Non-phosphate corrosion inhibiting compositions and methods for mitigating corrosion in cooling water applications

Abstract

Compositions and methods for inhibiting corrosion of metals in contact with aqueous systems are provided. For example, a corrosion inhibitor composition of an embodiment of the present invention may include an oxyanion of an amphoteric material, a silicate, and an additional component. The corrosion inhibitor may be substantially phosphate-free or phosphorus-free. The additional component may include, for example, a hydroxycarboxylic acid.

Description

Technical Field

[0001] This disclosure relates throughout to compositions and methods for controlling corrosion in aqueous systems. More specifically, this disclosure relates to compositions comprising oxy-anions of amphoteric metals and their use in inhibiting corrosion. Background Technology

[0002] Corrosion of metal surfaces in aqueous media has long been a problem in many industries, such as oil and gas, food and beverage, and washing / cleaning. For example, in oil and gas production processes, several corrosive components are present, such as brine, organic acids, carbon dioxide, hydrogen sulfide, and microorganisms. These corrosive components can lead to severe corrosion, as evidenced by pitting, embrittlement, and general metal loss. Metal surfaces can be constructed from high-alloy steels, including chromium steel, ferritic alloy steel, austenitic stainless steel, precipitation-hardening stainless steel, and high-nickel steel, but most commonly, cheaper carbon steel is combined with corrosion inhibitors or coatings. In deep-sea operations, the problem is even more problematic, as replacing corroded equipment is difficult and expensive.

[0003] Inexpensive inorganic phosphates are commonly used in cooling water treatment processes. This includes the use of orthophosphates as anionic corrosion inhibitors and the use of complex phosphates as cathodic inhibitors. When used, orthophosphates are typically supplied in the form of phosphoric acid or one of its sodium or potassium salts.

[0004] The use of phosphates in these water treatment processes has several drawbacks. For example, phosphates can provide nutrients for microbial growth, such as cyanobacteria and algae, which can have significant impacts on downstream ecosystems. Excessive biomass growth due to phosphorus nutrients in lakes and rivers can lead to reduced light penetration, degradation of organic growth, and subsequent depletion of oxygen in the water. To help address these issues, regional and national governments have enacted increasingly stringent phosphorus emission limits.

[0005] Therefore, as industry shows increasing interest in water treatment processes that do not rely on phosphates, there is a need for alternative methods and compositions of corrosion control chemicals for water treatment that utilize alternative chemicals. Summary of the Invention

[0006] This disclosure provides methods and compositions for inhibiting corrosion. In some embodiments, this disclosure provides a method for inhibiting corrosion of a metal surface in contact with a medium. The method includes adding a composition to the medium, wherein the composition comprises oxygen-containing anions of an amphoteric metal.

[0007] Amphoteric metals can be selected from the following groups: zinc, aluminum, tin, iron, titanium, zirconium, copper, and any combination thereof.

[0008] The oxygen-containing anions of zwitterionic metals can be selected from the group consisting of: sodium zincate, sodium stannate, sodium stannate, sodium aluminate, sodium titanate, sodium titanite, sodium zirconate, sodium cuprate, sodium ferrousate, sodium ferrite, potassium zincate, potassium stannate, potassium aluminate, potassium titanate, potassium titanite, potassium zirconate, potassium cuprate, potassium ferrousate, potassium ferrite, lithium zincate, lithium stannate, lithium aluminate, lithium titanate, lithium titanate, lithium zirconate, lithium cuprate, lithium ferrousate, lithium ferrite, and any combination thereof.

[0009] The method may also include adding silicates, silica, or combinations thereof to the medium. Silicates, silica, and / or combinations thereof may be added before, after, and / or together with the oxyanions of the zwitterionic metal.

[0010] In some embodiments, the oxy-anions of the amphoteric metal are premixed with silicates, silica and / or combinations thereof before being added to the medium.

[0011] In some embodiments, the method may further include reacting silicates, silicon dioxide, and / or combinations thereof with the oxygen-containing anions of a zwitterion to form oxygen-containing anions of zwitterion silicates.

[0012] The oxygen-containing anions of amphoteric metal silicates may be selected from the group consisting of: sodium aluminosilicate, sodium zinc silicate, sodium tin silicate, sodium stannous silicate, sodium titanyl silicate, sodium titanyl silicate, sodium zirconium silicate, sodium copper silicate, sodium ferrisilicate, sodium iron silicate, potassium aluminosilicate, potassium zinc silicate, potassium tin silicate, potassium stannous silicate, potassium titanyl silicate, potassium titanyl silicate, potassium zirconium silicate, potassium copper silicate, potassium ferrisilicate, potassium iron silicate, lithium aluminosilicate, lithium zinc silicate, lithium tin silicate, lithium stannous silicate, lithium titanyl silicate, lithium titanyl silicate, lithium zirconium silicate, lithium copper silicate, lithium ferrisilicate, lithium iron silicate, and any combination thereof.

[0013] The method may include adding about 0.1 ppm to about 400 ppm of an oxygen-containing anion of a zwitterionic metal to a medium. The method may also include adding about 0.1 ppm to about 200 ppm of silicate, silicon dioxide, or a combination thereof to a medium. The method may further include adding about 0.1 ppm to about 400 ppm of an oxygen-containing anion of a zwitterionic metal silicate to a medium.

[0014] In some embodiments, the method further includes adding additional components to the medium, wherein the additional components are selected from the group consisting of: fouling control agents, additional corrosion inhibitors, biocides, preservatives, acids, hydrogen sulfide scavengers, surfactants, scale inhibitors, pH adjusters, coagulants / flocculators, water purifiers, dispersants, antioxidants, polymer degradation inhibitors, permeability regulators, CO2 scavengers, O2 scavengers, gelling agents, lubricants, friction reducers, salts, stabilizers, yellow metal corrosion inhibitors, and any combination thereof.

[0015] Stabilizers may include, for example, hydroxycarboxylic acids, such as lactic acid, citric acid, succinic acid, tartaric acid, and any combination thereof.

[0016] In some embodiments, the stabilizer includes a dispersant comprising a copolymer comprising at least one monomer component selected from the group consisting of: acrylamidomethanesulfonic acid, dimethyl-2-oxobut-3-en-1-yl-ammonium-methanesulfonate, allyloxypolyethoxy(10)sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (i.e., 2-acrylamido-2-methyl-1-propanesulfonic acid or AMPS), 2-acrylamido-2-methylbutanesulfonic acid, acrylamidotert-butylsulfonate, 4-(allyloxy)benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methylallylsulfonic acid, allylhydroxypropanesulfonic acid, salts of any of the foregoing, and any combination thereof.

[0017] Stabilizers may include polyols selected from the group consisting of: polyglycerol; branched polyglycerol; cyclic polyglycerol; highly branched polyglycerol; polypropylene glycol; pentaerythritol ethoxylate; carboxymethylated polyglycerol, polypropylene glycol, pentaerythritol ethoxylate and sorbitol; hydroxycarboxyalkylated polyglycerol, polypropylene glycol, pentaerythritol ethoxylate and sorbitol; and hydroxysulfonylated polyglycerol, polypropylene glycol, pentaerythritol ethoxylate and sorbitol.

[0018] In some embodiments, the stabilizer includes a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, hypozoxytriacetic acid, polymers containing maleic acid, polymers containing acrylic acid, and any combination thereof.

[0019] Scale inhibitors may be selected from the group consisting of: polyacrylates, polymaleic anhydride, alkyl epoxycarboxylate, polyepoxysuccinic acid, polyaspartic acid, polyacrylamide copolymers, acrylic acid and hydroxypropyl acrylate copolymers, and any combination thereof.

[0020] The yellow metal corrosion inhibitor may be an azole-based corrosion inhibitor selected from the group consisting of: benzotriazole, tolyltriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, butylbenzotriazole, pentoxybenzotriazole, carboxybenzotriazole, tetrahydrotolyltriazole, chlorobenzotriazole, chlorotolyltriazole, benzimidazole, salts of any of the foregoing, and any combination thereof.

[0021] Preservatives may include sodium benzoate, benzoic acid, nitrite, sulfite, sodium sorbate, potassium sorbate, or any combination thereof.

[0022] In some embodiments, the amount of stabilizer added to the medium is from about 0.1 ppm to about 200 ppm.

[0023] In some embodiments, the additional component is added to the medium before, after, and / or simultaneously with the oxygen-containing anions of the zwitterionic metal silicate, optionally further including the addition of an additional component of about 0.1 ppm to about 5000 ppm to the medium.

[0024] In some implementations, the method does not include adding phosphate to the medium.

[0025] In some implementations, the metal surface includes steel, copper, cupronickel, brass, or any combination thereof.

[0026] In some embodiments, the composition comprises about 0.01 wt% to about 99 wt% of an amphoteric metal oxygen anion, about 0.1 wt% to about 30 wt% of a silicate, and about 0.1 wt% to about 50 wt% of additional components. In some embodiments, about 0.1 ppm to about 10,000 ppm of the composition is added to the medium.

[0027] The medium may contain corrosives selected from, for example, the group consisting of: carbon dioxide, oxygen, sodium chloride, calcium chloride, sodium sulfate, magnesium sulfate, and any combination thereof. The medium may include cooling water, hot circuit water, a glycol-water mixture, brine, or any mixture thereof.

[0028] This disclosure also provides compositions for inhibiting corrosion. In some embodiments, the compositions comprise zincates, stannites, stannates, or any combination thereof; silicates; and hydroxycarboxylic acids.

[0029] The composition may contain, for example, from about 0.01 wt% to about 99 wt% of zincate, stannite, stannate or combinations thereof; from about 0.1 wt% to about 30 wt% of silicate; and from about 0 wt% to about 50 wt% of hydroxycarboxylic acid.

[0030] The composition may contain sodium stannous acid, sodium silicate, and glycolic acid.

[0031] The composition may optionally contain a solvent.

[0032] In some embodiments, the composition has a pH of about 6 to about 14.

[0033] In some embodiments, the composition does not contain phosphorus.

[0034] The features and technical advantages of this disclosure have been summarized quite broadly above in order to provide a better understanding of the following detailed description. Other features and advantages of this disclosure, which form the subject matter of the claims of this application, will be described below. Attached Figure Description

[0035] The specific embodiments of the present invention are described below with reference to the accompanying drawings, in which:

[0036] Figure 1 Corrosion rate data from a pilot-scale cooling tower test using a combination of stannous silicate and saccharic acid are shown. Detailed Implementation

[0037] The following describes various implementation schemes and their elements. A better understanding of the relationships and functions of the various elements of the implementation schemes can be achieved by referring to the detailed descriptions below. However, the implementation schemes are not strictly limited to those explicitly described below.

[0038] Examples of methods and materials are described below, but similar or equivalent methods and materials to those described herein may be used in practice or to test this disclosure. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and are not intended to be limiting.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of any discrepancy, this document (including definitions) shall prevail.

[0040] Unless otherwise stated, the alkyl group, whether alone or as part of another group, as described herein is an optionally substituted straight-chain or branched saturated monovalent hydrocarbon substituent containing, for example, 1 to about 60 carbon atoms, or, for example, 1 to about 30 carbon atoms, in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, and so on.

[0041] As used herein, the term "aryl" or "aromatic," whether alone or as part of another group (e.g., arylene), refers to an optionally substituted carbocyclic aromatic group, such as a monocyclic or bicyclic group containing about 6 to about 12 carbons in the ring moiety, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. The term "aryl" also includes heteroaryl functional groups. It should be understood that the term "aryl," according to Huckel's Rule, applies to planar cyclic substituents containing 4n+2 electrons.

[0042] "Cycloalkyl" refers to a cyclic alkyl substituent containing, for example, about 3 to about 8 carbon atoms, preferably about 4 to about 7 carbon atoms, and more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The cyclic alkyl group may be unsubstituted or may be further substituted by alkyl groups such as methyl groups, ethyl groups, etc.

[0043] "Heteroaryl" refers to a 5- or 6-membered ring system, either monocyclic or bicyclic, wherein the heteroaryl group is unsaturated and satisfies Hückel's rule. Non-limiting examples of heteroaryl groups include furanyl, thiopheneyl, pyrroleyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiopheneyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzimidazolinyl, benzothiazolinyl, quinazolinyl, etc.

[0044] The compounds disclosed herein may be substituted with suitable substituents. As used herein, the term "suitable substituent" is intended to refer to a chemically acceptable functional group, preferably a portion that does not render the compound inactive. Such suitable substituents include, but are not limited to, halogenated groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroarylalkyl groups, arylalkoxy or heteroarylalkoxy groups, HO-(C=O)- groups, heterocyclic groups, cycloalkyl groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkyl carbonyl groups, alkoxy carbonyl groups, alkylamino carbonyl groups, dialkylamino carbonyl groups, aryl carbonyl groups, aryloxy carbonyl groups, alkyl sulfonyl groups, and aryl sulfonyl groups. In some embodiments, suitable substituents may include halogens, unsubstituted C1-C... 12Alkyl groups, unsubstituted C4-C6 aryl groups, or unsubstituted C1-C6 aryl groups 10 Alkoxy groups. Those skilled in the art will understand that many substituents can be replaced by other substituents.

[0045] The term "substituted" in "substituted alkyl" means that in the group under discussion (i.e., alkyl group), at least one hydrogen atom bonded to a carbon atom can be replaced by one or more of the following substituents: such as hydroxyl (-OH), alkylthio, phosphino, amide (-CON(R)). A (R) B ), where R A and R B Independently hydrogen, alkyl or aryl), amino (-N(R) A (R) B ), where R A and R B Independently, it can be hydrogen, alkyl, or aryl; halogen (fluorine, chlorine, bromine, or iodine); silyl; nitro (-NO2); or ether (-OR). A , where R A It is an alkyl or aryl group, an ester (-OC(O)R) A , where R A It is an alkyl or aryl group, or a ketone group (-C(O)R). A , where R A It can be alkyl or aryl), heterocyclic, etc.

[0046] When the term “substituted” introduces a list of groups that can be substituted, it means that the term applies to every member of that group. That is, the phrase “optionally substituted alkyl or aryl” should be interpreted as “optionally substituted alkyl or optional aryl”.

[0047] The terms “polymer,” “copolymer,” “polymerization,” “copolymerization,” etc., include not only polymers containing two monomer residues and polymerizing two different monomers together, but also (co)polymers containing more than two monomer residues and polymerizing more than two other monomers together. For example, polymers disclosed herein include terpolymers, quaternary copolymers, polymers containing more than four different monomers, and polymers containing two different monomer residues, composed of two different monomer residues, or substantially composed of two different monomer residues. Furthermore, as disclosed herein, “polymer” may also include homopolymers, which are polymers containing a single type of monomer unit.

[0048] Unless otherwise stated, the polymers disclosed herein may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, and / or functionally modified. The polymers disclosed herein may be in the form of, for example, solutions, dry powders, liquids, or dispersions.

[0049] The terms “weight percentage”, “weight%”, and their variations refer to the concentration of a substance when the weight of the substance is divided by the total weight of the composition containing the substance and multiplied by 100.

[0050] The term "corrosion scaling" refers to the scaling of a surface, such as a metal surface (e.g., a heat exchange surface), by deposits formed through corrosion. These deposits can form in situ or be formed by cracking and redeposition from other parts of the system.

[0051] As used herein, “corrosion inhibitor” is intended to mean at least one or any combination thereof of the disclosed corrosion inhibitor compound, corrosion inhibitor intermediate and corrosion inhibitor product formulation.

[0052] In some embodiments, the corrosion inhibitor compositions disclosed herein may comprise multiple components. For example, the corrosion inhibitor may comprise any mixture of oxyanions, silicates, and / or their salts. Furthermore, the compositions disclosed herein may comprise one or more additional corrosion inhibitors, such as alkyl, hydroxyalkyl, alkylaryl, aralkyl, or arylamine quaternary salts; monocyclic or polycyclic aromatic amine salts; imidazoline derivatives; mono, di, or trialkyl or alkyl phosphates; phosphate esters of hydroxylamines; phosphate esters of polyols; monomers or oligomeric fatty acids; and any combination thereof.

[0053] This disclosure relates in its entirety to corrosion inhibitor compositions for inhibiting the formation of scale and corrosion deposits on various metal surfaces. At least one aspect of this disclosure includes a composition comprising an oxyanion of an amphoteric metal. Specifically, the compositions of this disclosure may comprise oxyanions of an amphoteric metal, such as zinc, aluminum, tin, and other metals discussed below, which can inhibit corrosion of metal surfaces such as those containing steel (e.g., low-carbon steel). Due to instability issues, amphoteric metal salts cannot conventionally be formulated with silica compounds. Providing these oxyanions to react with silicates to form oxyanionic silicates, which offer excellent corrosion control on metal surfaces, thereby compensating for these instabilities, and providing compositions for inhibiting corrosion in non-phosphate brine treatment processes.

[0054] Exemplary and non-limiting examples of amphoteric metals include zinc, aluminum, tin, iron, titanium, zirconium, copper, and any combination thereof. These amphoteric metals can form oxygen-containing anions under high pH conditions. Metals may include, for example, tin(II), tin(iv), copper(II), zinc(II), or any combination thereof.

[0055] As discussed herein, such chemicals can be used as corrosion inhibitors and perform very well in corrosion control on metallic surfaces, such as low-carbon steel. In some embodiments, performance can be further enhanced by adding silica, silicates, and / or hydroxycarboxylic acids (such as lactic acid, citric acid, succinic acid, and / or tartaric acid).

[0056] In some embodiments, the oxyanion of the zwitterionic metal of this disclosure may be an oxyanion salt. For example, the oxyanion may include one or more of the following: zincates (such as sodium zincate), stansites (such as sodium stansite), stannates (such as sodium stannate), and / or sodium aluminate, sodium titanate, sodium titanate, sodium zirconate, sodium cuprate, sodium ferrite, sodium ferrite, potassium zincate, potassium stansite, potassium stannate, potassium aluminate, potassium titanate, potassium titanate, potassium zirconate, potassium cuprate, potassium ferrite, potassium ferrite, lithium zincate, lithium stansite, lithium stannate, lithium aluminate, lithium titanate, lithium titanate, lithium zirconate, lithium cuprate, lithium ferrite, lithium ferrite, and any combination thereof.

[0057] The corrosion inhibitor composition may contain, for example, oxygen-containing anions of an amphoteric metal based on about 0.01 wt% to about 99 wt% of the total weight of the corrosion inhibitor composition, such as about 0.01 wt% to about 90 wt%, about 0.01 wt% to about 80 wt%, about 0.01 wt% to about 70 wt%, about 0.01 wt% to about 60 wt%, about 0.01 wt% to about 50 wt%, about 0.1 wt% to about 50 wt%, about 0.1 wt% to about 60 wt%, about 0.1 wt% to about 70 wt%, about 0.1 wt% to about 80 wt%, about 0.1 wt% to about 90 wt%, about 1 wt% to about 99 wt%, about 10 wt% to about 99 wt%, about 20 wt% to about 99 wt%, about 30 wt% to about 99 wt%, about 40 wt% to about 99 wt%, and about 50 wt% to about 99 wt% of the total weight of the corrosion inhibitor composition.

[0058] The corrosion inhibitor composition and / or medium disclosed herein can be pH-controlled, for example, to provide a resulting solution with a threshold pH when the water treatment composition is dissolved. This pH can be controlled in various ways, such as by selecting and incorporating one or more acidifying and / or alkali components into the formulated water treatment composition and / or by incorporating one or more solid pH-adjusting components into the composition, which serve to alter the pH of the medium and / or the resulting solution formed from the solid composition. When used, one or more solid pH-adjusting components, which may not contain phosphorus, can also act as fillers in the composition, for example, increasing the volume of the water treatment composition in which the active components are dispersed.

[0059] In different formulations, the pH-adjusting components included in the water treatment composition can be acids, bases, and / or neutral salts. The selection and relative amounts of one or more pH-adjusting components used in the composition may vary depending on other specific components included in the composition and the solution pH provided by those other components. Examples of pH-adjusting components that may be used include, but are not limited to, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkali metal sulfates, alkaline earth metal sulfates, alkali metal bisulfates, alkaline earth metal bisulfates, alkali metal and / or alkaline earth metal silicates, inorganic acids, aminosulfonic acids, and / or organic acids (e.g., lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, malic acid, tartaric acid). In some specific embodiments, one or more pH-adjusting components used in the composition are selected from the group consisting of alkali metal sulfates, alkaline earth metal sulfates, alkali metal bisulfates, alkaline earth metal bisulfates, aminosulfonic acids, alkaline earth metal carbonates, citric acid, and combinations thereof.

[0060] In some respects, the pH of the composition or medium may be from about 6 to about 14, from about 6.5 to about 14, from about 7 to about 14, from about 7.5 to about 14, from about 8 to about 14, from about 8.5 to about 14, from about 9 to about 14, from about 9.5 to about 14, from about 10 to about 14, from about 10.5 to about 14, from about 11 to about 14, from about 11.5 to about 14, from about 12 to about 14, from about 12.5 to about 14, from about 13 to about 14, or from about 13.5 to about 14.

[0061] In some embodiments, the pH of the resulting composition may be from about 6 to about 14, from about 7 to about 13, from about 8 to about 12, from about 8.5 to about 12, or from about 9 to about 11.

[0062] The corrosion inhibitor compositions disclosed herein may optionally comprise fillers and / or binders. Exemplary fillers and / or binders that may be used include hydration chelating agents, such as hydrated aminocarboxylates, hydrated polycarboxylates or hydrated anionic polymers, hydrated citrates or hydrated tartrates, together with alkali metal carbonates. Examples of fillers that may be used include sodium sulfate, sodium chloride, silicates, silica, starch, sugars, C1-C... 10 Alkyl glycols (such as propylene glycol), etc. Examples of adhesives that can be used include carbonates, organic acetates (such as aminocarboxylates), etc. In other examples, the composition does not include separate fillers and / or adhesives.

[0063] Depending on the extent to which silicates, silicates, or combinations thereof are used, they may be added before, after, and / or together with the oxyanions of the zwitterion. In some aspects, as discussed below, reacting silicates, silicates, or combinations thereof with oxyanions can form oxyanionic silicates. In some embodiments, the oxyanions of the zwitterion and the silicates may be premixed before being added to the medium.

[0064] In some embodiments, based on the total weight of the corrosion inhibitor composition, the composition may contain about 0% to about 30% by weight of silicates, silica, or combinations thereof. For example, the composition may contain about 0% to about 25% by weight, about 0% to about 20% by weight, about 0% to about 15% by weight, about 0% to about 10% by weight, about 0% to about 5% by weight, about 1% to about 5% by weight, about 1% to about 10% by weight, about 1% to about 20% by weight, about 1% to about 30% by weight, about 5% to about 30% by weight, about 10% to about 30% by weight, or about 20% to about 30% by weight of silicates, silica, or combinations thereof.

[0065] According to certain aspects of this disclosure, silicon dioxide and / or silicates can react with oxyanions of amphoteric metals to form oxyanionic or oxyanionic silicates of amphoteric metal silicates. In such embodiments, non-limiting examples of amphoteric silicates include sodium aluminosilicate, sodium zinc silicate, sodium tin silicate, sodium stannous silicate, sodium titanyl silicate, sodium titanyl silicate, sodium zirconium silicate, sodium copper silicate, sodium ferrisilicate, sodium iron silicate, potassium aluminosilicate, potassium zinc silicate, potassium tin silicate, potassium stannous silicate, potassium titanyl silicate, potassium titanyl silicate, potassium zirconium silicate, potassium copper silicate, potassium ferrisilicate, potassium iron silicate, lithium aluminosilicate, lithium zinc silicate, lithium tin silicate, lithium stannous silicate, lithium titanyl silicate, lithium titanyl silicate, lithium zirconium silicate, lithium copper silicate, lithium ferrisilicate, lithium iron silicate, and any combination thereof.

[0066] Various methods exist for preparing and / or using the oxyanionic silicates of this disclosure, and these methods fall within the scope of this disclosure. For example, for stannous silicates, in some embodiments, stannous chloride may be added to deionized water (diH2O). The pH of the mixture can be increased by adding NaOH, followed by sodium silicate. In some embodiments, the addition of NaOH and sodium silicate can raise the pH of the final product to about 12 or higher. As discussed herein, performance can be further improved by use with hydroxycarboxylic acids (such as glycolic acids) and / or other stabilizers for corrosion control.

[0067] In some embodiments of this disclosure, the corrosion inhibitor composition may include additional components. These additional components may be added to the medium before, after, and / or simultaneously with the oxyanions of the zwitterionic metal or the oxyanions of the zwitterionic metal silicate.

[0068] In some aspects, additional components include stabilizers. Stabilizers may include, for example, lactic acid, citric acid, uronic acid, and / or tartaric acid.

[0069] In some embodiments, the additional components include hydroxycarboxylic acids, sulfonated homopolymers, sulfonated copolymers, polyols, polycarboxylic acids, chelating agents, or any combination thereof.

[0070] In some embodiments, the stabilizer includes a polymeric dispersant that is a polymer of at least one monomeric component selected from the group consisting of: acrylamidomethanesulfonic acid, dimethyl-2-oxobut-3-en-1-yl-ammonium-methanesulfonate, allyloxypolyethoxy(10)sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (i.e., 2-acrylamido-2-methyl-1-propanesulfonic acid or AMPS), 2-acrylamido-2-methylbutanesulfonic acid, acrylamidotert-butylsulfonate, 4-(allyloxy)benzenesulfonic acid, styrenesulfonic acid, allylsulfonic acid, methylallylsulfonic acid, allylhydroxypropanesulfonic acid, their salts, and any combination thereof.

[0071] In some embodiments, the stabilizer comprises a polyol selected from the group consisting of: polyglycerol; branched polyglycerol; cyclic polyglycerol; highly branched polyglycerol; polypropylene glycol; pentaerythritol ethoxylate; carboxymethylated polyglycerol, polypropylene glycol, pentaerythritol ethoxylate and sorbitol; hydroxycarboxyalkylated polyglycerol, polypropylene glycol, pentaerythritol ethoxylate and sorbitol; and hydroxysulfonylated polyglycerol, polypropylene glycol, pentaerythritol ethoxylate and sorbitol.

[0072] In some embodiments, the chelating agent is selected from the group consisting of: ethylenediaminetetraacetic acid, hyponitrotriacetic acid, polymers containing maleic acid, polymers containing acrylic acid, and any combination thereof.

[0073] Exemplary, non-limiting examples of scale inhibitors that can be used in conjunction with the compositions disclosed herein include one or more of polyacrylates, polymaleic anhydride, alkyl epoxycarboxylate, polyepoxysuccinic acid, polyaspartic acid, polyacrylamide copolymers, acrylic acid and hydroxypropyl acrylate copolymers, and any combination thereof.

[0074] In some implementations, additional components may include scale inhibitors, yellow metal corrosion inhibitors, corrosion inhibitors, and any combination thereof.

[0075] The yellow metal corrosion inhibitor may include, for example, azole-based corrosion inhibitors such as benzotriazole, tolyltriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, butylbenzotriazole, pentoxybenzotriazole, carboxybenzotriazole, tetrahydrotolyltriazole, halogen-resistant azoles (such as chlorobenzotriazole or chlorotolyltriazole), benzimidazole, salts of any of the foregoing, and any combination thereof.

[0076] In some embodiments, the preservative may include one or more of sodium benzoate, benzoic acid, nitrite, sulfite, sodium sorbate, and potassium sorbate.

[0077] The polycarboxylic acids disclosed herein can be used as scale inhibitors. It should be understood that the polycarboxylic acid component can be a carboxylic acid as discussed above, or residues of a molecule having at least two carboxyl moieties, such as dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, etc. In some embodiments, the polycarboxylic acid component is a copolymer. The copolymer can comprise polymeric residues of two or more monomers, consist substantially of polymeric residues of two or more monomers, or consist of polymeric residues of two or more monomers. The two or more monomers can include a first monomer and a second monomer different from the first monomer, the first monomer comprising a carboxylic acid or residues thereof, consisting substantially of a carboxylic acid or residues thereof, or consisting of a carboxylic acid or residues thereof. The first monomer can include a carboxylic acid or residues of a molecule having at least one carboxyl moieties, its salt, or its conjugate base. The carboxylic acid can comprise a single carboxyl moieties or multiple carboxyl moieties (e.g., dicarboxylic acids, such as maleic acid, etc.).

[0078] The corrosion inhibitor composition may contain about 0% to about 50% by weight of additional components based on the total weight of the corrosion inhibitor composition. For example, the composition may contain about 0% to about 40% by weight, about 0% to about 30% by weight, about 0% to about 20% by weight, about 0% to about 10% by weight, about 5% to about 50% by weight, about 10% to about 50% by weight, about 20% to about 50% by weight, about 30% to about 50% by weight, or about 40% to about 50% by weight of additional components.

[0079] Each component included in the corrosion inhibitor composition may be substantially free of phosphates and / or aluminates. Therefore, the entire corrosion inhibitor composition may be substantially free of phosphates and / or aluminates. The corrosion inhibition methods disclosed herein may not include the step of adding phosphates and / or aluminates to the medium. "Substantially free of phosphates and / or aluminates" means that no more than trace amounts of phosphates and / or aluminates are present in the composition or added in the method steps, such as less than about 1% by weight, less than about 0.75% by weight, less than about 0.5% by weight, less than about 0.25% by weight, less than about 0.1% by weight, less than about 0.05% by weight, less than 0.01% by weight, less than about 0.001% by weight, or about 0% by weight.

[0080] Each component of the corrosion inhibitor composition may be provided in any form, such as liquid or solid, and mixed together. After mixing and forming the resulting corrosion inhibitor composition, the composition may, in some respects, be completely chemically homogeneous. In other words, each part of the corrosion inhibitor composition may have the same constituent components in substantially the same relative weight percentage as each other part of the corrosion inhibitor composition.

[0081] Additional examples of components that may be present in a corrosion inhibitor composition include, but are not limited to, scale control agents, additional corrosion inhibitors, biocides, preservatives, acids, hydrogen sulfide scavengers, surfactants, scale inhibitors, pH adjusters, coagulants / flocculators, water purifiers, dispersants, antioxidants, polymer degradation inhibitors, permeability conditioners, CO2 scavengers, O2 scavengers, gelling agents, lubricants, friction reducers, salts, and any combination thereof.

[0082] Suitable biocides include, but are not limited to, oxidizing and non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein), amine compounds (e.g., quaternary ammonium compounds and coconut diamine), halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol (bromonitrile alcohol) and 2,2-dibromo-3-hypoacetamide (DBNPA)) and sulfur compounds (e.g., isothiazolone, carbamates, and metronidazole). Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, hydantoin chloride, stabilized sodium hypobromite, activated sodium bromide, hydantoin bromide, chlorine dioxide, ozone, and peroxides.

[0083] Suitable surfactants include, but are not limited to, anionic and nonionic surfactants. Anionic surfactants include, for example, alkyl aryl sulfonates, olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, alkyl and ethoxylated alkyl phosphates, and monoalkyl and dialkyl sulfosuccinates and sulfosuccinamides. Nonionic surfactants include, for example, alcohol alkoxylates; alkylphenol alkoxylates; block copolymers of ethylene, propylene, and butene oxides; alkyl dimethylamine oxides; alkyl-bis(2-hydroxyethyl)amine oxides; alkylamidopropyl dimethylamine oxides; alkylamidopropyl-bis(2-hydroxyethyl)amine oxides; alkyl polyglucosides; polyalkoxylated glycerol esters; dehydrated sorbitol esters and polyalkoxylated dehydrated sorbitol esters; and alkyl acyl polyethylene glycol esters and diesters.

[0084] In some embodiments, the corrosion inhibitor composition includes a solvent. Exemplary and non-limiting examples of solvents include water, acetic acid, butanediol, C1-C6 alkanols (such as methanol or ethanol), C1-C6 alkoxyalkanols, ethylene glycol ethers, hydrocarbons, ketones, ethers, alkylene glycols, amides, nitriles, sulfoxides, esters, alcohols, and any combination thereof.

[0085] The corrosion inhibitor composition may contain any amount of solvent (e.g., water), such as about 0.1 wt% to about 70 wt%, about 0.1 wt% to about 60 wt%, about 0.1 wt% to about 50 wt%, about 0.1 wt% to about 40 wt%, about 0.1 wt% to about 30 wt%, about 0.1 wt% to about 20 wt%, about 10 wt% to about 70 wt%, about 20 wt% to about 70 wt%, about 30 wt% to about 70 wt%, about 40 wt% to about 70 wt%, about 50 wt% to about 70 wt%, about 60 wt% to about 70 wt%, about 25 wt% to about 65 wt%, or about 35 wt% to about 55 wt%. In some aspects, the composition contains about 1 wt%, about 5 wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, or about 70 wt% of solvent.

[0086] The corrosion inhibitor compositions disclosed in this invention may also include a dispersant. The dispersant may be, for example, any polymer, copolymer, terpolymer, etc., comprising acrylic acid and / or acrylamide with a sulfonated monomer. An example of such a dispersant is a copolymer of acrylic acid / acrylamido-2-methylpropanesulfonic acid (AMPS). Another example of such a dispersant is a copolymer of acrylic acid / acrylamide. An additional example of such a dispersant is a terpolymer of acrylic acid / acrylamide / sulfonated acrylamide. The monomer ratios in each of the copolymers or terpolymers disclosed herein are intended to be covered by this disclosure. In one aspect, the dispersant is a terpolymer comprising acrylic acid / acrylamide / sulfonated acrylamide in a monomer ratio of about 40 / about 20 / about 40.

[0087] In addition, the dispersant may contain one or more quaternary ammonium compounds, such as benzyl-(C 12 -C 18 (Linear alkyl)-dimethyl-ammonium chloride. Additional non-limiting examples include alkylbenzylammonium chloride, benzylcocoyl (C) 12 -C 18 Dimethylammonium chloride, dicocoyl (C 12 -C 18 Dimethylammonium chloride, ditallow dimethylammonium chloride, di(hydrogenated tallow alkyl)dimethylquaternary ammonium methyl chloride, methyl bis(2-hydroxyethylcocoyl) 12 -C 18Quaternary ammonium chloride, dimethyl (2-ethyl) tallow ammonium methyl sulfate, n-dodecylbenzyl dimethyl ammonium chloride, n-octadecylbenzyl dimethyl ammonium chloride, n-dodecyl trimethyl ammonium sulfate, soybean alkyl trimethyl ammonium chloride, hydrogenated tallow alkyl (2-ethylhexyl) dimethyl quaternary ammonium methyl sulfate, and any combination thereof.

[0088] In some embodiments, the compositions disclosed herein may comprise one or more surfactants. Suitable surfactants include, but are not limited to, anionic surfactants, cationic surfactants, nonionic surfactants, and combinations thereof.

[0089] Anionic surfactants include alkyl aryl sulfonates, olefin sulfonates, alkane sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, as well as alkyl and ethoxylated alkyl phosphates, and monoalkyl and dialkyl sulfonated succinates and sulfonated succinates and combinations thereof.

[0090] Cationic surfactants include alkyl trimethyl quaternary ammonium salts, alkyl dimethyl benzyl quaternary ammonium salts, dialkyl dimethyl quaternary ammonium salts, imidazoline onion salts, and combinations thereof.

[0091] Nonionic surfactants include alcohol alkoxylates, alkylphenol alkoxylates, block copolymers of ethylene oxide, propylene oxide and butane oxide, alkyl dimethylamine oxides, alkyl bis(2-hydroxyethyl)amine oxides, alkylamidopropyl dimethylamine oxides, alkylamidopropyl bis(2-hydroxyethyl)amine oxides, alkyl polyglucosides, polyalkoxylated glycerol esters, sorbitol esters and polyalkoxylated sorbitol esters, and alkyl acyl polyethylene glycol esters and diesters, as well as combinations thereof.

[0092] It also includes betaine and sultane, amphoteric surfactants (such as alkyl amphoteric acetates and amphoteric diacetates, alkyl amphoteric propionates and amphoteric dipropionates, alkyl imino dipropionates and combinations thereof).

[0093] In some embodiments, the surfactant may be a quaternary ammonium compound, an amine oxide, an ionic or nonionic surfactant, or any combination thereof.

[0094] Suitable quaternary ammonium compounds include, but are not limited to, alkylbenzylammonium chloride, benzylcocoyl (C 12 -C 18 Dimethylammonium chloride, dicocoyl (C 12 -C 18 Dimethylammonium chloride, ditallow dimethylammonium chloride, di(hydrogenated tallow alkyl)dimethylquaternary ammonium methyl chloride, methyl bis(2-hydroxyethylcocoyl) 12 -C 18Quaternary ammonium chloride, dimethyl (2-ethyl) tallow ammonium methyl sulfate, n-dodecylbenzyl dimethyl ammonium chloride, n-octadecylbenzyl dimethyl ammonium chloride, n-dodecyl trimethyl ammonium sulfate, soybean alkyl trimethyl ammonium chloride, and hydrogenated tallow alkyl (2-ethylhexyl) dimethyl quaternary ammonium methyl sulfate.

[0095] This disclosure also provides a method for inhibiting corrosion of a metal surface in contact with a medium. The method comprises adding an effective amount of a composition to the medium, wherein the composition contains, is composed of, or is substantially composed of, an oxoanion of a zwitterionic metal, disclosed herein, and optionally in combination with any additional components disclosed herein, such as silicates, solvents, hydroxycarboxylic acids, etc. The composition and optional additional components may be added continuously, intermittently, automatically, and / or manually to the medium and / or the metal surface.

[0096] The medium may include, for example, liquids such as aqueous fluids and / or hydrocarbons, and / or gases. In some embodiments, the medium is an aqueous medium, such as produced water, seawater, municipal water, “grey” water, brackish water, fresh water, circulating water, brine, fracturing water, surface water, native water, groundwater, wastewater, or any combination of the foregoing. The aqueous medium may be a continuously flowing medium, such as produced water flowing from an underground reservoir or through a pipeline or tank. The aqueous medium may also be, for example, wastewater separated by a continuous manufacturing process and flowing into a wastewater treatment facility. In other embodiments, the aqueous medium is a batch or plug disposed substantially in a batch or static state within a metal container.

[0097] In some implementations, the medium includes cooling water, hot return water, ethylene glycol / water mixture, brine, or any mixture thereof.

[0098] The methods disclosed herein can be carried out, for example, in a cooling water system that supplies water to one or more processes, in which thermal energy from a relatively hot process flow is transferred to a relatively cool water flow via separate heat exchange surfaces. In some specific embodiments, the corrosion inhibitor compositions according to this disclosure can be used in open-loop cooling water systems, such as open-loop cooling water systems comprising one or more cooling towers that cool water via evaporative cooling.

[0099] The compositions disclosed in this invention can be used to inhibit corrosion of metal surfaces in contact with any type of corrosive agent in the medium, such as metal cations, metal complexes, metal chelates, organometallic complexes, aluminum ions, ammonium ions, barium ions, chromium ions, cobalt ions, cuprous ions, copper ions, calcium ions, ferrous ions, ferric ions, hydrogen ions, magnesium ions, manganese ions, molybdenum ions, nickel ions, potassium ions, sodium ions, strontium ions, titanium ions, uranium ions, vanadium ions, zinc ions, bromide ions, carbonate ions, chlorate ions, chloride ions, chlorite ions, dithionite ions, fluoride ions, hypochlorite ions, iodide ions, nitrate ions, nitrite ions, and oxygen ions. Perchlorate ions, peroxide ions, phosphate ions, phosphite ions, sulfate ions, sulfide ions, sulfite ions, bicarbonate ions, hydrogen phosphate ions, hydrogen phosphite ions, bisulfate ions, acids (such as carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, nitrous acid, sulfurous acid, peroxyacid or phosphoric acid), ammonia, bromine, carbon dioxide, chlorine, chlorine dioxide, fluorine, hydrogen chloride, hydrogen sulfide, iodine, nitrogen dioxide, nitric oxide, oxygen, ozone, sodium sulfate, magnesium sulfate, hydrogen peroxide, polysaccharides, metal oxides, sand, clay, silicon dioxide, titanium dioxide, mud, insoluble inorganic particles and / or organic particles, oxidizing agents, chelating agents, alcohols, and any combination of the foregoing substances.

[0100] In some embodiments, the medium is an aqueous medium with a pH of about 6 to about 14. For example, the aqueous medium may have a pH of about 7 to about 14, about 8 to about 14, about 9 to about 14, about 10 to about 14, about 11 to about 14, about 12 to about 14, about 13 to about 14, about 7 to about 13, about 8 to about 12, or about 9 to about 11.

[0101] The compositions disclosed in this invention can be used to inhibit corrosion of surfaces comprising a variety of different metals. In some embodiments, the metal surface includes steel, such as stainless steel, mild steel, or carbon steel. The metal surface may include, for example, copper, brass, and / or cupronickel.

[0102] In some implementations, the pipes or tanks (e.g., railway tank cars or oil tankers / tankers) contain metal surfaces.

[0103] In some embodiments, the methods disclosed herein further include adding a component to a medium. The component may be added before, after, and / or with the composition. The component may be added continuously, automatically, intermittently, and / or manually. In some embodiments, the composition contains the component. In some embodiments, the composition consists of reaction products, solvents, and components, or is substantially composed of reaction products, solvents, and components. The component may be any component and / or compound disclosed herein or contemplated, except for oxoanions of zwitterionic metals and oxoanions of zwitterionic metal silicates.

[0104] The composition (and optional components, if separate from the composition) may be added to the medium cleanly, dissolved in a solvent, partially dissolved in a solvent, and / or dispersed in a solvent. Addition may involve manual addition, automated addition, dripping, pouring, spraying, pumping, injection, or other methods of adding the composition and optional components to the medium and / or metal surface. In some embodiments, the composition may be heated prior to addition, such as to about 30°C to 100°C. In some embodiments, the composition is added directly to a metal surface that replaces the medium or is not a medium.

[0105] In some embodiments, the media and / or metal surfaces to be treated with the compositions disclosed in this invention may be located in cooling water systems, boiler water systems, oil wells, downhole rock formations, geothermal wells, ore washing processes, flotation and mineral processing processes, papermaking processes, gas scrubbers, air scrubbers, continuous casting processes, air conditioning and refrigeration processes, water recovery processes, water purification processes, membrane filtration processes, purifiers, municipal wastewater treatment processes, municipal water treatment processes, or drinking water systems.

[0106] In some embodiments, the compositions and methods disclosed herein can be used for textile care / laundry, for scaling control in the paper industry and / or as stabilizers / synergists for corrosion control of Zn, Mn, Sn, V or Ti-based low-carbon steel in aqueous media, and / or for mining operations.

[0107] In some respects, the effective amount of oxygen-containing anions of the zwitterionic metal added to the medium can be in the range of about 0.1 ppm to about 400 ppm, such as about 0.1 ppm to about 300 ppm, about 0.1 ppm to about 250 ppm, about 0.1 ppm to about 200 ppm, about 0.1 ppm to about 150 ppm, about 0.1 ppm to about 100 ppm, about 0.1 ppm to about 90 ppm, about 0.1 ppm to about 80 ppm, about 0.1 ppm to about 70 ppm, about 0.1 ppm to about 60 ppm, about 0.1 ppm to about 50 ppm, about 0.1 ppm to about 40 ppm, about 0.1 ppm to about 30 ppm, about 0.1 ppm to about 20 ppm. m, about 0.1 ppm to about 10 ppm, about 1 ppm to about 10 ppm, about 1 ppm to about 20 ppm, about 0.1 ppm to about 30 ppm, about 0.1 ppm to about 40 ppm, about 0.1 ppm to about 50 ppm, about 0.1 ppm, about 1 ppm, about 3 ppm, about 5 ppm, about 10 ppm, about 15 ppm, about 20 ppm, about 25 ppm, about 30 ppm, about 35 ppm, about 40 ppm, about 45 ppm, about 50 ppm, about 55 ppm, about 60 ppm, about 65 ppm, about 70 ppm, about 75 ppm, about 80 ppm, about 85 ppm, about 90 ppm, about 95 ppm and / or about 100 ppm.

[0108] In some respects, the effective amount of silicate, silica, or combinations thereof added to the medium may be in the range of about 0 ppm to about 200 ppm, about 0 ppm to about 150 ppm, about 0 ppm to about 100 ppm, about 0 ppm to about 50 ppm, about 0.1 ppm to about 200 ppm, about 0.1 ppm to about 100 ppm, about 0.1 ppm to about 90 ppm, about 0.1 ppm to about 80 ppm, about 0.1 ppm to about 70 ppm, about 0.1 ppm to about 60 ppm, about 0.1 ppm to about 50 ppm, about 1 ppm to about 200 ppm, about 5 ppm to about 200 ppm, about 10 ppm to about 200 ppm, about 20 ppm to about 200 ppm, about 40 ppm to about 200 ppm, about 60 ppm to about 200 ppm, about 80 ppm to about 200 ppm, or about 100 ppm to about 200 ppm.

[0109] In some aspects, the effective amount of oxyanionic or oxyanionic silicate added to the medium of zwitterionic metal silicate can be from about 0 ppm to about 200 ppm, from about 0 ppm to about 150 ppm, from about 0 ppm to about 100 ppm, from about 0 ppm to about 50 ppm, from about 0.1 ppm to about 200 ppm, from about 0.1 ppm to about 100 ppm, from about 0.1 ppm to about 90 ppm, from about 0.1 ppm to about 80 ppm, from about 0.1 ppm to about 70 ppm, from about 0.1 ppm to about 60 ppm, from about 0.1 ppm to about 50 ppm, from about 1 ppm to about 200 ppm, from about 5 ppm to about 200 ppm, from about 10 ppm to about 200 ppm. The range is approximately ppm, approximately 20 ppm to approximately 200 ppm, approximately 40 ppm to approximately 200 ppm, approximately 60 ppm to approximately 200 ppm, approximately 80 ppm to approximately 200 ppm, approximately 100 ppm to approximately 200 ppm, approximately 0.1 ppm, approximately 1 ppm, approximately 3 ppm, approximately 5 ppm, approximately 10 ppm, approximately 15 ppm, approximately 20 ppm, approximately 25 ppm, approximately 30 ppm, approximately 35 ppm, approximately 40 ppm, approximately 45 ppm, approximately 50 ppm, approximately 55 ppm, approximately 60 ppm, approximately 65 ppm, approximately 70 ppm, approximately 75 ppm, approximately 80 ppm, approximately 85 ppm, approximately 90 ppm, approximately 95 ppm, or approximately 100 ppm.

[0110] In some aspects, the amount of stabilizer added to the medium can be from about 0 to about 200 ppm, such as from about 0 ppm to about 150 ppm, from about 0 ppm to about 100 ppm, from about 0 ppm to about 50 ppm, from about 0.1 ppm to about 200 ppm, from about 0.1 ppm to about 100 ppm, from about 0.1 ppm to about 90 ppm, from about 0.1 ppm to about 80 ppm, from about 0.1 ppm to about 70 ppm, from about 0.1 ppm to about 60 ppm, from about 0.1 ppm to about 50 ppm, from about 1 ppm to about 200 ppm, from about 5 ppm to about 200 ppm, from about 10 ppm to about 200 ppm, from about 20 ppm. m to about 200 ppm, about 40 ppm to about 200 ppm, about 60 ppm to about 200 ppm, about 80 ppm to about 200 ppm, about 100 ppm to about 200 ppm, about 0.1 ppm, about 1 ppm, about 3 ppm, about 5 ppm, about 10 ppm, about 15 ppm, about 20 ppm, about 25 ppm, about 30 ppm, about 35 ppm, about 40 ppm, about 45 ppm, about 50 ppm, about 55 ppm, about 60 ppm, about 65 ppm, about 70 ppm, about 75 ppm, about 80 ppm, about 85 ppm, about 90 ppm, about 95 ppm or about 100 ppm.

[0111] In some respects, the effective amount of the additional component added to the medium can be in the range of 0 ppm to about 5000 ppm, such as about 0.1 ppm to about 5000 ppm, about 0.1 ppm to about 4000 ppm, about 0.1 ppm to about 3000 ppm, about 0.1 ppm to about 2000 ppm, about 0.1 ppm to about 1000 ppm, about 0.1 ppm to about 500 ppm, about 1 ppm to about 5000 ppm, about 100 ppm to about 5000 ppm, about 250 ppm to about 5000 ppm, about 500 ppm to about 5000 ppm, or about 1000 ppm to about 5000 ppm. In some respects, the amount of the added additional components is about 0.1 ppm, about 1 ppm, about 5 ppm, about 15 ppm, about 25 ppm, about 35 ppm, about 45 ppm, about 55 ppm, about 65 ppm, about 75 ppm, about 85 ppm, about 95 ppm, about 125 ppm, about 150 ppm, about 175 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 750 ppm, about 1000 ppm, about 1500 ppm, about 2000 ppm, about 2500 ppm, or about 3000 ppm.

[0112] The corrosion inhibitor composition can be used in media at a variety of concentration levels, such as from about 0.1 ppm to about 10,000 ppm, from about 0.1 ppm to about 8,000 ppm, from about 0.1 ppm to about 6,000 ppm, from about 0.1 ppm to about 4,000 ppm, from about 0.1 ppm to about 2,000 ppm, from about 0.1 ppm to about 1,000 ppm, from about 0.1 ppm to about 500 ppm, from about 0.1 ppm to about 100 ppm, from about 5 ppm to about 100 ppm, from about 5 ppm to about 500 ppm, or from about 5 to about 1,000 ppm. In some aspects, the concentration of the corrosion inhibitor composition in the medium may be about 0.1 ppm, about 0.5 ppm, about 1 ppm, about 10 ppm, about 25 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 750 ppm, about 1000 ppm, about 2000 ppm, about 3000 ppm, about 4000 ppm, about 5000 ppm, about 7500 ppm, or about 10000 ppm.

[0113] The corrosion inhibitor compositions disclosed herein are effective regardless of the amount of corrosive agent in the medium. In some embodiments, the corrosive agent may be present in amounts of at least about 10 ppm, at least about 50 ppm, at least about 100 ppm, at least about 300 ppm, at least about 500 ppm, at least about 1000 ppm, at least about 2000 ppm, at least about 5000 ppm, at least about 10,000 ppm, at least about 20,000 ppm, or less than about 100,000 ppm.

[0114] As can be seen in the following examples, the inventors have discovered synergistic combinations of components that inhibit or prevent pitting corrosion and other types of corrosion. In some aspects, the synergistic effect is between mixtures of oxyanions, silicates, and glycosaminoglycans and / or their salts and / or derivatives. Therefore, in one aspect, in cases involving pitting corrosion, the corrosion inhibitor composition according to this disclosure may comprise oxyanions of amphoteric materials (such as sodium stannous oxide) with mixtures of sodium silicate and glycosaminoglycans and / or their salts and / or derivatives.

[0115] The corrosion inhibitor compositions disclosed in this invention can be added to the system in any manner known in the art. For example, the inhibitor can be injected into the system via a chemical metering pump. Other acceptable injection methods include pretreatment / pre-coating of the metal surface before exposure to corrosive media, continuous injection, or batch treatment. Continuous addition / injection can be performed if suitable chemical injection equipment and chemical storage tanks are available on site. Otherwise, a specialized treatment vehicle can be used to treat the chemicals, applying large doses of chemicals at long intervals, typically once every one to two weeks, and in some cases, once a month. Batch application can be performed using a treatment truck, which includes a storage tank containing the corrosion inhibitor (and optionally other chemicals) and a large water tank. The treatment truck travels to the site location and treats each site.

[0116] The foregoing can be better understood by referring to the following embodiments, which are intended for illustrative purposes and are not intended to limit the scope of this disclosure or restrict its application in any way.

[0117] Example

[0118] The following are several illustrative examples of the compositions and methods disclosed herein. The following embodiments should be considered merely as illustrative of such methods and compositions and should not be construed as limiting in any way.

[0119] In the first embodiment, approximately 200 ppm of stannate solution was added to the river water as a corrosion inhibitor. Low-carbon steel sample blocks were immersed in the river water, stirred, and allowed to reach approximately 40°C for approximately 50 hours. A second experiment followed a similar procedure, but without the addition of a corrosion inhibitor. When comparing the two sample blocks after the experiments, the sample block that came into contact with the corrosion inhibitor was shiny and showed significantly less corrosion than the sample block that did not come into contact with the corrosion inhibitor.

[0120] Similar experiments were conducted, but this time the corrosion inhibitor composition contained sodium stannous silicate along with succinic acid. After approximately 50 hours, the untreated sample block was highly corroded, but the sample block treated with the corrosion inhibitor composition was shiny with minimal signs of corrosion.

[0121] Similar experiments were conducted using corrosion inhibitor compositions containing the amphoteric metals (and other optional components) listed in Table 1.

[0122] Table 1 :

[0123] Additional tests confirmed that the oxy-containing anions of the amphoteric metals (and metal silicates) disclosed in this invention, such as stan silicates, stannous silicates, etc., optionally combined with hydroxycarboxylic acids (e.g., succinic acid or tartaric acid), or wherein the hydroxycarboxylic acid is added alone to the medium, can effectively prevent corrosion in both soft and hard water containing high levels of calcium and alkalinity.

[0124] Figure 1 Corrosion rate data from a pilot-scale cooling tower test using a combination of stannous silicate and saccharic acid are shown. The pilot-scale cooling tower was tested in soft water at a pH level of approximately 8 for over a month, and the low-carbon steel pipes in contact with the medium remained shiny throughout the period with very little sign of corrosion. It can be seen that the corrosion rate for low-carbon steel (Ms) was measured to be approximately 0.4 mpy to 0.6 mpy, and the corrosion rate for brass (Br) was measured to be less than approximately 0.1 mpy.

[0125] All compositions and methods disclosed and claimed herein can be prepared and performed according to this disclosure without excessive experimentation. Although the invention may be embodied in many different forms, specific preferred embodiments of the invention are described in detail herein. This disclosure is exemplary of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated. Furthermore, unless expressly stated to the contrary, the term "a" is intended to include "at least one" or "one or more". For example, "stabilizer" is intended to include "at least one stabilizer" or "one or more stabilizers".

[0126] Any range given in absolute or approximate terms is intended to encompass both, and any definitions used herein are intended to be clarifying and not restrictive. While the numerical ranges and parameters that set forth the broad scope of the invention are approximate, the numerical values ​​set forth in the specific embodiments are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its corresponding experimental measurement. Furthermore, all ranges disclosed herein should be understood to encompass any and all subranges contained herein (including all fractional and overall values).

[0127] Any composition disclosed herein may comprise, consist of, or consist substantially of any element, component, and / or ingredient disclosed herein, or any combination of two or more elements, components, or ingredients disclosed herein.

[0128] Any method disclosed herein may include, consist of, or substantially consist of any method steps disclosed herein or any combination of two or more method steps disclosed herein.

[0129] The transitional phrase “includes”, “contains”, or “characterized in” is inclusive or open-ended and does not exclude additional unreferenced elements, components, ingredients, and / or method steps.

[0130] The transitional phrase "composed of" excludes any element, component, ingredient, and / or method step not specified in the claims.

[0131] The transitional phrase “consistent essentially of…” limits the scope of the claim to the specified elements, components, ingredients and / or steps, as well as those elements, components, ingredients and / or steps that do not substantially affect the essential and novel features of the claimed invention.

[0132] Unless otherwise specified, all molecular weights referred to herein are weight-average molecular weights, and all viscosities are measured at 25°C with pure (undiluted) polymers.

[0133] As used herein, the term “about” refers to a referenced value within the error caused by the standard deviation found in their respective test measurements, and if those errors are not certain, then “about” may refer to, for example, within 5%, 4%, 3%, 2%, or 1% of the referenced value.

[0134] Furthermore, this invention covers any and all possible combinations of some or all of the various embodiments described herein. It should also be understood that various changes and modifications to the currently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Therefore, the appended claims are intended to cover such changes and modifications.

Claims

1. A method for inhibiting corrosion of a metal surface in contact with a medium, comprising: A composition is added to the medium, wherein the composition comprises an oxygen-containing anion of a zwitterionic metal.

2. The method of claim 1, wherein the amphoteric metal is selected from the group consisting of zinc, aluminum, tin, iron, titanium, zirconium, copper, and any combination thereof.

3. The method according to claim 1, wherein the oxygen-containing anion of the amphoteric metal is selected from the group consisting of: sodium zincate, sodium stannate, sodium stannate, sodium aluminate, sodium titanate, sodium titanate, sodium zirconate, sodium cuprate, sodium ferrous acid, sodium ferrite, potassium zincate, potassium stannate, potassium aluminate, potassium titanate, potassium titanate, potassium zirconate, potassium cuprate, potassium ferrous acid, potassium ferrite, lithium zincate, lithium stannate, lithium aluminate, lithium titanate, lithium titanate, lithium zirconate, lithium cuprate, lithium ferrous acid, lithium ferrite, and any combination thereof.

4. The method of claim 1 further comprises adding silicates, silicon dioxide, or combinations thereof to the medium.

5. The method according to claim 4, wherein the silicate, the silicon dioxide, and / or combinations thereof are added before, after, and / or together with the oxygen-containing anions of the amphoteric metal.

6. The method according to claim 4, further comprising reacting the silicate, the silicon dioxide, and / or combinations thereof with the oxygen-containing anion of the amphoteric metal to form an oxygen-containing anion of the amphoteric metal silicate.

7. The method according to claim 6, wherein the oxygen-containing anion of the amphoteric metal silicate is selected from the group consisting of: sodium aluminosilicate, sodium zinc silicate, sodium tin silicate, sodium stannous silicate, sodium titanyl silicate, sodium titanyl silicate, sodium zirconium silicate, sodium copper silicate, sodium ferrisilicate, sodium iron silicate, potassium aluminosilicate, potassium zinc silicate, potassium tin silicate, potassium stannous silicate, potassium titanyl silicate, potassium titanyl silicate, potassium zirconium silicate, potassium copper silicate, potassium ferrisilicate, potassium iron silicate, lithium aluminosilicate, lithium zinc silicate, lithium tin silicate, lithium stannous silicate, lithium titanyl silicate, lithium titanyl silicate, lithium zirconium silicate, lithium copper silicate, lithium ferrisilicate, lithium iron silicate, and any combination thereof.

8. The method of claim 1, further comprising adding about 0.1 ppm to about 400 ppm of the oxygen-containing anion of the amphoteric metal to the medium.

9. The method of claim 4, further comprising adding about 0.1 ppm to about 200 ppm of the silicate, the silicon dioxide, or a combination thereof to the medium.

10. The method of claim 6, further comprising adding about 0.1 ppm to about 400 ppm of the oxygen-containing anion of the amphoteric metal silicate to the medium.

11. The method of claim 1, further comprising adding an additional component to the medium, wherein the additional component is selected from the group consisting of: fouling control agents, additional corrosion inhibitors, biocides, preservatives, acids, hydrogen sulfide scavengers, surfactants, scale inhibitors, pH adjusters, coagulants / flocculators, water purifiers, dispersants, antioxidants, polymer degradation inhibitors, permeability regulators, CO2 scavengers, O2 scavengers, gelling agents, lubricants, friction reducers, salts, stabilizers, yellow metal corrosion inhibitors, and any combination thereof.

12. The method of claim 11, wherein the stabilizer comprises a hydroxycarboxylic acid.

13. The method of claim 1, wherein the method does not include adding phosphate to the medium.

14. A composition comprising: Zincates, stannites, stannates, or any combination thereof; Silicates; and Hydroxycarboxylic acid.

15. The composition of claim 14 further comprises about 0.01% to about 99% by weight of the zincate, stannite, stannate, or combinations thereof; about 0.1% to about 30% by weight of the silicate; and about 0% to about 50% by weight of the hydroxycarboxylic acid.

16. The composition of claim 14, wherein the composition comprises sodium stannous acid, sodium silicate, and glycolic acid.

17. The composition according to claim 14, further comprising a solvent.

18. The composition of claim 14, wherein the composition has a pH of about 6 to about 14.

19. The composition of claim 14, wherein the composition does not contain phosphorus.

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