde-containing hydrocarbon; and at least one surfactant.

(9) Preferably, the corrosion inhibition package further comprises a propargyl alcohol or derivative thereof; and a solvent.

(10) Preferably, the dialdehyde-containing hydrocarbon is selected from the group consisting of: C.sub.1-C.sub.16 linear hydrocarbon comprising an aldehyde functional group at either extremity of the hydrocarbon. Preferably, the C.sub.1-C.sub.16 linear hydrocarbon comprising an aldehyde functional group at either extremity of the hydrocarbon is a C.sub.5-C.sub.12 linear hydrocarbon. Preferably also, the C.sub.5-C.sub.12 linear hydrocarbon comprising an aldehyde functional group at either extremity of the hydrocarbon is selected from the group consisting of: glutaraldehyde; succinaldehyde; malondialdehyde; adipaldehyde; heptanedial; nonanedial; undecanedial; and dodecanedial.

(11) According to a preferred embodiment, the dialdehyde-containing hydrocarbon is selected from the group consisting of: saturated dialdehyde-containing hydrocarbons and C.sub.5-C.sub.16 branched hydrocarbon dialdehyde.

(12) 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 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 a 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. Basocorr® PP is an example of such a compound. In preferred embodiments of the present invention, 2-Propyn-1-ol, complexed with methyloxirane is present in an amount ranging from 20% to 55% by volume of the total volume of the corrosion inhibition package.

(13) According to a preferred embodiment of the present invention, the corrosion inhibition package comprises a surfactant which is environmentally friendly. More preferably, the surfactant is capable of withstanding exposure to temperatures of up to least 220° C. for a duration of 2 to 4 hours in a closed environment without undergoing degradation.

(14) Preferably, the at least one amphoteric surfactant is selected from the group consisting of: a sultaine surfactant; a betaine surfactant; and combinations thereof. More preferably, the sultaine surfactant and betaine surfactant are selected from the group consisting of: an amido betaine surfactant; an amido sultaine surfactant; and combinations thereof. Yet even more preferably, the amido betaine surfactant and is selected from the group consisting of: an amido betaine comprising a hydrophobic tail from C.sub.8 to C.sub.16. Most preferably, the amido betaine comprising a hydrophobic tail from C.sub.8 to C.sub.16 is cocamidobetaine.

(15) Preferably also, the corrosion inhibition package further comprises an anionic surfactant. Preferably, the anionic surfactant is a carboxylic surfactant. More preferably, the carboxylic surfactant is a dicarboxylic surfactant. Even more preferably, the dicarboxylic surfactant comprises a hydrophobic tail ranging from C.sub.8 to C.sub.16. Most preferably, the dicarboxylic surfactant is sodium lauriminodipropionate

(16) Most preferred are embodiments of a corrosion inhibition package comprising cocamidopropyl betaine and β-Alanine, N-(2-carboxyethyl)-N-dodecyl-, sodium salt (1:1).

(17) According to a preferred embodiment of the present invention, when preparing an acidic composition comprising a corrosion inhibition package, metal iodides or iodates such as potassium iodide, sodium iodide, cuprous iodide and lithium iodide can be added as corrosion inhibitor intensifier. The iodide or iodate is preferably present in a weight/volume percentage ranging from 0.1 to 1.5%, more preferably from 0.25 to 1.25%, yet even more preferably 1% by weight/volume of the acidic composition. Most preferably, the iodide used is potassium iodide.

(18) Preferably, the solvent is selected from the group consisting of: methanol; ethanol; isopropanol; ethylene glycol; Di-n-hexyl-ether; and 2-Butoxyethanol; and combinations thereof.

(19) Preferably, the organic compound comprising at least two aldehyde functional groups is present in an amount ranging from 2% to 25% by weight of the total weight of the corrosion inhibition package. Preferably also, the propargyl alcohol or derivative thereof is present in an amount ranging from 10% to 55% by volume of the total weight of the corrosion inhibition package. Preferably also, the at least one surfactant is present in an amount ranging from 2% to 20% by volume of the total weight of the corrosion inhibition package. Preferably also, the solvent is present in an amount ranging from 10% to 45% by volume of the total weight of the corrosion inhibition package.

Example 1—Formulation and Process to Prepare an Acidic Composition Comprising a Corrosion Inhibitor Package According to a Preferred Embodiment of the Invention

(20) Start by combining methanesulphonic acid (42 wt % of the composition) with water (58 wt % of the composition) and mix thoroughly for a few minutes. Add a pre-determined volume of the corrosion inhibitor package according to a preferred embodiment of the present invention described in Table 1 below. Add 0.1 wt % of potassium iodide to the composition. Circulation is maintained until all products have been solubilized. Table 1 lists the components of the corrosion inhibitors used with acid composition, including their weight percentage as compared to the total weight of the composition and the CAS numbers of each component.

(21) TABLE-US-00001 TABLE 1 Composition of a corrosion inhibitor used in a composition according to a preferred embodiment of the present invention Component CI-D1 CI-D2 2-Propyn-1-ol, compd. with Vol % 45 45 methyloxirane .beta.-Alanine, N-(2- Vol % 11.6 11.6 (carboxyethyl)-N- dodecyl-, sodium salt (1:1) Cocamidopropyl betaine Vol % 11.6 11.6 Nonane-1,9-dial (NL) and 2- Vol % 7 0 methyloctane- 1,8-dial (MOL) Glutaric Dialdehyde Vol % 0 7 Isopropanol Vol % 24.8 24.8 Total Vol % 100 100

(22) The chemical formula for Nonane-1,9-dial (NL) and 2-methyloctane-1,8-dial (MOL) are:

(23) ##STR00001##

(24) The chemical formula of glutaric dialdehyde is:

(25) ##STR00002##

(26) The resulting composition of Example 1 is a clear liquid having a strong odour and a 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 100° C. It has a specific gravity of 1.21±0.02. It is completely soluble in water and its pH is less than 1.

(27) The composition is readily biodegradable, 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. Surrogate toxicity testing carried out on rats shows the LD50 to be not less than 1100 mg/kg.

(28) Corrosion Testing

(29) The compositions according to the present invention were exposed to corrosion testing. Various steel grades were exposed to various novel organic acid, modified acids and mineral acid compositions for periods of time ranging up to 6 hours at temperatures of up to 180° C.

(30) The following corrosion testing outlined in Tables 2 to 11 (below) for acid compositions with known corrosion inhibition packages, for acid compositions with proprietary corrosion inhibition packages and for compositions according to the present invention at various temperatures for various durations of exposure. With respect to uniform corrosion, a desirable result was one where the lb/ft.sup.2 corrosion number is at or below 0.05. More preferably, that number is at or below 0.02. Also desirable is the control of pitting corrosion as pitting weakens locally a metal, it is desirable to minimize or even completely eliminate pitting. Where coupons are identified, FIGS. 2, 3, 4 and 5 provide a photograph of the surface of the coupon post-corrosion testing. Pitting was noted in some coupons after exposure.

(31) The predominant cause of corrosion of metals by MSA is known to be pitting corrosion, the below testing allows to determine the effectiveness of the corrosion inhibition packages against this very serious type of corrosion. FIG. 1 provides a schematic view of various types of pitting corrosion and methods of identifying each groups of pitting corrosion. In a first case, the pitting corrosion can be identified by simple visual inspection. In a second case, the pitting corrosion can be identified with the use of special inspection tools. And in a third case, the pitting corrosion can be identified by microscopic examination.

(32) TABLE-US-00002 TABLE 2 Corrosion testing performed at 150° C. with MSA (21%) for a duration of 6 hours where the steel density is 7.86 g/cc Surface Steel Corrosion Loss area Mm/ Lb/ type inhibitor (g) (cm.sup.2) Mils/yr year ft2 J55 B900 2.0% CI- 0.1046 28.992 263.8452 6.7017 0.007 5, 1.5% CI-1A N80 A745 2.0% CI- 0.1997 28.0774 520.136 13.2115 0.015 5, 1.5% CI-1A L80 A929 2.0% CI- 0.1897 28.0774 494.0901 12.5499 0.014 5, 1.5% CI-1A CI-1A is a 10% potassium iodide solution. Thus, the total KI present is 0.15% CI-5 refers to a proprietary corrosion inhibitor package comprising a terpene; a cinnamaldehyde or a derivative thereof; at least one amphoteric surfactant; and a solvent.

(33) TABLE-US-00003 TABLE 3 Corrosion testing performed at 150° C. with MSA (21%) where the steel density is 7.86 g/cc Duration Steel Corrosion Loss Surface area of exposure type inhibitor (g) (cm.sup.2) (hr) Mils/yr Mm/year Lb/ft2 N80 A744 2.0% CI- 2.1114 28.0774 4 8248.987 209.5243 0.154 2, 1.5% CI-1A L80 A933 2.0% CI- 2.7938 28.0774 6 7276.695 184.8280 0.204 2, 1.5% CI-1A J55 B883 2.0% CI- 0.8099 28.992 6 2042.909 51.8899 0.057 2, 1.5% CI-1A CI-1A is a 10% potassium iodide solution. CI-2 refers to a commercially available corrosion inhibitor package.

(34) TABLE-US-00004 TABLE 4 Corrosion testing performed at 180° C. with MSA (21%) where the steel density is 7.86 g/cc Duration Steel Corrosion Loss Surface area of exposure type inhibitor (g) (cm.sup.2) (hr) Mils/yr Mm/year Lb/ft2 J55 B889 3.0% CI-5 0.1291 28.992 4 488.4668 12.4071 0.009 2.5% CI-1A 0.2% NE-1 J55 B890 3.0% CI-5 0.4215 28.992 6 1063.2 27.0053 0.030 2.5% CI-1A 0.2% NE-1 N80 A829 2.25% CI-5 0.2113 28.0774 4 825.5238 20.9683 0.015 2.0% CI-1A 0.2% NE-1 N80 A827 3.0% CI-5 0.4842 28.0774 6 1261.141 32.0330 0.035 2.5% CI-1A 0.2% NE-1 L80 A910 3.0% CI-5 0.1661 28.0774 4 648.9328 16.4829 0.012 2.5% CI-1A 0.2% NE-1 L80 A911 2.25% CI-5 0.2693 28.0774 4 1052.123 26.7239 0.020 2.0% CI-1A 0.2% NE-1 CI-1A refers to a 10% solution of potassium iodide; CI-5 refers to a proprietary corrosion inhibitor package comprising a terpene; a cinnamaldehyde or a derivative thereof; at least one amphoteric surfactant; and a solvent. NE -1 is a non-emulsifier.

(35) TABLE-US-00005 TABLE 5 Corrosion testing performed at 180° C. with MSA (21%) where the steel density is 7.86 g/cc for a duration of exposure of 4 hours Steel Coupon Corrosion Loss Surface Mils/yr Mm/year Lb/ft2 N80 A743 2.25% CI-2, 3.652 28.0774 14267.93 362.4053 0.267 L80 A934 2.25% CI-2 1.3818 28.0774 5398.527 137.1226 0.101 J55 B882 2.25% CI-2 0.3347 28.992 1266.381 32.1661 0.024 CI-1A is a 10% potassium iodide solution.

(36) TABLE-US-00006 TABLE 6 Corrosion testing performed at 150° C. with MSA (21%) where on L80 steel coupons where the steel density is 7.86 g/cc (coupon surface area 28.0774 cm.sup.2) Duration Corrosion Loss of Exposure inhibitor Coupon # (g) (hours) Mils/yr Mm/year Lb/ft2 2.0% CI-DA1, A953 0.0612 4 239.1010683 6.0732 0.004 1.5% CI-1A 2.0% CI-DA1, A954 0.1155 6 300.8297755 7.6411 0.008 1.5% CI-1A CI-1A is a 10% potassium iodide solution.

(37) TABLE-US-00007 TABLE 7 Corrosion testing performed at 180° C. with MSA (21%) where the steel density is 7.86 g/cc for a duration of exposure of 4 hours Steel Corrosion Weight loss Surface area type Coupon # inhibitor (g) (cm.sup.2) Mils/yr Mm/year Lb/ft2 L80 A952 2.25% CI- 0.1379 28.0774 538.7587798 13.6845 0.010 DA1, 2.0% CI-1A N80 A839 2.25% CI- 0.1483 28.0774 579.3903339 14.7165 0.011 DA1, 2.0% CI-1A J55 C045 2.25% CI- 0.1493 28.992 564.8961506 14.3484 0.011 DA1, 2.0% CI-1A CI-1A is a 10% potassium iodide solution.

(38) TABLE-US-00008 TABLE 8 Corrosion testing performed at 150° C. with MSA (21%) where on L80 steel coupons where the steel density is 7.86 g/cc (coupon surface area 28.0774 cm.sup.2) Corrosion Weight loss Exposure Coupon # inhibitor (g) time Mils/yr Mm/year Lb/ft2 A962 2.0% CI-DA2, 0.2033 4 794.268745 20.1744 0.015 1.5%CI-1A A963 2.0% CI-DA2, 0.169 6 440.1751694 11.1804 0.012 1.5%CI-1A CI-1A is a 10% potassium iodide solution.

(39) TABLE-US-00009 TABLE 9 Corrosion testing performed at 180° C. with MSA (21%) where the steel density is 7.86 g/cc for a duration of exposure of 4 hours Surface Steel Corrosion Loss area Mm/ Lb/ type inhibitor (g) (cm.sup.2) Mils/yr year ft2 L80 2.25% CI- 0.2058 28.0774 804.0359455 20.4225 0.015 DA2, 2.0% CI-1A N80 2.25% CI- 0.152 28.0774 593.8457906 15.0837 0.011 DA2, 2.0% CI-1A J55 2.25% CI- 0.1871 28.992 707.9174131 17.9811 0.013 DA2, 2.0% CI-1A CI-1A is a 10% potassium iodide solution.

(40) TABLE-US-00010 TABLE 10 Corrosion testing performed at 150° C. on L80 steel coupons at 400 psi pressure, with a coupon surface area of 31.806 cm.sup.2 and a density of 7.86 g/cm.sup.3 Dilution Time Wt. Loss Acid Blend (%) (Hrs) CI Package (g) mils/year mm/year lb/ft.sup.2 MSA 50% 6 2.0% CI- 0.1444 332.008 8.433 0.009 composition DA1, 1.5% of Example 1 CI-1A MSA 50% 6 2.0% CI- 0.2910 669.074 16.994 0.019 composition DA2, 1.5% of Example 1 CI-1A Lys-HCl* 50% 4 6.0% CI- 0.2907 1002.577 25.465 0.019 DA1, 4.5% CI-1A Lys-HCl* 50% 4 6.0% CI- 0.3879 1337.804 33.980 0.025 DA2, 4.5% CI-1A HCl 7.5%  6 6.0% CI- 0.6746 1551.057 39.397 0.043 DA1, 4.5% CI-1A HCl 7.5%  6 6.0% CI- 0.5174 1189.619 30.216 0.033 DA2, 4.5% CI-1A MEA- 50% 4 6.0% CI- 0.1809 623.895 15.847 0.012 HCl** DA1, 4.5% CI-1A MEA- 50% 4 6.0% CI- 0.1940 669.074 16.994 0.012 HCl** DA2, 4.5% CI-1A HCl 7.5%  4 6.0% CI- 0.2212 762.883 19.377 0.014 DA1, 4.5% CI-1A HCl 7.5%  4 6.0% CI- 0.1075 370.750 9.417 0.007 DA2, 4.5% CI-1A CI-1A is a 10% potassium iodide solution. *A modified acid composition as used in the testing reported above comprises lysine:HCl composition in a ratio of 1:4.5. This composition is obtained through the following mixing ratio: 370 ml of L50 solution + 300 ml 22Baume HCl; which leads to the following ratio: 1 mol Lysine monohydrochloride to 4.5 mol HCl. The L50 solution is a 1:2.1 molar ratio of lysine to HCl. **Monoethanolamine (MEA) and hydrochloric acid are used as starting reagents. To obtain a 1:4.1 molar ratio of MEA to HCl, one must first mix 165 g of MEA with 835 g of water. This forms the monoethanolamine solution. Subsequently, one takes 370 ml of the monoethanolamine solution and mixes with 350 ml of HCl aq. 36% (22 Baume).

(41) TABLE-US-00011 TABLE 11 Corrosion testing performed with TSA (30%) at 150° C. on L80 steel coupons at 400 psi pressure, with a coupon surface area of 31.806 cm.sup.2 and a density of 7.86 g/cm.sup.3 Acid Time Wt. Loss Blend (hrs) CI Package (g) mils/year mm/year lb/ft.sup.2 p-TSA 6 2.0% CI- 0.2373 545.606 13.858 0.015 (30%) DA1, 1.5% CI-1A p-TSA 6 2.0% CI- 0.4569 1050.516 26.683 0.029 (30%) DA2, 1.5% CI-1A p-TSA 4 2.0% CI- 0.1757 605.961 15.391 0.011 (30%) DA1, 1.5% CI-1A p-TSA 4 2.0% CI- 0.2245 774.264 19.666 0.014 (30%) DA2, 1.5% CI-1A p-TSA 6 2.0% CI-5, 0.2448 562.850 14.296 0.016 (30%) 1.5% CI-1A

(42) 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 downhole scaling. Moreover, it was noted upon visual inspection that the commercially available corrosion inhibitor package did not perform well in the prevention of pitting corrosion (see coupons A744, A933, B883) at temperature of 150° C. and, as expected, was even worse at 180° C. (see coupons A743, A934 and B882) which exhibited very large pits. The proprietary corrosion inhibition package (CI-5) performed well at 150° C. where coupons had few or no pits (see coupons B900, A745 and A929). Where pits were present, these were quite small. At 180° C., pits were more evident (see coupons B889, B890, A829, A827, A910 and A911). Overall, the pits were small but present. Two of the tested corrosion inhibition package according to preferred embodiments of the present invention (CI-DA1 and CI-DA2) showed no visible signs of pitting at 150° C. (see coupons A953, A954, A962 and A963). At 180° C., no pits were seen on coupons A952 and A839 while very minimal and light pitting was observed on coupon C045. Visual analysis of the coupons confirms that the compositions according to a preferred embodiment of the present invention were superior when considering the pitting corrosion predominant in the use of alkanesulfonic acids such as MSA.

(43) Overall, the corrosion rates using a composition according to preferred embodiments of the present invention obtained were up to 3 times less compared to composition using a similar corrosion inhibitor but with an aldehyde containing compound in place of an organic compound comprising at least two aldehyde functional groups. The difference being that CI-DA1 and CI-DA2 comprise a saturated dialdehyde instead of a monoaldehyde. It is hypothesized that the aldehyde reacts with the protonated tertiary amine group in sodium lauriminodipropionate. It appears the organic compound comprising at least two aldehyde functional groups reacts with sodium lauriminodipropionate and forms an aggregate with the ionic groups available and, therefore, is a much more effective film former.

(44) Moreover, preferred corrosion inhibitors according to the present invention have shown applicability with various types of acids (organic acids, mineral acids, and modified acids).

(45) Acidic compositions using the corrosion inhibitor compositions according to the present invention can be used in the following and non-limiting examples: injection/disposal in wells; squeezes and soaks or bullheads; acid fracturing, acid washes or matrix stimulations; fracturing spearheads (breakdowns); pipeline scale treatments; cement breakdowns or perforation cleaning; pH control; and de-scaling applications.

(46) Additionally, corrosion inhibition packages according to preferred embodiments of the present invention will allow the end user to utilize synthetic and modified acids that have the down-hole performance advantages, transportation and storage advantages as well as the health, safety and environmental advantages. The person skilled in the art will also understand that the corrosion package according to the present invention is useful when as also utilized with conventional acid systems.

(47) In addition to stability at high temperatures and desirable corrosion rates as discussed above, the use of synthetic and modified acids along with a corrosion package according to a preferred embodiment of the present invention, allows for reduction in skin corrosiveness, a more controlled or methodical spending or reacting property, minimizing near well bore damage typically caused by an ultra-aggressive reaction with the formation typically caused by HCl and increasing formation penetration providing superior production over time.

Uses of Corrosion Inhibition Packages According to Preferred Embodiments of the Present Invention

(48) The uses (or applications) of the corrosion inhibition packages according to the present invention when combined (or mixed) with acidic compositions upon dilution of the latter ranging from approximately 1 to 90% dilution, include, but are not limited to: injection/disposal well 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. As would be understood by the person skilled in the art, the methods of use generally comprise the following steps: providing a composition comprising a corrosion inhibitor package according to a preferred embodiment of the present; mixing said package with an acid composition; exposing a surface (such as a metal surface) to the acid composition comprising the package; allowing the acid composition a sufficient period of time to act upon said surface; and optionally, removing the acid composition when the exposure time has been determined to be sufficient for the operation to be complete or sufficiently complete. Another method of use comprises: injecting the acid composition comprising the package into a well and allowing sufficient time for the acid composition to perform its desired function. Yet another method of use comprises: exposing the acid composition comprising the package to a body of fluid (typically water) requiring a decrease in the pH and allowing sufficient exposure time for the acid composition to lower the pH to the desired level.

(49) One of the advantages of the use of a synthetic acid composition using a corrosion inhibition package according to a preferred embodiment of the present invention includes: 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 (with low to high salinity production water).

(50) An acidic composition comprising a corrosion inhibition package according to a preferred embodiment of the present invention can be used to treat scale formation inside a ultra-high SAGD (steam assisted gravity drainage) well wherein the SAGD or cyclical steam operation is halted and said synthetic or modified acid is injected into said well to treat scale formation inside said well, wherein the treatment does not require a cool-down period between stopping the steam and the injection of the synthetic or modified acid composition.

(51) 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.