Corrosion inhibitor compositions and methods of inhibiting corrosion

Abstract

The disclosure provides a composition including a corrosion inhibitor compound and a synergist. The composition may be used in a method of inhibiting corrosion of a metal surface. The method includes adding the composition to an aqueous medium that includes the metal surface and / or adding the compound and / or polymer directly to the metal surface. The composition may be applied to the metal surface, for example, using batch treatment and / or continuous injection. Examples of synergists include a lignin polymer, polyvinyl alcohol, cellulose, gelatin, or a combination thereof.

Description

TECHNICAL FIELD

[0001] The present disclosure generally relates to corrosion inhibitor compositions and methods of using the compositions to inhibit corrosion. More particularly, the present disclosure relates to corrosion inhibitor compositions comprising a synergist and methods of using the compositions to inhibit corrosion of a metallic surface.BACKGROUND

[0002] Corrosion inhibitors are often added into upstream oil and gas production fluids to protect carbon steel pipelines and infrastructure from corrosion. Oil and gas operators often treat carbon steel pipelines and production tubulars with batch corrosion inhibitor, although continuous injection of the inhibitor into the medium in contact with the metallic surface may also be used. Batch corrosion inhibitor products usually contain oil-soluble chemistries and are directly applied to the pipe / tube walls as a slug of chemical between two spheres, sometimes referred to as pigs, to coat the entire circumference of the interior surface of the wall. The directly applied film formed on the metal surface provides a barrier to the water electrolyte to inhibit corrosion. The frequency of reapplication depends on the severity of the operating environment and frequencies. Typical frequencies range from a few times per year, monthly, or even weekly.

[0003] There are continued research and development efforts across the industry to increase performance and / or decrease dose rates of corrosion inhibitors to not only assist in reducing costs but also to help lessen chemical usage to streamline logistics, reduce chemical handling with the associated health and safety benefits, and reduce the carbon footprint and increase the sustainability of the operations.BRIEF SUMMARY

[0004] The present disclosure provides methods and compositions for inhibiting corrosion of metallic surfaces.

[0005] In some embodiments, a method of inhibiting corrosion of a metal surface in contact with a medium is provided, which comprises adding a corrosion inhibitor compound to the medium, and adding a synergist to the medium, wherein the synergist is selected from the group consisting of a lignin polymer, polyvinyl alcohol, cellulose, gelatin, and any combination thereof.

[0006] A composition provided by the present disclosure may comprise a corrosion inhibitor compound and a synergist, wherein the synergist is selected from the group consisting of a lignin polymer, polyvinyl alcohol, cellulose, gelatin, and any combination thereof.

[0007] The present disclosure also provides a metal surface comprising any composition disclosed herein.

[0008] The foregoing has outlined rather broadly the features and technical advantages of the present disclosure in order that the detailed description that follows may be better understood. Additional features and advantages of the disclosure will be described hereinafter that form the subject of the claims of this application. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present disclosure. It should also be realized by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the disclosure as set forth in the appended claims.DETAILED DESCRIPTION

[0009] Various embodiments are described below. The relationship and functioning of the various elements of the embodiments will be better understood in light of the following detailed description. However, elements and embodiments are not strictly limited to those explicitly described below.

[0010] Examples of methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents and other reference materials mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0011] 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 conflict, the present document, including definitions, will control.

[0012] Unless otherwise indicated, an alkyl group as described herein alone or as part of another group is an optionally substituted linear or branched saturated monovalent hydrocarbon substituent containing from, for example, one to about sixty carbon atoms, such as one to about thirty carbon atoms, in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, and the like.

[0013] The terms “aryl” or “ar” as used herein alone or as part of another group (e.g., arylene) denote optionally substituted homocyclic aromatic groups, such as monocyclic or bicyclic groups containing from about 6 to about 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. The term “aryl” also includes heteroaryl functional groups. It is understood that the term “aryl” applies to cyclic substituents that are planar and comprise 4n+2 electrons, according to Huckel's Rule.

[0014] “Cycloalkyl” refers to a cyclic alkyl substituent containing from, for example, about 3 to about 8 carbon atoms, preferably from about 4 to about 7 carbon atoms, and more preferably from about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The cyclic alkyl groups may be unsubstituted or further substituted with alkyl groups, such as methyl groups, ethyl groups, and the like.

[0015] “Heteroaryl” refers to a monocyclic or bicyclic 5- or 6-membered ring system, wherein the heteroaryl group is unsaturated and satisfies Huckel's rule. Non-limiting examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, 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, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, quinazolinyl, and the like.

[0016] Compounds of the present disclosure may be substituted with suitable substituents. The term “suitable substituent,” as used herein, is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the compounds. Such suitable substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoro-alkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO—(C═O)— groups, heterocylic groups, cycloalkyl groups, amino groups, alkyl- and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylamino carbonyl groups, arylcarbonyl groups, aryloxy-carbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, suitable substituents may include halogen, an unsubstituted C1-C12 alkyl group, an unsubstituted C4-C6 aryl group, or an unsubstituted C1-C10 alkoxy group. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.

[0017] The term “substituted” as in “substituted alkyl,” means that in the group in question (e.g., the alkyl group), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups, such as hydroxy (—OH), alkylthio, phosphino, amido (—CON(RA)(RB), wherein RA and RB are independently hydrogen, alkyl, or aryl), amino (—N(RA)(RB), wherein RA and RB are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (—NO2), an ether (—ORA wherein RA is alkyl or aryl), an ester (—OC(O)RA wherein RA is alkyl or aryl), keto (—C(O)RA wherein RA is alkyl or aryl), heterocyclo, and the like.

[0018] When the term “substituted” introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase “optionally substituted alkyl or aryl” is to be interpreted as “optionally substituted alkyl or optionally substituted aryl.”

[0019] The terms “polymer,”“copolymer,”“polymerize,”“copolymerize,” and the like include not only polymers comprising two monomer residues and polymerization of two different monomers together, but also include (co) polymers comprising more than two monomer residues and polymerizing together more than two or more other monomers. For example, a polymer as disclosed herein includes a terpolymer, a tetrapolymer, polymers comprising more than four different monomers, as well as polymers comprising, consisting of, or consisting essentially of two different monomer residues. Additionally, a “polymer” as disclosed herein may also include a homopolymer, which is a polymer comprising a single type of monomer unit.

[0020] Unless specified differently, the polymers of the present disclosure may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, and / or functionally modified. A polymer of the present disclosure can be in the form of a solution, a dry powder, a liquid, or a dispersion, for example.

[0021] “Aqueous system” refers to any system containing one or more metallic surfaces / components, which are in contact with an aqueous medium (e.g., water) on a periodic or continuous basis.

[0022] “Aqueous industrial system” means any system that circulates an aqueous medium or a medium including water as a component. Non-limiting examples of “industrial aqueous systems” include cooling systems, boiler systems, heating systems, membrane systems, food and beverage systems, oil and gas systems, and any other system that circulates or includes water.

[0023] The present disclosure relates to corrosion inhibitor compounds, compositions, methods of inhibiting corrosion, and formulations useful for inhibiting corrosion. Inhibiting corrosion includes, for example, reducing corrosion, completely eliminating corrosion or prohibiting corrosion from occurring for some period of time, lowering a rate of corrosion, etc.

[0024] The technology disclosed herein effectively enhances corrosion inhibitor performance and leads to film persistency / increased lifetime of the applied film.

[0025] A composition of the present disclosure comprises a corrosion inhibitor compound and a synergist. In certain embodiments, a composition of the present disclosure consists of or consists essentially of a corrosion inhibitor compound, a synergist, and optionally a solvent and / or an additional component, as defined further below.

[0026] Illustrative, non-limiting examples of corrosion inhibitor compounds include an organic sulfur compound, an imidazoline, a carboxylic acid-containing compound, a fatty acid amine condensate, a substituted fatty acid ester, a substituted aromatic amine, a phosphoric acid ester, a quaternary ammonium compound, or a compound comprising multiple positive charges.

[0027] In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of, an imidazoline compound, a quaternary amine, a synergist, and optionally a solvent.

[0028] The imidazoline compound may have formula (I), (II), or (III):wherein R1, R4, and R5 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle, said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle each independently, at each occurrence, unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, —COR6, —CO2R7, —SO3R8, —PO3H2, —CON(R9)(R10), —OR11, and —N(R12)(R13);

[0030] R2 is a radical derived from a fatty acid;

[0031] R3 and Rx are each independently selected from a radical derived from an unsaturated acid;

[0032] R6, R7, R8, R9, R10, and R11 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;

[0033] R12 and R13 are each independently, at each occurrence, selected from hydrogen, alkyl, —COR14, —CO2R15, -alkyl-COR16, and -alkyl-CO2R17; and

[0034] R14, R15, R16, and R17 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

[0035] In the foregoing imidazolines, R groups of carboxylic acid moieties can be absent where the R═H and the carboxylic acid moiety is deprotonated. For example, R15 and / or R17 can be absent where the R12 and / or R13 is a deprotonated carboxylic acid moiety (e.g., where R12 is —CH2CH2CO2−). For an imidazoline compound, R1 can be unsubstituted alkyl. For example, R1 can be unsubstituted C1-C10-alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (e.g., n-pentyl, isopentyl, tert-pentyl, neopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl, or decyl). Further, R1 can be unsubstituted C2-C10-alkyl. For the imidazoline compounds, R1 can be unsubstituted C2-C8-alkyl. Further, R1 can be unsubstituted C2-C6-alkyl. In some embodiments, R1 is propyl, butyl, or hexyl.

[0036] In some embodiments, R1 is a substituted alkyl. For example, R1 may be a substituted C1-C10-alkyl, substituted C2-C10-alkyl, substituted C2-C8-alkyl, or substituted C2-C6-alkyl. Further, R1 may be a C1-C10-alkyl, C2-C10-alkyl, C2-C8-alkyl, or C2-C6-alkyl, substituted with one substituent selected from —COR6, —CO2R7, —SO3R8, —PO3H2, —CON(R9)(R10), —OR11, and —N(R12)(R13), wherein R6, R7, R8, R9, R10, R11, R12, and R13 are as defined above. More specifically, R1 may be a C2-C6-alkyl, substituted with one substituent selected from —N(R12)(R13), wherein R12 and R13 are each independently selected from hydrogen, alkyl, —COR14, —CO2R15, -alkyl-COR16, and -alkyl-CO2R17, wherein R14, R15, R16, and R17 are as defined above. Further, R1 may be a C2-C6-alkyl, substituted with one substituent selected from —N(R12)(R13), wherein R12 and R13 are each independently selected from hydrogen, C2-C6-alkyl, —COR14, —CO2R15, —C2-C6-alkyl-COR16, and —C2-C6-alkyl-CO2R17, wherein R14, R15, R16, and R17 are selected from hydrogen and C1-C34-alkyl. For these imidazolines, R1 may be a linear C2-C6-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each independently selected from hydrogen, —COR14, —CO2R15, —C2-C6-alkyl-COR16, and —C2-C6-alkyl-CO2R17, wherein R14, R15, R16, and R17 are selected from hydrogen and C1-C34-alkyl. For example, R1 may be a linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14, wherein R14 is —C17H35, —C17H33, or —C17H31. Further, R1 may be a linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen.

[0037] For the imidazolines of formulae (I), (II), and (III), R2 may be a C4-C34-alkyl or C4-C34-alkenyl. For example, R2 may be a —(CH2)3CH3; —(CH2)4CH3; —(CH2)5CH3; —(CH2)6CH3; —(CH2)7CH3; —(CH2)8CH3; —(CH2)9CH3; —(CH2)10CH3; —(CH2)11CH3; —(CH2)12CH3; —(CH2)13CH3; —(CH2)14CH3; —(CH2)15CH3; —(CH2)16CH3; —(CH2)17CH3; —(CH2)18CH3; —(CH2)19CH3; —(CH2)20CH3; —(CH2)21CH3; —(CH2)22CH3; —(CH2)23CH3; —(CH2)24CH3; —(CH2)25CH3; —(CH2)26CH3; —(CH2)27CH3; —(CH2)28CH3; —(CH2)29CH3; —(CH2)30CH3; —(CH2)31CH3; —(CH2)32CH3; —(CH2)33CH3; —(CH2)34CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CH(CH2)7CH3; —(CH2)3CH═CHCH2CH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CH(CH2)4CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)3CH═CHCH═CHCH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)4CH═CH(CH2)8CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CHs; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)6CH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)6CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CH(CH2)3CH3; —(CH2)7CH═CH(CH2)5CH3; —(CH2)7CH═CH(CH2)7CH3; —(CH2)7CH═CHCH═CHCH═CH(CH2)3CH3; —(CH2)7CH═CHCH═CH(CH2)5CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH═CHCH2CH2CH═CHCH2CH3; —(CH2)7CH═CHCH═CHCH═CHCH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)5CH3; —(CH2)9CH═CHCH2CH═CH(CH2)4CH3; —(CH2)9CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)7CH3; —(CH2)11CH═CH(CH2)5CH3; —(CH2)11CH═CH(CH2)7CH3; —(CH2)11CH═CHCH2CH═CH(CH2)4CH3; or —(CH2)13CH═CH(CH2)7CH3.

[0038] In some embodiments, R2 may be a radical derived from a saturated or unsaturated fatty acid. Suitable saturated fatty acids include, but are not limited to, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, pentacosylic acid, cerotic acid, heptacosylic acid, montanic acid, nonacosylic acid, melissic acid, henatriacontylic acid, lacceroic acid, psyllic acid, geddic acid, ceroplastic acid, and hexatriacontylic acid.

[0039] Suitable unsaturated fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, hexadecatrienoic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, heneicosapentaenoic acid, clupanodonic acid, osbond acid, (9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoic acid, nisinic acid, γ-linolenic acid, eicosadienoic acid, dihomo-γ-linolenic acid, docosadienoic acid, adrenic acid, tetracosatetraenoic acid, (6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid, (Z)-Eicos-11-enoic acid, mead acid, erucic acid, nervonic acid, rumenic acid, α-calendic acid, β-calendic acid, jacaric acid, α-eleostearic acid, β-eleostearic acid, catalpic acid, punicic acid, rumelenic acid, α-parinaric acid, β-parinaric acid, bosseopentaenoic acid, pinolenic acid, and podocarpic acid.

[0040] In some embodiments, R2 is derived from coconut oil, beef tallow, or tall oil fatty acids (TOFA).

[0041] In some embodiments, R3 may be —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and alkyl, and wherein Re is hydrogen (—H) or alkyl. For example, R3 may be —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and C1-C6-alkyl, and wherein Re is hydrogen (—H) or C1-C6-alkyl. Further, R3 may be —CH2CH2CO2Re, wherein Re is hydrogen (—H) or C1-C6-alkyl. Additionally, Re can be absent where the R3 is a deprotonated carboxylic acid moiety (e.g., where R3 is —CH2CH2CO2—).

[0042] In accordance with certain embodiments of the present disclosure, R3 can be derived from an acrylic acid. Suitable acrylic acids include, but are not limited to, acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-(trifluoromethyl)acrylic acid. For example, R3 can be derived from acrylic acid (H2C═CHCO2H).

[0043] Imidazolines of formulae (I), (II), or (III) may have Rx equal to —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and alkyl, and wherein Re is hydrogen (—H) or alkyl. Further, Rx can be —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and C1-C6-alkyl, and wherein Re is hydrogen (—H) or C1-C6-alkyl. Additionally, Rx may be —CH2CH2CO2Re, wherein Re is hydrogen (—H) or C1-C6-alkyl. Further, Re can be absent where the Rx is a deprotonated carboxylic acid moiety (e.g., where Rx is —CH2CH2CO2—).

[0044] For the imidazolines described herein, Rx can be derived from an acrylic acid. Suitable acrylic acids include, but are not limited to, acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-(trifluoromethyl)acrylic acid. For example, Rx can be derived from acrylic acid (H2C═CHCO2H).

[0045] Imidazolines of formulae (I), (II), or (III) can have R4 and R5 each independently be an unsubstituted C1-C10-alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (e.g., n-pentyl, isopentyl, tert-pentyl, neopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl, or decyl) or hydrogen. Further, R4 and R5 can each independently be an unsubstituted C1-C6 alkyl group or hydrogen. In some embodiments, R4 and R5 are each hydrogen (—H).

[0046] Imidazolines of formulae (I), (II), or (III) can have R6, R7, R8, R9, R10, and R11 each independently be, at each occurrence, selected from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. For example, R6, R7, R8, R9, R10, and R11 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C34-alkyl, and unsubstituted C2-C34-alkenyl. Further, R6, R7, R8, R9, R10, and R11 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C10-alkyl, and unsubstituted C2-C10-alkenyl. Further, R6, R7, R8, R9, R10, and R11 can each independently be, at each occurrence, selected from hydrogen, and a radical derived from a fatty acid.

[0047] R12 and R13 can each independently be, at each occurrence, selected from hydrogen, C1-C10-alkyl, —COR14, —CO2R15, —C1-C10-alkyl-COR16, and —C1-C10-alkyl-CO2R17. Further, R12 and R13 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C10-alkyl, —COR14, —CO2R15, —C1-C10-alkyl-COR16, and —C1-C10-alkyl-CO2R17.

[0048] R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. Further, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C34-alkyl, and unsubstituted C2-C34-alkenyl. Additionally, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C10-alkyl, and unsubstituted C2-C10-alkenyl. Further, R15 and / or R17 can be absent where the carboxylic acid moiety is deprotonated.

[0049] Imidazoline compounds of the present disclosure can have R14, R15, R16, and R17 each independently be, at each occurrence, selected from hydrogen, and a radical derived from a fatty acid. Further, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, C4-C34-alkyl, and C4-C34-alkenyl. Additionally, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen; —(CH2)3CH3; —(CH2)4CH3; —(CH2)5CH3; —(CH2)6CH3; —(CH2)7CH3; —(CH2)8CH3; —(CH2)9CH3; —(CH2)10CH3; —(CH2)11CH3; —(CH2)12CH3; —(CH2)13CH3; —(CH2)14CH3; —(CH2)15CH3; —(CH2)16CH3; —(CH2)17CH3; —(CH2)18CH3; —(CH2)19CH3; —(CH2)20CH3; —(CH2)21CH3; —(CH2)22CH3; —(CH2)23CH3; —(CH2)24CH3; —(CH2)25CH3; —(CH2)26CH3; —(CH2)27CH3; —(CH2)28CH3; —(CH2)29CH3; —(CH2)30CH3; —(CH2)31CH3; —(CH2)32CH3; —(CH2)33CH3; —(CH2)34CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CH(CH2)7CH3; —(CH2)3CH═CHCH2CH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CH(CH2)4CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)3CH═CHCH═CHCH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)4CH═CH(CH2)8CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)6CH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)6CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CH(CH2)3CH3; —(CH2)7CH═CH(CH2)5CH3; —(CH2)7CH═CH(CH2)7CH3; —(CH2)7CH═CHCH═CHCH═CH(CH2)3CH3; —(CH2)7CH═CHCH═CH(CH2)5CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH═CHCH2CH2CH═CHCH2CH3; —(CH2)7CH═CHCH═CHCH═CHCH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)5CH3; —(CH2)9CH═CHCH2CH═CH(CH2)4CH3; —(CH2)9CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)7CH3; —(CH2)11CH═CH(CH2)5CH3; —(CH2)11CH═CH(CH2)7CH3; —(CH2)11CH═CHCH2CH═CH(CH2)4CH3; and —(CH2)13CH═CH(CH2)7CH3.

[0050] For the imidazolines of formulae (I), (II), and (III), R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, a radical derived from a saturated fatty acid, and a radical derived from an unsaturated fatty acid. Suitable saturated fatty acids include, but are not limited to, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, pentacosylic acid, cerotic acid, heptacosylic acid, montanic acid, nonacosylic acid, melissic acid, henatriacontylic acid, lacceroic acid, psyllic acid, geddic acid, ceroplastic acid, and hexatriacontylic acid.

[0051] Suitable unsaturated fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, hexadecatrienoic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, heneicosapentaenoic acid, clupanodonic acid, osbond acid, (9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoic acid, nisinic acid, γ-linolenic acid, eicosadienoic acid, dihomo-γ-linolenic acid, docosadienoic acid, adrenic acid, tetracosatetraenoic acid, (6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid, (Z)-Eicos-11-enoic acid, mead acid, erucic acid, nervonic acid, rumenic acid, α-calendic acid, β-calendic acid, jacaric acid, α-eleostearic acid, β-eleostearic acid, catalpic acid, punicic acid, rumelenic acid, α-parinaric acid, β-parinaric acid, bosseopentaenoic acid, pinolenic acid, and podocarpic acid.

[0052] Further, R14, R15, R16, and R17 are each independently, at each occurrence, hydrogen or a radical derived from coconut oil, beef tallow, or tall oil fatty acids (TOFA).

[0053] In some embodiments, the imidazoline is a compound of formula (I), wherein R1 is unsubstituted C2-C6-alkyl; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0054] In some embodiments, the imidazoline is a compound of formula (I), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14 wherein R14 is —C17H35, —C17H33, or —C17H31; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0055] In certain embodiments, the imidazoline is a compound of formula (I), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen or is absent (e.g., R12 is —C2-alkyl-CO2—); R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0056] In some embodiments, the imidazoline is a compound of formula (II), wherein R1 is unsubstituted C2-C6-alkyl; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); Rx is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., Rx is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0057] In some embodiments, the imidazoline is a compound of formula (II), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14, wherein R14 is —C17H35, —C17H33, or —C17H31; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); Rx is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., Rx is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0058] In certain embodiments, the imidazoline can be a compound of formula (II), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen or is absent (e.g., R12 is —C2-alkyl-CO2—); R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); Rx is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., Rx is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0059] In some embodiments, the imidazoline can be a compound of formula (III), wherein R1 is unsubstituted C2-C6-alkyl; R2 is —C17H35, —C17H33, or —C17H31; R4 is hydrogen; and R5 is hydrogen.

[0060] In some embodiments, the imidazoline can be a compound of formula (III), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14, wherein R14 is —C17H35, —C17H33, or —C17H31; R2 is —C17H35, —C17H33, or —C17H31; R4 is hydrogen; and R5 is hydrogen.

[0061] In certain embodiments, the imidazoline can be a compound of formula (III), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen or is absent (e.g., R12 is —C2-alkyl-CO2—); R2 is —C17H35, —C17H33, or —C17H31; R4 is hydrogen; and R5 is hydrogen.

[0062] It is to be understood, whether explicitly set forth or not, that formula (I), formula (II), and formula (III) are each intended to encompass the tautomeric, racemic, enantiomeric, diastereomeric, zwitterionic, and salt forms of said formulas. The imidazolines can exist in a zwitterionic form where R3 and / or Rx is derived from an acrylic acid.

[0063] In accordance with the present disclosure, the corrosion inhibitor compound may be a quaternary amine. Suitable quaternary amines include, but are not limited to, alkyl, hydroxyalkyl, alkylaryl, arylalkyl or arylamine quaternary salts.

[0064] Suitable alkyl, hydroxyalkyl, alkylaryl arylalkyl or arylamine quaternary salts include those alkylaryl, arylalkyl and arylamine quaternary salts of the formula [N+R5aR6aR7aR8a][X−] wherein R5a, R6a, R7a, and R8a contain one to 18 carbon atoms, and X is Cl, Br or I. For the quaternary amine, R5a, R6a, R7a, and R8a can each independently be selected from the group consisting of alkyl (e.g., C1-C18 alkyl), hydroxyalkyl (e.g., C1-C18 hydroxyalkyl), and arylalkyl (e.g., benzyl). The mono or polycyclic aromatic amine salt with an alkyl or alkylaryl halide include salts of the formula [N+R5aR6aR7aR8a][X−] wherein R5a, R6a, R7a, and R8a contain one to 18 carbon atoms, and X is Cl, Br or I.

[0065] Suitable quaternary ammonium salts include, but are not limited to, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammonium chloride, tetraoctyl ammonium chloride, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammonium chloride, phenyltriethyl ammonium chloride, cetyl benzyldimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dimethyl alkyl benzyl quaternary ammonium compounds, monomethyl dialkyl benzyl quaternary ammonium compounds, trimethyl benzyl quaternary ammonium compounds, and trialkyl benzyl quaternary ammonium compounds, wherein the alkyl group can contain between about 1 and about 24 carbon atoms, about 10 and about 18 carbon atoms, or about 12 to about 16 carbon atoms, such as for example, C12-16 benzyl dimethyl ammonium chloride. Suitable quaternary ammonium compounds (quats) include, but are not limited to, trialkyl, dialkyl, dialkoxy alkyl, monoalkoxy, benzyl, and imidazolinium quaternary ammonium compounds, salts thereof, the like, and combinations thereof. The quaternary ammonium salt can be an alkylamine benzyl quaternary ammonium salt, a benzyl triethanolamine quaternary ammonium salt, or a benzyl dimethylaminoethanolamine quaternary ammonium salt.

[0066] The quaternary amine can be a benzalkonium salt represented by the formula:wherein n is 8, 10, 12, 14, 16, or 18; and X is Cl, Br or I.The quaternary amine can be a mixture of benzalkonium salts wherein n is 8, 10, 12, 14, 16, and 18.

[0068] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, 16, and 18.

[0069] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, and 16.

[0070] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, 16, and 18 and X is Cl.

[0071] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, and 16, and X is Cl.

[0072] The quaternary amine can be an alkyl pyridinium quaternary salt such as those represented by the general formula:wherein R9a is an alkyl group, an aryl group, or an arylalkyl group, wherein said alkyl groups have from 1 to about 18 carbon atoms and B is Cl, Br or I.Among these compounds are alkyl pyridinium salts and alkyl pyridinium benzyl quats. Examples include methyl pyridinium chloride, ethyl pyridinium chloride, propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridinium chloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzyl pyridinium and an alkyl benzyl pyridinium chloride. In some embodiments, the alkyl is a C1-C6 hydrocarbyl group.

[0074] The compositions disclosed herein include a phosphonium compound, such as a phosphonium salt. Suitable phosphonium salts include, but are not limited to, alkyltris(hydroxyorgano)phosphonium salts, alkenyltris(hydroxyorgano)phosphonium salts, and tetrakis(hydroxyorgano)phosphonium salts. The alkyltris(hydroxyorgano)phosphonium salts can be C1-C3-alkyltris(hydroxymethyl)phosphonium salts. The alkenyltris(hydroxyorgano)phosphonium salts can be C2-C3-alkenyltris(hydroxymethyl)phosphonium salts. The tetrakis(hydroxyorgano)phosphonium salts can be tetrakis(hydroxymethyl)phosphonium salts, including, but not limited to, tetrakis(hydroxymethyl)phosphonium sulphate (THPS), tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis(hydroxymethyl)phosphonium formate, tetrakis(hydroxymethyl)phosphonium acetate, and tetrakis(hydroxymethyl)phosphonium oxalate. In some embodiments, the phosphonium salt is THPS.

[0075] The compound comprising multiple positive charges may be derived from a polyamine through its reactions with an activated olefin and an epoxide, wherein the activated olefin has the following formula:wherein X is NH or O; R2 is H, CH3, or an unsubstituted, linear or branched C2-C10 alkyl, alkenyl, or alkynyl group; R3 is absent or an unsubstituted, linear C1-C30 alkylene group; Y is —NR4R5R6(+); R4, R5, and R6 are independently a C1-C10 alkyl group; wherein the epoxide has the following formula;R7 is H or alkyl; and R8 is alkyl, or —(CH2)k—O-alkyl, wherein k is an integer of 1-30; wherein the polyamine and activated olefin undergo aza Michael Addition reaction and the polyamine and epoxide undergo ring opening reaction. In some embodiments, the compound comprises a nonionic group.In some embodiments, the compound has one of the generic formula of NA2-[R10′]n-NA2, (RNA)n-RNA2, NA2-(RNA)n-RNA2, or NA2-(RN(R′))n—RNA2, wherein R10′ is a linear or branched, unsubstituted or substituted C2-C10 alkylene group, or combination thereof; R is —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)CH2—, a linear or branched, unsubstituted or substituted C4-C10 alkylene group, or combination thereof; R′ is —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)CH2—, a linear or branched, unsubstituted or substituted C4-C10 alkyl group, RNAB, RNARNAB, or RN(RNAB)2; n can be from 2 to 1,000,000; A is a combination of H,wherein X is NH or O; R2 is H, CH3, or an unsubstituted, linear or branched C2-C10 alkyl, alkenyl, or alkynyl group; R3 is absent or an unsubstituted, linear C1-C30 alkylene group; Y is —NR4R5R6(+); R4, R5, and R6 are independently a C1-C10 alkyl group; R7 is H or alkyl; and R8 is alkyl, or —(CH2)k—O-alkyl, wherein k is an integer of 1-30.The compound may be a multiple charged cationic compound having aIn some aspects, the treatment chemical can be 2-mercaptoethanol, a diethylenetriamine (DETA): tall oil fatty acid (TOFA) imidazoline, a reaction product of trimethylamine (TEA) and TOFA, a reaction product of TOFA and tetraethylenepentamine (TEPA), an alkyl pyridine, an ethoxylated branched nonylphenol phosphate ester, a benzyl-(C12 to C18 linear alkyl)-dimethylammonium chloride, 5-carboxy-4-hexyl-2-cyclohexene octanoic acid, 6-carboxy-4-hexyl-2-cyclohexene octanoic acid, maleated TOFA, an acrylated DETA:TOFA imidazoline, and any combination thereof.In some embodiments, the corrosion inhibitor may be selected from, for example, benzyl ammonium chloride, acrylated imidazoline, 2-mercaptoethanol, a quaternary ammonium compound, a phosphate ester, a substituted aromatic amine, an alkyl pyridine, a fatty acid amine condensate, and any combination thereof.In certain embodiments, the corrosion inhibitor compound comprises an amine compound, a polyamine compound, a thiol-containing compound, a carboxylic acid, a dicarboxylic acid, mercaptoethanol, a maleated compound, an aromatic amine compound, a phosphate ester, a quaternary ammonium compound, an imidazoline compound, or any combination thereof.The polyamine compound comprises, for example, a diamine compound, a triamine compound, and / or a quaternary ammonium compound.Illustrative, non-limiting examples of diamines include 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. Illustrative, non-limiting examples of triamines include coco-amine acetate, N-dodecyl-1,3-propanediamine and bis(3-aminopropyl) dodecylamine.

[0082] The amount of corrosion inhibitor compound in a composition is not particularly limited. For example, a composition may comprise from about 1 wt. % to about 99 wt. % of the corrosion inhibitor compound, such as from about 5 wt. % to about 99 wt. %, about 15 wt. % to about 99 wt. %, about 25 wt. % to about 99 wt. %, about 35 wt. % to about 99 wt. %, about 45 wt. % to about 99 wt. %, about 55 wt. % to about 99 wt. %, about 65 wt. % to about 99 wt. %, about 75 wt. % to about 99 wt. %, about 85 wt. % to about 99 wt. %, about 95 wt. % to about 99 wt. %, about 5 wt. % to about 90 wt. %, about 5 wt. % to about 80 wt. %, about 5 wt. % to about 70 wt. %, about 5 wt. % to about 60 wt. %, about 5 wt. % to about 50 wt. %, about 5 wt. % to about 40 wt. %, about 5 wt. % to about 30 wt. %, about 5 wt. % to about 20 wt. %, about 5 wt. % to about 10 wt. %, about 10 wt. % to about 90 wt. %, about 20 wt. % to about 80 wt. %, about 30 wt. % to about 70 wt. %, or about 40 wt. % to about 60 wt. %.

[0083] The synergist of the present disclosure may be selected from, for example, a lignin polymer, polyvinyl alcohol, cellulose, gelatin, or any combination thereof.

[0084] Lignins comprise phenylpropanoid alcohols (typically coniferyl, sinapyl, and coumaryl alcohols) with hydroxyl, methoxyl, and / or carbonyl functional groups. For example, a lignin polymer may comprise phenyl propane units, which are formed from hydroxyl- and methoxy-substituted phenylpropane units. Lignins are a type of hydrocarbon polymer including aliphatic and / or aromatic structures and may include both guaiacyl lignins and guaiacyl-syringyl lignins. In some embodiments, a lignin polymer may comprise one or more monomer units selected from coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol. The amount / mol % of each monomer in the polymer may vary depending on the source of the lignin, for example.

[0085] The weight average molecular weight of the lignin polymer is also variable from about 1,000 Da to about 100,000 Da, such as from about 1,000 Da to about 80,000 Da, about 1,000 Da to about 60,000 Da, about 1,000 Da to about 40,000 Da, about 1,000 Da to about 20,000 Da, about 1,000 Da to about 10,000 Da, about 1,000 Da to about 5,000 Da, about 5,000 Da to about 100,000 Da, about 10,000 Da to about 100,000 Da, about 20,000 Da to about 100,000 Da, about 30,000 Da to about 100,000 Da, about 40,000 Da to about 100,000 Da, about 50,000 Da to about 100,000 Da, about 60,000 Da to about 100,000 Da, about 5,000 Da to about 50,000 Da, about 10,000 Da to about 40,000, or about 20,000 Da to about 30,000 Da.

[0086] Polyvinyl alcohol is a water-soluble synthetic polymer having the general formula [CH2CH(OH)]n. The “n” variable is not particularly limited and may be selected from about 1 to about 10,000, such as from about 1 to about 8,000, about 1 to about 6,000, about 1 to about 4,000, about 1 to about 2,000, about 1 to about 1,000, about 1 to about 800, about 1 to about 600, about 1 to about 400, about 100 to about 10,000, about 200 to about 10,000, about 400 to about 10,000, about 600 to about 10,000, about 800 to about 10,000, about 1,000 to about 10,000, about 2,000 to about 10,000, about 4,000 to about 10,000, about 6,000 to about 10,000, about 400 to about 8,000, about 600 to about 7,000, or about 700 to about 6,000.

[0087] The polyvinyl alcohol polymer can have any molecular weight, such as about 10,000 Da to about 500,000 Da, about 20,000 Da to about 500,000 Da, about 30,000 Da to about 500,000 Da, about 40,000 Da to about 500,000 Da, about 50,000 Da to about 500,000 Da, about 60,000 Da to about 500,000 Da, about 70,000 Da to about 500,000 Da, about 80,000 Da to about 500,000 Da, about 90,000 Da to about 500,000 Da, about 100,000 Da to about 500,000 Da, about 200,000 Da to about 500,000 Da, about 300,000 Da to about 500,000 Da, about 10,000 Da to about 300,000 Da, about 10,000 Da to about 100,000 Da, about 10,000 Da to about 80,000 Da, about 10,000 Da to about 60,000 Da, about 20,000 Da to about 300,000 Da, or about 30,000 Da to about 200,000 Da.

[0088] Any type of cellulose may be utilized as a synergist in accordance with the present disclosure. For example, the cellulose may be selected from macrocellulose, microcellulose, nanocellulose, or any combination thereof.

[0089] Gelatin is understood to be a collection of peptides and proteins produced by partial hydrolysis of collagen extracted from the skin, bones, and / or connective tissues of animals, such as cattle, chickens, pigs, and fish.

[0090] The amount of synergist in the composition is not particularly limited. For example, the composition may comprise from about 0.1 wt. % to about 25 wt. % of the synergist, such as from about 0.1 wt. % to about 20 wt. %, about 0.1 wt. % to about 15 wt. %, about 0.1 wt. % to about 10 wt. %, about 0.1 wt. % to about 5 wt. %, about 0.1 wt. % to about 1 wt. %, about 1 wt. % to about 20 wt. %, about 5 wt. % to about 20 wt. %, about 10 wt. % to about 20 wt. %, about 15 wt. % to about 20 wt. %, about 0.5 wt. % to about 10 wt. %, about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. %.

[0091] In some embodiments, a composition may comprise from about 0.5 wt. % to about 5 wt. % of the corrosion inhibitor compound and from about 0.005 wt. % to about 0.1 wt. % of the synergist. For example, a composition may comprise from about 1 wt. % to about 2 wt. % of the corrosion inhibitor compound and from about 0.01 wt. % to about 0.09 wt. % of the synergist. In some embodiments, the composition comprises a greater weight percentage of the corrosion inhibitor compound than the synergist.

[0092] A composition of the present disclosure may comprise a variety of weight ratios of the corrosion inhibitor compound to the synergist. For example, a composition may comprise a weight ratio of the corrosion inhibitor compound to the synergist of about 50,000:1 to about 1:2, about 25,000:1 to about 1:2, about 10,000:1 to about 1:2, about 5,000:1 to about 1:2, about 1,000:1 to about 1:2, about 500:1 to about 1:2, about 250:1 to about 1:2, about 100:1 to about 1:2, about 50:1 to about 1:2, about 25:1 to about 1:2, about 10:1 to about 1:2, about 5:1 to about 1:2, or about 1:1 to about 1:2.

[0093] A composition of the present disclosure may optionally comprise a solvent. Suitable solvents include, but are not limited to, an alcohol, a hydrocarbon, a ketone, an ether, an aromatic, an amide, a nitrile, a sulfoxide, an ester, a glycol ether, water, and combinations thereof.

[0094] In some embodiments, the solvent is selected from the group consisting of water, a C1-C6 alkanol, a C1-C6 alkoxyalkanol, an alcohol, a glycol ether, a hydrocarbon, a ketone, an ether, an aromatic, an alkylene glycol, an amide, a nitrile, a sulfoxide, an ester, and any combination thereof.

[0095] For example, the solvent can be water, isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, xylene, or any combination thereof.

[0096] Representative polar solvents suitable for formulation with the composition (or corrosion inhibitor compound by itself or the synergist by itself) include water, brine, seawater, an alcohol (including straight chain or branched aliphatic, such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), a glycol and a glycol derivative (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol monobutyl ether, etc.), a ketone (such as cyclohexanone, diisobutylketone), N-methylpyrrolidinone (NMP), N,N-dimethylformamide, and the like.

[0097] Representative non-polar solvents suitable for formulation with the composition (or corrosion inhibitor compound by itself or the synergist by itself) include an aliphatic, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and the like; and an aromatic, such as toluene, xylene, heavy aromatic naphtha, a fatty acid derivative (e.g., an acid, an ester, an amide), and the like.

[0098] In some embodiments, the solvent is methanol, isopropanol, 2-ethylhexanol, or a combination thereof. In certain embodiments, the solvent is methanol, isopropanol, 2-ethylhexanol, water, or a combination thereof.

[0099] A composition of the present disclosure may include from about 0 wt. % to about 99 wt. % of the solvent, such as from about 5 wt. % to about 95 wt. %, about 5 wt. % to about 85 wt. %, about 5 wt. % to about 75 wt. %, about 5 wt. % to about 65 wt. %, about 5 wt. % to about 55 wt. %, about 5 wt. % to about 45 wt. %, about 5 wt. % to about 35 wt. %, about 5 wt. % to about 25 wt. %, about 5 wt. % to about 15 wt. %, about 15 wt. % to about 95 wt. %, about 25 wt. % to about 95 wt. %, about 35 wt. % to about 95 wt. %, about 40 wt. % to about 85 wt. %, or about 40 wt. % to about 80 wt. % of the solvent.

[0100] An aqueous composition of the present disclosure may comprise any suitable pH. For example, a composition of the present disclosure may comprise a pH of about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, or about 14, such as from about 1 to about 11, about 2 to about 10, about 3 to about 9, or about 4 to about 8.

[0101] The present disclosure also provides metal surfaces comprising any of the metals disclosed herein, or any combination of the metals disclosed herein, further comprising any of the compositions and / or compounds disclosed herein.

[0102] The compounds, synergists, and compositions disclosed herein may be used in various methods for inhibiting corrosion of metal surfaces.

[0103] For example, the present disclosure provides a method of inhibiting corrosion of a metal surface in contact with a medium. The method comprises adding any corrosion inhibitor compound disclosed herein to the medium, and adding any synergist disclosed herein to the medium.

[0104] The corrosion inhibitor compound may be added to the medium before, after, and / or with the synergist. If the corrosion inhibitor is added with / at the same time as the synergist, the two components may be added together as a single composition or they may be added separately but at the same time, typically at adjacent injection points. The corrosion inhibitor compound and the synergist may be added simultaneously and / or sequentially, continuously or intermittently. The corrosion inhibitor compound and the synergist may be added at the same location or at different locations in the medium. In some cases, the corrosion inhibitor compound and / or the synergist may be added directly to the metal surface in the absence of the medium. The metal surface may then be exposed to the medium and, if appropriate, additional inhibitor and / or synergist may be injected into the medium.

[0105] The amount of corrosion inhibitor added to the medium is not particularly limited. For example, the amount may be from about 0.1 ppm to about 10,000 ppm, about 0.1 ppm to about 7,500 ppm, about 0.1 ppm to about 5,000 ppm, about 0.1 ppm to about 2,500 ppm, about 0.1 ppm to about 1,000 ppm, about 0.1 ppm to about 500 ppm, about 0.1 ppm to about 250 ppm, about 0.1 ppm to about 100 ppm, about 1 ppm to about 10,000 ppm, about 50 ppm to about 10,000 ppm, about 100 ppm to about 10,000 ppm, about 250 ppm to about 10,000 ppm, about 500 ppm to about 10,000 ppm, about 1,000 ppm to about 10,000 ppm, about 2,500 ppm to about 10,000 ppm, about 5,000 ppm to about 10,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1,000 ppm, about 10 ppm to about 1,000 ppm, about 50 ppm to about 1,000 ppm, or about 25 ppm to about 500 ppm.

[0106] The amount of synergist added to the medium is not particularly limited. For example, the amount may be from about 0.1 ppm to about 5,000 ppm, about 0.1 ppm to about 2,500 ppm, about 0.1 ppm to about 2,000 ppm, about 0.1 ppm to about 1,500 ppm, about 0.1 ppm to about 1,000 ppm, about 0.1 ppm to about 500 ppm, about 0.1 ppm to about 250 ppm, about 1 ppm to about 100 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 1,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 3,000 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 500 ppm, about 10 ppm to about 1,000 ppm, about 50 ppm to about 1,000 ppm, or about 25 ppm to about 500 ppm.

[0107] Methods of the present disclosure contemplate adding a composition comprising the corrosion inhibitor compound and the synergist to the medium. Methods also contemplate adding the corrosion inhibitor compound and the synergist separately to the medium. If added together in a composition, the composition may include (or exclude) any solvent disclosed herein. If added separately, the corrosion inhibitor compound and / or the synergist may be added in any solvent disclosed herein.

[0108] Methods disclosed herein may comprise (or exclude) adding one or more additional components to the medium. The additional component(s) may be added before, after, and / or with the corrosion inhibitor compound and / or the synergist. Compositions disclosed herein may comprise (or exclude) one or more additional components (aside from the synergist, corrosion inhibitor compound, and optional solvent).

[0109] Illustrative, non-limiting examples of additional components include a fouling control agent, an additional corrosion inhibitor, a corrosion inhibitor intensifier, a biocide, a preservative, an acid, an anti-emulsifier, an iron chelating agent, a hydrogen sulfide scavenger, a surfactant, an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, a gas hydrate inhibitor, a pH modifier, an emulsion breaker, a reverse emulsion breaker, a coagulant / flocculant agent, an emulsifier, a water clarifier, a dispersant, an antioxidant, a polymer degradation prevention agent, a permeability modifier, a foaming agent, an antifoaming agent, a CO2 scavenger, an O2 scavenger, a gelling agent, a lubricant, a friction reducing agent, a salt, a clay stabilizer, a bactericide, a salt substitute, a relative permeability modifier, a breaker, a fluid loss control additive, an iron control agent, a drag reducing agent, a flow improver, a viscosity reducer, or any combination thereof.

[0110] A hydrate inhibitor may include, for example, a mono-alkyl amide, a di-alkyl amide, an alkyl quaternary ammonium salt, and any combination thereof.

[0111] An asphaltene inhibitor may include, for example, an alkylphenol / formaldehyde resin, a polyisobutylene esters, a polyisobutylene imides, a polyalkyl acrylate, and any combination thereof.

[0112] A paraffin inhibitor may include, for example, a polyalkyl acrylate, an olefin / maleic anhydride polymer, and any combination thereof.

[0113] A biocide may include, for example, glutaraldehyde, tetrakis(hydroxymethyl)phosphonium sulphate, a quaternary ammonium compound, chlorine, hypochlorite, ClO2, bromine, ozone, hydrogen peroxide, peracetic acid, peroxycarboxylic acid, peroxysulphate, dibromonitrilopropionamide, isothiazolone, terbutylazine, polymeric biguanide, methylene bisthiocyanate, and any combination thereof.

[0114] A scale inhibitor may include, for example, a phosphonate, a sulfonate, a phosphate, a phosphate ester, a polymer comprising a phosphonate or phosphonate ester group, a polymeric organic acid, a peroxycarboxylic acid, and any combination thereof. In some embodiments, the scale inhibitor may be selected from a compound comprising an amine and / or a quaternary amine, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), DETA phosphonate, and any combination thereof.

[0115] In some embodiments, the scale inhibitor is an acid-based scale inhibitor, such as phosphonic acid. In some embodiments, the scale inhibitor comprises an anionic group. The anionic group may comprise, for example, a carboxylate group or a sulfate group. In some embodiments, the scale inhibitor may include a phosphorous atom, a phosphorous-oxygen double bond, and / or a phosphono group.

[0116] In some embodiments, the scale inhibitor is selected from the group consisting of hexamethylene diamine tetrakis (methylene phosphonic acid), diethylene triamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), polyacrylic acid (PAA), phosphino carboxylic acid (PPCA), diglycol amine phosphonate (DGA phosphonate), 1-hydroxyethylidene 1,1-diphosphonate (HEDP phosphonate), bisaminoethylether phosphonate (BAEE phosphonate), 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS), and any combination thereof.

[0117] In certain embodiments, the scale inhibitor is a polymer comprising an anionic monomer. The anionic monomer may be selected from, for example, acrylic acid, methacrylic acid, vinyl sulfonic acid, vinyl phosphonic acid, maleic anhydride, itaconic acid, crotonic acid, maleic acid, fumaric acid, styrene sulfonic acid, and any combination thereof.

[0118] The fouling control agent may comprise, for example, a quaternary compound.

[0119] The acid may comprise, for example, hydrochloric acid, hydrofluoric acid, citric acid, formic acid, acetic acid, or any combination thereof.

[0120] The hydrogen sulfide scavenger may comprise, for example, an oxidant, inorganic peroxide, chlorine dioxide, a C1-C10 aldehyde, formaldehyde, glyoxal, glutaraldehyde, acrolein, methacrolein, a triazine, or any combination thereof.

[0121] The additional component may be added to the medium before, after, and / or with the corrosion inhibitor compound and / or the synergist. The amount of additional component added to the medium is not particularly limited. For example, from about 1 ppm to about 5,000 ppm of the additional component may be added to the medium, such as about 1 ppm to about 2,500 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1,500 ppm, about 1 ppm to about 1,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 100 ppm, about 25 ppm to about 5,000 ppm, about 25 ppm to about 2,500 ppm, about 25 ppm to about 1,500 ppm, about 25 ppm to about 1,000 ppm, or about 25 ppm to about 500 ppm.

[0122] If a composition of the present disclosure comprises the additional component, the composition may comprise from, for example, about 0.1 wt. % to about 25 wt. % of the component, such as from about 0.1 wt. % to about 20 wt. %, about 0.1 wt. % to about 15 wt. %, about 0.1 wt. % to about 10 wt. %, about 0.1 wt. % to about 5 wt. %, about 1 wt. % to about 5 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % to about 15 wt. %, about 5 wt. % to about 15 wt. %, or about 5 wt. % to about 20 wt. %.

[0123] The methods, compounds, and compositions disclosed herein may be used in any industrial systems, such as an aqueous industrial system, as well as an industrial system that includes hydrogen-containing mediums and / or carbon dioxide-containing mediums. In some embodiments, the compositions, compounds, and methods of the present disclosure may be used to inhibit corrosion of a metallic surface present in an oil and / or gas production well and / or pipeline.

[0124] The compositions, compounds, and methods disclosed herein can be applied in any industry where it is desirable to inhibit corrosion. For example, a composition can be applied to a gas or liquid produced or used in the production, transportation, storage, and / or separation of crude oil or natural gas.

[0125] The medium in which the compositions and / or compounds of the disclosure are introduced can be contained in and / or exposed to many different types of devices / components. For example, the medium may be contained in an apparatus that transports fluid or gas from one point to another, such as an oil and / or gas pipeline. The device / component may be part of an oil and / or gas refinery, such as a pipeline, a separation vessel, a dehydration unit, or a gas line. The medium may also be contained in and / or exposed to a device / component used in oil extraction and / or production, such as a wellhead.

[0126] In some embodiments, one or more of a pipeline, a heat exchanger, a storage vessel, a flowline, a downhole tubular, a casing, a tank (e.g., railroad tank car or a tank truck / tanker), a separator, or any combination thereof, comprises the metal surface, which contacts the medium.

[0127] In certain embodiments, a subterranean formation and / or a pipeline comprises the metallic surface to be treated by a composition and / or compound of the present disclosure. Certain methods disclosed herein comprise adding a composition and / or compound disclosed herein to a medium that comprises the metallic surface. Alternatively and / or additionally, the methods disclosed herein may comprise applying the composition and / or compound directly to the metallic surface as opposed to, for example, adding to a liquid medium in contact with the metallic surface. In some embodiments, the composition and / or compound may be applied to the interior wall of the pipeline when the interior wall is dry or substantially dry.

[0128] In some embodiments, the pipeline is intended to transport a liquid medium / process fluid, such as an aqueous medium or a medium comprising aqueous and non-aqueous liquids (e.g., an aqueous / hydrocarbon mixture produced from a subterranean reservoir), and the composition and / or compound is applied in the absence of the process fluid. The components of the process fluid may include, for example, water, hydrocarbons, brine, crude oil, refined oil, gas, liquefied natural gas, carbon dioxide, liquid hydrogen, and any combination thereof.

[0129] A medium of the present disclosure may comprise, for example, produced water, fresh water, recycled water, salt water, surface water, condensed water, cooling water, injection water, waste water, geothermal water, sewage water, nuclear cooling water, carbon dioxide, hydrogen, or any mixture thereof.

[0130] An aqueous medium may comprise, for example, water, gas, and / or a liquid hydrocarbon. The liquid hydrocarbon may be any type of liquid hydrocarbon including, but not limited to, crude oil, heavy oil, processed residual oil, bitminous oil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene. The medium may also comprise a refined hydrocarbon product.

[0131] A medium (e.g., a fluid and / or a gas) treated with a composition and / or compound of the present disclosure can be at any selected temperature, such as ambient temperature or an elevated temperature. For example, the medium (e.g., water, liquid hydrocarbon, gas, etc.) may be at a temperature of from about 40° C. to about 250° C. In some embodiments, the medium may be at a temperature of from about −50° C. to about 300° C., about 0° C. to about 200° C., about 10° C. to about 100° C., or about 20° C. to about 90° C.

[0132] The presently disclosed compositions, compounds, and methods are useful for inhibiting corrosion of surfaces comprising any metal or combination of metals. In some aspects, the metal surface comprises steel, such as stainless steel or carbon steel. In some aspects, the metal surface comprises iron, aluminum, zinc, chromium, manganese, nickel, tungsten, molybdenum, titanium, vanadium, cobalt, niobium, or copper. The metal surface may also comprise any combination of the foregoing metals and / or any one or more of boron, phosphorus, sulfur, silicon, oxygen, and nitrogen.

[0133] In some aspects of the present disclosure, a metal surface may comprise metallic-chrome steel, ferritic-alloy steel, austenitic-steel, precipitation-hardened steel, high-nickel steel, carbon steel, or a combination thereof.

[0134] The presently disclosed corrosion inhibitor compounds, compositions, and methods are useful for inhibiting corrosion of metal surfaces in contact with any type of corrodent in the medium, such as a metal cation, a metal complex, a metal chelate, an organometallic complex, an aluminum ion, an ammonium ion, a barium ion, a chromium ion, a cobalt ion, a cuprous ion, a cupric ion, a calcium ion, a ferrous ion, a ferric ion, a hydrogen ion, a magnesium ion, a manganese ion, a molybdenum ion, a nickel ion, a potassium ion, a sodium ion, a strontium ion, a titanium ion, a uranium ion, a vanadium ion, a zinc ion, a bromide ion, a carbonate ion, a chlorate ion, a chloride ion, a chlorite ion, a dithionate ion, a fluoride ion, a hypochlorite ion, an iodide ion, a nitrate ion, a nitrite ion, an oxide ion, a perchlorate ion, a peroxide ion, a phosphate ion, a phosphite ion, a sulfate ion, a sulfide ion, a sulfite ion, a hydrogen carbonate ion, a hydrogen phosphate ion, a hydrogen phosphite ion, a hydrogen sulfate ion, a hydrogen sulfite ion, an acid, such as carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, nitrous acid, sulfurous acid, a peroxy acid, or phosphoric acid, ammonia, bromine, carbon dioxide, chlorine, chlorine dioxide, fluorine, hydrogen chloride, hydrogen sulfide, iodine, nitrogen dioxide, nitrogen monoxide, oxygen, ozone, sulfur dioxide, hydrogen peroxide, a polysaccharide, a metal oxide, sand, a clay, silicon dioxide, titanium dioxide, mud, a brine, an organic acid, an insoluble inorganic and / or organic particulate, an oxidizing agent, a chelating agent, an alcohol, and any combination of the foregoing.

[0135] The compositions and / or compounds disclosed herein may be added to a medium and / or metallic surface using a variety of different application methods known in the art. In some embodiments, the compositions and / or compounds may added continuously or intermittently to the medium, either automatically or manually, by using, for example, chemical injection pumps. In some embodiments, the compounds and / or compositions may be applied to the metal surface, such as an inner wall of a pipeline, using a pig system. For example, a pig system may include a lead pig and a filming pig spaced apart axially from the lead pig to define an application storage space therebetween. The compounds and / or compositions may be located in the application storage space. Once both the lead pig and the filming pig are located in the pipeline, a force may be applied, for example, to the filming pig to move the lead pig and the filming pig in the lateral direction through the pipeline. In certain embodiments, the force is derived from a pressurized fluid, a mechanical actuator, a hydraulic actuator, an air compressor, or any combination thereof.

[0136] The lead pig may, for example, prepare the surface of the pipe by removing residue through mechanical scraping. As the filming pig travels behind the lead pig, it uniformly applies the composition and / or compound in the application storage space to the interior surface of the pipe.

[0137] A method of preparing a pipeline for application of an even layer of the composition and / or compound to the interior surface of the pipeline may include several steps. For example, the method may include inserting the lead pig into the pipe and adding the composition and / or compound to the pipe upstream of the lead pig. Next, the method includes inserting the filming pig into the pipe upstream of the composition and / or compound such that the composition and / or compound is located in the application storage space. Once the lead pig and the filming pig are in place, the method includes applying a force to the filming pig to cause the filming pig and the lead pig to move in the lateral direction through the pipeline. While traveling, the lead pig may clean an interior wall of the pipeline and the filming pig applies the composition and / or compound to the interior wall of the pipeline.

[0138] The lead pig and the filming pig may be added or removed from the pipeline by any means known in the art. For example, the pipeline may have bypass sections, e.g. a pig launch and a pig receiver, in fluid communication with the main pipe in order to launch and receive the lead and filming pigs. The pig launcher may be used to launch the lead pig and the filming pig into the pipe, while the pig receiver may be used to receive the lead pig and the filming pig after moving through the pipeline.

[0139] The pig receiver may include a sensor configured to detect when the lead and filming pigs arrive at the pig receiver section of the pipeline. The pig receiver section may have different valves to control pressurization of the pipeline in order to safely remove the pigs from the pipeline. Once the pigs are removed, the valves may be reopened to return the system to the original condition.

[0140] During application of a composition and / or compound of the present disclosure, a method disclosed herein may include reducing a flow rate of the process fluid within the pipeline while applying the composition. For example, the flow rate may be reduced by about 10% to about 75% of the standard operating flow rate. In some embodiments, the flow rate is reduced by about 15% to about 70%, about 20% to about 65%, about 25% to about 60%, or about 25% to about 50%.

[0141] The compositions and / or compounds disclosed herein can be added to a medium at various levels of water cut. For example, the water cut can be from about 0% to about 100% volume / volume (v / v), from about 1% to about 80% v / v, or from about 1% to about 60% v / v. The medium may be an aqueous medium that contains various levels of salinity. For example, the medium can have a salinity of about 0% to about 25%, about 1% to about 24%, or about 10% to about 25% weight / weight (w / w) total dissolved solids (TDS).

[0142] The foregoing may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the disclosure or its application in any way.EXAMPLES

[0143] Corrosion tests were performed using pre-weighed C1018 mild steel coupons (¼″×7⅜″) with sandblast finish. The coupon was dipped for about 5 seconds in a blend under assessment and allowed to drip for about 10 seconds to allow for excess product to be removed. The coupon was then placed in a vessel containing CO2 saturated fluids of 3% NaCl brine without liquid hydrocarbon and closed. The vessel was then mounted on a wheel in a temperature-controlled cabinet at about 60° C. The wheel was then rotated at about 26 rpm. After 24 hours, and then again at 48 hours and 72 hours, the fluids were replaced with chemical-free brine and ran for a further 24 hours. After the last brine replenishment at 72 hours, the test was continued for a further 24 hours to a total of about 96 hours. After the test, the coupons were removed from the vessel, cleaned, and re-weighed. The corrosion rate was determined by weight loss and the percentage inhibition was determined by comparison to a blank, i.e., a test carried out under otherwise the same conditions but in the absence of any chemical treatment. The results are shown below in Table 1.TABLE 1Corrosion RateSampleChemistry(mpy)% Protection1Blank18.6N / A2Blank19.1N / A31% fatty amine condensate10.644(CAS No. 68910-85-0) Rxnproduct of polyalkylene, talloil fatty acid, and linoleicacid dimer) withdodecylbenzenesulfonic acid(DDBSA) and linoleic aciddimer41% fatty amine condensate10.047(CAS No. 68910-85-0) withDDBSA and linoleic acid dimer51% TOFA:DETA imidazoline11.83761% TOFA:DETA imidazoline12.13671% fatty amine condensate7.859(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% lignin81% fatty amine condensate7.162(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% lignin91% TOFA:DETA imidazoline +8.8530.01% lignin101% TOFA:DETA imidazoline +8.4550.01% lignin111% fatty amine condensate7.759(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% polyanilinegrafted to lignin121% fatty amine condensate7.361(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% lignin131% TOFA:DETA imidazoline +11.9370.01% polyaniline grafted tolignin141% TOFA:DETA imidazoline +11.1420.01% polyaniline grafted tolignin

[0144] Additional corrosion tests were conducted using polyvinyl alcohol as the synergist. The tests were carried out using the following conditions to evaluate the corrosion inhibition performance of the sample on a carbon steel electrode (C1018 grade). The corrosion rate was assessed electrochemically using linear polarization resistance (LPR) methodology. Tests were conducted at about 80° C. with CO2 saturated fluids with 3% NaCl brine (100% brine) with a continuous CO2 sparge at atmospheric pressure. A pre-corrosion time (i.e., with no corrosion inhibitor) was carried out for about 3 hours before the candidate chemical sample (diluted in appropriate solvent) was injected either individually or in combination with another chemistry to achieve the following additions: mercaptoethanol (10 ppm active dose); substituted aromatic amine (10 ppm active dose); dimethyl benzyl ammonium chloride (10 ppm active dose); polyvinyl alcohol (200 ppm active dose); mercaptoethanol (8 ppm active dose)+polyvinyl alcohol (100 ppm active dose); substituted aromatic amine (8 ppm active dose)+polyvinyl alcohol (100 ppm active dose); and dimethyl benzyl ammonium chloride (8 ppm active dose)+polyvinyl alcohol (100 ppm active dose).

[0145] The inhibited corrosion rate at about 15 hours after chemical injection was noted and a percentage inhibition determined by comparing with the corrosion rate of a carbon steel electrode under otherwise the same conditions in the absence of the sample corrosion inhibitor after the same time of exposure to the corrosive environment. The results are shown in Table 2.TABLE 2CandidateCandidateCorrosionCandidateCandidateDosageDosageChemistry #1Chemistry #2RateChemistryChemistryCandidateCandidateActiveActiveAfter 15CandidateCandidate#1#2ChemistryChemistryInjectedInjectedh of ClChemistryChemistryActivityActivity#1#2in Testin TestInjection%#1#2(%)(%)(ppm)(ppm)(ppm)(ppm)(mpy)ProtectionN / AN / AN / AN / AN / AN / AN / AN / A502N / AMercaptoethanolN / A20N / A50N / A10N / A6188SubstitutedN / A20N / A50N / A10N / A38723aromatic amineDimethyl benzylN / A20N / A50N / A10N / A40819ammonium chloridePolyvinyl alcoholN / A100N / A200N / A200N / A25549MercaptoethanolPolyvinyl201004010081004591alcoholSubstitutedPolyvinyl2010040100810026547aromatic aminealcoholDimethyl benzylPolyvinyl2010040100810024651ammonium chloridealcohol

[0146] Additional corrosion tests were conducted using cellulose as the synergist. The tests were carried out using the following conditions to evaluate the corrosion inhibition performance of the sample on a carbon steel electrode (C1018 grade). The corrosion rate was assessed electrochemically using LPR methodology. Tests were conducted at about 80° C. with CO2 saturated fluids with 3% NaCl brine (100% brine) with a continuous CO2 sparge at atmospheric pressure. A pre-corrosion time (i.e., with no corrosion inhibitor) was carried out for about 3 hours before the candidate chemical sample (diluted in appropriate solvent) was injected either individually or in combination with another chemistry to achieve the additions below.

[0147] The inhibited corrosion rate at about 15 hours after chemical injection was noted and a percentage inhibition determined by comparing with the corrosion rate of a carbon steel electrode under otherwise the same conditions in the absence of the sample corrosion inhibitor after the same time of exposure to the corrosive environment. The results are shown in Table 3.TABLE 3Dimethyl benzyl ammonium chlorideN / A20N / A50N / A10N / A40819Polyanionic cellulose (PAC) bondingN / A1.25N / A800N / A10N / A33633chemical 500613-PAC-HVCellulose nanocrystal (CNC) bondingN / A1.25N / A800N / A10N / A44711chemical SF-CNC-PL200 353567 (8.84nm diameter 146 nm length), surfaceion: anion Cotton pulp dissolving pulppreparation method hydrolysis with60% sulfuric acid)Cellulose nanocrystal (CNC) bondingN / A1.25N / A800N / A10N / A34232chemical SF-CNC-PL200-353567 ( .5nm diameter 200 nm length) surfaceion: anion Cotton MCC preparationmethod TEMPO / NaBr / NaClOOxidation)Cellulose nanofiber (CNF) bondingN / A0.125N / A8000N / A10N / A32036chemical C-CNF-PL20-gel 252567 10-20 um diameter 20-30 um length)Coniferous wood bleached kraft pulpsurface modification Cationicmodification of 2,3-epoxypropyltrimethylammoniumchlorided charge density mmol / g 1.09)Cellulose nanofiber (CNF) bondingN / A1.25N / A800N / A10N / A34332chemical TO-CNF-PL20-powder252567 (10-20 um diameter 10-20 umlength) Coniferous wood bleachedkraft pulp surface modificationTEMPO / NaBr / NaClO oxidizedCarboxyl group 1. mmol / g)Sodium carboxymethylcelluloseN / A1.25N / A800N / A10N / A28543Aldrich PCode 1003617057 sourceMKCS48 419273-100 gCellulose acetate Aldrich PcodeN / A1.25N / A800N / A10N / A4321410035673 source MKC57296,18095 -25 g2-hydroxycellulose Aldrich PcodeN / A1.25N / A800N / A10N / A437131003568597 source MKCT0293434965-250 gSubstituted aromatic amineSodium201.25254005525250carboxymethylcelluloseAldrich. PCode 1003617057source MKC 869 4192 3-100 gSubstituted aromatic amineCellulose acetate Aldrich201.25254005537725Pcode 10035673 sourceMKC57296 1809 -25 gSubstituted aromatic amine2-hydroxycellulose Aldrich201.25254005537925Pcode 1003568597 sourceMKCT0293 434965-250 gDimethyl benzyl ammonium chlorideCellulose nanocrystal (CNC)201.25254005540220bonding chemical SF-CNC-PL200 353567 (8. 4 nmdiameter 146 nm length),surface ion: anion, Cottonpulp dissolving pulppreparation method hydrolysiswith 60% sulfuric acid)Dimethyl benzyl ammonium chlorideSodium201.25254005527146carboxymethylcelluloseAldrich PCode 1003517057,source MKCS48 9 419273-100 gDimethyl benzyl ammonium chloride2-hydroxycellulose Aldrich201.25254005535829Pcode 1003568597 sourceMKCT0293 434965-250 g indicates data missing or illegible when filed

[0148] Additional corrosion tests were conducted using gelatin as the synergist. The tests were carried out using the following conditions to evaluate the corrosion inhibition performance of the sample on a carbon steel electrode (C1018 grade). The corrosion rate was assessed electrochemically using LPR methodology. Tests were conducted at about 80° C. with CO2 saturated fluids with 3% NaCl brine (100% brine) with a continuous CO2 sparge at atmospheric pressure. A pre-corrosion time (i.e., with no corrosion inhibitor) was carried out for about 3 hours before the candidate chemical sample (diluted in appropriate solvent) was injected either individually or in combination with another chemistry to achieve the additions below.

[0149] The inhibited corrosion rate at about 15 hours after chemical injection was noted and a percentage inhibition determined by comparing with the corrosion rate of a carbon steel electrode under otherwise the same conditions in the absence of the sample corrosion inhibitor after the same time of exposure to the corrosive environment. The results are shown in Table 4.TABLE 4CandidateCandidateChemistryChemistryCorrosionCandidateCandidateDosageDosage#1#2RateChemistryChemistryCandidateCandidateActiveActiveAfter 15CandidateCandidate#1#2ChemistryChemistryInjectedInjectedh of ClLab BookChemistryChemistryActivityActivity#1#2in Testin TestInjection%Number#1#2(%)(%)(ppm)(ppm)(ppm)(ppm)(mpy)ProtectionBlankN / AN / AN / AN / AN / AN / AN / AN / A502N / AJJM / 10102 / 161AMercaptoethanolN / A20N / A50N / A10N / A6185JJM / 10102 / 161OSubstitutedN / A20N / A50N / A10N / A3572aromatic amineJJM / 10102 / 161EPhosphate esterN / A20N / A50N / A10N / A86 3JJM / 10102 / 161FDimethyl benzylN / A20N / A50N / A10N / A40819ammoniumchlorideJJM / 10102 / 161ZGelatinN / A100N / A200N / A200N / A14272JJM / 10102 / 161A +MercaptoethanolGelatin201004010081001597JJM / 10102 / 161ZJJM / 10102 / 161O +SubstitutedGelatin2010040100810015467JJM / 10102 / 161Zaromatic amineJJM / 10102 / 161E +Phosphate esterGelatin2010040100810088JJM / 10102 / 161ZJJM / 10102 / 161F +Dimethyl benzylGelatin2010040100810013274JJM / 10102 / 161Zammoniumchloride indicates data missing or illegible when filed

[0150] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While this invention may be embodied in many different forms, there are described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, use of the term “a” is intended to include “at least one” or “one or more.” For example, “a corrosion inhibitor compound” is intended to include “at least one corrosion inhibitor compound” or “one or more corrosion inhibitor compounds.”

[0151] Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any definitions used herein are intended to be clarifying and not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges (including all fractional and whole values) subsumed therein.

[0152] Any composition disclosed herein may comprise, consist of, or consist essentially of any element, component and / or ingredient disclosed herein or any combination of two or more of the elements, components or ingredients disclosed herein.

[0153] Any method disclosed herein may comprise, consist of, or consist essentially of any method step disclosed herein or any combination of two or more of the method steps disclosed herein.

[0154] The transitional phrase “comprising,” which is synonymous with “including,”“containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements, components, ingredients and / or method steps.

[0155] The transitional phrase “consisting of” excludes any element, component, ingredient, and / or method step not specified in the claim.

[0156] The transitional phrase “consisting essentially of” limits the scope of a claim to the specified elements, components, ingredients and / or steps, as well as those that do not materially affect the basic and novel characteristic(s) of the claimed invention.

[0157] Unless specified otherwise, all molecular weights referred to herein are weight average molecular weights and all viscosities were measured at 25° C. with neat (not diluted) polymers.

[0158] As used herein, the term “about” refers to the cited value being within the errors arising from the standard deviation found in their respective testing measurements, and if those errors cannot be determined, then “about” may refer to, for example, within 5%, 4%, 3%, 2%, or 1% of the cited value.

[0159] Furthermore, the invention encompasses 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 presently 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. It is therefore intended that such changes and modifications be covered by the appended claims.

Examples

examples

[0143]Corrosion tests were performed using pre-weighed C1018 mild steel coupons (¼″×7⅜″) with sandblast finish. The coupon was dipped for about 5 seconds in a blend under assessment and allowed to drip for about 10 seconds to allow for excess product to be removed. The coupon was then placed in a vessel containing CO2 saturated fluids of 3% NaCl brine without liquid hydrocarbon and closed. The vessel was then mounted on a wheel in a temperature-controlled cabinet at about 60° C. The wheel was then rotated at about 26 rpm. After 24 hours, and then again at 48 hours and 72 hours, the fluids were replaced with chemical-free brine and ran for a further 24 hours. After the last brine replenishment at 72 hours, the test was continued for a further 24 hours to a total of about 96 hours. After the test, the coupons were removed from the vessel, cleaned, and re-weighed. The corrosion rate was determined by weight loss and the percentage inhibition was determined by comparison to a blank, i.e...

TECHNICAL FIELD

[0001] The present disclosure generally relates to corrosion inhibitor compositions and methods of using the compositions to inhibit corrosion. More particularly, the present disclosure relates to corrosion inhibitor compositions comprising a synergist and methods of using the compositions to inhibit corrosion of a metallic surface.BACKGROUND

[0002] Corrosion inhibitors are often added into upstream oil and gas production fluids to protect carbon steel pipelines and infrastructure from corrosion. Oil and gas operators often treat carbon steel pipelines and production tubulars with batch corrosion inhibitor, although continuous injection of the inhibitor into the medium in contact with the metallic surface may also be used. Batch corrosion inhibitor products usually contain oil-soluble chemistries and are directly applied to the pipe / tube walls as a slug of chemical between two spheres, sometimes referred to as pigs, to coat the entire circumference of the interior surface of the wall. The directly applied film formed on the metal surface provides a barrier to the water electrolyte to inhibit corrosion. The frequency of reapplication depends on the severity of the operating environment and frequencies. Typical frequencies range from a few times per year, monthly, or even weekly.

[0003] There are continued research and development efforts across the industry to increase performance and / or decrease dose rates of corrosion inhibitors to not only assist in reducing costs but also to help lessen chemical usage to streamline logistics, reduce chemical handling with the associated health and safety benefits, and reduce the carbon footprint and increase the sustainability of the operations.BRIEF SUMMARY

[0004] The present disclosure provides methods and compositions for inhibiting corrosion of metallic surfaces.

[0005] In some embodiments, a method of inhibiting corrosion of a metal surface in contact with a medium is provided, which comprises adding a corrosion inhibitor compound to the medium, and adding a synergist to the medium, wherein the synergist is selected from the group consisting of a lignin polymer, polyvinyl alcohol, cellulose, gelatin, and any combination thereof.

[0006] A composition provided by the present disclosure may comprise a corrosion inhibitor compound and a synergist, wherein the synergist is selected from the group consisting of a lignin polymer, polyvinyl alcohol, cellulose, gelatin, and any combination thereof.

[0007] The present disclosure also provides a metal surface comprising any composition disclosed herein.

[0008] The foregoing has outlined rather broadly the features and technical advantages of the present disclosure in order that the detailed description that follows may be better understood. Additional features and advantages of the disclosure will be described hereinafter that form the subject of the claims of this application. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present disclosure. It should also be realized by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the disclosure as set forth in the appended claims.DETAILED DESCRIPTION

[0009] Various embodiments are described below. The relationship and functioning of the various elements of the embodiments will be better understood in light of the following detailed description. However, elements and embodiments are not strictly limited to those explicitly described below.

[0010] Examples of methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents and other reference materials mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.

[0011] 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 conflict, the present document, including definitions, will control.

[0012] Unless otherwise indicated, an alkyl group as described herein alone or as part of another group is an optionally substituted linear or branched saturated monovalent hydrocarbon substituent containing from, for example, one to about sixty carbon atoms, such as one to about thirty carbon atoms, in the main chain. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, and the like.

[0013] The terms “aryl” or “ar” as used herein alone or as part of another group (e.g., arylene) denote optionally substituted homocyclic aromatic groups, such as monocyclic or bicyclic groups containing from about 6 to about 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. The term “aryl” also includes heteroaryl functional groups. It is understood that the term “aryl” applies to cyclic substituents that are planar and comprise 4n+2 electrons, according to Huckel's Rule.

[0014] “Cycloalkyl” refers to a cyclic alkyl substituent containing from, for example, about 3 to about 8 carbon atoms, preferably from about 4 to about 7 carbon atoms, and more preferably from about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The cyclic alkyl groups may be unsubstituted or further substituted with alkyl groups, such as methyl groups, ethyl groups, and the like.

[0015] “Heteroaryl” refers to a monocyclic or bicyclic 5- or 6-membered ring system, wherein the heteroaryl group is unsaturated and satisfies Huckel's rule. Non-limiting examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, 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, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, quinazolinyl, and the like.

[0016] Compounds of the present disclosure may be substituted with suitable substituents. The term “suitable substituent,” as used herein, is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the compounds. Such suitable substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoro-alkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO—(C═O)— groups, heterocylic groups, cycloalkyl groups, amino groups, alkyl- and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylamino carbonyl groups, arylcarbonyl groups, aryloxy-carbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, suitable substituents may include halogen, an unsubstituted C1-C12 alkyl group, an unsubstituted C4-C6 aryl group, or an unsubstituted C1-C10 alkoxy group. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.

[0017] The term “substituted” as in “substituted alkyl,” means that in the group in question (e.g., the alkyl group), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups, such as hydroxy (—OH), alkylthio, phosphino, amido (—CON(RA)(RB), wherein RA and RB are independently hydrogen, alkyl, or aryl), amino (—N(RA)(RB), wherein RA and RB are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (—NO2), an ether (—ORA wherein RA is alkyl or aryl), an ester (—OC(O)RA wherein RA is alkyl or aryl), keto (—C(O)RA wherein RA is alkyl or aryl), heterocyclo, and the like.

[0018] When the term “substituted” introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase “optionally substituted alkyl or aryl” is to be interpreted as “optionally substituted alkyl or optionally substituted aryl.”

[0019] The terms “polymer,”“copolymer,”“polymerize,”“copolymerize,” and the like include not only polymers comprising two monomer residues and polymerization of two different monomers together, but also include (co) polymers comprising more than two monomer residues and polymerizing together more than two or more other monomers. For example, a polymer as disclosed herein includes a terpolymer, a tetrapolymer, polymers comprising more than four different monomers, as well as polymers comprising, consisting of, or consisting essentially of two different monomer residues. Additionally, a “polymer” as disclosed herein may also include a homopolymer, which is a polymer comprising a single type of monomer unit.

[0020] Unless specified differently, the polymers of the present disclosure may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, and / or functionally modified. A polymer of the present disclosure can be in the form of a solution, a dry powder, a liquid, or a dispersion, for example.

[0021] “Aqueous system” refers to any system containing one or more metallic surfaces / components, which are in contact with an aqueous medium (e.g., water) on a periodic or continuous basis.

[0022] “Aqueous industrial system” means any system that circulates an aqueous medium or a medium including water as a component. Non-limiting examples of “industrial aqueous systems” include cooling systems, boiler systems, heating systems, membrane systems, food and beverage systems, oil and gas systems, and any other system that circulates or includes water.

[0023] The present disclosure relates to corrosion inhibitor compounds, compositions, methods of inhibiting corrosion, and formulations useful for inhibiting corrosion. Inhibiting corrosion includes, for example, reducing corrosion, completely eliminating corrosion or prohibiting corrosion from occurring for some period of time, lowering a rate of corrosion, etc.

[0024] The technology disclosed herein effectively enhances corrosion inhibitor performance and leads to film persistency / increased lifetime of the applied film.

[0025] A composition of the present disclosure comprises a corrosion inhibitor compound and a synergist. In certain embodiments, a composition of the present disclosure consists of or consists essentially of a corrosion inhibitor compound, a synergist, and optionally a solvent and / or an additional component, as defined further below.

[0026] Illustrative, non-limiting examples of corrosion inhibitor compounds include an organic sulfur compound, an imidazoline, a carboxylic acid-containing compound, a fatty acid amine condensate, a substituted fatty acid ester, a substituted aromatic amine, a phosphoric acid ester, a quaternary ammonium compound, or a compound comprising multiple positive charges.

[0027] In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of, an imidazoline compound, a quaternary amine, a synergist, and optionally a solvent.

[0028] The imidazoline compound may have formula (I), (II), or (III):wherein R1, R4, and R5 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle, said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle each independently, at each occurrence, unsubstituted or substituted with 1 to 3 substituents independently selected from halogen, —COR6, —CO2R7, —SO3R8, —PO3H2, —CON(R9)(R10), —OR11, and —N(R12)(R13);

[0030] R2 is a radical derived from a fatty acid;

[0031] R3 and Rx are each independently selected from a radical derived from an unsaturated acid;

[0032] R6, R7, R8, R9, R10, and R11 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;

[0033] R12 and R13 are each independently, at each occurrence, selected from hydrogen, alkyl, —COR14, —CO2R15, -alkyl-COR16, and -alkyl-CO2R17; and

[0034] R14, R15, R16, and R17 are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

[0035] In the foregoing imidazolines, R groups of carboxylic acid moieties can be absent where the R═H and the carboxylic acid moiety is deprotonated. For example, R15 and / or R17 can be absent where the R12 and / or R13 is a deprotonated carboxylic acid moiety (e.g., where R12 is —CH2CH2CO2−). For an imidazoline compound, R1 can be unsubstituted alkyl. For example, R1 can be unsubstituted C1-C10-alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (e.g., n-pentyl, isopentyl, tert-pentyl, neopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl, or decyl). Further, R1 can be unsubstituted C2-C10-alkyl. For the imidazoline compounds, R1 can be unsubstituted C2-C8-alkyl. Further, R1 can be unsubstituted C2-C6-alkyl. In some embodiments, R1 is propyl, butyl, or hexyl.

[0036] In some embodiments, R1 is a substituted alkyl. For example, R1 may be a substituted C1-C10-alkyl, substituted C2-C10-alkyl, substituted C2-C8-alkyl, or substituted C2-C6-alkyl. Further, R1 may be a C1-C10-alkyl, C2-C10-alkyl, C2-C8-alkyl, or C2-C6-alkyl, substituted with one substituent selected from —COR6, —CO2R7, —SO3R8, —PO3H2, —CON(R9)(R10), —OR11, and —N(R12)(R13), wherein R6, R7, R8, R9, R10, R11, R12, and R13 are as defined above. More specifically, R1 may be a C2-C6-alkyl, substituted with one substituent selected from —N(R12)(R13), wherein R12 and R13 are each independently selected from hydrogen, alkyl, —COR14, —CO2R15, -alkyl-COR16, and -alkyl-CO2R17, wherein R14, R15, R16, and R17 are as defined above. Further, R1 may be a C2-C6-alkyl, substituted with one substituent selected from —N(R12)(R13), wherein R12 and R13 are each independently selected from hydrogen, C2-C6-alkyl, —COR14, —CO2R15, —C2-C6-alkyl-COR16, and —C2-C6-alkyl-CO2R17, wherein R14, R15, R16, and R17 are selected from hydrogen and C1-C34-alkyl. For these imidazolines, R1 may be a linear C2-C6-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each independently selected from hydrogen, —COR14, —CO2R15, —C2-C6-alkyl-COR16, and —C2-C6-alkyl-CO2R17, wherein R14, R15, R16, and R17 are selected from hydrogen and C1-C34-alkyl. For example, R1 may be a linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14, wherein R14 is —C17H35, —C17H33, or —C17H31. Further, R1 may be a linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen.

[0037] For the imidazolines of formulae (I), (II), and (III), R2 may be a C4-C34-alkyl or C4-C34-alkenyl. For example, R2 may be a —(CH2)3CH3; —(CH2)4CH3; —(CH2)5CH3; —(CH2)6CH3; —(CH2)7CH3; —(CH2)8CH3; —(CH2)9CH3; —(CH2)10CH3; —(CH2)11CH3; —(CH2)12CH3; —(CH2)13CH3; —(CH2)14CH3; —(CH2)15CH3; —(CH2)16CH3; —(CH2)17CH3; —(CH2)18CH3; —(CH2)19CH3; —(CH2)20CH3; —(CH2)21CH3; —(CH2)22CH3; —(CH2)23CH3; —(CH2)24CH3; —(CH2)25CH3; —(CH2)26CH3; —(CH2)27CH3; —(CH2)28CH3; —(CH2)29CH3; —(CH2)30CH3; —(CH2)31CH3; —(CH2)32CH3; —(CH2)33CH3; —(CH2)34CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CH(CH2)7CH3; —(CH2)3CH═CHCH2CH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CH(CH2)4CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)3CH═CHCH═CHCH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)4CH═CH(CH2)8CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CHs; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)6CH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)6CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CH(CH2)3CH3; —(CH2)7CH═CH(CH2)5CH3; —(CH2)7CH═CH(CH2)7CH3; —(CH2)7CH═CHCH═CHCH═CH(CH2)3CH3; —(CH2)7CH═CHCH═CH(CH2)5CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH═CHCH2CH2CH═CHCH2CH3; —(CH2)7CH═CHCH═CHCH═CHCH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)5CH3; —(CH2)9CH═CHCH2CH═CH(CH2)4CH3; —(CH2)9CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)7CH3; —(CH2)11CH═CH(CH2)5CH3; —(CH2)11CH═CH(CH2)7CH3; —(CH2)11CH═CHCH2CH═CH(CH2)4CH3; or —(CH2)13CH═CH(CH2)7CH3.

[0038] In some embodiments, R2 may be a radical derived from a saturated or unsaturated fatty acid. Suitable saturated fatty acids include, but are not limited to, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, pentacosylic acid, cerotic acid, heptacosylic acid, montanic acid, nonacosylic acid, melissic acid, henatriacontylic acid, lacceroic acid, psyllic acid, geddic acid, ceroplastic acid, and hexatriacontylic acid.

[0039] Suitable unsaturated fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, hexadecatrienoic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, heneicosapentaenoic acid, clupanodonic acid, osbond acid, (9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoic acid, nisinic acid, γ-linolenic acid, eicosadienoic acid, dihomo-γ-linolenic acid, docosadienoic acid, adrenic acid, tetracosatetraenoic acid, (6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid, (Z)-Eicos-11-enoic acid, mead acid, erucic acid, nervonic acid, rumenic acid, α-calendic acid, β-calendic acid, jacaric acid, α-eleostearic acid, β-eleostearic acid, catalpic acid, punicic acid, rumelenic acid, α-parinaric acid, β-parinaric acid, bosseopentaenoic acid, pinolenic acid, and podocarpic acid.

[0040] In some embodiments, R2 is derived from coconut oil, beef tallow, or tall oil fatty acids (TOFA).

[0041] In some embodiments, R3 may be —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and alkyl, and wherein Re is hydrogen (—H) or alkyl. For example, R3 may be —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and C1-C6-alkyl, and wherein Re is hydrogen (—H) or C1-C6-alkyl. Further, R3 may be —CH2CH2CO2Re, wherein Re is hydrogen (—H) or C1-C6-alkyl. Additionally, Re can be absent where the R3 is a deprotonated carboxylic acid moiety (e.g., where R3 is —CH2CH2CO2—).

[0042] In accordance with certain embodiments of the present disclosure, R3 can be derived from an acrylic acid. Suitable acrylic acids include, but are not limited to, acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-(trifluoromethyl)acrylic acid. For example, R3 can be derived from acrylic acid (H2C═CHCO2H).

[0043] Imidazolines of formulae (I), (II), or (III) may have Rx equal to —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and alkyl, and wherein Re is hydrogen (—H) or alkyl. Further, Rx can be —C(RaRb)—C(RcRd)—CO2Re, wherein Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen (—H), halogen, and C1-C6-alkyl, and wherein Re is hydrogen (—H) or C1-C6-alkyl. Additionally, Rx may be —CH2CH2CO2Re, wherein Re is hydrogen (—H) or C1-C6-alkyl. Further, Re can be absent where the Rx is a deprotonated carboxylic acid moiety (e.g., where Rx is —CH2CH2CO2—).

[0044] For the imidazolines described herein, Rx can be derived from an acrylic acid. Suitable acrylic acids include, but are not limited to, acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-(trifluoromethyl)acrylic acid. For example, Rx can be derived from acrylic acid (H2C═CHCO2H).

[0045] Imidazolines of formulae (I), (II), or (III) can have R4 and R5 each independently be an unsubstituted C1-C10-alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (e.g., n-pentyl, isopentyl, tert-pentyl, neopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl, or decyl) or hydrogen. Further, R4 and R5 can each independently be an unsubstituted C1-C6 alkyl group or hydrogen. In some embodiments, R4 and R5 are each hydrogen (—H).

[0046] Imidazolines of formulae (I), (II), or (III) can have R6, R7, R8, R9, R10, and R11 each independently be, at each occurrence, selected from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. For example, R6, R7, R8, R9, R10, and R11 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C34-alkyl, and unsubstituted C2-C34-alkenyl. Further, R6, R7, R8, R9, R10, and R11 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C10-alkyl, and unsubstituted C2-C10-alkenyl. Further, R6, R7, R8, R9, R10, and R11 can each independently be, at each occurrence, selected from hydrogen, and a radical derived from a fatty acid.

[0047] R12 and R13 can each independently be, at each occurrence, selected from hydrogen, C1-C10-alkyl, —COR14, —CO2R15, —C1-C10-alkyl-COR16, and —C1-C10-alkyl-CO2R17. Further, R12 and R13 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C10-alkyl, —COR14, —CO2R15, —C1-C10-alkyl-COR16, and —C1-C10-alkyl-CO2R17.

[0048] R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. Further, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C34-alkyl, and unsubstituted C2-C34-alkenyl. Additionally, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, unsubstituted C1-C10-alkyl, and unsubstituted C2-C10-alkenyl. Further, R15 and / or R17 can be absent where the carboxylic acid moiety is deprotonated.

[0049] Imidazoline compounds of the present disclosure can have R14, R15, R16, and R17 each independently be, at each occurrence, selected from hydrogen, and a radical derived from a fatty acid. Further, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, C4-C34-alkyl, and C4-C34-alkenyl. Additionally, R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen; —(CH2)3CH3; —(CH2)4CH3; —(CH2)5CH3; —(CH2)6CH3; —(CH2)7CH3; —(CH2)8CH3; —(CH2)9CH3; —(CH2)10CH3; —(CH2)11CH3; —(CH2)12CH3; —(CH2)13CH3; —(CH2)14CH3; —(CH2)15CH3; —(CH2)16CH3; —(CH2)17CH3; —(CH2)18CH3; —(CH2)19CH3; —(CH2)20CH3; —(CH2)21CH3; —(CH2)22CH3; —(CH2)23CH3; —(CH2)24CH3; —(CH2)25CH3; —(CH2)26CH3; —(CH2)27CH3; —(CH2)28CH3; —(CH2)29CH3; —(CH2)30CH3; —(CH2)31CH3; —(CH2)32CH3; —(CH2)33CH3; —(CH2)34CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CH(CH2)7CH3; —(CH2)3CH═CHCH2CH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CH(CH2)4CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)3CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)3CH═CHCH═CHCH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)4CH═CH(CH2)8CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)4CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2 CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)5CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)6CH═CHCH═CHCH═CH(CH2)4CH3; —(CH2)6CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CH(CH2)3CH3; —(CH2)7CH═CH(CH2)5CH3; —(CH2)7CH═CH(CH2)7CH3; —(CH2)7CH═CHCH═CHCH═CH(CH2)3CH3; —(CH2)7CH═CHCH═CH(CH2)5CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH═CHCH2CH2CH═CHCH2CH3; —(CH2)7CH═CHCH═CHCH═CHCH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CH(CH2)4CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)7CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)5CH3; —(CH2)9CH═CHCH2CH═CH(CH2)4CH3; —(CH2)9CH═CHCH2CH═CHCH2CH═CHCH2CH3; —(CH2)9CH═CH(CH2)7CH3; —(CH2)11CH═CH(CH2)5CH3; —(CH2)11CH═CH(CH2)7CH3; —(CH2)11CH═CHCH2CH═CH(CH2)4CH3; and —(CH2)13CH═CH(CH2)7CH3.

[0050] For the imidazolines of formulae (I), (II), and (III), R14, R15, R16, and R17 can each independently be, at each occurrence, selected from hydrogen, a radical derived from a saturated fatty acid, and a radical derived from an unsaturated fatty acid. Suitable saturated fatty acids include, but are not limited to, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, pentacosylic acid, cerotic acid, heptacosylic acid, montanic acid, nonacosylic acid, melissic acid, henatriacontylic acid, lacceroic acid, psyllic acid, geddic acid, ceroplastic acid, and hexatriacontylic acid.

[0051] Suitable unsaturated fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, hexadecatrienoic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, heneicosapentaenoic acid, clupanodonic acid, osbond acid, (9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoic acid, nisinic acid, γ-linolenic acid, eicosadienoic acid, dihomo-γ-linolenic acid, docosadienoic acid, adrenic acid, tetracosatetraenoic acid, (6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid, (Z)-Eicos-11-enoic acid, mead acid, erucic acid, nervonic acid, rumenic acid, α-calendic acid, β-calendic acid, jacaric acid, α-eleostearic acid, β-eleostearic acid, catalpic acid, punicic acid, rumelenic acid, α-parinaric acid, β-parinaric acid, bosseopentaenoic acid, pinolenic acid, and podocarpic acid.

[0052] Further, R14, R15, R16, and R17 are each independently, at each occurrence, hydrogen or a radical derived from coconut oil, beef tallow, or tall oil fatty acids (TOFA).

[0053] In some embodiments, the imidazoline is a compound of formula (I), wherein R1 is unsubstituted C2-C6-alkyl; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0054] In some embodiments, the imidazoline is a compound of formula (I), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14 wherein R14 is —C17H35, —C17H33, or —C17H31; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0055] In certain embodiments, the imidazoline is a compound of formula (I), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen or is absent (e.g., R12 is —C2-alkyl-CO2—); R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0056] In some embodiments, the imidazoline is a compound of formula (II), wherein R1 is unsubstituted C2-C6-alkyl; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); Rx is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., Rx is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0057] In some embodiments, the imidazoline is a compound of formula (II), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14, wherein R14 is —C17H35, —C17H33, or —C17H31; R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); Rx is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., Rx is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0058] In certain embodiments, the imidazoline can be a compound of formula (II), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen or is absent (e.g., R12 is —C2-alkyl-CO2—); R2 is —C17H35, —C17H33, or —C17H31; R3 is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., R3 is —CH2CH2CO2—); Rx is —CH2CH2CO2Re, wherein Re is hydrogen (—H), C1-C6-alkyl, or Re is absent (e.g., Rx is —CH2CH2CO2—); R4 is hydrogen; and R5 is hydrogen.

[0059] In some embodiments, the imidazoline can be a compound of formula (III), wherein R1 is unsubstituted C2-C6-alkyl; R2 is —C17H35, —C17H33, or —C17H31; R4 is hydrogen; and R5 is hydrogen.

[0060] In some embodiments, the imidazoline can be a compound of formula (III), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 is hydrogen and R13 is —COR14, wherein R14 is —C17H35, —C17H33, or —C17H31; R2 is —C17H35, —C17H33, or —C17H31; R4 is hydrogen; and R5 is hydrogen.

[0061] In certain embodiments, the imidazoline can be a compound of formula (III), wherein R1 is linear C2-alkyl, substituted with one substituent that is a terminal —N(R12)(R13), wherein R12 and R13 are each a —C2-alkyl-CO2R17, wherein R17 is hydrogen or is absent (e.g., R12 is —C2-alkyl-CO2—); R2 is —C17H35, —C17H33, or —C17H31; R4 is hydrogen; and R5 is hydrogen.

[0062] It is to be understood, whether explicitly set forth or not, that formula (I), formula (II), and formula (III) are each intended to encompass the tautomeric, racemic, enantiomeric, diastereomeric, zwitterionic, and salt forms of said formulas. The imidazolines can exist in a zwitterionic form where R3 and / or Rx is derived from an acrylic acid.

[0063] In accordance with the present disclosure, the corrosion inhibitor compound may be a quaternary amine. Suitable quaternary amines include, but are not limited to, alkyl, hydroxyalkyl, alkylaryl, arylalkyl or arylamine quaternary salts.

[0064] Suitable alkyl, hydroxyalkyl, alkylaryl arylalkyl or arylamine quaternary salts include those alkylaryl, arylalkyl and arylamine quaternary salts of the formula [N+R5aR6aR7aR8a][X−] wherein R5a, R6a, R7a, and R8a contain one to 18 carbon atoms, and X is Cl, Br or I. For the quaternary amine, R5a, R6a, R7a, and R8a can each independently be selected from the group consisting of alkyl (e.g., C1-C18 alkyl), hydroxyalkyl (e.g., C1-C18 hydroxyalkyl), and arylalkyl (e.g., benzyl). The mono or polycyclic aromatic amine salt with an alkyl or alkylaryl halide include salts of the formula [N+R5aR6aR7aR8a][X−] wherein R5a, R6a, R7a, and R8a contain one to 18 carbon atoms, and X is Cl, Br or I.

[0065] Suitable quaternary ammonium salts include, but are not limited to, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammonium chloride, tetraoctyl ammonium chloride, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammonium chloride, phenyltriethyl ammonium chloride, cetyl benzyldimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dimethyl alkyl benzyl quaternary ammonium compounds, monomethyl dialkyl benzyl quaternary ammonium compounds, trimethyl benzyl quaternary ammonium compounds, and trialkyl benzyl quaternary ammonium compounds, wherein the alkyl group can contain between about 1 and about 24 carbon atoms, about 10 and about 18 carbon atoms, or about 12 to about 16 carbon atoms, such as for example, C12-16 benzyl dimethyl ammonium chloride. Suitable quaternary ammonium compounds (quats) include, but are not limited to, trialkyl, dialkyl, dialkoxy alkyl, monoalkoxy, benzyl, and imidazolinium quaternary ammonium compounds, salts thereof, the like, and combinations thereof. The quaternary ammonium salt can be an alkylamine benzyl quaternary ammonium salt, a benzyl triethanolamine quaternary ammonium salt, or a benzyl dimethylaminoethanolamine quaternary ammonium salt.

[0066] The quaternary amine can be a benzalkonium salt represented by the formula:wherein n is 8, 10, 12, 14, 16, or 18; and X is Cl, Br or I.The quaternary amine can be a mixture of benzalkonium salts wherein n is 8, 10, 12, 14, 16, and 18.

[0068] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, 16, and 18.

[0069] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, and 16.

[0070] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, 16, and 18 and X is Cl.

[0071] The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, and 16, and X is Cl.

[0072] The quaternary amine can be an alkyl pyridinium quaternary salt such as those represented by the general formula:wherein R9a is an alkyl group, an aryl group, or an arylalkyl group, wherein said alkyl groups have from 1 to about 18 carbon atoms and B is Cl, Br or I.Among these compounds are alkyl pyridinium salts and alkyl pyridinium benzyl quats. Examples include methyl pyridinium chloride, ethyl pyridinium chloride, propyl pyridinium chloride, butyl pyridinium chloride, octyl pyridinium chloride, decyl pyridinium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzyl pyridinium and an alkyl benzyl pyridinium chloride. In some embodiments, the alkyl is a C1-C6 hydrocarbyl group.

[0074] The compositions disclosed herein include a phosphonium compound, such as a phosphonium salt. Suitable phosphonium salts include, but are not limited to, alkyltris(hydroxyorgano)phosphonium salts, alkenyltris(hydroxyorgano)phosphonium salts, and tetrakis(hydroxyorgano)phosphonium salts. The alkyltris(hydroxyorgano)phosphonium salts can be C1-C3-alkyltris(hydroxymethyl)phosphonium salts. The alkenyltris(hydroxyorgano)phosphonium salts can be C2-C3-alkenyltris(hydroxymethyl)phosphonium salts. The tetrakis(hydroxyorgano)phosphonium salts can be tetrakis(hydroxymethyl)phosphonium salts, including, but not limited to, tetrakis(hydroxymethyl)phosphonium sulphate (THPS), tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis(hydroxymethyl)phosphonium formate, tetrakis(hydroxymethyl)phosphonium acetate, and tetrakis(hydroxymethyl)phosphonium oxalate. In some embodiments, the phosphonium salt is THPS.

[0075] The compound comprising multiple positive charges may be derived from a polyamine through its reactions with an activated olefin and an epoxide, wherein the activated olefin has the following formula:wherein X is NH or O; R2 is H, CH3, or an unsubstituted, linear or branched C2-C10 alkyl, alkenyl, or alkynyl group; R3 is absent or an unsubstituted, linear C1-C30 alkylene group; Y is —NR4R5R6(+); R4, R5, and R6 are independently a C1-C10 alkyl group; wherein the epoxide has the following formula;R7 is H or alkyl; and R8 is alkyl, or —(CH2)k—O-alkyl, wherein k is an integer of 1-30; wherein the polyamine and activated olefin undergo aza Michael Addition reaction and the polyamine and epoxide undergo ring opening reaction. In some embodiments, the compound comprises a nonionic group.In some embodiments, the compound has one of the generic formula of NA2-[R10′]n-NA2, (RNA)n-RNA2, NA2-(RNA)n-RNA2, or NA2-(RN(R′))n—RNA2, wherein R10′ is a linear or branched, unsubstituted or substituted C2-C10 alkylene group, or combination thereof; R is —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)CH2—, a linear or branched, unsubstituted or substituted C4-C10 alkylene group, or combination thereof; R′ is —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)CH2—, a linear or branched, unsubstituted or substituted C4-C10 alkyl group, RNAB, RNARNAB, or RN(RNAB)2; n can be from 2 to 1,000,000; A is a combination of H,wherein X is NH or O; R2 is H, CH3, or an unsubstituted, linear or branched C2-C10 alkyl, alkenyl, or alkynyl group; R3 is absent or an unsubstituted, linear C1-C30 alkylene group; Y is —NR4R5R6(+); R4, R5, and R6 are independently a C1-C10 alkyl group; R7 is H or alkyl; and R8 is alkyl, or —(CH2)k—O-alkyl, wherein k is an integer of 1-30.The compound may be a multiple charged cationic compound having aIn some aspects, the treatment chemical can be 2-mercaptoethanol, a diethylenetriamine (DETA): tall oil fatty acid (TOFA) imidazoline, a reaction product of trimethylamine (TEA) and TOFA, a reaction product of TOFA and tetraethylenepentamine (TEPA), an alkyl pyridine, an ethoxylated branched nonylphenol phosphate ester, a benzyl-(C12 to C18 linear alkyl)-dimethylammonium chloride, 5-carboxy-4-hexyl-2-cyclohexene octanoic acid, 6-carboxy-4-hexyl-2-cyclohexene octanoic acid, maleated TOFA, an acrylated DETA:TOFA imidazoline, and any combination thereof.In some embodiments, the corrosion inhibitor may be selected from, for example, benzyl ammonium chloride, acrylated imidazoline, 2-mercaptoethanol, a quaternary ammonium compound, a phosphate ester, a substituted aromatic amine, an alkyl pyridine, a fatty acid amine condensate, and any combination thereof.In certain embodiments, the corrosion inhibitor compound comprises an amine compound, a polyamine compound, a thiol-containing compound, a carboxylic acid, a dicarboxylic acid, mercaptoethanol, a maleated compound, an aromatic amine compound, a phosphate ester, a quaternary ammonium compound, an imidazoline compound, or any combination thereof.The polyamine compound comprises, for example, a diamine compound, a triamine compound, and / or a quaternary ammonium compound.Illustrative, non-limiting examples of diamines include 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. Illustrative, non-limiting examples of triamines include coco-amine acetate, N-dodecyl-1,3-propanediamine and bis(3-aminopropyl) dodecylamine.

[0082] The amount of corrosion inhibitor compound in a composition is not particularly limited. For example, a composition may comprise from about 1 wt. % to about 99 wt. % of the corrosion inhibitor compound, such as from about 5 wt. % to about 99 wt. %, about 15 wt. % to about 99 wt. %, about 25 wt. % to about 99 wt. %, about 35 wt. % to about 99 wt. %, about 45 wt. % to about 99 wt. %, about 55 wt. % to about 99 wt. %, about 65 wt. % to about 99 wt. %, about 75 wt. % to about 99 wt. %, about 85 wt. % to about 99 wt. %, about 95 wt. % to about 99 wt. %, about 5 wt. % to about 90 wt. %, about 5 wt. % to about 80 wt. %, about 5 wt. % to about 70 wt. %, about 5 wt. % to about 60 wt. %, about 5 wt. % to about 50 wt. %, about 5 wt. % to about 40 wt. %, about 5 wt. % to about 30 wt. %, about 5 wt. % to about 20 wt. %, about 5 wt. % to about 10 wt. %, about 10 wt. % to about 90 wt. %, about 20 wt. % to about 80 wt. %, about 30 wt. % to about 70 wt. %, or about 40 wt. % to about 60 wt. %.

[0083] The synergist of the present disclosure may be selected from, for example, a lignin polymer, polyvinyl alcohol, cellulose, gelatin, or any combination thereof.

[0084] Lignins comprise phenylpropanoid alcohols (typically coniferyl, sinapyl, and coumaryl alcohols) with hydroxyl, methoxyl, and / or carbonyl functional groups. For example, a lignin polymer may comprise phenyl propane units, which are formed from hydroxyl- and methoxy-substituted phenylpropane units. Lignins are a type of hydrocarbon polymer including aliphatic and / or aromatic structures and may include both guaiacyl lignins and guaiacyl-syringyl lignins. In some embodiments, a lignin polymer may comprise one or more monomer units selected from coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol. The amount / mol % of each monomer in the polymer may vary depending on the source of the lignin, for example.

[0085] The weight average molecular weight of the lignin polymer is also variable from about 1,000 Da to about 100,000 Da, such as from about 1,000 Da to about 80,000 Da, about 1,000 Da to about 60,000 Da, about 1,000 Da to about 40,000 Da, about 1,000 Da to about 20,000 Da, about 1,000 Da to about 10,000 Da, about 1,000 Da to about 5,000 Da, about 5,000 Da to about 100,000 Da, about 10,000 Da to about 100,000 Da, about 20,000 Da to about 100,000 Da, about 30,000 Da to about 100,000 Da, about 40,000 Da to about 100,000 Da, about 50,000 Da to about 100,000 Da, about 60,000 Da to about 100,000 Da, about 5,000 Da to about 50,000 Da, about 10,000 Da to about 40,000, or about 20,000 Da to about 30,000 Da.

[0086] Polyvinyl alcohol is a water-soluble synthetic polymer having the general formula [CH2CH(OH)]n. The “n” variable is not particularly limited and may be selected from about 1 to about 10,000, such as from about 1 to about 8,000, about 1 to about 6,000, about 1 to about 4,000, about 1 to about 2,000, about 1 to about 1,000, about 1 to about 800, about 1 to about 600, about 1 to about 400, about 100 to about 10,000, about 200 to about 10,000, about 400 to about 10,000, about 600 to about 10,000, about 800 to about 10,000, about 1,000 to about 10,000, about 2,000 to about 10,000, about 4,000 to about 10,000, about 6,000 to about 10,000, about 400 to about 8,000, about 600 to about 7,000, or about 700 to about 6,000.

[0087] The polyvinyl alcohol polymer can have any molecular weight, such as about 10,000 Da to about 500,000 Da, about 20,000 Da to about 500,000 Da, about 30,000 Da to about 500,000 Da, about 40,000 Da to about 500,000 Da, about 50,000 Da to about 500,000 Da, about 60,000 Da to about 500,000 Da, about 70,000 Da to about 500,000 Da, about 80,000 Da to about 500,000 Da, about 90,000 Da to about 500,000 Da, about 100,000 Da to about 500,000 Da, about 200,000 Da to about 500,000 Da, about 300,000 Da to about 500,000 Da, about 10,000 Da to about 300,000 Da, about 10,000 Da to about 100,000 Da, about 10,000 Da to about 80,000 Da, about 10,000 Da to about 60,000 Da, about 20,000 Da to about 300,000 Da, or about 30,000 Da to about 200,000 Da.

[0088] Any type of cellulose may be utilized as a synergist in accordance with the present disclosure. For example, the cellulose may be selected from macrocellulose, microcellulose, nanocellulose, or any combination thereof.

[0089] Gelatin is understood to be a collection of peptides and proteins produced by partial hydrolysis of collagen extracted from the skin, bones, and / or connective tissues of animals, such as cattle, chickens, pigs, and fish.

[0090] The amount of synergist in the composition is not particularly limited. For example, the composition may comprise from about 0.1 wt. % to about 25 wt. % of the synergist, such as from about 0.1 wt. % to about 20 wt. %, about 0.1 wt. % to about 15 wt. %, about 0.1 wt. % to about 10 wt. %, about 0.1 wt. % to about 5 wt. %, about 0.1 wt. % to about 1 wt. %, about 1 wt. % to about 20 wt. %, about 5 wt. % to about 20 wt. %, about 10 wt. % to about 20 wt. %, about 15 wt. % to about 20 wt. %, about 0.5 wt. % to about 10 wt. %, about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. %.

[0091] In some embodiments, a composition may comprise from about 0.5 wt. % to about 5 wt. % of the corrosion inhibitor compound and from about 0.005 wt. % to about 0.1 wt. % of the synergist. For example, a composition may comprise from about 1 wt. % to about 2 wt. % of the corrosion inhibitor compound and from about 0.01 wt. % to about 0.09 wt. % of the synergist. In some embodiments, the composition comprises a greater weight percentage of the corrosion inhibitor compound than the synergist.

[0092] A composition of the present disclosure may comprise a variety of weight ratios of the corrosion inhibitor compound to the synergist. For example, a composition may comprise a weight ratio of the corrosion inhibitor compound to the synergist of about 50,000:1 to about 1:2, about 25,000:1 to about 1:2, about 10,000:1 to about 1:2, about 5,000:1 to about 1:2, about 1,000:1 to about 1:2, about 500:1 to about 1:2, about 250:1 to about 1:2, about 100:1 to about 1:2, about 50:1 to about 1:2, about 25:1 to about 1:2, about 10:1 to about 1:2, about 5:1 to about 1:2, or about 1:1 to about 1:2.

[0093] A composition of the present disclosure may optionally comprise a solvent. Suitable solvents include, but are not limited to, an alcohol, a hydrocarbon, a ketone, an ether, an aromatic, an amide, a nitrile, a sulfoxide, an ester, a glycol ether, water, and combinations thereof.

[0094] In some embodiments, the solvent is selected from the group consisting of water, a C1-C6 alkanol, a C1-C6 alkoxyalkanol, an alcohol, a glycol ether, a hydrocarbon, a ketone, an ether, an aromatic, an alkylene glycol, an amide, a nitrile, a sulfoxide, an ester, and any combination thereof.

[0095] For example, the solvent can be water, isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, xylene, or any combination thereof.

[0096] Representative polar solvents suitable for formulation with the composition (or corrosion inhibitor compound by itself or the synergist by itself) include water, brine, seawater, an alcohol (including straight chain or branched aliphatic, such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), a glycol and a glycol derivative (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol monobutyl ether, etc.), a ketone (such as cyclohexanone, diisobutylketone), N-methylpyrrolidinone (NMP), N,N-dimethylformamide, and the like.

[0097] Representative non-polar solvents suitable for formulation with the composition (or corrosion inhibitor compound by itself or the synergist by itself) include an aliphatic, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and the like; and an aromatic, such as toluene, xylene, heavy aromatic naphtha, a fatty acid derivative (e.g., an acid, an ester, an amide), and the like.

[0098] In some embodiments, the solvent is methanol, isopropanol, 2-ethylhexanol, or a combination thereof. In certain embodiments, the solvent is methanol, isopropanol, 2-ethylhexanol, water, or a combination thereof.

[0099] A composition of the present disclosure may include from about 0 wt. % to about 99 wt. % of the solvent, such as from about 5 wt. % to about 95 wt. %, about 5 wt. % to about 85 wt. %, about 5 wt. % to about 75 wt. %, about 5 wt. % to about 65 wt. %, about 5 wt. % to about 55 wt. %, about 5 wt. % to about 45 wt. %, about 5 wt. % to about 35 wt. %, about 5 wt. % to about 25 wt. %, about 5 wt. % to about 15 wt. %, about 15 wt. % to about 95 wt. %, about 25 wt. % to about 95 wt. %, about 35 wt. % to about 95 wt. %, about 40 wt. % to about 85 wt. %, or about 40 wt. % to about 80 wt. % of the solvent.

[0100] An aqueous composition of the present disclosure may comprise any suitable pH. For example, a composition of the present disclosure may comprise a pH of about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, or about 14, such as from about 1 to about 11, about 2 to about 10, about 3 to about 9, or about 4 to about 8.

[0101] The present disclosure also provides metal surfaces comprising any of the metals disclosed herein, or any combination of the metals disclosed herein, further comprising any of the compositions and / or compounds disclosed herein.

[0102] The compounds, synergists, and compositions disclosed herein may be used in various methods for inhibiting corrosion of metal surfaces.

[0103] For example, the present disclosure provides a method of inhibiting corrosion of a metal surface in contact with a medium. The method comprises adding any corrosion inhibitor compound disclosed herein to the medium, and adding any synergist disclosed herein to the medium.

[0104] The corrosion inhibitor compound may be added to the medium before, after, and / or with the synergist. If the corrosion inhibitor is added with / at the same time as the synergist, the two components may be added together as a single composition or they may be added separately but at the same time, typically at adjacent injection points. The corrosion inhibitor compound and the synergist may be added simultaneously and / or sequentially, continuously or intermittently. The corrosion inhibitor compound and the synergist may be added at the same location or at different locations in the medium. In some cases, the corrosion inhibitor compound and / or the synergist may be added directly to the metal surface in the absence of the medium. The metal surface may then be exposed to the medium and, if appropriate, additional inhibitor and / or synergist may be injected into the medium.

[0105] The amount of corrosion inhibitor added to the medium is not particularly limited. For example, the amount may be from about 0.1 ppm to about 10,000 ppm, about 0.1 ppm to about 7,500 ppm, about 0.1 ppm to about 5,000 ppm, about 0.1 ppm to about 2,500 ppm, about 0.1 ppm to about 1,000 ppm, about 0.1 ppm to about 500 ppm, about 0.1 ppm to about 250 ppm, about 0.1 ppm to about 100 ppm, about 1 ppm to about 10,000 ppm, about 50 ppm to about 10,000 ppm, about 100 ppm to about 10,000 ppm, about 250 ppm to about 10,000 ppm, about 500 ppm to about 10,000 ppm, about 1,000 ppm to about 10,000 ppm, about 2,500 ppm to about 10,000 ppm, about 5,000 ppm to about 10,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1,000 ppm, about 10 ppm to about 1,000 ppm, about 50 ppm to about 1,000 ppm, or about 25 ppm to about 500 ppm.

[0106] The amount of synergist added to the medium is not particularly limited. For example, the amount may be from about 0.1 ppm to about 5,000 ppm, about 0.1 ppm to about 2,500 ppm, about 0.1 ppm to about 2,000 ppm, about 0.1 ppm to about 1,500 ppm, about 0.1 ppm to about 1,000 ppm, about 0.1 ppm to about 500 ppm, about 0.1 ppm to about 250 ppm, about 1 ppm to about 100 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 1,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 3,000 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 500 ppm, about 10 ppm to about 1,000 ppm, about 50 ppm to about 1,000 ppm, or about 25 ppm to about 500 ppm.

[0107] Methods of the present disclosure contemplate adding a composition comprising the corrosion inhibitor compound and the synergist to the medium. Methods also contemplate adding the corrosion inhibitor compound and the synergist separately to the medium. If added together in a composition, the composition may include (or exclude) any solvent disclosed herein. If added separately, the corrosion inhibitor compound and / or the synergist may be added in any solvent disclosed herein.

[0108] Methods disclosed herein may comprise (or exclude) adding one or more additional components to the medium. The additional component(s) may be added before, after, and / or with the corrosion inhibitor compound and / or the synergist. Compositions disclosed herein may comprise (or exclude) one or more additional components (aside from the synergist, corrosion inhibitor compound, and optional solvent).

[0109] Illustrative, non-limiting examples of additional components include a fouling control agent, an additional corrosion inhibitor, a corrosion inhibitor intensifier, a biocide, a preservative, an acid, an anti-emulsifier, an iron chelating agent, a hydrogen sulfide scavenger, a surfactant, an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, a gas hydrate inhibitor, a pH modifier, an emulsion breaker, a reverse emulsion breaker, a coagulant / flocculant agent, an emulsifier, a water clarifier, a dispersant, an antioxidant, a polymer degradation prevention agent, a permeability modifier, a foaming agent, an antifoaming agent, a CO2 scavenger, an O2 scavenger, a gelling agent, a lubricant, a friction reducing agent, a salt, a clay stabilizer, a bactericide, a salt substitute, a relative permeability modifier, a breaker, a fluid loss control additive, an iron control agent, a drag reducing agent, a flow improver, a viscosity reducer, or any combination thereof.

[0110] A hydrate inhibitor may include, for example, a mono-alkyl amide, a di-alkyl amide, an alkyl quaternary ammonium salt, and any combination thereof.

[0111] An asphaltene inhibitor may include, for example, an alkylphenol / formaldehyde resin, a polyisobutylene esters, a polyisobutylene imides, a polyalkyl acrylate, and any combination thereof.

[0112] A paraffin inhibitor may include, for example, a polyalkyl acrylate, an olefin / maleic anhydride polymer, and any combination thereof.

[0113] A biocide may include, for example, glutaraldehyde, tetrakis(hydroxymethyl)phosphonium sulphate, a quaternary ammonium compound, chlorine, hypochlorite, ClO2, bromine, ozone, hydrogen peroxide, peracetic acid, peroxycarboxylic acid, peroxysulphate, dibromonitrilopropionamide, isothiazolone, terbutylazine, polymeric biguanide, methylene bisthiocyanate, and any combination thereof.

[0114] A scale inhibitor may include, for example, a phosphonate, a sulfonate, a phosphate, a phosphate ester, a polymer comprising a phosphonate or phosphonate ester group, a polymeric organic acid, a peroxycarboxylic acid, and any combination thereof. In some embodiments, the scale inhibitor may be selected from a compound comprising an amine and / or a quaternary amine, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), DETA phosphonate, and any combination thereof.

[0115] In some embodiments, the scale inhibitor is an acid-based scale inhibitor, such as phosphonic acid. In some embodiments, the scale inhibitor comprises an anionic group. The anionic group may comprise, for example, a carboxylate group or a sulfate group. In some embodiments, the scale inhibitor may include a phosphorous atom, a phosphorous-oxygen double bond, and / or a phosphono group.

[0116] In some embodiments, the scale inhibitor is selected from the group consisting of hexamethylene diamine tetrakis (methylene phosphonic acid), diethylene triamine tetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid), polyacrylic acid (PAA), phosphino carboxylic acid (PPCA), diglycol amine phosphonate (DGA phosphonate), 1-hydroxyethylidene 1,1-diphosphonate (HEDP phosphonate), bisaminoethylether phosphonate (BAEE phosphonate), 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS), and any combination thereof.

[0117] In certain embodiments, the scale inhibitor is a polymer comprising an anionic monomer. The anionic monomer may be selected from, for example, acrylic acid, methacrylic acid, vinyl sulfonic acid, vinyl phosphonic acid, maleic anhydride, itaconic acid, crotonic acid, maleic acid, fumaric acid, styrene sulfonic acid, and any combination thereof.

[0118] The fouling control agent may comprise, for example, a quaternary compound.

[0119] The acid may comprise, for example, hydrochloric acid, hydrofluoric acid, citric acid, formic acid, acetic acid, or any combination thereof.

[0120] The hydrogen sulfide scavenger may comprise, for example, an oxidant, inorganic peroxide, chlorine dioxide, a C1-C10 aldehyde, formaldehyde, glyoxal, glutaraldehyde, acrolein, methacrolein, a triazine, or any combination thereof.

[0121] The additional component may be added to the medium before, after, and / or with the corrosion inhibitor compound and / or the synergist. The amount of additional component added to the medium is not particularly limited. For example, from about 1 ppm to about 5,000 ppm of the additional component may be added to the medium, such as about 1 ppm to about 2,500 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1,500 ppm, about 1 ppm to about 1,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250 ppm, about 1 ppm to about 100 ppm, about 25 ppm to about 5,000 ppm, about 25 ppm to about 2,500 ppm, about 25 ppm to about 1,500 ppm, about 25 ppm to about 1,000 ppm, or about 25 ppm to about 500 ppm.

[0122] If a composition of the present disclosure comprises the additional component, the composition may comprise from, for example, about 0.1 wt. % to about 25 wt. % of the component, such as from about 0.1 wt. % to about 20 wt. %, about 0.1 wt. % to about 15 wt. %, about 0.1 wt. % to about 10 wt. %, about 0.1 wt. % to about 5 wt. %, about 1 wt. % to about 5 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % to about 15 wt. %, about 5 wt. % to about 15 wt. %, or about 5 wt. % to about 20 wt. %.

[0123] The methods, compounds, and compositions disclosed herein may be used in any industrial systems, such as an aqueous industrial system, as well as an industrial system that includes hydrogen-containing mediums and / or carbon dioxide-containing mediums. In some embodiments, the compositions, compounds, and methods of the present disclosure may be used to inhibit corrosion of a metallic surface present in an oil and / or gas production well and / or pipeline.

[0124] The compositions, compounds, and methods disclosed herein can be applied in any industry where it is desirable to inhibit corrosion. For example, a composition can be applied to a gas or liquid produced or used in the production, transportation, storage, and / or separation of crude oil or natural gas.

[0125] The medium in which the compositions and / or compounds of the disclosure are introduced can be contained in and / or exposed to many different types of devices / components. For example, the medium may be contained in an apparatus that transports fluid or gas from one point to another, such as an oil and / or gas pipeline. The device / component may be part of an oil and / or gas refinery, such as a pipeline, a separation vessel, a dehydration unit, or a gas line. The medium may also be contained in and / or exposed to a device / component used in oil extraction and / or production, such as a wellhead.

[0126] In some embodiments, one or more of a pipeline, a heat exchanger, a storage vessel, a flowline, a downhole tubular, a casing, a tank (e.g., railroad tank car or a tank truck / tanker), a separator, or any combination thereof, comprises the metal surface, which contacts the medium.

[0127] In certain embodiments, a subterranean formation and / or a pipeline comprises the metallic surface to be treated by a composition and / or compound of the present disclosure. Certain methods disclosed herein comprise adding a composition and / or compound disclosed herein to a medium that comprises the metallic surface. Alternatively and / or additionally, the methods disclosed herein may comprise applying the composition and / or compound directly to the metallic surface as opposed to, for example, adding to a liquid medium in contact with the metallic surface. In some embodiments, the composition and / or compound may be applied to the interior wall of the pipeline when the interior wall is dry or substantially dry.

[0128] In some embodiments, the pipeline is intended to transport a liquid medium / process fluid, such as an aqueous medium or a medium comprising aqueous and non-aqueous liquids (e.g., an aqueous / hydrocarbon mixture produced from a subterranean reservoir), and the composition and / or compound is applied in the absence of the process fluid. The components of the process fluid may include, for example, water, hydrocarbons, brine, crude oil, refined oil, gas, liquefied natural gas, carbon dioxide, liquid hydrogen, and any combination thereof.

[0129] A medium of the present disclosure may comprise, for example, produced water, fresh water, recycled water, salt water, surface water, condensed water, cooling water, injection water, waste water, geothermal water, sewage water, nuclear cooling water, carbon dioxide, hydrogen, or any mixture thereof.

[0130] An aqueous medium may comprise, for example, water, gas, and / or a liquid hydrocarbon. The liquid hydrocarbon may be any type of liquid hydrocarbon including, but not limited to, crude oil, heavy oil, processed residual oil, bitminous oil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene. The medium may also comprise a refined hydrocarbon product.

[0131] A medium (e.g., a fluid and / or a gas) treated with a composition and / or compound of the present disclosure can be at any selected temperature, such as ambient temperature or an elevated temperature. For example, the medium (e.g., water, liquid hydrocarbon, gas, etc.) may be at a temperature of from about 40° C. to about 250° C. In some embodiments, the medium may be at a temperature of from about −50° C. to about 300° C., about 0° C. to about 200° C., about 10° C. to about 100° C., or about 20° C. to about 90° C.

[0132] The presently disclosed compositions, compounds, and methods are useful for inhibiting corrosion of surfaces comprising any metal or combination of metals. In some aspects, the metal surface comprises steel, such as stainless steel or carbon steel. In some aspects, the metal surface comprises iron, aluminum, zinc, chromium, manganese, nickel, tungsten, molybdenum, titanium, vanadium, cobalt, niobium, or copper. The metal surface may also comprise any combination of the foregoing metals and / or any one or more of boron, phosphorus, sulfur, silicon, oxygen, and nitrogen.

[0133] In some aspects of the present disclosure, a metal surface may comprise metallic-chrome steel, ferritic-alloy steel, austenitic-steel, precipitation-hardened steel, high-nickel steel, carbon steel, or a combination thereof.

[0134] The presently disclosed corrosion inhibitor compounds, compositions, and methods are useful for inhibiting corrosion of metal surfaces in contact with any type of corrodent in the medium, such as a metal cation, a metal complex, a metal chelate, an organometallic complex, an aluminum ion, an ammonium ion, a barium ion, a chromium ion, a cobalt ion, a cuprous ion, a cupric ion, a calcium ion, a ferrous ion, a ferric ion, a hydrogen ion, a magnesium ion, a manganese ion, a molybdenum ion, a nickel ion, a potassium ion, a sodium ion, a strontium ion, a titanium ion, a uranium ion, a vanadium ion, a zinc ion, a bromide ion, a carbonate ion, a chlorate ion, a chloride ion, a chlorite ion, a dithionate ion, a fluoride ion, a hypochlorite ion, an iodide ion, a nitrate ion, a nitrite ion, an oxide ion, a perchlorate ion, a peroxide ion, a phosphate ion, a phosphite ion, a sulfate ion, a sulfide ion, a sulfite ion, a hydrogen carbonate ion, a hydrogen phosphate ion, a hydrogen phosphite ion, a hydrogen sulfate ion, a hydrogen sulfite ion, an acid, such as carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, nitrous acid, sulfurous acid, a peroxy acid, or phosphoric acid, ammonia, bromine, carbon dioxide, chlorine, chlorine dioxide, fluorine, hydrogen chloride, hydrogen sulfide, iodine, nitrogen dioxide, nitrogen monoxide, oxygen, ozone, sulfur dioxide, hydrogen peroxide, a polysaccharide, a metal oxide, sand, a clay, silicon dioxide, titanium dioxide, mud, a brine, an organic acid, an insoluble inorganic and / or organic particulate, an oxidizing agent, a chelating agent, an alcohol, and any combination of the foregoing.

[0135] The compositions and / or compounds disclosed herein may be added to a medium and / or metallic surface using a variety of different application methods known in the art. In some embodiments, the compositions and / or compounds may added continuously or intermittently to the medium, either automatically or manually, by using, for example, chemical injection pumps. In some embodiments, the compounds and / or compositions may be applied to the metal surface, such as an inner wall of a pipeline, using a pig system. For example, a pig system may include a lead pig and a filming pig spaced apart axially from the lead pig to define an application storage space therebetween. The compounds and / or compositions may be located in the application storage space. Once both the lead pig and the filming pig are located in the pipeline, a force may be applied, for example, to the filming pig to move the lead pig and the filming pig in the lateral direction through the pipeline. In certain embodiments, the force is derived from a pressurized fluid, a mechanical actuator, a hydraulic actuator, an air compressor, or any combination thereof.

[0136] The lead pig may, for example, prepare the surface of the pipe by removing residue through mechanical scraping. As the filming pig travels behind the lead pig, it uniformly applies the composition and / or compound in the application storage space to the interior surface of the pipe.

[0137] A method of preparing a pipeline for application of an even layer of the composition and / or compound to the interior surface of the pipeline may include several steps. For example, the method may include inserting the lead pig into the pipe and adding the composition and / or compound to the pipe upstream of the lead pig. Next, the method includes inserting the filming pig into the pipe upstream of the composition and / or compound such that the composition and / or compound is located in the application storage space. Once the lead pig and the filming pig are in place, the method includes applying a force to the filming pig to cause the filming pig and the lead pig to move in the lateral direction through the pipeline. While traveling, the lead pig may clean an interior wall of the pipeline and the filming pig applies the composition and / or compound to the interior wall of the pipeline.

[0138] The lead pig and the filming pig may be added or removed from the pipeline by any means known in the art. For example, the pipeline may have bypass sections, e.g. a pig launch and a pig receiver, in fluid communication with the main pipe in order to launch and receive the lead and filming pigs. The pig launcher may be used to launch the lead pig and the filming pig into the pipe, while the pig receiver may be used to receive the lead pig and the filming pig after moving through the pipeline.

[0139] The pig receiver may include a sensor configured to detect when the lead and filming pigs arrive at the pig receiver section of the pipeline. The pig receiver section may have different valves to control pressurization of the pipeline in order to safely remove the pigs from the pipeline. Once the pigs are removed, the valves may be reopened to return the system to the original condition.

[0140] During application of a composition and / or compound of the present disclosure, a method disclosed herein may include reducing a flow rate of the process fluid within the pipeline while applying the composition. For example, the flow rate may be reduced by about 10% to about 75% of the standard operating flow rate. In some embodiments, the flow rate is reduced by about 15% to about 70%, about 20% to about 65%, about 25% to about 60%, or about 25% to about 50%.

[0141] The compositions and / or compounds disclosed herein can be added to a medium at various levels of water cut. For example, the water cut can be from about 0% to about 100% volume / volume (v / v), from about 1% to about 80% v / v, or from about 1% to about 60% v / v. The medium may be an aqueous medium that contains various levels of salinity. For example, the medium can have a salinity of about 0% to about 25%, about 1% to about 24%, or about 10% to about 25% weight / weight (w / w) total dissolved solids (TDS).

[0142] The foregoing may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the disclosure or its application in any way.EXAMPLES

[0143] Corrosion tests were performed using pre-weighed C1018 mild steel coupons (¼″×7⅜″) with sandblast finish. The coupon was dipped for about 5 seconds in a blend under assessment and allowed to drip for about 10 seconds to allow for excess product to be removed. The coupon was then placed in a vessel containing CO2 saturated fluids of 3% NaCl brine without liquid hydrocarbon and closed. The vessel was then mounted on a wheel in a temperature-controlled cabinet at about 60° C. The wheel was then rotated at about 26 rpm. After 24 hours, and then again at 48 hours and 72 hours, the fluids were replaced with chemical-free brine and ran for a further 24 hours. After the last brine replenishment at 72 hours, the test was continued for a further 24 hours to a total of about 96 hours. After the test, the coupons were removed from the vessel, cleaned, and re-weighed. The corrosion rate was determined by weight loss and the percentage inhibition was determined by comparison to a blank, i.e., a test carried out under otherwise the same conditions but in the absence of any chemical treatment. The results are shown below in Table 1.TABLE 1Corrosion RateSampleChemistry(mpy)% Protection1Blank18.6N / A2Blank19.1N / A31% fatty amine condensate10.644(CAS No. 68910-85-0) Rxnproduct of polyalkylene, talloil fatty acid, and linoleicacid dimer) withdodecylbenzenesulfonic acid(DDBSA) and linoleic aciddimer41% fatty amine condensate10.047(CAS No. 68910-85-0) withDDBSA and linoleic acid dimer51% TOFA:DETA imidazoline11.83761% TOFA:DETA imidazoline12.13671% fatty amine condensate7.859(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% lignin81% fatty amine condensate7.162(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% lignin91% TOFA:DETA imidazoline +8.8530.01% lignin101% TOFA:DETA imidazoline +8.4550.01% lignin111% fatty amine condensate7.759(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% polyanilinegrafted to lignin121% fatty amine condensate7.361(CAS No. 68910-85-0) withDDBSA and linoleic aciddimer + 0.01% lignin131% TOFA:DETA imidazoline +11.9370.01% polyaniline grafted tolignin141% TOFA:DETA imidazoline +11.1420.01% polyaniline grafted tolignin

[0144] Additional corrosion tests were conducted using polyvinyl alcohol as the synergist. The tests were carried out using the following conditions to evaluate the corrosion inhibition performance of the sample on a carbon steel electrode (C1018 grade). The corrosion rate was assessed electrochemically using linear polarization resistance (LPR) methodology. Tests were conducted at about 80° C. with CO2 saturated fluids with 3% NaCl brine (100% brine) with a continuous CO2 sparge at atmospheric pressure. A pre-corrosion time (i.e., with no corrosion inhibitor) was carried out for about 3 hours before the candidate chemical sample (diluted in appropriate solvent) was injected either individually or in combination with another chemistry to achieve the following additions: mercaptoethanol (10 ppm active dose); substituted aromatic amine (10 ppm active dose); dimethyl benzyl ammonium chloride (10 ppm active dose); polyvinyl alcohol (200 ppm active dose); mercaptoethanol (8 ppm active dose)+polyvinyl alcohol (100 ppm active dose); substituted aromatic amine (8 ppm active dose)+polyvinyl alcohol (100 ppm active dose); and dimethyl benzyl ammonium chloride (8 ppm active dose)+polyvinyl alcohol (100 ppm active dose).

[0145] The inhibited corrosion rate at about 15 hours after chemical injection was noted and a percentage inhibition determined by comparing with the corrosion rate of a carbon steel electrode under otherwise the same conditions in the absence of the sample corrosion inhibitor after the same time of exposure to the corrosive environment. The results are shown in Table 2.TABLE 2CandidateCandidateCorrosionCandidateCandidateDosageDosageChemistry #1Chemistry #2RateChemistryChemistryCandidateCandidateActiveActiveAfter 15CandidateCandidate#1#2ChemistryChemistryInjectedInjectedh of ClChemistryChemistryActivityActivity#1#2in Testin TestInjection%#1#2(%)(%)(ppm)(ppm)(ppm)(ppm)(mpy)ProtectionN / AN / AN / AN / AN / AN / AN / AN / A502N / AMercaptoethanolN / A20N / A50N / A10N / A6188SubstitutedN / A20N / A50N / A10N / A38723aromatic amineDimethyl benzylN / A20N / A50N / A10N / A40819ammonium chloridePolyvinyl alcoholN / A100N / A200N / A200N / A25549MercaptoethanolPolyvinyl201004010081004591alcoholSubstitutedPolyvinyl2010040100810026547aromatic aminealcoholDimethyl benzylPolyvinyl2010040100810024651ammonium chloridealcohol

[0146] Additional corrosion tests were conducted using cellulose as the synergist. The tests were carried out using the following conditions to evaluate the corrosion inhibition performance of the sample on a carbon steel electrode (C1018 grade). The corrosion rate was assessed electrochemically using LPR methodology. Tests were conducted at about 80° C. with CO2 saturated fluids with 3% NaCl brine (100% brine) with a continuous CO2 sparge at atmospheric pressure. A pre-corrosion time (i.e., with no corrosion inhibitor) was carried out for about 3 hours before the candidate chemical sample (diluted in appropriate solvent) was injected either individually or in combination with another chemistry to achieve the additions below.

[0147] The inhibited corrosion rate at about 15 hours after chemical injection was noted and a percentage inhibition determined by comparing with the corrosion rate of a carbon steel electrode under otherwise the same conditions in the absence of the sample corrosion inhibitor after the same time of exposure to the corrosive environment. The results are shown in Table 3.TABLE 3Dimethyl benzyl ammonium chlorideN / A20N / A50N / A10N / A40819Polyanionic cellulose (PAC) bondingN / A1.25N / A800N / A10N / A33633chemical 500613-PAC-HVCellulose nanocrystal (CNC) bondingN / A1.25N / A800N / A10N / A44711chemical SF-CNC-PL200 353567 (8.84nm diameter 146 nm length), surfaceion: anion Cotton pulp dissolving pulppreparation method hydrolysis with60% sulfuric acid)Cellulose nanocrystal (CNC) bondingN / A1.25N / A800N / A10N / A34232chemical SF-CNC-PL200-353567 ( .5nm diameter 200 nm length) surfaceion: anion Cotton MCC preparationmethod TEMPO / NaBr / NaClOOxidation)Cellulose nanofiber (CNF) bondingN / A0.125N / A8000N / A10N / A32036chemical C-CNF-PL20-gel 252567 10-20 um diameter 20-30 um length)Coniferous wood bleached kraft pulpsurface modification Cationicmodification of 2,3-epoxypropyltrimethylammoniumchlorided charge density mmol / g 1.09)Cellulose nanofiber (CNF) bondingN / A1.25N / A800N / A10N / A34332chemical TO-CNF-PL20-powder252567 (10-20 um diameter 10-20 umlength) Coniferous wood bleachedkraft pulp surface modificationTEMPO / NaBr / NaClO oxidizedCarboxyl group 1. mmol / g)Sodium carboxymethylcelluloseN / A1.25N / A800N / A10N / A28543Aldrich PCode 1003617057 sourceMKCS48 419273-100 gCellulose acetate Aldrich PcodeN / A1.25N / A800N / A10N / A4321410035673 source MKC57296,18095 -25 g2-hydroxycellulose Aldrich PcodeN / A1.25N / A800N / A10N / A437131003568597 source MKCT0293434965-250 gSubstituted aromatic amineSodium201.25254005525250carboxymethylcelluloseAldrich. PCode 1003617057source MKC 869 4192 3-100 gSubstituted aromatic amineCellulose acetate Aldrich201.25254005537725Pcode 10035673 sourceMKC57296 1809 -25 gSubstituted aromatic amine2-hydroxycellulose Aldrich201.25254005537925Pcode 1003568597 sourceMKCT0293 434965-250 gDimethyl benzyl ammonium chlorideCellulose nanocrystal (CNC)201.25254005540220bonding chemical SF-CNC-PL200 353567 (8. 4 nmdiameter 146 nm length),surface ion: anion, Cottonpulp dissolving pulppreparation method hydrolysiswith 60% sulfuric acid)Dimethyl benzyl ammonium chlorideSodium201.25254005527146carboxymethylcelluloseAldrich PCode 1003517057,source MKCS48 9 419273-100 gDimethyl benzyl ammonium chloride2-hydroxycellulose Aldrich201.25254005535829Pcode 1003568597 sourceMKCT0293 434965-250 g indicates data missing or illegible when filed

[0148] Additional corrosion tests were conducted using gelatin as the synergist. The tests were carried out using the following conditions to evaluate the corrosion inhibition performance of the sample on a carbon steel electrode (C1018 grade). The corrosion rate was assessed electrochemically using LPR methodology. Tests were conducted at about 80° C. with CO2 saturated fluids with 3% NaCl brine (100% brine) with a continuous CO2 sparge at atmospheric pressure. A pre-corrosion time (i.e., with no corrosion inhibitor) was carried out for about 3 hours before the candidate chemical sample (diluted in appropriate solvent) was injected either individually or in combination with another chemistry to achieve the additions below.

[0149] The inhibited corrosion rate at about 15 hours after chemical injection was noted and a percentage inhibition determined by comparing with the corrosion rate of a carbon steel electrode under otherwise the same conditions in the absence of the sample corrosion inhibitor after the same time of exposure to the corrosive environment. The results are shown in Table 4.TABLE 4CandidateCandidateChemistryChemistryCorrosionCandidateCandidateDosageDosage#1#2RateChemistryChemistryCandidateCandidateActiveActiveAfter 15CandidateCandidate#1#2ChemistryChemistryInjectedInjectedh of ClLab BookChemistryChemistryActivityActivity#1#2in Testin TestInjection%Number#1#2(%)(%)(ppm)(ppm)(ppm)(ppm)(mpy)ProtectionBlankN / AN / AN / AN / AN / AN / AN / AN / A502N / AJJM / 10102 / 161AMercaptoethanolN / A20N / A50N / A10N / A6185JJM / 10102 / 161OSubstitutedN / A20N / A50N / A10N / A3572aromatic amineJJM / 10102 / 161EPhosphate esterN / A20N / A50N / A10N / A86 3JJM / 10102 / 161FDimethyl benzylN / A20N / A50N / A10N / A40819ammoniumchlorideJJM / 10102 / 161ZGelatinN / A100N / A200N / A200N / A14272JJM / 10102 / 161A +MercaptoethanolGelatin201004010081001597JJM / 10102 / 161ZJJM / 10102 / 161O +SubstitutedGelatin2010040100810015467JJM / 10102 / 161Zaromatic amineJJM / 10102 / 161E +Phosphate esterGelatin2010040100810088JJM / 10102 / 161ZJJM / 10102 / 161F +Dimethyl benzylGelatin2010040100810013274JJM / 10102 / 161Zammoniumchloride indicates data missing or illegible when filed

[0150] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While this invention may be embodied in many different forms, there are described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. In addition, unless expressly stated to the contrary, use of the term “a” is intended to include “at least one” or “one or more.” For example, “a corrosion inhibitor compound” is intended to include “at least one corrosion inhibitor compound” or “one or more corrosion inhibitor compounds.”

[0151] Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any definitions used herein are intended to be clarifying and not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges (including all fractional and whole values) subsumed therein.

[0152] Any composition disclosed herein may comprise, consist of, or consist essentially of any element, component and / or ingredient disclosed herein or any combination of two or more of the elements, components or ingredients disclosed herein.

[0153] Any method disclosed herein may comprise, consist of, or consist essentially of any method step disclosed herein or any combination of two or more of the method steps disclosed herein.

[0154] The transitional phrase “comprising,” which is synonymous with “including,”“containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements, components, ingredients and / or method steps.

[0155] The transitional phrase “consisting of” excludes any element, component, ingredient, and / or method step not specified in the claim.

[0156] The transitional phrase “consisting essentially of” limits the scope of a claim to the specified elements, components, ingredients and / or steps, as well as those that do not materially affect the basic and novel characteristic(s) of the claimed invention.

[0157] Unless specified otherwise, all molecular weights referred to herein are weight average molecular weights and all viscosities were measured at 25° C. with neat (not diluted) polymers.

[0158] As used herein, the term “about” refers to the cited value being within the errors arising from the standard deviation found in their respective testing measurements, and if those errors cannot be determined, then “about” may refer to, for example, within 5%, 4%, 3%, 2%, or 1% of the cited value.

[0159] Furthermore, the invention encompasses 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 presently 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. It is therefore intended that such changes and modifications be covered by the appended claims.

Examples

examples

[0143]Corrosion tests were performed using pre-weighed C1018 mild steel coupons (¼″×7⅜″) with sandblast finish. The coupon was dipped for about 5 seconds in a blend under assessment and allowed to drip for about 10 seconds to allow for excess product to be removed. The coupon was then placed in a vessel containing CO2 saturated fluids of 3% NaCl brine without liquid hydrocarbon and closed. The vessel was then mounted on a wheel in a temperature-controlled cabinet at about 60° C. The wheel was then rotated at about 26 rpm. After 24 hours, and then again at 48 hours and 72 hours, the fluids were replaced with chemical-free brine and ran for a further 24 hours. After the last brine replenishment at 72 hours, the test was continued for a further 24 hours to a total of about 96 hours. After the test, the coupons were removed from the vessel, cleaned, and re-weighed. The corrosion rate was determined by weight loss and the percentage inhibition was determined by comparison to a blank, i.e...

Claims

1. A method of inhibiting corrosion of a metal surface in contact with a medium, comprising:adding a corrosion inhibitor compound to the medium, andadding a synergist to the medium, wherein the synergist is selected from the group consisting of a lignin polymer, a polyvinyl alcohol, cellulose, gelatin, and any combination thereof.

2. The method of claim 1, further comprising adding the corrosion inhibitor compound before, after, and / or with the synergist.

3. The method of claim 1, wherein the corrosion inhibitor compound and the synergist are added simultaneously and / or sequentially.

4. The method of claim 1, wherein the corrosion inhibitor compound and the synergist are added at the same location or at different locations in the medium.

5. The method of claim 1, further comprising adding the corrosion inhibitor compound and / or the synergist to the metal surface in the absence of the medium.

6. The method of claim 1, wherein the corrosion inhibitor compound comprises an amine compound, a polyamine compound, a thiol-containing compound, a carboxylic acid, a dicarboxylic acid, mercaptoethanol, a maleated compound, an aromatic amine compound, a phosphate ester, a quaternary ammonium compound, an imidazoline compound, or any combination thereof, optionally wherein the polyamine compound comprises a diamine compound, a triamine compound, and / or a quaternary ammonium compound.

7. The method of claim 6, wherein the polyamine compound is an alkyl quaternary salt, a hydroxyalkyl quaternary salt, an alkylaryl quaternary salt, an arylalkyl quaternary salt, or an arylamine quaternary salt.

8. The method of claim 1, wherein the medium comprises produced water, fresh water, recycled water, salt water, surface water, condensed water, cooling water, injection water, waste water, geothermal water, sewage water, nuclear cooling water, carbon dioxide, hydrogen, or any mixture thereof.

9. The method of claim 1, further comprising adding from about 0.1 ppm to about 10,000 ppm of the corrosion inhibitor compound to the medium and / or from about 0.1 ppm to about 5,000 ppm of the synergist to the medium.

10. The method of claim 1, wherein the corrosion inhibitor compound and / or the synergist comprise a solvent selected from the group consisting of water, a C1-C6 alkanol, a C1-C6 alkoxyalkanol, an alcohol, a glycol ether, a hydrocarbon, a ketone, an ether, an aromatic, an alkylene glycol, an amide, a nitrile, a sulfoxide, an ester, and any combination thereof.

11. The method of claim 1, wherein one or more of a pipeline, a flowline, a downhole tubular, a casing, a tank, or a separator comprises the metal surface.

12. The method of claim 1, wherein a composition comprises the corrosion inhibitor compound and the synergist, wherein the composition comprises from about 0.1 wt. % to about 25 wt. % of the synergist and / or from about 1 wt. % to about 99 wt. % of the corrosion inhibitor compound.

13. The method of claim 1, further comprising adding to the medium an additional component selected from the group consisting of a fouling control agent, an additional corrosion inhibitor, a biocide, a preservative, an acid, an anti-emulsifier, an iron chelating agent, a hydrogen sulfide scavenger, a surfactant, an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, a gas hydrate inhibitor, a pH modifier, an emulsion breaker, a reverse emulsion breaker, a coagulant / flocculant agent, an emulsifier, a water clarifier, a dispersant, an antioxidant, a polymer degradation prevention agent, a permeability modifier, a foaming agent, an antifoaming agent, a CO2 scavenger, an O2 scavenger, a gelling agent, a lubricant, a friction reducing agent, a salt, and any combination thereof.

14. The method of claim 1, wherein the cellulose is selected from the group consisting of macrocellulose, microcellulose, nanocellulose, and any combination thereof.

15. A composition, comprising:a corrosion inhibitor compound and a synergist, wherein the synergist is selected from the group consisting of a lignin polymer, polyvinyl alcohol, cellulose, gelatin, and any combination thereof.

16. The composition of claim 15, further comprising a medium selected from the group consisting of produced water, fresh water, recycled water, salt water, surface water, condensed water, cooling water, injection water, waste water, geothermal water, sewage water, nuclear cooling water, carbon dioxide, hydrogen, and any combination thereof.

17. The composition of claim 15, wherein the corrosion inhibitor compound comprises an amine compound, a polyamine compound, a thiol-containing compound, a carboxylic acid, a dicarboxylic acid, mercaptoethanol, a maleated compound, an aromatic amine compound, a phosphate ester, a quaternary ammonium compound, an imidazoline compound, or any combination thereof.

18. The composition of claim 15, further comprising a solvent selected from the group consisting of water, a C1-C6 alkanol, a C1-C6 alkoxyalkanol, an alcohol, a glycol ether, a hydrocarbon, a ketone, an ether, an aromatic, an alkylene glycol, an amide, a nitrile, a sulfoxide, an ester, and any combination thereof.

19. The composition of claim 15, further comprising an additional component selected from the group consisting of a fouling control agent, an additional corrosion inhibitor, a biocide, a preservative, an acid, an anti-emulsifier, an iron chelating agent, a hydrogen sulfide scavenger, a surfactant, an asphaltene inhibitor, a paraffin inhibitor, a scale inhibitor, a gas hydrate inhibitor, a pH modifier, an emulsion breaker, a reverse emulsion breaker, a coagulant / flocculant agent, an emulsifier, a water clarifier, a dispersant, an antioxidant, a polymer degradation prevention agent, a permeability modifier, a foaming agent, an antifoaming agent, a CO2 scavenger, an O2 scavenger, a gelling agent, a lubricant, a friction reducing agent, a salt, and any combination thereof.

20. A metal surface comprising the composition of claim 15.

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