Improved corrosion inhibitor compositions

Abstract

A metal stabilizing composition comprising (i) one or more oxidized sugar products; and (ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof. A method of treating a water-containing system comprising introducing to the system a metal stabilizing composition comprising (i) one or more oxidized sugar products; (ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof; and (iii) a solvent.

Description

IMPROVED CORROSION INHIBITOR COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit of U.S. provisional patent application Serial No. 63 / 618,836 filed January 8, 2024 and entitled “CORROSION INHIBITOR COMPOSITIONS," which is hereby incorporated herein by reference in its entirety for all purposes.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not applicable.TECHNICAL FIELD

[0003] The disclosure relates generally to corrosion inhibition. More particularly, the disclosure relates to inhibition of corrosion and scale. Still more particularly, the disclosure relates to biobased corrosion inhibitors.BACKGROUND

[0004] Corrosion is the result of a complex series of reactions. For example, corrosion can occur between water and metal surfaces (e.g., metal piping) and materials in which the water is stored or transported. The corrosion process is an oxidation / reduction reaction that results in refined or processed metal being changed to its more stable state. Conventional formulations to solve corrosion and scale issues in industrial areas such as oil and gas typically are generally effective, but often employ phosphate and / or nitrogen based-compounds. The use of conventional corrosion and / or scale inhibitors can present a number of challenges such as eutrophication, supplychain issues, and toxicity. An ongoing need exists for corrosion and / or scale inhibitors that can overcome one or more of the challenges associated with conventional corrosion and / or scale inhibitors.BRIEF SUMMARY OF THE DISCLOSURE

[0005] Disclosed herein is a metal stabilizing composition comprising (i) one or more oxidized sugar products; and (ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof.

[0006] Also disclosed herein is a method of treating a water-containing system comprising introducing to the system a metal stabilizing composition comprising(i) one or more oxidized sugar products; (ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof; and (iii) a solvent.

[0007] Embodiments described herein comprise a combination of features and characteristics intended to address various shortcomings associated with certain prior devices, systems, and methods. The foregoing has outlined rather broadly the features and technical characteristics of the disclosed embodiments in order that the detailed description that follows may be better understood. The various characteristics and features described above, as well as others, will be readily apparent to those skilled in the art upon reading the following detailed description, and by referring to the accompanying drawings. It should be appreciated that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes as the disclosed embodiments. It should also be realized that such equivalent constructions do not depart from the spirit and scope of the principles disclosed herein.DETAILED DESCRIPTION

[0008] The following discussion is directed to various exemplary embodiments. However, one skilled in the art will understand that the examples disclosed herein have broad application, and that the discussion of any embodiment is meant only to be exemplary of that embodiment, and not intended to suggest that the scope of the disclosure, including the claims, is limited to that embodiment.

[0009] Certain terms are used throughout the following description and claims to refer to particular features or components. As one skilled in the art will appreciate, different persons may refer to the same feature or component by different names. This document does not intend to distinguish between components or features that differ in name but not function. The drawing figures are not necessarily to scale. Certain features and components herein may be shown exaggerated in scale or in somewhat schematic form and some details of conventional elements may not be shown in interest of clarity and conciseness.

[0010] Unless the context dictates the contrary, all ranges set forth herein should be interpreted as being inclusive of their endpoints, and open-ended ranges should be interpreted to include only commercially practical values. In addition, with respect to all ranges disclosed herein, such ranges are intended to include any combination of the mentioned upper and lower limits even if the particular combination is not specifically listed. All lists of values should be considered as inclusive of intermediate values unless the context indicates the contrary. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11 , 0.12, 0.13, etc.).

[0011] In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to... .” As used herein, the phrases “consist(s) of’ and “consisting of” are used to refer to exclusive components of a composition, meaning only those expressly recited components are included in the composition; whereas the phrases “consist(s) essentially of’ and “consisting essentially of” are used to refer to the primary components of a composition, meaning that only small or trace amounts of components other than the expressly recited components (e.g., impurities, byproducts, etc. ) may be included in the composition. For example, a composition consisting of X and Y refers to a composition that only includes X and Y, and thus, does not include any other components ; and a composition consisting essentially of X and Y refers to a composition that primarily comprises X and Y, but may include small or trace amounts of components other than X and Y. In embodiments described herein , any such small or trace amounts of components other than those expressly recited following the phrase “consist (s) essentially of’ or “consisting essentially of’ preferably represent less than 5.0 wt% of the composition, more preferably less than 4.0 wt% of the composition, even more preferably less than 3.0 wt% of the composition, and still more preferably less than 1.0 wt% of the composition. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc. Use of the term "optionally" with respect to any element of a claim is intended to meanthat the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim.

[0012] As used herein, the terms “approximately,” “about,” “substantially,” and the like mean within 10% (i.e. , plus or minus 10%) of the recited value. Thus, for example, a recited angle of “about 80 degrees” refers to an angle ranging from 72 degrees to 88 degrees.

[0013] Disclosed herein are improved corrosion inhibitor compositions which stabilize the integrity of metal surfaces subject to contact with aqueous fluids. Hereinafter these compositions are termed metal- stabilizing compositions and designated MSC. In one or more aspects, the MSC comprises (i) one or more sugar oxidation products and (ii) one or more corrosion inhibitors.

[0014] In one or more aspects, the MSC comprises one or more sugar oxidation products. In one or more aspects, the one or more sugar oxidation products are oxidation products of glucose.

[0015] Additionally, or alternatively, in an aspect, the one or more sugar oxidation products comprise a glucose oxidation product, a gluconic acid oxidation product, a gluconate, or a combination thereof. The glucose oxidation product, gluconic acid oxidation product, or combination thereof may be buffered to a suitable pH.

[0016] Additionally, or alternatively, the one or more sugar oxidation products comprise glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, gluconic acid oxidation products or a combination thereof. Additionally, or alternatively, the one or more sugar oxidation products comprise galactonic acid, galactaric acid, an oxidation product comprising predominantly (e.g., greater than about 50 weight percent) galactonic acid and / or galactaric acid with minor component species of n-keto-acids, C2 to C6 diacids or a combination thereof. Additionally, or alternatively, in one or more aspects, the one or more sugar oxidation products comprise glutamic acid. Additionally, or alternatively, the one or more sugar oxidation products comprise glucodialdose, 2- ketoglucose or a combination thereof.

[0017] In an aspect, the one or more one or more sugar oxidation products comprise less than about 5 wt.% maltose, maltotriose, fructose, higher molecular weight polysaccharides, oxidation products thereof or a combination thereof based on the total weight of the MSC.

[0018] In an aspect, the one or more one or more sugar oxidation products comprise glucaric acid, gluconic acid or a mixture of gluconic acid and glucaric acid. In one ormore aspects, the MSC comprises a mixture of gluconic acid and glucaric acid where the ratio of gluconic acid:glucaric acid may range from about 0.1 :10 to about 10:0.1 , alternatively about 0.15: 10, or about 0.5: 10, about 1 :10, about 1 :5, about 1 :4, about 1 :3, about 1 :2, about 1 :1 , about 10:0.1 , about 10:0.5, about 10:1 , about 5: 1 , about 4: 1 , about 3:1 , or about 2:1.

[0019] In one or more aspects, the one or more sugar oxidation products are present in an amount of about 0.1 wt.%, or about 0.25 wt.%, orabout 0.5 wt.%, or about 0.75 wt.%, or about 1 wt.%, or about 1 .25 wt.%, or about 1 .5 wt.%, or about 1 .75 wt.%, or about 2 wt.%, or about 2.25 wt.%, or about 2.5 wt.%, or about 2.75 wt.%, or about 3 wt.%, or about 3.25 wt.%, or about 3.5 wt.%, or about 3.75 wt.%, or about 4 wt.%, or about 4.25 wt.%, or about 4.5 wt.%, or about 4.75 wt.%, or about 5 wt.%, or about 10 wt.%, or about12.5 wt.%, or about 15 wt.%, or about 17.5 wt.%, or about 20 wt.%, or about 22.5 wt.%, or about 25 wt.%, or about 27.5 wt.%, or about 30 wt.%, or about 32.5 wt.%, or about 35 wt.%, or about 37.5 wt.%, or about 40 wt.%, or about 42.5 wt.%, or about 45 wt.%, or about 47.5 wt.%, or about 50 wt.%, or about 52.5 wt.%, or about 55 wt.%, or about57.5 wt.%, or about 60 wt.%, or about 62.5 wt.%, or about 65 wt.%, or about 67.5 wt.%, or about 70 wt.%, or about 72.5 wt.%, or about 75 wt.%, or about 77.5 wt.%, or about 80 wt.%, or about 82.5 wt.%, or about 85 wt.%, or about 87.5 wt.%, or about 90 wt.%, or about 92.5 wt.%, or about 95 wt.%, or about 97.5 wt.%, or about 100 wt.%, or about 0.1 wt.% to about 100 wt.%, or about 1 wt.% to about 95 wt.%, or about 5 wt.% to about 90 wt.%, or about 10 wt.% to about 90 wt.%, or about 15 wt.% to about 85 wt.%, or about 20 wt.% to about 80 wt.%, or about 25 wt.% to about 75 wt.%, or about 40 wt.% to about 60 wt.%, or about 50 wt.%, or about 0.1 wt.% to about 10 wt.%, or about 1 wt.% to about 20 wt.%, or about 5 wt.% to about 50 wt.%, or about 1 wt.% to about 80 wt.%, or from about 5 wt.% to about 80 wt.%, or from about 1 wt.% to about 55 wt.% or about 20 wt.% to about 75 wt.% based on the total weight of the MSC. In some aspects, the MSC has one or more sugar oxidation products present in an amount between any of the end points listed herein. In alternative aspects, the one or more sugar oxidation products may be present in the MSC in an amount ranging from about 0.01 wt.% to about 80 wt.%, alternatively from about 0.01 wt.% to about 10 wt.%, alternatively from about 20 wt.% to about 80 wt.% or alternatively, from about 1 wt.% to about 30 wt.% based on the total weight of the MSC.

[0020] In one ormore aspects, the MSC comprises a corrosion inhibitor. Without wishing to be limited by theory, corrosion inhibitors work by the principle of shifting theelectrochemical corrosion potential of the corroding metal in the positive direction indicating the retardation of the anodic process (anodic control), or displacement in the negative direction indicating mainly retardation of the cathodic process (cathodic control).

[0021] Nonlimiting examples of corrosion inhibitors suitable for use in the present disclosure include heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, and combinations thereof.

[0022] In an aspect the corrosion inhibitor is a heterocyclic organic compound. Nonlimiting examples of heterocyclic organic compounds include thiazoles, triazoles, imidizoles and combinations thereof. Thiazoles and triazoles are five-atom aromatic ring molecules that contain a nitrogen atom and at least one other atom selected from the group consisting of nitrogen, oxygen, and sulfur as part of the ring. The azole-based compounds can be divided into three major classes, namely, N-, N&O-, and N&S- containing azole sets.

[0023] In an aspect, the corrosion inhibitor comprises imidazole, imidazoline, pyrazole,1 .2.3-triazole, 1 ,2,4-triazole, tetrazole, pentazole, oxazole, isoxazole, 1 ,2,4-oxadiazole,1.3.4-oxadiazole, 1 ,2,5-oxadiazole, thiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, mercaptobenzothiazole, mercaptobenzimidazole, butyl benzotriazole 1 ,3,4-thiadiazole, benzotriazole, tolytriazole, (2-pyrrole carbonyl) benzotriazole, (2-thienyl carbonyl)- benzotriazole, amino-1 ,2,4-triazole, diamino-1 ,2,4triazole, mercapto-1 H-1 ,2,4-triazole, methyl-2-phenyl-imidazole, amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, phenyl-1-H- tetrazole, chlorotolyltriazole, derivatives thereof, or combinations thereof.

[0024] In one or more aspects, the corrosion inhibitor is a molybdate or a heteropolymolybdate. Nonlimiting examples of molybdates for use as a corrosion inhibitor include ammonium orthomolybdate, lithium molybdate, sodium molybdate, magnesium molybdate, potassium molybdate, calcium molybdate, and combinations thereof.

[0025] In an aspect, the conventional corrosion inhibitor is a phosphorous-containing compound. Nonlimiting examples of phosphorus-containing compounds suitable for use in the present disclosure include phosphate esters, phosphonates, aminotrimethylene phosphonic acid (ATMP), 1-hydroxyethylidene-1 ,1-diphosphonic acid (HEDP), hydrolzed polymaleic anhydride (HPMA), 2-hydrophosphonocarboxylic (HPAA), polyamino polyether phosphonate (PAPEMP), aminoethlethanolamine (AEEA), diethylenetriamine penta (DTPMP), bis(hexamethylene triamine penta (methylenephosphonic acid)) (BHMT), diethylene triamine penta (methylene phosphonic acid) (BTPMP), 2-phosphonobutane-1 ,2,4-tricarboxylicacid (PBTC), and anionic polymers or copolymers with phosphorous functional groups incorporated in the polymer chain.

[0026] Conventional corrosion inhibitors may be present in the MSC in amounts ranging from about 10 wt.% to about 99 wt.%, alternatively from about 20 wt.% to about 90 wt.% or alternatively from about 50 wt.% to about 90 wt.% based on the total weight of the MSC.

[0027] In an aspect, the MSC further comprises an optional solvent. In general, any solvent compatible with the MSC and / or activity to be undertaken may be utilized. In an aspect, the solvent comprises water, an alcohol, a polyol or a combination thereof.

[0028] In an aspect, the solvent comprises a polyol. For example, the solvent can be an aliphatic polyol such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol1 ,2-propanediol, 1 ,3-propanediol, 1 ,2- butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, neopentyl glycol, 1 ,2- hexanediol, 1 ,6-hexanediol, 1 ,2-octanediol, 1 ,8-octanediol, 1 ,2-decanediol, 1 ,10- decanediol, glycerol, 2,2-dimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1 ,2,4-butanetriol, 2,2,4-trimethyl-1 ,3- pentanediol, or a combination thereof.

[0029] In other aspects, the solvent comprises an alcohol. Non-limiting examples of suitable alcohols that can be utilized as a solvent include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol, cyclohexanol, and the like, and combinations thereof. In an aspect, the solvent comprises water, methanol, ethanol, ethylene glycol, propylene glycol, or a combination thereof.

[0030] In an aspect, the solvent may be present in an amount of from about 10% to about 99% based on the total volume of the composition. In an alternative aspect, solvent may be present in the MSC in an amount that constitutes the remainder of the composition once all other components are accounted for.

[0031] An MSC of the type disclosed herein may be introduced to an aqueous system in amounts effective to facilitate some user and / or process targeted activity (e.g., corrosion inhibition). For example, to effectively inhibit corrosion, the MSC may have to be present at or above a certain concentration. The minimum inhibitor level required to prevent corrosion is commonly referred to as "minimum inhibitory concentration" (MIC) or "minimum effective concentration" (MEC). In one or more aspects, a system havingan MSC introduced may be monitored to ensure the amount of the corrosion inhibitor composition retains some MIC or MEC for that particular system. For example, the amount of MSC present in a water-containing system may range from about 50 ppm to about 5000 ppm, or from about 100 ppm to about 4900 ppm or from about 150 ppm to about 4750 ppm or from about 250 ppm to about 4500 ppm, or from about 500 ppm to about 4000 ppm or from about 750 ppm to about 3750 ppm or from about 1000 ppm to about 3500 ppm or from about 1250 ppm to about 3250 ppm or from about 1500 ppm to about 3000 ppm or from about 1750 ppm to about 2750 ppm or from about 2000 ppm to about 2500 ppm or about 100 ppm, or about 125 ppm, or about 150 ppm, or about 175 ppm, or about 200 ppm, or about 225 ppm, or about 250 ppm, or about 275 ppm, or about 300 ppm, or about 325 ppm, or about 350 ppm, or about 375 ppm, or about 400 ppm, or about 425 ppm, or about 450 ppm, or about 475 ppm, or about 500 ppm, or about 525 ppm, or about 550 ppm, or about 575 ppm, or about 600 ppm, or about 625 ppm, or about 650 ppm, or about 675 ppm, or about 700 ppm, or about 725 ppm, or about 750 ppm, or about 775 ppm, or about 800 ppm, or about 825 ppm, or about 850 ppm, or about 875 ppm, or about 900 ppm, or about 925 ppm, or about 950 ppm, or about 975 ppm, or about 1000 ppm, or about 1025 ppm, or about 1050 ppm, or about 1075 ppm, or about 110 ppm, or about 1125 ppm, or about 1150 ppm, or about 1175 ppm, or about 1200 ppm, or about 1225 ppm, or about 1250 ppm, or about 1275 ppm, or about 1300 ppm, or about 1325 ppm, or about 1350 ppm, or about 1375 ppm, or about 1400 ppm, or about 1425 ppm, or about 1450 ppm, or about 1475 ppm, or about 1500 ppm, or about 1525 ppm, or about 1550 ppm, or about 1575 ppm, or about 1600 ppm, or about 1625 ppm, or about 1650 ppm, or about 1675 ppm, or about 1700 ppm, or about 1725 ppm, or about 1750 ppm, or about 1775 ppm, or about 1800 ppm, or about 1825 ppm, or about 1850 ppm, or about 1875 ppm, or about 1900 ppm, or about 1925 ppm, or about 1950 ppm, or about 1975 ppm, or about 2000 ppm, or about 2025 ppm, or about 2050 ppm, or about 2075 ppm, or about 2100 ppm, or about 2125 ppm, or about 2150 ppm, or about 2175 ppm, or about 2200 ppm, or about 2225 ppm, or about 2250 ppm, or about 2275 ppm, or about 2300 ppm, or about 2325 ppm, or about 2350 ppm, or about 2375 ppm, or about 2400 ppm, or about 2425 ppm, or about 2450 ppm, or about 2475 ppm, or about 2500 ppm, or about 2525 ppm, or about 2550 ppm, or about 2575 ppm, or about 2600 ppm, or about 2625 ppm, or about 2650 ppm, or about 2675 ppm, or about 2700 ppm, or about 2725 ppm, or about 2750 ppm, or about 2775 ppm, or about 2800 ppm, or about 2825 ppm, or about 2850 ppm, or about 2875ppm, or about 2900 ppm, or about 2925 ppm, or about 2950 ppm, or about 2975 ppm, or about 3000 ppm, or about 3025 ppm, or about 3050 ppm, or about 3075 ppm, or about 3100 ppm, or about 3125 ppm, or about 3150 ppm, or about 3175 ppm, or about 3200 ppm, or about 3225 ppm, or about 3250 ppm, or about 3275 ppm, or about 3300 ppm, or about 3325 ppm, or about 3350 ppm, or about 3375 ppm, or about 3400 ppm, or about 3425 ppm, or about 3450 ppm, or about 3475 ppm, or about 3500 ppm, or about 3525 ppm, or about 3550 ppm, or about 3575 ppm, or about 3600 ppm, or about 3625 ppm, or about 3650 ppm, or about 3675 ppm, or about 3700 ppm, or about 3725 ppm, or about 3750 ppm, or about 3775 ppm, or about 3800 ppm, or about 3825 ppm, or about 3850 ppm, or about 3875 ppm, or about 3900 ppm, or about 3925 ppm, or about 3950 ppm, or about 3975 ppm, or about 4000 ppm, or about 4025 ppm, or about 4050 ppm, or about 4075 ppm, or about 4100 ppm, or about 4125 ppm, or about 4150 ppm, or about 4175 ppm, or about 4200 ppm, or about 4225 ppm, or about 4250 ppm, or about 4275 ppm, or about 4300 ppm, or about 4325 ppm, or about 4350 ppm, or about 4375 ppm, or about 4400 ppm, or about 4425 ppm, or about 4450 ppm, or about 4475 ppm, or about 4500 ppm, or about 4525 ppm, or about 4550 ppm, or about 4575 ppm, or about 4600 ppm, or about 4625 ppm, or about 4650 ppm, or about 4675 ppm, or about 4700 ppm, or about 4725 ppm, or about 4750 ppm, or about 4775 ppm, or about 4800 ppm, or about 4825 ppm, or about 4850 ppm, or about 4875 ppm, or about 4900 ppm, or about 4925 ppm, or about 4950 ppm, or about 4975 ppm, or about 5000 ppm.

[0032] In one or more aspects, an MSC may also function to inhibit the formation of scale. Herein, scale refers to hard mineral coatings and corrosion deposits made up of solids and sediments that collect on or in distribution systems, piping, storage reservoirs and water conduits. In an aspect, the MSC may reduce scaling in a system comprising industrial water to an amount that is from about 10% to about 90%, alternatively from about 20% to about 80% or alternatively from about 30% to about 80% of the amount of scale formed in the absence of a corrosion inhibitor composition of the type disclosed herein.

[0033] In some aspects, a synergistic effect is observed between a sugar oxidation product as disclosed herein an MSC. Specifically, the MSC may allow for a reduction in the minimal concentration of corrosion inhibitors needed to effectively address a corrosion issue. In other words, with the addition of one or more sugar oxidation products, the amount of corrosion inhibitors needed to achieve the same level ofcorrosion inhibition may be reduced by equal to or greater than about 5%, or equal to or greater than about 7%, or equal to or greater than about 10%, or equal to or greater than about 12%, or equal to or greater than about 14%, or equal to or greater than about 15%, or equal to or greater than about 17%, or equal to or greater than about 18%, or equal to or greater than about 20%, or equal to or greater than about 22%, or equal to or greater than about 25%, or equal to or greater than about 27%, or equal to or greater than about 30%.

[0034] In one or more aspects, the MSC has the the one or more sugar oxidation products and corrosion inhibitor present in an amount sufficient to provide a sugar oxidation product to corrosion inhibitor ratio of from about 20:1 to about 1 :20 or from about 1 :15 to about 15:1 or from about 1 :10 to about 10:1 or from about 1 :5 to about 5:1 .Disclosed herein are composition comprising one or more sugar oxidation products and a corrosion inhibitor which is provided to increase the performance of corrosion and scale inhibitors in numerous applications, such as in systems utilizing industrial water or in oilfield operations. In one or more aspects, the MSC is utilized to provide improved carbon steel corrosion inhibition and scale control for upstream oil and gas applications.EXAMPLES

[0035] The presently disclosed subject matter having been generally described, the following examples are given as particular aspects of the subject matter and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims in any manner.EXAMPLE 1

[0036] The effectiveness of corrosion inhibitor compositions of the present disclosure was evaluated. The sample components are presented in Table 1. The corrosion inhibition effects were determined for sample coupons having C1018 metallurgy. C1018 refers to a low carbon steel having a higher manganese content than mild steel and various other low carbon steels. Specifically, using a 3% NaCI brine solution continuously sparged with CO2 at 60 °C, the corrosion inhibition effects were determined by Linear Polarization Resistance in Kettle Tests using Carbon Steel C1018 electrodes for a duration of 18 hours. The electrochemical technique, commonly referred to as Linear Polarization Resistance, is a corrosion monitoring method that allows corrosion rates to be measured directly, in real time. The test is performed inelectrolytically conducting liquids, using polarization resistance as particularly useful as a method to rapidly identify corrosion upsets and initiate remedial action, thereby prolonging plant life and minimizing unscheduled downtime. The technique is utilized to maximum effect, when installed as a continuous monitoring system. The results are presented in Table 2.Table 1Table 2

[0037] The MSC was a blend of quaternary ammonium chloride and polyoxyethylene tridecyl ether phosphate supplemented with the indicated weight percentage of sodium gluconate. The MSC blend using a combination of corrosion inhibitor and sodium gluconate was as effective as the inhibition observed when using twice the amount of corrosion inhibitor (e.g., phosphate esters) alone.EXAMPLE 2

[0038] A scale inhibition test using turbidity was performed using a water composition having the ion levels listed in Table 3. The effectiveness of the MSC as a scale inhibitor was determined by measuring the amount of suspended particles (turbidity) in a solution that is prone to scaling, where a lower turbidity indicates better scale inhibition as fewer large scale particles are forming; essentially, the scale inhibitor prevents the formationof visible scale deposits by keeping the mineral particles dispersed in the solution, which can be measured by a turbidity meter. The scale inhibition test was performed at 65 °C, pH 5.8 and 100% CO2 and the sample components are presented in Table 4 while experimental results are presented in Table 5. The MIC was identified as the point at which particles did not appear in the liquid.Table 3Table 4Table 5

[0039] The results demonstrate the MSC resulted in a lower MIC, indicating a more effective calcium carbonate scale inhibitor. The results demonstrate that surprisingly the corrosion inhibiting compositions of the type disclosed herein (i.e., MSC) offered significantly better corrosion and scale inhibition.ADDITIONAL DISCLOSURE

[0040] A first aspect which is a metal stabilizing composition comprising (i) one or more oxidized sugar products; and (ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof.

[0041] A second aspect which is the composition of the first aspect further comprising a solvent.

[0042] A third aspect which is the composition of any of the first through second aspects wherein the inhibitor comprises imidazole, pyrazole, 1 ,2,3-triazole, 1 ,2,4-triazole, tetrazole, pentazole, oxazole, isoxazole, 1 ,2,4-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,5- oxadiazole, thiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, mercaptobenzothiazole, mercaptobenzimidazole, butyl benzotriazole 1 ,3,4-thiadiazole, benzotriazole, tolytriazole, (2-pyrrole carbonyl) benzotriazole, (2-thienyl carbonyl)-benzotriazole, amino-1 ,2,4-triazole, diamino-1 ,2,4triazole, mercapto-1 H-1 ,2,4-triazole, methyl-2- phenyl-imidazole, amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, phenyl-1-H-tetrazole, derivatives thereof, or a combination thereof.

[0043] A fourth aspect which is the composition of any of the first through third aspects wherein the inhibitor comprises include ammonium orthomolybdate, lithium molybdate, sodium molybdate, magnesium molybdate, potassium molybdate, calcium molybdate or a combination thereof.

[0044] A fifth aspect which is the composition of any of the first through fourth aspects wherein the inhibitor comprises a phosphorus-containing compound.

[0045] A sixth aspect which is the composition of the fifth aspect wherein the inhibitor comprises aminotrimethylene phosphonic acid (ATMP), 1-hydroxyethylidene-1 ,1- diphosphonic acid (HEDP), hydrolyzed polymaleic anhydride (HPMA), 2- hydrophosphonocarboxylic (HPAA), polyamino polyether phosphonate (PAPEMP), aminoethlethanolamine (AEEA), diethylenetriamine penta (DTPMP), bis(hexamethylene triamine penta (methylene phosphonic acid)) (BHMT), diethylene triamine penta (methylene phosphonic acid) (BTPMP), 2-phosphonobutane-1 ,2,4- tricarboxylic acid (PBTC), or a combination thereof.

[0046] A seventh aspect which is the composition of any of the first through sixth aspects wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, a gluconic acid oxidation product, a gluconate, glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, galactonic acid, galactaric acid, glutamicacid, a lactone of gluconic acid, a lactone of glucaric acid, a lactone of galactaric acid, a lactone of galactonic acid, glucodialdose, 2-ketoglucose, disaccharides, oxidized disaccharides, n-keto-acids, C2 to C6 diacids, salts thereof or combinations thereof.

[0047] An eighth aspect which is the composition of any of the first through seventh aspects wherein the one or more sugar oxidation products comprise a mixture of gluconic acid and glucaric acid.

[0048] A ninth aspect which is the composition of the eighth aspect wherein the ratio of gluconic acid:glucaric acid ranges from about 0.1 :10 to about 10:0.1.

[0049] A tenth aspect which is the composition of any of the second through ninth aspect wherein the solvent comprises water, an alcohol, a polyol or combinations thereof.

[0050] An eleventh aspect which is the composition of any of the second through tenth aspects, wherein the solvent comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycoll ,2-propanediol, 1 ,3-propanediol, 1 ,2- butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, neopentyl glycol, 1 ,2- hexanediol, 1 ,6-hexanediol, 1 ,2-octanediol, 1 ,8-octanediol, 1 ,2-decanediol, 1 ,10- decanediol, glycerol, 2,2-dimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1 ,2,4-butanetriol, 2,2,4-trimethyl-1 ,3- pentanediol, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol, cyclohexanol, or a combination thereof.

[0051] A twelfth aspect which is a method of treating a water-containing system comprising introducing to the system a metal stabilizing composition comprising (i) one or more oxidized sugar products; (ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof; and (iii) a solvent.

[0052] A thirteenth aspect which is the method of the twelfth aspect wherein the inhibitor comprises imidazole, pyrazole, 1 ,2,3-triazole, 1 ,2,4-triazole, tetrazole, pentazole, oxazole, isoxazole, 1 ,2,4-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,5-oxadiazole, thiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, mercaptobenzothiazole, mercaptobenzimidazole, butyl benzotriazole 1 ,3,4-thiadiazole, benzotriazole, tolytriazole, (2-pyrrole carbonyl) benzotriazole, (2-thienyl carbonyl)-benzotriazole, amino-1 ,2,4-triazole, diamino- 1 ,2,4triazole, mercapto-1 H-1 ,2,4-triazole, methyl-2-phenyl-imidazole, amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, phenyl-1-H-tetrazole, derivatives thereof, or a combination thereof.

[0053] A fourteenth aspect which is the method of any of the twelfth through thirteenth aspects wherein the inhibitor comprises include ammonium orthomolybdate, lithium molybdate, sodium molybdate, magnesium molybdate, potassium molybdate, calcium molybdate or a combination thereof.

[0054] A fifteenth aspect which is the method of any of the twelfth through fourteenth aspects wherein the inhibitor comprises a phosphorus-containing compound.

[0055] A sixteenth aspect which is the method of any of the twelfth through fifteenth aspects wherein the inhibitor comprises aminotrimethylene phosphonic acid (ATMP), 1- hydroxyethylidene-1 ,1-diphosphonic acid (HEDP), hydrolyzed polymaleic anhydride (HPMA), 2-hydrophosphonocarboxylic (HPAA), polyamino polyether phosphonate (PAPEMP), aminoethlethanolamine (AEEA), diethylenetriamine penta (DTPMP), bis(hexamethylene triamine penta (methylene phosphonic acid)) (BHMT), diethylene triamine penta (methylene phosphonic acid) (BTPMP), 2-phosphonobutane-1 ,2,4- tricarboxylic acid (PBTC), or a combination thereof.

[0056] A seventeenth aspect which is the method of any of the twelfth through sixteenth aspects wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, a gluconic acid oxidation product, a gluconate, glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, galactonic acid, galactaric acid, glutamic acid, a lactone of gluconic acid, a lactone of glucaric acid, a lactone of galactaric acid, a lactone of galactonic acid, glucodialdose, 2-ketoglucose, disaccharides, oxidized disaccharides, n-keto-acids, C2 to C6 diacids, salts thereof or combinations thereof.

[0057] An eighteenth aspect which is the method of any of the twelfth through seventeenth aspect wherein the one or more sugar oxidation products comprise a mixture of gluconic acid and glucaric acid.

[0058] A nineteenth aspect which is the method of any of the twelfth through eighteenth aspects wherein the ratio of gluconic acid:glucaric acid ranges from about 0.1 :10 to about 10:0.1.

[0059] A twentieth aspect which is the method of any of the twelfth through nineteenth aspects wherein the solvent comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol1 ,2-propanediol, 1 ,3-propanediol, 1 ,2- butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5-pentanediol, neopentyl glycol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-octanediol, 1 ,8-octanediol, 1 ,2-decanediol, 1 ,10- decanediol, glycerol, 2,2-dimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1 ,2,4-butanetriol, 2,2,4-trimethyl-1 ,3- pentanediol, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol, cyclohexanol, or a combination thereof.

[0060] A twenty-first aspect which is the method of any of the twelfth through twentieth aspects wherein the metal stabilizing composition is present in an amount of from about 50 ppm to about 5000 ppm.

[0061] While preferred embodiments have been shown and described, modifications thereof can be made by one skilled in the art without departing from the scope or teachings herein. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of the systems, apparatus, and processes described herein are possible and are within the scope of the disclosure. For example, the relative dimensions of various parts, the materials from which the various parts are made, and other parameters can be varied. Accordingly, the scope of protection is not limited to the embodiments described herein, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims. Unless expressly stated otherwise, the steps in a method claim may be performed in any order. The recitation of identifiers such as (a), (b), (c) or (1 ), (2), (3) before steps in a method claim are not intended to and do not specify a particular order to the steps, but rather are used to simplify subsequent reference to such steps.

[0062] Each and every claim is incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description and are an addition to the aspects of the present invention. The discussion of a reference herein is not an admission that it is prior art to the presently disclosed subject matter, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. In the event of conflict, the present specification, including definitions, is intended to control.

Claims

CLAIMSWhat is claimed is:1 . A metal stabilizing composition, comprising:(i) one or more oxidized sugar products; and(ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof.

2. The composition of claim 1 , further comprising a solvent.

3. The composition of claim 1 , wherein the inhibitor comprises imidazole, pyrazole,1 .2.3-triazole, 1 ,2,4-triazole, tetrazole, pentazole, oxazole, isoxazole, 1 ,2,4-oxadiazole,1.3.4-oxadiazole, 1 ,2,5-oxadiazole, thiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, mercaptobenzothiazole, mercaptobenzimidazole, butyl benzotriazole 1 ,3,4-thiadiazole, benzotriazole, tolytriazole, (2-pyrrole carbonyl) benzotriazole, (2-thienyl carbonyl)- benzotriazole, amino-1 ,2,4-triazole, diamino-1 ,2,4triazole, mercapto-1 H-1 ,2,4-triazole, methyl-2-phenyl-imidazole, amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, phenyl-1-H- tetrazole, derivatives thereof, or a combination thereof.

4. The composition of claim 1 , wherein the inhibitor comprises include ammonium orthomolybdate, lithium molybdate, sodium molybdate, magnesium molybdate, potassium molybdate, calcium molybdate or a combination thereof.

5. The composition of claim 1 , wherein the inhibitor comprises a phosphorus- containing compound.

6. The composition of claim 5, wherein the inhibitor comprises aminotrimethylene phosphonic acid (ATMP), 1-hydroxyethylidene-1 ,1-diphosphonic acid (HEDP), hydrolyzed polymaleic anhydride (HPMA), 2-hydrophosphonocarboxylic (HPAA), polyamino polyether phosphonate (PAPEMP), aminoethlethanolamine (AEEA), diethylenetriamine penta (DTPMP), bis(hexamethylene triamine penta (methylene phosphonic acid)) (BHMT), diethylene triamine penta (methylene phosphonic acid)(BTPMP), 2-phosphonobutane-1 ,2,4-tricarboxylic acid (PBTC), or a combination thereof.

7. The composition of claim 1 , wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, a gluconic acid oxidation product, a gluconate, glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, galactonic acid, galactaric acid, glutamic acid, a lactone of gluconic acid, a lactone of glucaric acid, a lactone of galactaric acid, a lactone of galactonic acid, glucodialdose, 2- ketoglucose, disaccharides, oxidized disaccharides, n-keto-acids, C2 to C6 diacids, salts thereof or combinations thereof.

8. The composition of claim 1 , wherein the one or more sugar oxidation products comprise a mixture of gluconic acid and glucaric acid.

9. The composition of claim 8, wherein the ratio of gluconic acid:glucaric acid ranges from about 0.1 :10 to about 10:0.1.

10. The composition of claim 2, wherein the solvent comprises water, an alcohol, a polyol or combinations thereof.

11. The composition of claim 2, wherein the solvent comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol1 ,2- propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5- pentanediol, neopentyl glycol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-octanediol, 1 ,8- octanediol, 1 ,2-decanediol, 1 ,10-decanediol, glycerol, 2,2-dimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1 ,2,4- butanetriol, 2,2,4-trimethyl-1 ,3-pentanediol, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol, cyclohexanol, or a combination thereof.

12. A method of treating a water-containing system comprising introducing to the system a metal stabilizing composition comprising:(i) one or more oxidized sugar products;(ii) an inhibitor selected from the group consisting of heterocyclic organic compounds, molybdates, metal salts, water soluble organic polymers, phosphate esters, phosphonates, imidazolines, triazoles, imidazoles, or a combination thereof; and(iii) a solvent.

13. The method of claim 12, wherein the inhibitor comprises imidazole, pyrazole,1.2.3-triazole, 1 ,2,4-triazole, tetrazole, pentazole, oxazole, isoxazole, 1 ,2,4-oxadiazole,1.3.4-oxadiazole, 1 ,2,5-oxadiazole, thiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, mercaptobenzothiazole, mercaptobenzimidazole, butyl benzotriazole 1 ,3,4-thiadiazole, benzotriazole, tolytriazole, (2-pyrrole carbonyl) benzotriazole, (2-thienyl carbonyl)- benzotriazole, amino-1 ,2,4-triazole, diamino-1 ,2,4triazole, mercapto-1 H-1 ,2,4-triazole, methyl-2-phenyl-imidazole, amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, phenyl-1-H- tetrazole, derivatives thereof, or a combination thereof.

14. The method of claim 12, wherein the inhibitor comprises include ammonium orthomolybdate, lithium molybdate, sodium molybdate, magnesium molybdate, potassium molybdate, calcium molybdate or a combination thereof.

15. The method of claim 12, wherein the inhibitor comprises a phosphorus- containing compound.

16. The method of claim 12, wherein the inhibitor comprises aminotrimethylene phosphonic acid (ATMP), 1-hydroxyethylidene-1 ,1-diphosphonic acid (HEDP), hydrolyzed polymaleic anhydride (HPMA), 2-hydrophosphonocarboxylic (HPAA), polyamino polyether phosphonate (PAPEMP), aminoethlethanolamine (AEEA), diethylenetriamine penta (DTPMP), bis(hexamethylene triamine penta (methylene phosphonic acid)) (BHMT), diethylene triamine penta (methylene phosphonic acid) (BTPMP), 2-phosphonobutane-1 ,2,4-tricarboxylic acid (PBTC), or a combination thereof.

17. The method of claim 12, wherein the one or more sugar oxidation products comprise aldonic acid, uronic acid, aldaric acid, a gluconic acid oxidation product, a gluconate, glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products,galactonic acid, galactaric acid, glutamic acid, a lactone of gluconic acid, a lactone of glucaric acid, a lactone of galactaric acid, a lactone of galactonic acid, glucodialdose, 2- ketoglucose, disaccharides, oxidized disaccharides, n-keto-acids, C2 to C6 diacids, salts thereof or combinations thereof.

18. The method of claim 12, wherein the one or more sugar oxidation products comprise a mixture of gluconic acid and glucaric acid.

19. The method of claim 18, wherein the ratio of gluconic acid:glucaric acid ranges from about 0.1 : 10 to about 10:0.1.

20. The method of claim 12, wherein the solvent comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol1 ,2- propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5- pentanediol, neopentyl glycol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-octanediol, 1 ,8- octanediol, 1 ,2-decanediol, 1 ,10-decanediol, glycerol, 2,2-dimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1 ,2,4- butanetriol, 2,2,4-trimethyl-1 ,3-pentanediol, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol, cyclohexanol, or a combination thereof.21 . The method of claim 12, wherein the metal stabilizing composition is present in an amount of from about 50 ppm to about 5000 ppm.

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