Compositions for corrosion inhibition

Abstract

A corrosion inhibitor comprising at least one organic acid and at least on azole-containing compound. A reaction addition product of at least one organic acid and at least one sugar oxidation product. A method comprising contacting one or more organic acids with one or more azoles under conditions suitable for the formation of at least one addition product; and contacting the at least one addition product with an aqueous fluid to form a corrosion inhibitor.

Description

COMPOSITIONS FOR CORROSION INHIBITIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit and priority of U.S. provisional patent application Serial No 63 / 703,353 filed October 4, 2024, and entitled “COMPOSITIONS FOR CORROSION INHIBITION,” 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 present disclosure relates generally to compositions and methods for use in corrosion inhibition. More specifically, the present disclosure relates to corrosion inhibition in an industrial fluid system. Still more specifically, the present disclosure relates to corrosion inhibition in an industrial fluid having yellow metal surfaces.BACKGROUND

[0004] Corrosion inhibitors are chemical substances that, when added to the environment in which a metal (e.g., metal surface) would otherwise corrode, will reduce, slow down or prevent corrosion of the metal. In aqueous systems in which metallic materials of construction are exposed to the water, various forms of corrosion are possible. For example, yellow metal corrosion protection is standard in refineries and petrochemical plants, which use heat exchangers that contain copper-based components for their high thermal conductivity and antifouling properties.

[0005] The conventional technology for addressing corrosion of yellow metals is the introduction of corrosion inhibitors. Compounds specific for inhibiting the corrosion of copper and copper alloys are commonly seen in water treatment streams. These types of inhibitors have significant limitations. For example, (i) the conventional corrosion inhibitors are poorly soluble in water and are difficult to formulate with other active ingredients; (ii) are degraded by oxidizing biocides based on chlorine and bromine; and (iii) the solubility of benzo and tolyl triazoles (commonly used yellow metal corrosion inhibitors) is poor across the middle of the pH range. For example, due to solubility issues with azoles it is typical practice to either elevate the formulation pHabove 12 with bases or lower it to less than 2 with acids. Even then, the amount of azole that is soluble in the formulation is low. Products at these extreme pH values have hazard and handling issues. Another problem with the current inhibitors is the volatility of cost and availability caused by competing demand for the feedstocks and trade barriers.An ongoing need exists for improved materials that function as yellow metal corrosion inhibitors that can address one or more of the aforementioned challenges.BRIEF SUMMARY OF THE DISCLOSURE

[0006] Disclosed herein is a corrosion inhibitor comprising at least one organic acid and at least on azole-containing compound.

[0007] Also disclosed herein is a reaction addition product of at least one organic acid and at least one sugar oxidation product.

[0008] Also disclosed herein is a method comprising contacting one or more organic acids with one or more azoles under conditions suitable for the formation of at least one addition product; and contacting the at least one addition product with an aqueous fluid to form a corrosion inhibitor.

[0009] Aspects 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 aspects 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 aspects disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes as the disclosed aspects. It should also be realized that such equivalent constructions do not depart from the spirit and scope of the principles disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] For a detailed description of various exemplary aspects, reference will now be made to the accompanying drawings in which:

[0011] Figure 1 depicts the chemical structure of glucodialdose (GDA).

[0012] Figure 2 depicts the reaction of GDA with an azole to form an adduct.DETAILED DESCRIPTION

[0013] The following discussion is directed to various exemplary aspects. However, one skilled in the art will understand that the examples disclosed herein have broad application, and that the discussion of any aspect is meant only to be exemplary of that aspect, and not intended to suggest that the scope of the disclosure, including the claims, is limited to that aspect.

[0014] 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.

[0015] 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.).

[0016] 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 aspects 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 mean that the subject element is required, or additionally or alternatively , is not required. Both alternatives are intended to be within the scope of the claim. 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.

[0017] Disclosed herein are compositions and methods for corrosion inhibition. In one or more aspects, the compositions disclosed herein inhibit the corrosion of yellow metals and are designated yellow metal corrosion inhibitors or YMCI. Although reference is made to the inhibition of yellow metals, the present compositions may provide corrosion inhibition for other metal surfaces.

[0018] Herein yellow metals refer to copper and copper-based alloys including, for example, bronzes, and brasses, though the YMCI disclosed herein can be used with any alloys containing copper and / or pure copper. Copper metallurgies are commonly used in cooling water treatment systems for heat exchanger tubing, pump impellers and various other applications owing to its natural corrosion resistance and high thermal conductivity.

[0019] In one or more aspects, any surface comprising a yellow metal may exhibit reduced corrosion when contacted with a YMCI of the present disclosure. For example, a surface that is contacted with a YMCI may comprise a brass alloy, also known as Muntz metal, that contains an average composition of 60 weight percent(wt.%) copper and 40 wt.% zinc. Other nonlimiting examples of yellow metals include yellow brass (C27000), also known as heavy brass, which has a typical chemistry of 61 wt.% to 67 wt.% Cu, 1 wt.% Sn, 1 wt.% to 3 wt.% Pb, and 29 wt.% to 35 wt.% Zn; G metal, also known as high grade, which has a typical chemistry of Cu-10Sn-2Zn; M meta, which is a grade with a composition between those of red brass and G metal, which has a typical chemistry of Cu-6Sn-1 ,5Pb-4Zn; admiralty brass which has a typical chemistry of Cu-1 Sn-29Zn; and nickel silver, also known as German silver, which has a nickel content that spans at broad range from 7.5 wt.% to 18 wt.% and a copper content ranging from about 55 wt.% to 65 wt.%.

[0020] In one or more aspects, the YMCI is the reaction product of an organic acid and an azole. In other aspects, the YMCI is a blend of an organic acid and an azole. Hereinafter it is to be understood that YMCI is used as the term referring either to the reaction product or to the blend. Azoles refer to a broad class of five-membered heterocyclic aromatic compounds whose framework contains from one and up to five nitrogen atom(s) and can also contain at least one S or O atom as a part of the azole conjugated ring (N,S and N,0 subclasses of azoles, respectively). Organic acids are a large family of compounds that includes, primarily, carboxylic acids, as well as phosphonic and sulfonic acids. The term "acid" is also occasionally used with compounds that do not belong in any of the above categories, yet have properties characteristic of an organic acid.

[0021] In some aspects, the organic is a sugar oxidation product such as 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 Ce diacids, salts thereof or combinations thereof.

[0022] The organic acid may be in equilibrium with it lactone form. In one or more aspects, the lactone is derived from a sugar such as glucose. Nonlimiting examples of lactones derivable from glucose include glucono-delta lactone (GDL), glucaric acid 1 ,4:6, 3 dilactone (GAdL), derivatives thereof or combinations thereof. In one or more aspects, the lactones may be unsubstituted. In alternative aspects, the lactones aresubstituted. In an aspect, the lactone comprises GDL whose chemical structure is depicted in Figure 1 .

[0023] Hereinafter the disclosure will focus on the use of GDL as the lactone for production of the YMCI. However, it is contemplated that any organic acid or lactone of the type disclosed herein may be use in formation of the YMCI (e.g., substituted GDL or GAdL or unsubstituted GAdL).

[0024] In an aspect, the organic acid comprises a mixture of gluconic acid and glucaric acid. In such aspects, 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 .

[0025] In some aspec, the YMCI comprises at least one acid selected from the group consisting essentially of glucaric acid, glucoheptonic acid, galatonic acid, galataric acid, lactic acid, citric acid, isocitric acid, tartaric acid, glutaric acid, adipic acid, acetic acid, formic acid, malic acid propionic acid, butyric acid, sorbic acid, fumaric acid, benzoic acid, succinic acid, ascorbic acid, quinic acid, shikimic acid, maleic acid and combinations thereof.

[0026] In one or more aspects, the amount of organic acid used in the formation of the YMCI or as a blend is about 0.1 wt.%, or about 0.25 wt.%, or about 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 about 12.5 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 about32.5 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 about 57.5 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 about87.5 wt.%, or about 90 wt.%, or about 92.5 wt.%, or about 95 wt.%, or about 97.5 wt.%, or about 100 wt.%, additionally or alternatively about 0.1 wt.% to about 99 wt.%, additionally or alternatively about 1 wt.% to about 95 wt.%, additionally or alternativelyabout 5 wt.% to about 90 wt.%, additionally or alternatively about 10 wt.% to about 90 wt.%, additionally or alternatively about 15 wt.% to about 85 wt.%, additionally or alternatively about 20 wt.% to about 80 wt.%, additionally or alternatively about 25 wt.% to about 75 wt.%, additionally or alternatively about 40 wt.% to about 60 wt.%, additionally or alternatively about 50 wt.%, additionally or alternatively about 0.1 wt.% to about 10 wt.%, additionally or alternatively about 1 wt.% to about 20 wt.%, additionally or alternatively about 5 wt.% to about 50 wt.% based on the total weight of the YMCI. In some aspects, the YMCI has the organic acid present in an amount (either for formation of an adduct as a blend) between any of the end points listed herein.

[0027] Nonlimiting examples of azoles suitable for use in the formation of a YMCI (either as an adduct or as a component of a blend) include tolyltriazole, benzotriazole (BTA), 5-pentyl-BTA, 5-chloro-BTA, N-[benzotriazol-1-yl-(phenyl)-methylene]-N- phenylhydrazine, N-[benzotriazol-1-yl-(4-methoxy-phenyl)-methylene]-N-phenyl- hydrazine, 1 -(2-pyrrole carbonyl)-benzotriazole 1 ,2,4-triazole, 3 4-amino-5-ethyl- 4H1 ,2,4-triazole-3thiol], 4-amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, bis-(4-amino- 5-mercapto-1 ,2,4-triazol-3-yl)-butane;2-mercaptobenzoxazole, 5-(4’- dimetylaminobenzylidene)-2,4-dioxotetrahydro-1 ,3-thiazole, benzothiazole, imidazole, derivatives thereof, and combinations thereof.

[0028] In one or more aspects, a YMCI of the present disclosure is prepared by contacting a sugar oxidation product (e.g., GDA) and an azole (e.g., BTZ) under conditions suitable for the formation a reaction product that is an adduct of the sugar oxidation product and azole that has an amide functionality. For example, a benzotriazole may undergo reaction with GDL to form a gluconamide compound which is the YMCI. This is depicted schematically in Figure 2.

[0029] Conditions suitable for the formation of a reaction product may include one or more of the following parameters: a ratio of lactone:organic acid of from about 100:1 to about 1 :100: additionally or alternatively 1 :1 : additionally or alternatively about 9:1 ; additionally or alternatively about 1 :9; a reaction media of aqueous solvent such as and aqueous buffer ; a mixture of an aqueous solvent and an organic co-solvent; a pH of less than about 7; additionally or alternatively from about 1 to about 6.9, additionally or alternatively from about 1 to about 5; a temperature of from about 25 °C to about200 °C; a pressure of from about 1 atm to about 30 atm; and a reaction time of from about 5 min to about 72 hours.

[0030] The reaction product comprising a lactone-azole adduct with an amide functionality may be used as a YMCI without further processing. In other aspects, the reaction product comprising the YMCI may be purified using any suitable methodologies to achieve one or more user and / or process goals.

[0031] In one or more aspects, a YMCI of the present disclosure is prepared by contacting an organic acid (e.g., GDA) and an azole (e.g., BZT) at a ratio of about 10:1 to about 1 :10; additinally or alternatively abotu 1 :1 to form a blend.

[0032] A YMCI of the present disclosure (e.g., reaction product of an azole-compound and lactone or blend) may display an increased solubility when compared with the solubility of the azole compound alone. For example, the YMCI may have a solubility in an aqueous fluid that is increased by from about 10% to about 250% when compared to the solubility of the azole compound used to prepared the YMCI alone in the same aqueous fluid; additionally or alternatively from about 50% to about 200%; additionally or alternatively from about 100% to about 200%; additionally or alternatively about10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 100%, about 110%, about 120%, about 130%, about 140%, about 150%, about 160%, about 170%, about 180%, about 190%, about 200%, about 210%, about 220%, about 230%, about 240%, about 250%.

[0033] In one or more aspects, disclosed herein is a composition comprising the gluconamide of an azole compound which is useful as a corrosion inhibitor. In other aspects, disclosed herein is a blend of an organic acid and an azole; additionally or alternatively of the lactone of a sugar oxidation product and an azole. In other aspects an adduct formed from reacting a sugar oxidation product or derivative thereof and an azole.

[0034] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of gluconic acid which contains an equilibrium amount of the respective lactones.

[0035] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and relatedcompositions wherein an amine compound is added to a concentrated acidic solution of glucaric acid which contains an equilibrium amount of the respective lactones.

[0036] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of glucaric and gluconic acid which contains an equilibrium amount of the respective lactones.

[0037] In one or more aspects disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of aldaric, uronic acids.

[0038] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of aldaric, uronic acids and wherein the acid solution comprises glucaric acid, gluconic acid, glucuronic acid, glucose oxidation products, and gluconic acid oxidation products.

[0039] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of aldaric, uronic acids and wherein the acid solution is comprised of sugar oxidation products comprising disaccharides, oxidized disaccharides, uronic acid, and aldaric acid.

[0040] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of aldaric, uronic acids and wherein the acid solution comprises gluconic acid, glucaric acid, glucuronic acid, n-keto-acids and C2-C6 diacids.

[0041] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of aldaric, uronic acids wherein the acid solution comprises galactonic acid andgalactaric acid oxidation product comprising predominantly galactonic acid and / or galactaric acid with minor component species of n-keto-acids and C2-C6 diacids.

[0042] In one or more aspects, disclosed herein is a process for producing a composition comprising the gluconamide of an azole compound and related compositions wherein an amine compound is added to a concentrated acidic solution of aldaric, uronic acids, and wherein the acid solution comprises glucoheptonic acid.

[0043] In one or more aspects, a YMCI (adduct of an azole and organic acid or blend of an azole and organic acid) may be a component of a corrosion inhibition formulation that is introduced to a industrial fluid system having surfaces comprising one or more yellow metals. For example, the YMCI may be a component of a formulation containing other additives such asantioxidants, chelating agents, corrosion inhibitors, rust inhibitors, viscosity-index improvers, pourpoint surfactants, anti-wear additives, complexing agents, precipitation inhibitors, biocides, buffering agents, or combinations thereof.

[0044] In one or more aspects, a method of the present disclosure comprises contacting an organic acid or lactone thereof (e.g., GDL) with an azole under conditions suitable for the formation of a reaction product comprising an adduct of the organic and acid and azole. The reaction product may be a component of a formulation that is introduced to an industrial fluid system.

[0045] In one or more aspects, a method of the present disclosure comprises contacting an organic acid or lactone thereof (e.g., GDL) with an azole to form a blend. The blend may be a component of a formulation that is introduced to an industrial fluid system.

[0046] In one or more aspects, the industrial fluid is selected from the group consisting of: cooling water systems such as cooling towers; heat transfer systems such as boiler systems; refinery systems such as systems for the processing hydrocarbon feedstock; pulp and paper making systems; food and beverage systems such as thermal processing systems; and, mechanical coolant systems such as combustion engine coolant systems. It is contemplated that the YMCI may be used as a corrosion inhibitor in other fluid systems.

[0047] In one or more aspects, the formulation comprising a YMCI that is introduced to the industrial fluid system is introduced at any suitable point and in any suitable amount to provide a final concentration of YMCI that reduces corrosion of the metalsurfaces (e.g., yellow metal surfaces) present in the industrial fluid system. In some aspects, introduction of the YMCI alone or as a component of a formulation to the industrial fluid system may be metered. In such aspects, the concentration of YMCI in the industrial fluid system may be monitored to assure the YMCI concentration is within some user and / or process desired range. In some aspects, introduction of the YMCI may be metered to maintain some use and / or process desired concentration range and additional YMCI introduced to the industrial fluid system as needed. Monitoring of the YMCI concentration in an industrial fluid system may be carried manually or monitoring may be automated.

[0048] Disclosed herein is a corrosion inhibitor (e.g., YMCI adduct product) which promises to overcome the limitations of the current generation of copper and yellow metal corrosion inhibitors. A simple and inexpensive manufacturing process has also been disclosed. Disclosed herein is a reaction of gluconic and glucaric acid products with azoles to produce a new composition (e.g., benzotriazole gluconamides) which are expected to improve performance properties compared to the existing commercial azoles.

[0049] A YMCI is characterized by a hydrophilic gluconic functional group covalently bonded to the imide site of the triazoles. This functional group improves water solubility and protects the imide hydrogen from attack by oxidizing biocides. In one or more aspects, solubility a YMCI of the present disclosure has a solubility in aqueous fluid that is increased by from about 10% to about 250% when compared to the solublity of the azole used to produce the YMCI.

[0050] This will allow formulators to use increased amounts of the YMCI in formulated multifunctional products. Without wishing to be limited by theory, the glucose functional group may bond to the imide hydrogen providing protection to that vulnerable part of the molecule from attack by oxidizing agents. In addition, the hydroxyl groups of the glucose functional group will provide enhanced surface activity on metal surfaces.ADDITIONAL DISCLOSURE

[0051] The following are nonlimiting exemplary aspects of the presently disclosed subject matter:

[0052] A first aspect which is a corrosion inhibitor comprising at least one organic acid and at least on azole.

[0053] A second aspect which is the inhibitor of the first aspect wherein the organic acid comprises a sugar oxidation product.

[0054] A third aspect which is the inhibitor of any of the first through second aspects wherein the organic acid comprises aldonic acid, uranic acid, aldaric acid, or a combination thereof.

[0055] A fourth aspect which is the inhibitor of any of the first through third aspects wherein the organic acid comprises 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.

[0056] A fifth aspect which is the inhibitor of any of the first through fourth aspects wherein the organic acid comprises a lactone of a sugar oxidation product.

[0057] A sixth aspect which is the inhibitor of any of the first through fifth aspects wherein the organic acid comprises a mixture of gluconic acid and glucaric acid.

[0058] A seventh aspect which is the inhibitor of the sixth aspect wherein the ratio of gluconic acid:glucaric acid is from about 0.1 : 10 to about 10:0.1.

[0059] An eighth aspect which is the inhibitor of any of the first through sixth aspects wherein the organic acid is selected from the group consisting of glucaric acid, glucoheptonic acid, galatonic acid, galataric acid, isocitric acid, glutaric acid, citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

[0060] A ninth aspect which is the inhibitor of any of the first through eighth aspects wherein the azole comprises tolyltriazole, benzotriazole (BTA), 5-pentyl-BTA, 5- chloro-BTA, N-[benzotriazol-1-yl-(phenyl)-methylene]-N-phenylhydrazine, N- [benzotriazol-1 -yl-(4-methoxy-phenyl)-methylene]-N-phenyl-hydrazine, 1 -(2-pyrrole carbonyl)-benzotriazole 1 ,2,4-triazole, 3 4-amino-5-ethyl-4H1 ,2,4-triazole-3thiol], 4- amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, bis-(4-amino-5-mercapto-1 ,2,4-triazol- 3-yl)-butane;2-mercaptobenzoxazole, 5-(4’-dimetylaminobenzylidene)-2,4- dioxotetrahydro-1 ,3-thiazole, benzothiazole, imidazole, derivatives thereof orcombinations thereof.

[0061] A tenth aspect which is a reaction addition product of at least one organic acid and at least one sugar oxidation product.

[0062] An eleventh aspect which is the product of the tenth aspects wherein the organic acid comprises a mixture of gluconic acid and glucaric acid.

[0063] A twelfth aspect which is the product of any of the tenth through eleventh aspects wherein the ratio of gluconic acid:glucaric acid is from about 0.1 :10 to about 10:0.1.

[0064] A thirteenth aspect which is the product of any of the tenth through twelfth aspects wherein the organic acid is selected from the group consisting of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

[0065] A fourteenth aspect which is a method comprising contacting one or more organic acids with one or more azoles under conditions suitable for the formation of at least one addition product; and contacting the at least one addition product with an aqueous fluid to form a corrosion inhibitor.

[0066] A fifteenth aspect which is the method of the fourteenth aspect further comprising introducing the corrosion inhibitor to an industrial fluid system; and inhibiting corrosion using the corrosion inhibitor.

[0067] A sixteenth aspect which is the method of any of the fourteenth through fifteenth aspects wherein the industrial fluid system is selected from the group consisting of: cooling water systems; heat transfer systems; refinery systems; pulp and paper making systems; food and beverage systems; and mechanical coolant systems.

[0068] A seventeenth aspect which is the method of any of the fourteenth through sixteenth aspects wherein the organic acid comprises a lactone of a sugar oxidation product.

[0069] A eighteenth aspect which is the method of any of the foureenth through seventeenth aspects wherein the organic acid comprises a mixture of gluconic acid and glucaric acid.

[0070] An nineteenth aspect which is the method of the eighteenth aspect wherein the ratio of gluconic acid:glucaric acid is from about 0.1 :10 to about 10:0.1.

[0071] A twentieth aspect which is the method of any of the fourteenth through ninetenth aspects wherein the organic acid is selected from the group cconsisting of glucaric acid, glucoheptonic acid, galatonic acid, galataric acid, isocitric acid, glutaric acid, citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimicacid, maleic acid and combinations thereof.

[0072] A twenty-first aspect which is the method of any of the thirteenth through twentieth aspects wherein the azole comprises tolyltriazole, benzotriazole (BTA), 5- pentyl-BTA, 5-chloro-BTA, N-[benzotriazol-1 -yl-(phenyl)-methylene]-N- phenylhydrazine, N-[benzotriazol-1-yl-(4-methoxy-phenyl)-methylene]-N-phenyl- hydrazine, 1 -(2-pyrrole carbonyl)-benzotriazole 1 ,2,4-triazole, 3 4-amino-5-ethyl- 4H1 ,2,4-triazole-3thiol], 4-amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, bis-(4-amino- 5-mercapto-1 ,2,4-triazol-3-yl)-butane;2-mercaptobenzoxazole, 5-(4’- dimetylaminobenzylidene)-2,4-dioxotetrahydro-1 ,3-thiazole, benzothiazole, imidazole, derivatives thereof orcombinations thereof.EXAMPLES

[0073] The aspects having been generally described, the following example is given as particular aspects of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the example is given by way of illustration and is not intended to limit the specification or the claims in any manner.

[0074] A comparison of azole solubility alone or in a YCMI was made. In the formulations PBTC is phosphonobutane tricarboxylic acid, HEDP is hydroxyethylidene diphosphonic acid; PTSA is p-Toluenesulfonic acid, TTA is tolytriazole, BZT is benzotriazole and ACUMER™ 2000 Polymer is an anti-scale I anti-corrosiofn water treatment formulation commercially available from DOW. GOGA is a mixture of glucaric and gluconic acid commercially available from Solugen.

[0075] In the first experiment, a corrosion inhibitor formulation (reference) was prepared with 3.38 wt.% BZT and a pH of 1.2 while a second corrosion inhibitor was prepared containing 10 wt.% of GOGA and 11.29 wt.% of BZT at a pH of 1.15. The reference formulation and YMCI formulation are presented in Tables 1A and 1 B, respectively.Table 1A Table 1 B3416-2250124FRM023-PCT

[0076] In a second trial, a corrosion inhibitorformulation (reference) was prepared with 1.96 wt.% TTA and a pH of 1.34 while a second corrosion inhibitor was prepared containing 10 wt.% of GOGA and 3.15 wt.% of TTA at a pH of 1.26. The reference formulation and YMCI formulation are presented in Tables 2A and 2B, respectively.Table 2A Table 2B

[0077] In the a third trial, a corrosion inhibitor formulation (reference) was prepared with 5.04 wt.% of a mix of BZT and TTA in an amount of and a pH of 1.55 while a second corrosion inhibitor was prepared containing 10 wt.% of GOGA and 6.30 wt.% of a mix of BZT and TTA at a pH of 1.20. The reference formulation and YMCI formulation are presented in Tables 3A and 3B, respectively.Table 3A Table 3B

[0078] The results demonstrate that the use of an organic acid (GOGA) increased the solubility of the azole-compounds. Table 4 provides the solubilty increase for each trial, in the presence or absence of 10 wt.% GOGA.Table 4

[0079] The results demonstrate that the solubility of the azole increases with the addition of an organic acid and consequently a YMCI of the present disclosure may provide even more benefit as an adduct of the azole and organic acid.

[0080] While aspects of the disclosure have been shown and described, modifications thereof can be made without departing from the spirit and teachings of the presently disclosed subject matter. The aspects and examples described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the subject matter disclosed herein are possible and are within the scope of the present disclosure. All test methods are those in effect as of the filing date of this disclosure.

[0081] At least one aspect is disclosed and variations, combinations, and / or modifications of the aspect(s) and / or features of the aspect(s) made by a person having ordinary skill in the art are within the scope of the disclosure. Alternative aspects that result from combining, integrating, and / or omitting features of the aspect(s) are also within the scope of the disclosure. 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, 5, 6, . . . ; greater than 0.10 includes 0.11 , 0.12, 0.13, 0.14, 0.15, . . .). For example,whenever a numerical range with a lower limit, Rl, and an upper limit, Ru, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=RI +k* (Ru-RI), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, > 50 percent, 51 percent, 52 percent... 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed. Use of the term “optionally” with respect to any element of a claim means that the element is required, or alternatively, the element is not required, both alternatives being within the scope of the claim. Use of broader terms such as comprises, includes, and having should be understood to provide support for narrower terms such as consisting of, consisting essentially of, and comprised substantially of.

[0082] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. 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 detailed description of the presently disclosed subject matter.

Claims

CLAIMSWhat is claimed is:1 . A corrosion inhibitor, comprising: at least one organic acid; and at least on azole.

2. The inhibitor of claim 1 , wherein the organic acid comprises a sugar oxidation product.

3. The inhibitor of claim 1 , wherein the organic acid comprises aldonic acid, uronic acid, aldaric acid, or a combination thereof.

4. The inhibitor of claim 1 , wherein the organic acid comprises 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.

5. The inhibitor of claim 1 , wherein the organic acid comprises a lactone of a sugar oxidation product.

6. The inhibitor of claim 1 , wherein the organic acid comprises a mixture of gluconic acid and glucaric acid.

7. The inhibitor of claim 6, wherein the ratio of gluconic acid:glucaric acid is from about 0.1 :10 to about 10:0.1 .

8. The inhibitor of claim 1 , wherein the organic acid is selected from the group consisting of glucaric acid, glucoheptonic acid, galatonic acid, galataric acid, isocitric acid, glutaric acid, citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoicacid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

9. The inhibitor of claim 1 , wherein the azole comprises tolyltriazole, benzotriazole(BTA), 5-pentyl-BTA, 5-chloro-BTA, N-[benzotriazol-1-yl-(phenyl)-methylene]-N- phenylhydrazine, N-[benzotriazol-1-yl-(4-methoxy-phenyl)-methylene]-N-phenyl- hydrazine, 1 -(2-pyrrole carbonyl)-benzotriazole 1 ,2,4-triazole, 3 4-amino-5-ethyl- 4H1 ,2,4-triazole-3thiol], 4-amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, bis-(4-amino- 5-mercapto-1 ,2,4-triazol-3-yl)-butane;2-mercaptobenzoxazole, 5-(4’- dimetylaminobenzylidene)-2,4-dioxotetrahydro-1 ,3-thiazole, benzothiazole, imidazole, derivatives thereof orcombinations thereof.

10. A reaction addition product of at least one organic acid and at least one sugar oxidation product.

11. The product of claim 10, wherein the organic acid comprises a mixture of gluconic acid and glucaric acid.

12. The product of claim 1 1 , wherein the ratio of gluconic acid:glucaric acid is from about 0.1 :10 to about 10:0.1.

13. The product of claim 10, wherein the organic acid is selected from the group consisting of citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

14. A method comprising: contacting one or more organic acids with one or more azoles under conditions suitable for the formation of at least one addition product; and contacting the at least one addition product with an aqueous fluid to form a corrosion inhibitor.

15. The method of claim 14, further comprising: introducing the corrosion inhibitor to an industrial fluid system; and inhibiting corrosion using the corrosion inhibitor.

16. The method of claim 14, wherein the industrial fluid system is selected from the group consisting of: cooling water systems; heat transfer systems; refinery systems; pulp and paper making systems; food and beverage systems; and mechanical coolant systems.

17. The method of claim 14, wherein the organic acid comprises a lactone of a sugar oxidation product.

18. The method of claim 14, wherein the organic acid comprises a mixture of gluconic acid and glucaric acid.

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

20. The method of claim 14, wherein the organic acid is selected from the group cconsisting of glucaric acid, glucoheptonic acid, galatonic acid, galataric acid, isocitric acid, glutaric acid, citric acid, lactic acid, hydrochloric acid, malic acid, acetic acid, formic acid, propionic acid, butyric acid, sorbic acid, fumaric acid, tartaric acid, benzoic acid, succinic acid, ascorbic acid, adipic acid, quinic acid, isocitric acid, shikimic acid, maleic acid and combinations thereof.

21. The method of claim 14, wherein the azole comprises tolyltriazole, benzotriazole (BTA), 5-pentyl-BTA, 5-chloro-BTA, N-[benzotriazol-1-yl-(phenyl)- methylene]-N-phenylhydrazine, N-[benzotriazol-1-yl-(4-methoxy-phenyl)-methylene]- N-phenyl-hydrazine, 1-(2-pyrrole carbonyl)-benzotriazole 1 ,2,4-triazole, 3 4-amino-5- ethyl-4H1 ,2,4-triazole-3thiol], 4-amino-3-hydrazino-5-mercapto-1 ,2,4-triazole, bis-(4- amino-5-mercapto-1 ,2,4-triazol-3-yl)-butane;2-mercaptobenzoxazole, 5-(4’- dimetylaminobenzylidene)-2,4-dioxotetrahydro-1 ,3-thiazole, benzothiazole, imidazole, derivatives thereof or combinations thereof.

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