US20240060188A1

US20240060188A1 - Development of hydrogen compatible chemicals and test methods for energy sector application

Info

Publication number: US20240060188A1
Application number: US18/447,746
Authority: US
Inventors: Jeffery Caleb Clark; Ana FERRER CARRERA; Geeta Rana; Yolanda Maria DE-ABREU; Matthew Aaron Trevino; Jeremy Wayne Bartels
Original assignee: Championx USA Inc
Current assignee: Championx USA Inc
Priority date: 2022-08-12
Filing date: 2023-08-10
Publication date: 2024-02-22
Also published as: WO2024035875A1

Abstract

The present disclosure provides compositions and methods for use with hydrogen gas. A method may include adding hydrogen gas to a medium and adding a production chemical to the medium. As examples, the production chemical may be a corrosion inhibitor, an anti-foulant, a hydrate anti-agglomerate, a kinetic hydrate inhibitor, an amine for gas sweetening, a regenerable H2S scavenger, a non-regenerable H2S scavenger, an alcohol for gas dehydration, an alcohol for hydrate control, a thermodynamic hydrate inhibitor, or any combination thereof. The present disclosure also provides test methods to determine the susceptibility of a production chemical to reaction with hydrogen gas.

Description

TECHNICAL FIELD

The present disclosure generally relates to methods and compositions that can be used with hydrogen gas.

BACKGROUND

Hydrogen mixture with hydrocarbons, such as oil or natural gas, is a potentially attractive solution to significantly reduce greenhouse gases. Engineering work is under way to understand whether existing energy infrastructure can be used to generate, transport, store, and utilize hydrogen.
While the engineering industry is preparing for hydrogen use in existing infrastructure, attention must be paid to chemicals that would need to be applied in the presence of hydrogen. Hydrogen often reacts with certain organic molecules to form saturated compounds and many chemicals applied within the energy sector include molecules that are susceptible to these hydrogenation reactions.

BRIEF SUMMARY

The present disclosure provides compositions and methods for use with hydrogen gas. In some embodiments, a method of treating a medium in an industrial process is disclosed. The method includes adding hydrogen gas to the medium and adding a production chemical to the medium.
In certain embodiments, a composition of the present disclosure comprises a production chemical and optionally hydrogen gas. The production chemical may comprise a corrosion inhibitor, an anti-foulant, a hydrate anti-agglomerate, a kinetic hydrate inhibitor, an amine for gas sweetening, a regenerable H₂S scavenger, a non-regenerable H₂S scavenger, an alcohol for gas dehydration or hydrate control, a thermodynamic hydrate inhibitor, or any combination thereof.
In accordance with some embodiments, the present disclosure also provides a method comprising adding a production chemical to an autoclave, adding hydrogen gas to the autoclave, monitoring a pressure within the autoclave, and determining if the hydrogen gas reacted with the production chemical.
Moreover, the present disclosure provides a method of inhibiting embrittlement or cracking of a surface in contact with a medium. The method comprises adding a composition to the surface and/or the medium, wherein the composition comprises a corrosion inhibitor and optionally a solvent and/or a production chemical, wherein the medium comprises natural gas, hydrogen gas, hydrogen sulfide gas, ammonia, or any combination thereof. In some embodiments, the medium comprises natural gas and optionally one or more of hydrogen gas, hydrogen sulfide gas, and/or ammonia. In certain embodiments, the medium comprises one or more of methane, ethane, propane, nitrogen, and/or carbon dioxide, and optionally one or more of hydrogen gas, hydrogen sulfide gas, and/or ammonia.
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

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. 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.
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.
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+2n electrons, according to Huckel's Rule.
“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.
“Halogen” or “halo” refers to F, Cl, Br, and I.
“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.
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-C₁₂alkyl group, an unsubstituted C₄-C₆aryl group, or an unsubstituted C₁-C₁₀alkoxy group. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.
The term “substituted” as in “substituted alkyl,” means that in the group in question (i.e., 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(R_A)(R_B), wherein R_Aand R_Bare independently hydrogen, alkyl, or aryl), amino(—N(R_A)(R_B), wherein R_Aand R_Bare independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (—NO₂), an ether (—OR_Awherein R_Ais alkyl or aryl), an ester (—OC(O)R_Awherein R_Ais alkyl or aryl), keto (—C(O)R_Awherein R_Ais alkyl or aryl), heterocyclo, and the like.
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.”
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.
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.
In certain aspects, the present application provides compositions comprising a production chemical and optionally hydrogen gas. The present application also provides test methods that determine the susceptibility of a production chemical to a hydrogenation reaction in a hydrogen rich environment. Additionally, the application discloses the development of chemicals that are not susceptible to hydrogenation reactions and maintain functionality for their intended use.
The hydrogen referred to in the present disclosure may be obtained from many different sources or processes. For example, “green hydrogen” is hydrogen produced through a water electrolysis process. Carbon dioxide is not emitted during the process. Electricity is used to decompose water into oxygen and hydrogen gas. While “blue hydrogen” may be sourced from fossil fuel, carbon dioxide produced during the process is captured and stored underground, thereby making the overall process carbon neutral. As an additional example, “pink hydrogen” is generated through the electrolysis of water using electricity from a nuclear power plant. Again, the source of the hydrogen to be used in accordance with the present disclosure is not limited so any type of hydrogen may be used in accordance with the present disclosure, such as green, blue, pink, gray, black, brown, turquoise, purple, white, red, or where it is generated in the value chain.
In some embodiments, the present disclosure provides a composition comprising hydrogen gas and a production chemical. The production chemical may be, for example, resistant to hydrogen, which means, for example, that the production chemical does not react with any hydrogen present in its environment. The production chemical may comprise, for example, a corrosion inhibitor, an anti-foulant, a hydrate anti-agglomerate, a kinetic hydrate inhibitor, an amine for gas sweetening, a regenerable H₂S scavenger, a non-regenerable H₂S scavenger, an alcohol for gas dehydration or hydrate control, a thermodynamic hydrate inhibitor, or any combination thereof.
Examples of corrosion inhibitor compounds include, but are not limited to, an organic sulfur compound, an imidazoline, a carboxylic acid, 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.
In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of, an imidazoline compound, a quaternary amine, an anti-emulsifier compound, and optionally a solvent. In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of, an imidazoline compound, a quaternary amine, a phosphonium compound, an anti-emulsifier compound, and optionally a solvent.
The imidazoline compound may have formula (I), (II), or (III):

- wherein R¹, R⁴, and R⁵are 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);
- R²is a radical derived from a fatty acid;
- R³and Rx are each independently selected from a radical derived from an unsaturated acid;
- R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl;
- R¹²and R¹³are each independently, at each occurrence, selected from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷; and
- R¹⁴, R¹⁵, R¹⁶, and R¹⁷are each independently, at each occurrence, selected from hydrogen, alkyl, and alkenyl.

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, R¹⁵and/or R¹⁷can be absent where the R¹²and/or R¹³is a deprotonated carboxylic acid moiety (e.g., where R¹²is —CH₂CH₂CO₂ ⁻). For an imidazoline compound, R 1 can be unsubstituted alkyl. For example, R¹can 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, R¹can be unsubstituted C₂-C₁₀-alkyl. For the imidazoline compounds, R¹can be unsubstituted C₂-C₈-alkyl. Further, R¹can be unsubstituted C₂-C₆-alkyl. In some embodiments, R¹is propyl, butyl, or hexyl.
In some embodiments, R¹is a substituted alkyl. For example, R¹may be a substituted C₁-C₁₀-alkyl, substituted C₂-C₁₀-alkyl, substituted C₂-C₈-alkyl, or substituted C₂-C₆-alkyl. Further, R¹may 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 R¹³are as defined above. More specifically, R¹may be a C₂-C₆-alkyl, substituted with one substituent selected from —N(R¹²)(R¹³), wherein R¹²and R¹³are each independently selected from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷, wherein R¹⁴, R¹⁵, R¹⁶, and R¹⁷are as defined above. Further, R¹may be a C₂-C₆-alkyl, substituted with one substituent selected from —N(R¹²)(R¹³), wherein R¹²and R¹³are each independently selected from hydrogen, C₂-C₆-alkyl, —COR¹⁴, —CO₂R¹⁵, —C₂-C₆-alkyl-COR¹⁶, and —C₂-C₆-alkyl-CO₂R¹⁷, wherein R¹⁴, R¹⁵, R¹⁶, and R¹⁷are selected from hydrogen and C₁-C₃₄-alkyl. For these imidazolines, R¹may be a linear C₂-C₆-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²and R¹³are each independently selected from hydrogen, —COR¹⁴, —CO₂R¹⁵, —C₂-C₆-alkyl-COR¹⁶, and —C₂-C₆-alkyl-CO₂R¹⁷, wherein R¹⁴, R¹⁵, R¹⁶, and R¹⁷are selected from hydrogen and C₁-C₃₄-alkyl. For example, R¹may be a linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²is hydrogen and R¹³is —COR¹⁴, wherein R¹⁴is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁. Further, R¹may be a linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²and R¹³are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷is hydrogen.
For the imidazolines of formulae (I), (II), and (III), R²may be a C₄-C₃₄-alkyl or C₄-C₃₄-alkenyl. For example, R²may 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═CHCH₂CH₃; —(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═CHCH₂CH₃; —(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.
In some embodiments, R²may 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. Suitable unsaturated fatty acids include, but are not limited to, myristoleic acid, palm itoleic 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. In some embodiments, R²is derived from coconut oil, beef tallow, or tall oil fatty acids (TOFA).
In some embodiments, R³may be —C(R^aR^b)—C(R^cR^d)—CO₂R^e, wherein R^a, R^b, R^c, and R^dare each independently selected from the group consisting of hydrogen (—H), halogen, and alkyl, and wherein R^eis hydrogen (—H) or alkyl. For example, R³may be —C(R^aR^b)—C(R^cR^d)—CO₂R^e, wherein R^a, R^b, R^c, and R^dare each independently selected from the group consisting of hydrogen (—H), halogen, and C₁-C₆-alkyl, and wherein R^eis hydrogen (—H) or C₁-C₆-alkyl. Further, R³may be —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H) or C₁-C₆-alkyl. Additionally, R^ecan be absent where the R³is a deprotonated carboxylic acid moiety (e.g., where R³is —CH₂CH₂CO₂ ⁻).
In accordance with certain embodiments of the present disclosure, R³can 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, R³can be derived from acrylic acid (H₂C═CHCO₂H).
Imidazolines of formulae (I), (II), or (III) may have R^xequal to —C(R^aR^b)—C(R^cR^d)—CO₂R^e, wherein R^a, R^b, R^c, and R^dare each independently selected from the group consisting of hydrogen (—H), halogen, and alkyl, and wherein R^eis hydrogen (—H) or alkyl. Further, R^xcan be —C(R^aR^b)—C(R^cR^d)—CO₂R^e, wherein R^a, R^b, R^c, and R^dare each independently selected from the group consisting of hydrogen (—H), halogen, and C₁-C₆-alkyl, and wherein R^eis hydrogen (—H) or C₁-C₆-alkyl. Additionally, R^xmay be —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H) or C₁-C₆-alkyl. Further, R^ecan be absent where the R^xis a deprotonated carboxylic acid moiety (e.g., where R^xis —CH₂CH₂CO₂ ⁻).
For the imidazolines described herein, R^xcan 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, R^xcan be derived from acrylic acid (H₂C═CHCO₂H).
Imidazolines of formulae (I), (II), or (III) can have R⁴and R⁵each 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, R⁴and R⁵can each independently be an unsubstituted C₁-C₆alkyl group or hydrogen. In some embodiments, R⁴and R⁵are each hydrogen (—H).
Imidazolines of formulae (I), (II), or (III) can have R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹each independently be, at each occurrence, selected from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. For example, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹can 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 R¹¹can 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 R¹¹can each independently be, at each occurrence, selected from hydrogen, and a radical derived from a fatty acid.
R¹²and R¹³can each independently be, at each occurrence, selected from hydrogen, C₁-C₁₀-alkyl, —COR¹⁴, —CO₂R¹⁵, —C₁-C₁₀-alkyl-COR¹⁶, and —C₁-C₁₀-alkyl-CO₂R¹⁷. Further, R¹²and R¹³can each independently be, at each occurrence, selected from hydrogen, unsubstituted C₁-C₁₀-alkyl, —COR¹⁴, —CO₂R¹⁵, —C₁-C₁₀-alkyl-COR¹⁶, and —C₁-C₁₀-alkyl-CO₂R¹⁷.
R¹⁴, R¹⁵, R¹⁶, and R¹⁷can each independently be, at each occurrence, selected from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. Further, R¹⁴, R¹⁵, R¹⁶, and R¹⁷can each independently be, at each occurrence, selected from hydrogen, unsubstituted C₁-C₃₄-alkyl, and unsubstituted C₂-C₃₄-alkenyl. Additionally, R¹⁴, R¹⁵, R¹⁶, and R¹⁷can each independently be, at each occurrence, selected from hydrogen, unsubstituted C₁-C₁₀-alkyl, and unsubstituted C₂-C₁₀-alkenyl. Further, R¹⁵and/or R¹⁷can be absent where the carboxylic acid moiety is deprotonated.
Imidazoline compounds of the present disclosure can have R¹⁴, R¹⁵, R¹⁶, and R¹⁷each independently be, at each occurrence, selected from hydrogen, and a radical derived from a fatty acid. Further, R¹⁴, R¹⁵, R¹⁶, and R¹⁷can each independently be, at each occurrence, selected from hydrogen, C₄-C₃₄-alkyl, and C₄-C₃₄-alkenyl. Additionally, R¹⁴, R¹⁵, R¹⁶, and R¹⁷can 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═CHCH₂CH₃; —(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═CHCH₂CH₃; —(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.
For the imidazolines of formulae (I), (II), and (III), R¹⁴, R¹⁵, R¹⁶, and R¹⁷can 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, palm itic 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. Suitable unsaturated fatty acids include, but are not limited to, myristoleic acid, palm itoleic 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.
Further, R¹⁴, R¹⁵, R¹⁶, and R¹⁷are each independently, at each occurrence, hydrogen or a radical derived from coconut oil, beef tallow, or tall oil fatty acids (TOFA).
In some embodiments, the imidazoline is a compound of formula (I), wherein R¹is unsubstituted C₂-C₆-alkyl; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³is —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R³is —CH₂CH₂CO₂ ⁻); R⁴is hydrogen; and R⁵is hydrogen.
In some embodiments, the imidazoline is a compound of formula (I), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²is hydrogen and R¹³is —COR¹⁴wherein R¹⁴is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³is —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R³is —CH₂CH₂CO₂ ⁻); R⁴is hydrogen; and R⁵is hydrogen.
In certain embodiments, the imidazoline is a compound of formula (I), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²and R¹³are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷is hydrogen or is absent (e.g., R¹²is —C₂-alkyl-CO₂ ⁻); R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³is —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R³is —CH₂CH₂CO₂ ⁻); R⁴is hydrogen; and R⁵is hydrogen.
In some embodiments, the imidazoline is a compound of formula (II), wherein R¹is unsubstituted C₂-C₆-alkyl; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³is —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R³is —CH₂CH₂CO₂ ⁻); R^xis —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R^xis —CH₂CH₂CO₂ ⁻); R⁴is hydrogen; and R⁵is hydrogen.
In some embodiments, the imidazoline is a compound of formula (II), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²is hydrogen and R¹³is —COR¹⁴, wherein R¹⁴is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³is —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R³is —CH₂CH₂CO₂ ⁻); R^xis —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R^xis —CH₂CH₂CO₂ ⁻); R⁴is hydrogen; and R⁵is hydrogen.
In certain embodiments, the imidazoline can be a compound of formula (II), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²and R¹³are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷is hydrogen or is absent (e.g., R¹²is —C₂-alkyl-CO₂ ⁻); R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³is —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R³is —CH₂CH₂CO₂ ⁻); R^xis —CH₂CH₂CO₂R^e, wherein R^eis hydrogen (—H), C₁-C₆-alkyl, or R^eis absent (e.g., R^xis —CH₂CH₂CO₂ ⁻); R⁴is hydrogen; and R⁵is hydrogen.
In some embodiments, the imidazoline can be a compound of formula (III), wherein R¹is unsubstituted C₂-C₆-alkyl; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴is hydrogen; and R⁵is hydrogen.
In some embodiments, the imidazoline can be a compound of formula (III), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²is hydrogen and R¹³is —COR¹⁴, wherein R¹⁴is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴is hydrogen; and R⁵is hydrogen.
In certain embodiments, the imidazoline can be a compound of formula (III), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹²and R¹³are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷is hydrogen or is absent (e.g., R¹²is —C₂-alkyl-CO₂ ⁻); R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴is hydrogen; and R⁵is hydrogen.
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 R³and/or R^xis derived from an acrylic acid.
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.
Suitable alkyl, hydroxyalkyl, alkylaryl arylalkyl or arylamine quaternary salts include those alkylaryl, arylalkyl and arylamine quaternary salts of the formula [N⁺R^5aR^6aR^7aR^8a][X⁻] wherein R^5a, R^6a, R^7a, and R^8acontain one to 18 carbon atoms, and X is Cl, Br or I. For the quaternary amine, R^5a, R^6a, R^7a, and R^8acan each independently be selected from the group consisting of alkyl (e.g., C₁-C₁₈alkyl), hydroxyalkyl (e.g., C₁-C₁₈hydroxyalkyl), and arylalkyl (e.g., benzyl). The mono or polycyclic aromatic amine salt with an alkyl or alkylaryl halide include salts of the formula [N⁺R^5aR^6aR^7aR^8a][X⁻] wherein R^5a, R^6a, R^7a, and R^8acontain one to 18 carbon atoms, and X is Cl, Br or I.
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, C_12-16benzyl 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.
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.
The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, 16, and 18.
The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, and 16.
The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, 16, and 18 and X is Cl.
The quaternary amine can be a mixture of benzalkonium salts wherein n is 12, 14, and 16, and X is Cl.
The quaternary amine can be an alkyl pyridinium quaternary salt such as those represented by the general formula:
wherein R^9ais 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-C₆hydrocarbyl group.
In some embodiments, the corrosion inhibitor may comprise the following generic structure:
wherein R and R₁are each independently selected from the group consisting of a C₁-C₁₂alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl.
In certain embodiments, the corrosion inhibitor may comprise the following generic structure:
wherein R and R₁are each independently selected from the group consisting of a C₁-C₁₂alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl;
wherein R₂is selected from the group consisting of a C₁-C₄alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl; and
wherein X− is an anion, such as Cl⁻, F⁻, or Br⁻.
In some embodiments, the corrosion inhibitor may comprise the following generic structure:
wherein R, R₁, and R₂are each independently selected from the group consisting of a C₁-C₄alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl;
wherein R3 is selected from the group consisting of a C₆-C₁₈alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; and
wherein X− is an anion, such as Cl⁻, F⁻, or Br⁻.
In certain embodiments, the corrosion inhibitor may comprise the following generic structure:
wherein R is selected from the group consisting of a C₆-C₁₈alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; and
wherein X− is an anion, such as Cl⁻, F⁻, or Br⁻.
The corrosion inhibitor 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; R²is H, CH₃, or an unsubstituted, linear or branched C₂-C₁₀alkyl, alkenyl, or alkynyl group; R³is absent or an unsubstituted, linear C₁-C₃₀alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; R⁴, R⁵, and R⁶are independently a C₁-C₁₀alkyl group; wherein the epoxide has the following formula;
R⁷is H or alkyl; and R⁸is 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-[R^10′]_n—NA₂, (RNA)_n-RNA₂, NA₂-(RNA)_n-RNA₂, or NA₂-(RN(R′))_n-RNA₂, wherein R^10′is a linear or branched, unsubstituted or substituted C₂-C₁₀alkylene group, or combination thereof; R is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstituted or substituted C₄-C₁₀alkylene group, or combination thereof; R′ is —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, a linear or branched, unsubstituted or substituted C₄-C₁₀alkyl group, RNAB, RNARNAB, or RN(RNAB)₂; n can be from 2 to 1,000,000; A is a combination of H,
and
wherein X is NH or O; R²is H, CH₃, or an unsubstituted, linear or branched C₂-C₁₀alkyl, alkenyl, or alkynyl group; R³is absent or an unsubstituted, linear C₁-C₃₀alkylene group; Y is —NR₄R₅R₆ ⁽⁺⁾; R⁴, R⁵, and R⁶are independently a C₁-C₁₀alkyl group; R⁷is H or alkyl; and R⁸is alkyl, or —(CH₂)_k—O-alkyl, wherein k is an integer of 1-30.
In certain embodiments, the compound may be a multiple charged cationic compound having a
group and a
group.
In some embodiments of the present disclosure, the corrosion inhibitor and/or composition excludes an ester, an imidazoline, a benzylic-based compound, a double bond, or any combination thereof.
As noted above, the production chemical may comprise a hydrate anti-agglomerate and/or a kinetic hydrate inhibitor. Hydrate anti-agglomerates and kinetic hydrate inhibitors are used in the energy industry for controlling gas hydrates. Typically, kinetic hydrate inhibitors are polymers that adsorb on gas hydrate crystal faces and interfere with the nucleation and growth of gas hydrate crystals. Hydrate anti-agglomerates are surface active molecules that attach to and disperse fine gas hydrate crystals, preventing their agglomeration and growth into masses that could become plugs. When relatively small gas hydrate crystals begin to form, hydrate anti-agglomerates attach to them to make their surfaces hydrophobic, which mediates the capillary attraction between the crystals and water and disperses the crystals into a hydrocarbon phase. This results in a transportable slurry that can flow to the processing facility.
In accordance with certain embodiments of the present disclosure, a hydrate anti-agglomerate may be a compound selected from the group consisting of Formula 1A, Formula 1B, and any combination thereof,
wherein A is an optionally substituted pyrrole, pyrroline, pyrrolidine, piperidine, pyrazole, pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine, triazole, isoxazole, isoxazoline, isoxazolidine, oxazole, oxazoline, thiazole, isothiazole, oxadiazole, oxatriazole, dioxazole, oxathiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, isoxazine, oxadiazine, morpholine, azepane, azepine, caprolactam, or quinoline; R₁is hydrogen, optionally substituted alkyl, alkenyl, alkynyl, or aryl; R₂is hydrogen, optionally substituted alkyl, alkenyl, or alkynyl; Z is —NR₃—C(O)—, —C(O)—NR₃—, —O—C(O)—, —C(O)—O—, —S—C(O)—, —C(O)—S—, —O—C(O)—NR₃—, —NR₃—C(O)—O—, —NR₃—C(O)—NR₃—, or absent; R₃is hydrogen, optionally substituted alkyl, alkenyl, alkynyl, or aryl; n is an integer from 0 to 25; and X⁻is an anion.
In some embodiments, the hydrate anti-agglomerate may be selected from a formula below:
wherein n, Z, R₁, R₂, and X are as defined in connection with Formula 1B and R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, and R₂₉are each independently hydrogen, alkyl, alkoxy, aminoalkyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy, carboxyalkenyl, aryl, aryloxy, or carboxyaryl; R₃₀is hydrogen, alkyl, or aryl; and R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R_36,and R₃₇are each independently hydrogen, alkyl, alkoxy, aminoalkyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy, carboxyalkenyl, aryl, aryloxy, or carboxyaryl. The compound of Formula 1B can also have the structure of Formula 2B, 5B, 7B, 8B, 9B, or 10B.
In some embodiments, the hydrate anti-agglomerate may be selected from a formula below:
wherein n, Z, R₁, and R₂are as defined in connection with Formula 1A and R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, and R₂₉are each independently hydrogen, alkyl, alkoxy, aminoalkyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy; carboxyalkenyl, aryl, aryloxy, or carboxyaryl; R₃₀is hydrogen, alkyl, or aryl; and R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, and R₃₆are each independently hydrogen, alkyl, alkoxy, aminoalkyl, carboxyl, carboxyalkyl, alkenyl, alkenoxy; carboxyalkenyl, aryl, aryloxy, or carboxyaryl. The anti-agglomerant compound of Formula 1A can also have the structure of Formula 2A, 3A, 4A, 5A, 7A, 8A, 9A, or 11A.
In certain embodiments, the hydrate anti-agglomerate comprises:
Compositions disclosed herein comprising a hydrate anti-agglomerate may have particular properties for advantageous use in a well, transport, or other system. For example, the composition may have a viscosity of less than about 250 cP, such as from about 1 cP to about 200 cP, about 1 cP to about 150 cP, about 1 cP to about 100 cP, about 1 cP to about 75 cP, about 1 cP to about 50 cP, or about 1 cP to about 25 cP, to provide a composition that can be easily pumped throughout a system.
With respect to the kinetic hydrate inhibitor, the present disclosure includes compounds selected from the following generic structures:
wherein n=about 5-100, such as about 5-90, about 5-80, about 5-70, about 5-60, about 5-50, about 5-40, about 5-30, about 5-20, about 5-10, about 10-20, about 10-30, about 10-40, about 10-50, or about 10-60;
wherein n=about 5-300, such as about 50-300, about 100-300, about 150-300, about 200-300, or about 250-300;
wherein n=about 5-100, such as about 5-90, about 5-80, about 5-70, about 5-60, about 5-50, about 5-40, about 5-30, about 5-20, or about 5-10; and
wherein n=about 1-20, such as from about 1-15, about 1-10, about 1-5, about 5-10, about 5-15, or about 5-20, m=about 1-10, about 1-9, about 1-8, about 1-7, about 1-6, about 1-5, about 1-4, about 1-3, or about 1-2, and wherein X− is an anion, such as Cl⁻, F⁻, or Br⁻.
Additional examples of kinetic hydrate inhibitors include compounds selected from the following generic structures:
wherein R is independently selected from the group consisting of hydrogen, functionalized or unfunctionalized alkyl, cycloalkyl, and aryl groups, wherein any of the aforementioned groups may be present with or without one or more heteroatoms. The symbol “m” may be a number from about 1 to about 60, such as about 1 to about 36 or about 1 to about 18, “n” may be a number from about 1 to about 60, such as about 1 to about 36 or about 1 to about 18, “o” may be a number from about 1 to about 60, such as about 1 to about 36 or about 1 to about 18 and “M” may be selected from H, Na, K, Li, Ca, Ba, Mg2+, Al3+, and NH₄+, for example.
In some embodiments, the kinetic hydrate inhibitor comprises the following chemical structure:
wherein “y” can be 1 or 2.
In some embodiments, the kinetic hydrate inhibitor and/or the composition does not comprise nitrogen. In some embodiments, the kinetic hydrate inhibitor is not branched. In certain embodiments, the kinetic hydrate inhibitor is aliphatic.
In certain embodiments, the kinetic hydrate inhibitor comprises a compound selected from the group consisting of N-vinyl-2-caprolactam, a terpolymer of N-vinyl-2-caprolactam, 2-acrylamido-2-methylpropane sulfonic acid, N-vinyl-2- pyrrolidone, and any combination thereof. The kinetic hydrate inhibitor may comprise branched or linear polymers comprising acyclic and/or cyclic nitrogen and ketone functionalities, such as poly-N-vinyl-2-caprolactam, and cyclic or acyclic N-vinyl amides, such as N-vinyl lactams.
Additional examples of kinetic hydrate inhibitors and anti-agglomerates include, but are not limited to, polysaccharides (such as hydroxyethylcellulose, carboxymethylcellulose, starch, starch derivatives, and xanthan), lactams (such as polyvinylcaprolactam and polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidones), surfactants (such as fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkyl glucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates, alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaine, and alkyl amido betaines), hydrocarbon-based dispersants (such as lignosulfonates, iminodisuccinates, and polyaspartates), amino acids, proteins, and combinations thereof.
A thermodynamic hydrate inhibitor is also contemplated as a production chemical and may be, for example, methanol, ethylene glycol, ethanol, or any combination thereof. Also, the production chemical may comprise a non-regenerable H₂S scavenger, such as a hemiacetal compound and/or a triazine molecule. Further, the production chemical may comprise an alcohol for gas dehydration or hydrate control, such as ethylene glycol, diethylene glycol, and/or triethylene glycol. Additionally, the production chemical may comprise a regenerable H₂S scavenger, such as a scavenger that undergoes an oxidation-reduction reaction between an electron poor substrate, such as Fe³⁺, and hydrogen sulfide. The electron poor substance can then be regenerated with ambient oxygen.
In accordance with certain aspects of the present disclosure, the production chemical may be selected from the group consisting of 3-(C₁₂-C₁₅alkoxy)-2-hydroxypropyl-trimethyl-ammonium chloride, a quaternary ammonium compound, an alkylpyridine, and any combination thereof.
The quaternary ammonium compound may be selected from, for example, a trialkyl quaternary ammonium compound, an alkylpyridinium quaternary ammonium salt, coco-dimethyl benzyl ammonium chloride, a trimethyl alklyl benzyl ammonium chloride, and any combination thereof.
In certain aspects, the quaternary ammonium compound may comprise the following structure:
wherein R is selected from the group consisting of C₆-C₁₈alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; and
wherein X− is an anion, such as Cl⁻, F⁻, or Br⁻.
In accordance with the present disclosure, an anti-foulant may be selected from the reaction product of a tetraethlylene and a saturated carboxylic acid.
Depending upon the desired application of the compositions disclosed herein, in certain embodiments, the compositions may comprise a hydrocarbon. For example, a composition disclosed herein may comprise, consist of, or consist essentially of hydrogen gas, a production chemical, and a hydrocarbon.
As illustrative examples, the hydrocarbon may be selected from the group consisting of methane, ethane, ethylene, propane, butane, pentane, hexane, heptane, octane, nonane, decane, 1-butene, 2-butene, 1,4-butadiene, and any combination thereof.
Depending upon the desired application of the compositions disclosed herein, in certain embodiments, a medium may comprise the composition. In some embodiments, a composition disclosed herein may comprise, consist of, or consist essentially of hydrogen gas, a production chemical, and a medium.
As illustrative examples, the medium may be selected from a wet gas medium, a dry gas medium, a dry gas medium comprising a gas condensate, a wet gas medium comprising a gas condensate, a wet gas medium comprising water and a gas condensate, an aqueous medium, a non-aqueous medium, an organic medium, a gaseous medium, and any combination thereof.
In some embodiments, a composition and/or medium disclosed herein may comprise natural gas, which is a mixture of various gasses that may or may not include any combination of methane, ethane, propane, butane, pentane, hexane, nitrogen, carbon dioxide, oxygen, and hydrogen.
In some embodiments, the production chemical comprises 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.
In some aspects, the production chemical comprises 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 benzy-(C₁₂to C₁₈linear 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 certain embodiments, the production chemical may comprise an amine, such as when the chemical is used in gas sweetening processes (e.g., a process to remove hydrogen sulfide). Illustrative, non-limiting examples of amines include primary, secondary, and tertiary amines. Additional examples include methydiethanolamine (MDEA), MDEA/piperazine, ethanolamine, diethanolamine, diisopropylamine, imethylethanolamine, and any combination thereof.
In some embodiments, the production chemical may comprise a glycol, such as when the chemical is used in a dehydration process to dehydrate natural gas. For example, the production chemical can be added to any location in a gas dehydration system. Illustrative, non-limiting examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, and any combination thereof.
In some embodiments, the production chemical may comprise a biocide. Illustrative, non-limiting examples of biocides include oxidizing and non-oxidizing biocides. Examples of non-oxidizing biocides include aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein), amine-type compounds (e.g., quaternary amine compounds and cocodiamine), halogenated compounds (e.g., bronopol and 2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g., isothiazolone, carbamates, and metronidazole), quaternary phosphonium salts (e.g., tetrakis(hydroxymethyl)phosphonium sulfate (THPS)), and any combination thereof. Examples of oxidizing biocides include sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, a chlorinated hydantoin, stabilized sodium hypobromite, activated sodium bromide, a brominated hydantoin, chlorine dioxide, ozone, a peroxide, and any combination thereof.
In some embodiments, the compositions of the present disclosure may further 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. 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, and any combination thereof.
Representative polar solvents suitable for formulation with the composition 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.
Representative non-polar solvents suitable for formulation with the composition 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.
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.
A composition of the present disclosure may include from about 0 to about 99 wt. % of the solvent. For example, a composition of the present disclosure may comprise about 5 wt. %, about 10 wt. %, about 15 wt. %, about 20 wt. %, about 25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45 wt. %, about 50 wt. %, about 55 wt. %, about 60 wt. %, about 65 wt. %, about 70 wt. %, about 75 wt. %, about 80 wt. %, about 85 wt. %, about 90 wt. %, or about 95 wt. % of the solvent.
In certain embodiments, the production chemical comprises the following generic structure:
wherein R is selected from a C₁-C₁₈alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl; and
wherein n is 0, 1, 2, 3, 4, 5, or 6. This molecule may function as, for example, a corrosion inhibitor and/or an anti-foulant.
The compositions of the present disclosure may comprise various amounts of the compounds and/or components disclosed herein, such as the production chemical and the hydrogen gas.
For example, a composition may comprise from about 1 wt. % to about 100 wt. % of the production chemical, such as from about 1 wt. % to about 90 wt. %, about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %, about 1 wt. % to about 60 wt. %, about 1 wt. % to about 50 wt. %, about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. %.
The compositions (and/or mediums) of the present disclosure may comprise from about 0 wt. % to about 99 wt. % of the hydrogen gas, such as from about 1 wt. % to about 90 wt. %, about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %, about 1 wt. % to about 60 wt. %, about 1 wt. % to about 50 wt. %, about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. %.
The compositions of the present disclosure may comprise from about 0 wt. % to about 99 wt. % of any other component disclosed herein, such as solvent. For example, a composition may comprise from about 1 wt. % to about 95 wt. % of the component, such as from about 1 wt. % to about 90 wt. %, about 1 wt. % to about 80 wt. %, about 1 wt. % to about 70 wt. %, about 1 wt. % to about 60 wt. %, about 1 wt. % to about 50 wt. %, about 1 wt. % to about 40 wt. %, about 1 wt. % to about 30 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. %.
In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of a corrosion inhibitor compound and hydrogen gas. In certain embodiments, a composition comprises, consists of, or consists essentially of a corrosion inhibitor compound, hydrogen gas, an additional component disclosed herein, and optionally natural gas.
In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of a hydrate anti-agglomerate and hydrogen gas. In certain embodiments, a composition comprises, consists of, or consists essentially of a hydrate anti-agglomerate, hydrogen gas, and an additional component disclosed herein.
In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of a kinetic hydrate inhibitor and hydrogen gas. In certain embodiments, a composition comprises, consists of, or consists essentially of a kinetic hydrate inhibitor, hydrogen gas, and an additional component disclosed herein.
In some embodiments, a composition disclosed herein comprises, consists of, or consists essentially of an anti-foulant and hydrogen gas. In certain embodiments, a composition comprises, consists of, or consists essentially of an anti-foulant, hydrogen gas, and an additional component disclosed herein.
In certain embodiments, the composition comprises, consists of, or consists essentially of the production chemical.
The compositions of the present disclosure can be used in any industry where hydrogen gas may be present. 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. A medium to which the composition can be introduced may be an aqueous medium. In some embodiments, the aqueous medium can comprise water, gas, and optionally liquid hydrocarbon.
A medium to which the composition can be introduced may, in some embodiments, be 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 fluid or gas may also be a refined hydrocarbon product.
In some embodiments, the methods of the present disclosure may be carried out when ammonia and/or hydrogen gas are present. Under certain conditions, hydrogen gas may be converted to ammonia, and/or ammonia may be converted to hydrogen gas. Ammonia and hydrogen gas may have a negative impact on equipment used to carry out various industrial processes and may cause, for example, hydrogen-induced cracking, hydrogen embrittlement, and/or ammonia stress cracking (also known as ammonia stress corrosion cracking) on the surfaces of the equipment. In particular, ammonia at low pressures may cause cracking and/or embrittlement and hydrogen gas at high pressures may cause cracking and/or embrittlement on a surface. To prevent or inhibit such cracking and/or embrittlement, a composition comprising, for example, any corrosion inhibitor (or combination of corrosion inhibitors) disclosed herein may be added to a medium in contact with the surface susceptible to cracking and/or embrittlement. In some embodiments, the medium comprises a dry gas and/or natural gas.
In accordance with the present disclosure, ammonia stress corrosion cracking is a specific type of cracking that occurs on a metallic surface that is expose to a medium containing ammonia. Without wishing to be bound by theory, it is thought that ammonia may be absorbed onto the metallic surface.
With respect to hydrogen embrittlement, the present disclosure contemplates a situation where a surface suffers a reduction in strength/toughness and ductility because atomic hydrogen has diffused into the surface. The small-sized hydrogen atom can travel and diffuse into a lattice of the metal surface and accumulate at, for example, dislocations and grain boundaries. The atomic hydrogen significantly affects the mechanical properties of the metallic surface and renders it weaker and more fragile. In some cases, the surface may become brittle without necessarily showing any visual evidence of cracking.
In accordance with the present disclosure, hydrogen-induced cracking refers to a process where hydrogen is absorbed into a surface and then recombines in voids in the surface to form hydrogen molecules. The hydrogen molecules exert a high level of pressure, causing the surface to crack.
In some instances, if the source of hydrogen is hydrogen sulfide, hydrogen-induced cracking may be referred to as sulfide stress corrosion cracking. The methods and compositions disclosed herein are also effective for the treatment of sulfide stress corrosion cracking.
Still further, the methods and compositions disclosed herein are effective for the treatment of hydrogen blistering, which occurs when atomic hydrogen is absorbed into a surface and then recombines to form a hydrogen molecule near the area of the surface that is exposed to the corrosive environment.
In some embodiments, the present disclosure provides a method of inhibiting embrittlement or cracking of a surface in contact with a medium. The method comprises adding a composition disclosed herein, in any amount contemplated herein, to any medium disclosed herein, wherein the composition comprises, consists of, or consists essentially of a corrosion inhibitor and optionally any other component, solvent, and/or production chemical disclosed herein. In some embodiments, the medium comprises natural gas, hydrogen gas, hydrogen sulfide gas, ammonia, or any combination thereof. In certain embodiments, the surface may be a metallic surface.
As illustrative, non-limiting examples, the corrosion inhibitor may be selected from the group consisting of an organic sulfur compound, an imidazoline, a carboxylic acid, 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. Any corrosion inhibitor contemplated by or explicitly disclosed in the present application may be used.
As illustrative, non-limiting examples, the medium may be a wet gas medium, a dry gas medium, a dry gas medium comprising a gas condensate, a wet gas medium comprising a gas condensate, a wet gas medium comprising water and a gas condensate, an aqueous medium, a non-aqueous medium, an organic medium, a gaseous medium, and any combination thereof.
In some embodiments, the medium may be present within a pipeline, a gas processing plant, a refinery, a storage tank, and/or an ethylene plant.
In some embodiments, the surface comprises a metal selected from the group consisting of steel, carbon steel, alloy steel, stainless steel, iron, copper, aluminum, magnesium, brass, zinc, titanium, nickel, tin, lead, and any combination thereof.
The amount of corrosion inhibitor in the composition is not particularly limited and may be any amount disclosed in or contemplated by the present disclosure. For example, the composition may comprise from about 1 wt. % to about 100 wt. % of the corrosion inhibitor or any subrange disclosed in the present application.
Moreover, the amount of the composition added to the medium and/or surface may be selected from, for example, about 1 ppm to about 50,000 ppm or any subrange disclosed in the present application.
A medium, such as a fluid or gas, treated with a composition 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, etc.) or gas can be at a temperature of from about 40° C. to about 250° C. In some embodiments, the medium can 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.
The compositions 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. In some embodiments, the medium may be an aqueous medium that contains various levels of salinity. For example, the fluid 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).
The medium in which the compositions of the disclosure are introduced can be contained in/present within and/or exposed to many different types of devices. For example, the medium can be contained in a device that transports fluid or gas from one point to another, such as an oil and/or gas pipeline. The device can 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 can also be contained in and/or exposed to a device used in oil extraction and/or production, such as a wellhead.
The compositions disclosed herein may be introduced into a medium, such as a fluid or gas, by any appropriate method. For example, if corrosion prevention is desired, the composition may be added at a point in a flow line upstream from the point at which corrosion prevention is desired. The composition may be injected using mechanical equipment, such as chemical injection pumps, piping tees, injection fittings, atomizers, quills, and the like. The compositions disclosed herein may be introduced with or without a solvent. The compositions may be pumped into an oil and/or gas pipeline using an umbilical line. Capillary injection systems may also be used to deliver the compositions to a selected fluid. In some embodiments, the compositions may be introduced into a liquid and mixed. In some embodiments, the compositions may be injected into a gas stream as an aqueous or non-aqueous solution, mixture, or slurry. In certain embodiments, the fluid or gas may be passed through an absorption tower comprising a composition disclosed herein.
In some embodiments, the compositions disclosed herein may be added during a process for removing black powder, which is a mineral particulate contaminant that may be present in a hydrocarbon transmission line.
In certain embodiments, the compositions disclosed herein may be added during a “pigging” process, wherein highly viscous fluids are conveyed out of pipelines. A cleaning device, referred to as a pig, is pumped through the pipeline under pressure and contaminants are transported out of the pipeline.
During a hydrogen transportation process, ammonia is used as a carrier for the hydrogen. The hydrogen is carried at very low temperatures. The compositions disclosed herein may be added to the ammonia during the transportation process.
Generally, the compositions comprising a kinetic hydrate inhibitor will be utilized in certain types of downhole applications. A kinetic hydrate inhibitor is useful when the downhole application involves off-shore applications. When utilized, the kinetic hydrate inhibitor composition may be dosed into an aqueous liquid utilized in a downhole application at a constant dosage rate or a variable dosage rate. The kinetic hydrate inhibitor composition may be dosed continuously or intermittently.
Generally, the kinetic hydrate inhibitor compositions may be dosed into an aqueous liquid utilized in a downhole application at a rate of from about 1,000 mg to about 100,000 mg per liter of aqueous liquid, including from about 1,000 mg to about 50,000 mg, about 1,000 mg to about 30,000 mg, from about 1,000 mg to about 10,000 mg, or about 1,000 mg to about 5,000 mg per liter of aqueous liquid.
Certain aspects of the present disclosure relate to methods for inhibiting gas hydrate agglomeration in a medium, such as a fluid comprising a hydrocarbon and water. For example, a method may comprise adding to the medium an effective amount of a composition disclosed herein, wherein the composition includes a hydrate anti-agglomerate. The hydrate anti-agglomerant is present in an amount which, upon addition to a hydrocarbon fluid at a location, such as a well head, a riser or a flow line of a sub-sea oil system, will prevent gas hydrate agglomeration.
Generally, the hydrate anti-agglomerate may be added into a medium, such as into a mixture of a hydrocarbon and water, at any concentration effective to inhibit the formation of gas hydrate agglomerates under the given conditions. Accordingly, the effective amount of the compound can range from about 0.1 vol. % to about 10 vol. %, based on the amount of water, such as produced water, in the industrial system, such as a well system. In some embodiments, the effective amount of the hydrate anti-agglomerate ranges from about 0.1 vol. % to about 5 vol. %. The effective amount can also range from about 0.5 vol. % to about 5 vol. %. The effective amount of the hydrate anti-agglomerate can be provided to the system in one or more doses on a continuous or intermittent basis.
Compositions of the present disclosure can be added at various locations throughout the industrial systems contemplated herein. For example, a composition may be injected at a wellhead, below the wellhead, or in a riser or a flow line of a sub-sea oil system. The compositions can also be added to pipelines, for example. In embodiments where the production chemical comprises an anti-foulant, the composition may be added before a compressor, for example, and/or into a pipeline, conduit, storage container, transportation container, housing, etc., where hydrogen may be present.
In accordance with certain embodiments of the present disclosure, a method of treating a medium in an industrial process is provided. The method comprises adding hydrogen gas to the medium and adding a production chemical to the medium. The hydrogen gas may be added before, after, and/or as a composition with the production chemical. In certain embodiments, at least some of the hydrogen gas is added separately from the production chemical. In certain embodiments, at least some of the hydrogen gas is combined with a hydrocarbon before being added to the medium.
The medium may be present within a component of an industrial system, such as in a pipeline, a gas processing plant, a refinery, or an ethylene plant.
In some embodiments, the medium is a wet gas medium, a dry gas medium, a dry gas medium comprising a gas condensate, a wet gas medium comprising a gas condensate, a wet gas medium comprising water and a gas condensate, an aqueous medium, a non-aqueous medium, an organic medium, a gaseous medium, and any combination thereof.
In accordance with certain embodiments, the medium is not present in a subterranean formation. In accordance with certain embodiments, the hydrogen gas and the production chemical are not added to a subterranean formation.
In accordance with the methods disclosed herein, the effective amount of the production chemical added to the system and/or the medium of the system can be selected based on the desired application. In some embodiments, the effective amount is from about 1 ppm to about 50,000 ppm. For example, the effective amount may be from about 1 ppm to about 40,000 ppm, from about 1 ppm to about 30,000 ppm, from about 1 ppm to about 20,000 ppm, from about 1 ppm to about 10,000 ppm, from about 1 ppm to about 9,000 ppm, from about 1 ppm to about 8,000 ppm, from about 1 ppm to about 7,000 ppm, from about 1 ppm to about 6,000 ppm, from about 1 ppm to about 5,000 ppm, from about 1 ppm to about 4,000 ppm, from about 1 ppm to about 3,000 ppm, from about 1 ppm to about 2,000 ppm, from about 1 ppm to about 1,000 ppm, from about 1 ppm to about 500 ppm, from about 1 ppm to about 250 ppm, or from about 1 ppm to about 100 ppm. In some embodiments, the effective amount is from about 5 ppm to about 2,000 ppm.
The present disclosure also provides test methods that can determine the susceptibility of a chemical to a hydrogenation reaction in a hydrogen rich environment. Thus, the methods can be used, for example, to determine if a particular production chemical will retain its intended function in the presence of hydrogen gas. For example, if the intended function of a production chemical is to inhibit corrosion, the test methods disclosed herein will allow a skilled artisan to determine if the production chemical will be able to function as a corrosion inhibitor in the presence of hydrogen.
In some embodiments, a method comprises adding a production chemical to an autoclave, adding hydrogen gas to the autoclave, monitoring a pressure within the autoclave, and determining if the hydrogen gas reacted with the production chemical. In certain embodiments, a transition metal catalyst is added to the autoclave. In certain embodiments, a Pd/C catalyst is added to the autoclave.
In accordance with some embodiments, the autoclave may contain about 500 to about 1,000 psig of the hydrogen gas before the monitoring step commences. The pressure may be monitored continuously or intermittently. In certain embodiments, the pressure is monitored for about 2 hours to about 336 hours. In accordance with some embodiments, a reduction in pressure over time indicates that the production chemical reacted with the hydrogen and may thus not be an appropriate production chemical to select for an industrial application where hydrogen gas may be present.
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

To determine if production chemical compatibility with hydrogen would be problematic, static autoclaves were used to test Product 1, which includes the ester reaction product of triethanolamine and tall oil fatty acid as well as the amide reaction product of tetraethylenepentamine and tall oil fatty acid in the presence of hydrogen with palladium on carbon as a catalyst for the reaction. Product 1 contains an ester and an amide, both of which contain unsaturated alkyl chains. The unsaturated alkyl groups and ester functional groups have the potential to react with hydrogen. The hydrogen compatibility test of the present disclosure quickly determined that the compatibility of the production chemical with hydrogen would be of concern.
Product 1 was placed in a static autoclave and about 2 g of Pd/C were added as a catalyst to the autoclave. The autoclave was then charged with hydrogen to about 600 psig and left for 12 days. The temperature of the test was about 60° C. and the chemical was left stirring at about 100 rpm throughout the duration of the test. The gas chosen for the experiment was 100% hydrogen, although the reaction could occur at lower partial pressures of H₂. After about 24 hours, the pressure dropped to about 400 psig, which accounted for a pressure loss of about 200 psig (˜33% loss), and remained there until the end of the test. The material was then collected and filtered. Upon cooling, the product became a solid material, which indicated incompatibility with hydrogen.
Additionally, an alkyl pyridine was subjected to the same test conditions as Product 1 and at the end of the test, it remained a liquid and saw much less of a pressure reduction over the same time. Additionally, NMR was used to compare pre and post-test material and there was no observable difference based on the spectra. While alkylpyridine contains sites of unsaturation, they are not as susceptible to hydrogenation conditions as the three double bonds are resonance stabilized.
Additional laboratory experiments were conducted to show the unexpectedly superior performance of the presently disclosed compositions as inhibitors of hydrogen-induced cracking or embrittlement of the metal surface by the methodology described below.
The evaluations were conducted using A516-70 grade steel. Baseline samples were evaluated utilizing 350 ml static autoclave vessels. Tests included placing metal samples into the static vessel for about 24 hours and about 72 hours. Once inside the vessel, the metal samples were pressurized with either ammonia gas, hydrogen gas, or a mixture of hydrogen and ammonia. The metal samples were then left pressurized in the presence of each gas at a static state for the desired test duration at ambient temperature or about 60° C. Once the test duration had passed, the metal samples were extracted, cleaned, and examined under a microscope for surface irregularities indicating embrittlement and/or cracking. Under the most severe conditions (the conditions that produced the most surface irregularities), tests were conducted with various corrosion inhibitors in an attempt to inhibit the formation of surface irregularities. The corrosion inhibitor was applied directly to the coupon by dipping the coupon into a solution of corrosion inhibitor containing approximately 25 wt. % corrosion inhibitor. The excess corrosion inhibitor was allowed to drip for about 30 seconds and then excess corrosion inhibitor was removed by blotting with an absorbent paper napkin. One of the corrosion inhibitors tested comprised an alkyl pyridine and a second corrosion inhibitor tested comprised a salted polyamine fatty acid condensate. It was observed that under the same conditions, both corrosion inhibitor compositions were able to inhibit the surface irregularities observed in the blanks.
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 production chemical” is intended to include “at least one production chemical” or “one or more production chemicals.”
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.
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.
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.
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.
The transitional phrase “consisting of” excludes any element, component, ingredient, and/or method step not specified in the claim.
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.
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.
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.
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.

Claims

What is claimed is:

1. A method of treating a medium in an industrial process, comprising:

adding hydrogen gas to the medium, and

adding a production chemical to the medium.

2. The method of claim 1, wherein the hydrogen gas is added before, after, and/or with the production chemical.

3. The method of claim 1, wherein the production chemical comprises a corrosion inhibitor, an anti-foulant, a hydrate anti-agglomerate, a kinetic hydrate inhibitor, an amine for gas sweetening, a regenerable H₂S scavenger, a non-regenerable H₂S scavenger, an alcohol for gas dehydration, an alcohol for hydrate control, a thermodynamic hydrate inhibitor, or any combination thereof.

4. The method of claim 1, wherein the medium is present within a pipeline, a gas processing plant, a refinery, an ethylene plant, or any combination thereof.

5. The method of claim 1, wherein the medium is not present within a subterranean formation.

6. The method of claim 1, wherein the hydrogen gas and the production chemical are not added to a subterranean formation.

7. The method of claim 1, wherein at least some of the hydrogen gas is added separately from the production chemical.

8. The method of claim 3, wherein the corrosion inhibitor is selected from the group consisting of an organic sulfur compound, an imidazoline, a carboxylic acid, 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.

9. The method of claim 1, wherein the hydrogen gas is combined with a hydrocarbon before being added to the medium.

10. A method, comprising:

adding a production chemical to an autoclave,

adding hydrogen gas to the autoclave,

monitoring a pressure within the autoclave, and

determining if the hydrogen gas reacted with the production chemical.

11. The method of claim 10, wherein a Pd/C or a transition metal catalyst is added to the autoclave.

12. The method of claim 10, wherein the autoclave comprises about 500 to about 1,000 psig of the hydrogen gas before the monitoring step commences.

13. A method of inhibiting embrittlement or cracking of a surface in contact with a medium, comprising:

adding a composition to the surface and/or the medium, wherein the composition comprises a corrosion inhibitor and optionally a solvent and/or a production chemical, wherein the medium comprises natural gas, hydrogen gas, hydrogen sulfide gas, ammonia, or any combination thereof.

14. The method of claim 13, wherein the corrosion inhibitor is selected from the group consisting of an organic sulfur compound, an imidazoline, a carboxylic acid, 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.

15. The method of claim 13, wherein the medium is a wet gas medium, a dry gas medium, a dry gas medium comprising a gas condensate, a wet gas medium comprising a gas condensate, a wet gas medium comprising water and a gas condensate, an aqueous medium, a non-aqueous medium, an organic medium, a gaseous medium, and any combination thereof.

16. The method of claim 13, wherein the medium is present within a pipeline, a gas processing plant, a refinery, a storage tank, an ethylene plant, or any combination thereof.

17. The method of claim 13, wherein the surface comprises a metal selected from the group consisting of steel, carbon steel, alloy steel, stainless steel, iron, copper, aluminum, magnesium, brass, zinc, titanium, nickel, tin, lead, and any combination thereof.

18. The method of claim 13, wherein the composition comprises from about 1 wt. % to about 100 wt. % of the corrosion inhibitor.

19. The method of claim 13, wherein from about 1 ppm to about 50,000 ppm of the corrosion inhibitor is added to the medium and/or surface.

20. The method of claim 13, wherein the solvent is selected from the group consisting of an alcohol, a hydrocarbon, a ketone, an ether, an aromatic, an amide, a nitrile, a sulfoxide, an ester, a glycol ether, water, and any combination thereof.