Additives for hydrogen-containing mediums

Abstract

The disclosure provides systems, methods, and compositions for treating a medium. A method may include adding a composition including an additive to the medium. Examples of additives include a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof. A medium may include, for example, hydrogen, and other components, such as an acid and / or an impurity.

Description

ADDITIVES FOR HYDROGEN-CONTAINING MEDIUMSTECHNICAL FIELD

[0001] The present disclosure generally relates to additives for hydrogencontaining mediums. More particularly, the disclosure relates to methods, systems, and compositions including additives for treating impurities in hydrogen-containing mediums.BACKGROUND

[0002] Hydrogen is anticipated to play a crucial role in the global energy transition, serving as a clean and versatile energy carrier. Its significance lies in its potential to decarbonize various sectors of the economy. In liquid hydrogen pipelines, several acids, including sulfuric acid, sulfurous acid, nitric acid, and nitrous acid, can be present. These acids can cause significant problems, such as corrosion, which can compromise the integrity and safety of the pipelines. The acids can cause extensive corrosion of the metal pipeline and / or they can accelerate the degradation of protective coatings and liners on the inner wall of the pipeline, thereby reducing their lifespan and effectiveness.

[0003] The presence of acids and oxygen can lead to electrochemical reactions that result in the oxidation of metals, producing metal oxides and other compounds that weaken the pipeline material. These acids can also lead to stress corrosion cracking, where the combined effect of tensile stress and a corrosive environment causes the pipeline to crack and fail.

[0004] Typically, these acids are countered by using higher alloy steel, corrosion-resistant alloys, and / or corrosion-resistant composite materials. However, these materials add significant cost to the overall operation. Other means include the use of corrosion inhibitors, but not only can these be expensive, oftentimes corrosion inhibitors may be specifically tailored to one cause or variety of corrosion but not another.

[0005] There are multiple sources of hydrogen, including green, blue, brown, grey and turquoise. Blue, grey and turquoise are produced fromnatural gas with carbon capture and storage (CCS) technologies, natural gas without carbon capture, and through the gasification of methane coupled with CCS, respectively. Thus, while these streams are predominately hydrogen, they also may include various impurities that can result in acid formation and corrosion in liquid hydrogen pipelines.

[0006] For example, water present in hydrogen pipelines can lead to the formation of hydrates, which can block pipelines and / or lead to corrosion if combined with, for example, carbon dioxide. Carbon dioxide may form carbonic acid when dissolved in water. Also, if hydrogen sulfide is present, it can react with water to form sulfurous acid and it can lead to cracking, such as sulfide stress cracking and hydrogen-induced cracking. Oxygen impurities can react with hydrogen in addition to the pipeline materials. In the presence of water, oxygen can accelerate the corrosion of metals by forming rust (iron oxides and hydroxides in the case of iron or steel pipelines). Sulfur dioxide can dissolve in water to form sulfurous acid, which is highly corrosive to metals used in pipeline construction. Additionally, nitrogen oxides can dissolve in water to form nitric acid and / or nitrous acid, which are highly corrosive.BRIEF SUMMARY

[0007] The present disclosure provides a method of treating a medium. The method comprises adding a composition comprising an additive to the medium. The additive may be selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof. The medium may comprise hydrogen.

[0008] The present disclosure also provides compositions for treating hydrogen-containing mediums. The compositions comprise hydrogen, an impurity, and an additive selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfidescavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof.

[0009] The present disclosure also provides a method of inhibiting corrosion of a metal surface in contact with a medium. The method comprises adding a composition to the medium, wherein the composition comprises an additive selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof, and wherein the medium comprises hydrogen and an impurity and / or an acid selected from the group consisting of sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and any combination thereof.

[0010] The present disclosure further provides a device (e.g., a pipeline, a reaction vessel, and / or a storage container) comprising hydrogen and an additive, wherein the additive is selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof.

[0011] Additionally, the present disclosure provides a system comprising a pipeline containing hydrogen and an impurity. The system also comprises an impurity removal unit coupled to the pipeline, wherein the impurity removal unit receives at least a portion of the hydrogen from a first location on the pipeline, removes the impurity and / or converts the impurity to a compound that can be removed by the impurity removal unit, and sends an impurity depleted hydrogen to a second location on the pipeline downstream of the first location.

[0012] 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.DETAILED DESCRIPTION

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] “Cycloalkyl” refers to a cyclic alkyl substituent containing from, for example, about 3 to about 8 carbon atoms, such as from about 4 to about 7 carbon atoms or about 4 to 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.

[0019] “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.

[0020] 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 anunsubstituted C1-C10 alkoxy group. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.

[0021] 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 RAand RB are independently hydrogen, alkyl, or aryl), amino(— N(RA)(RB), wherein RA and Reare 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.

[0022] 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.”

[0023] 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.

[0024] Unless specified differently, the polymers of the present disclosure may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, organic, inorganic, 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.

[0025] In some embodiments, the methods and compositions disclosed herein are effective for inhibiting corrosion. Inhibiting corrosion includes, for example, reducing corrosion, completely eliminating corrosion, prohibiting corrosion from occurring for some period of time, lowering a rate of corrosion, etc.

[0026] The compositions disclosed herein include an additive for removing an impurity in a medium. The term “removing” includes reacting with, adsorbing, absorbing, complexing with, binding, dissolving, or otherwise drawing out impurities in the medium, sometimes changing the form of the impurity, converting the impurity to a different compound, or otherwise rendering the impurity unavailable for interaction with other components in the medium. If not properly removed / treated, the impurity may lead to the formation of an acid, which will lead to corrosion of metal surfaces.

[0027] In accordance with certain embodiments of the present disclosure, the additive disclosed herein may react with an acid in the medium and / or an impurity (which leads to acid formation) in the medium.

[0028] An “impurity” of the present disclosure may be, in some embodiments, a compound or component of a medium, such as a medium comprising hydrogen, that leads to the formation of an acid. Illustrative, nonlimiting examples of impurities include water, carbon dioxide, hydrogen sulfide, oxygen, a sulfur oxide, a sulfur dioxide, a nitrogen oxide, a metal oxide, and any combination thereof.

[0029] The compositions of the present disclosure include one or more additives that can react with and / or assist with the removal of one or more impurities in a medium. Illustrative, non-limiting examples of additives include a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof.

[0030] Illustrative, non-limiting examples of dehydrating agents include silica gel, calcium chloride, phosphorus pentoxide, sodium sulfate, anhydrous magnesium sulfate, a molecular sieve, sulfuric acid, calcium oxide, activatedalumina, barium oxide, phosphorus oxychloride, thionyl chloride, dimethyl sulfoxide, acetic anhydride, triethyl orthoformate, dimethylformamide, a brine (e.g., calcium chloride brine), a glycol (e.g., ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol), a liquid desiccant (e.g., a lithium chloride solution), glycerol, ethanol, acetic acid, sugar syrup, and any combination thereof.

[0031] Illustrative, non-limiting examples of carbon dioxide scavengers include an amine (e.g., a primary amine, such as ethanolamine, monoethanolamine, and / or diethanolamine - a secondary amine, such as diethylamine and / or methylamine - a tertiary amine, such as triethanolamine and / or methyldiethanolamine), a metal oxide (e.g., calcium oxide, magnesium oxide), an ionic liquid (e.g., an imidazolium-based ionic liquid, such as 1-ethyl- 3-methylimidazolium acetate, or a phosphonium-based ionic liquid), activated carbon, a zeolite, sodium hydroxide, lithium hydroxide, an amine-containing polymer (e.g., a polyethyleneimine and / or a polyethyleneimine-coated silica), a solid amine sorbent, an enzyme-based compound (e.g., carbonic anhydrase), and any combination thereof.

[0032] Illustrative, non-limiting examples of oxygen scavengers include hydrazine, ascorbic acid, iron powder, a tannin, glucose oxidase, sodium erythorbate, sulfur dioxide, a sulfite (e.g., potassium metabisulfite, sodium sulfite, sodium bisulfite, and / or ammonium bisulfite), diethylhydroxylamine, carbohydrazide, methyl ethyl ketoxime, and any combination thereof.

[0033] Illustrative, non-limiting examples of hydrogen sulfide scavengers include an iron-containing compound (e.g., iron chloride and / or iron sulfate), an amine (e.g., monoethanolamine, diethanolamine, methyldiethanolamine, hexamethylenetetramine, and / or dibutylamine), a sodium-containing compound, such as sodium hydroxide or sodium carbonate, a zinc-containing compound (e.g., zinc oxide), a calcium-containing compound (e.g., calcium hydroxide and / or calcium carbonate), an oxidizing agent (e.g., hydrogen peroxide and / or chlorine), a triazine (e.g., hexahydro-1 , 3, 5-triazine and / or methyl-1 ,3, 5-triazine-2, 4, 6-trione), an ammonium-containing compound (e.g.,ammonium hydroxide and / or ammonium carbonate), formaldehyde, acrolein, and any combination thereof.

[0034] Illustrative, non-limiting examples of sulfur oxide scavengers include a calcium-containing compound, such as calcium carbonate and / or calcium hydroxide, a sodium-containing compound, such as sodium carbonate and / or sodium hydroxide, ammonia, magnesium hydroxide, iron oxide, zinc oxide, ammonium hydroxide, and any combination thereof.

[0035] Illustrative, non-limiting examples of nitrogen oxide scavengers include ammonia, urea, hydrazine, iron oxide, activated carbon, a catalytic converter (with platinum, palladium, and / or rhodium), and any combination thereof.

[0036] In some embodiments, particular additive chemistries may be selected to ensure compatibility, solubility, and / or dispersibility of the contents (e.g., fluids) in the hydrogen pipeline and limit or avoid the formation of undesired by-products.

[0037] The amount of additive in a composition of the present disclosure is not particularly limited. For example, a composition of the present disclosure may comprise from about 0.1 wt. % to about 100 wt. % of one or more additives, such as about 1 wt. % to about 100 wt. %, about 10 wt. % to about 100 wt. %, about 20 wt. % to about 100 wt. %, about 30 wt. % to about 100 wt. %, about 40 wt. % to about 100 wt. %, about 50 wt. % to about 100 wt. %, about 60 wt. % to about 100 wt. %, about 70 wt. % to about 100 wt. %, about 80 wt. % to about 100 wt. %, about 90 wt. % to about 100 wt. %, 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. % of the one or more additives.

[0038] Compositions of the present disclosure may also comprise a solvent. Illustrative, non-limiting examples of solvents include an alcohol, anamine, a hydrocarbon, heavy aromatic naphtha, xylene, acetone, an oil, toluene, and any combination thereof.

[0039] The amount of solvent in a composition of the present disclosure is not particularly limited. For example, a composition of the present disclosure may comprise from about 0.1 wt. % to about 100 wt. % of one or more solvents, such as about 1 wt. % to about 99 wt. %, about 10 wt. % to about 99 wt. %, about 20 wt. % to about 99 wt. %, about 30 wt. % to about 99 wt. %, about 40 wt. % to about 99 wt. %, about 50 wt. % to about 99 wt. %, about 60 wt. % to about 99 wt. %, about 70 wt. % to about 99 wt. %, about 80 wt. % to about 99 wt. %, about 90 wt. % to about 99 wt. %, 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. % of the one or more solvents.

[0040] The compositions of the present disclosure may include (or exclude) one or more additional components (other than the additive) and / or one or more additional components may be added to the medium before, after, and / or with an additive of the present disclosure.

[0041] Illustrative, non-limiting examples of additional components include a fouling control agent, a corrosion inhibitor, a corrosion inhibitor intensifier, a biocide, a preservative, an acid, an anti-emulsifier, an iron chelating agent, 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 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.

[0042] A hydrate inhibitor may include, for example, a mono-alkyl amide, a di-alkyl amide, an alkyl quaternary ammonium salt, and any combination thereof.

[0043] An asphaltene inhibitor may include, for example, an alkylphenol / formaldehyde resin, a polyisobutylene ester, a polyisobutylene imide, a polyalkyl acrylate, and any combination thereof.

[0044] A paraffin inhibitor may include, for example, a polyalkyl acrylate, an olefin I maleic anhydride polymer, and any combination thereof.

[0045] A biocide may include, for example, glutaraldehyde, tetrakis(hydroxymethyl)phosphonium sulphate, a quaternary ammonium compound, chlorine, hypochlorite, CIO2, bromine, ozone, hydrogen peroxide, peracetic acid, peroxycarboxylic acid, peroxysulphate, dibromonitrilopropionamide, isothiazolone, terbutylazine, polymeric biguanide, methylene bisthiocyanate, and any combination thereof.

[0046] 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.

[0047] 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.

[0048] 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 triaminepenta (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.

[0049] 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.

[0050] The fouling control agent may comprise, for example, a quaternary compound.

[0051] The acid may comprise, for example, hydrochloric acid, hydrofluoric acid, citric acid, formic acid, acetic acid, or any combination thereof.

[0052] The corrosion inhibitor may comprise, for example, an imidazoline compound, a pyridinium compound, a quaternary ammonium compound, a phosphate ester, an amine, an amide, a carboxylic acid, a thiol, and any combination thereof.

[0053] The surfactant may be non-ionic, cationic, anionic, amphoteric, or zwitterionic.

[0054] 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. %.

[0055] The compositions disclosed herein may be used in various methods for treating mediums. For example, a method of treating a medium in accordance with the present disclosure may comprise adding a composition comprising an additive to the medium. The additive may be any additive orcombination of additives disclosed herein, such as a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof.

[0056] The medium may comprise hydrogen. The medium may also comprise an impurity and / or an acid.

[0057] Illustrative, non-limiting examples of acids include sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and any combination thereof.

[0058] Illustrative, non-limiting examples of impurities include water, oxygen, hydrogen sulfide, sulfur dioxide, a nitrogen oxide, carbon dioxide, a metal oxide, or any combination thereof.

[0059] The methods of the present disclosure may also include methods of inhibiting corrosion of a metal surface in contact with a medium. The methods may comprise adding a composition to the medium, wherein the composition comprises an additive selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof, and wherein the medium comprises hydrogen and an impurity and / or an acid selected from the group consisting of sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and any combination thereof.

[0060] The additive may remove, react with, or otherwise prevent the impurity from producing an acid. If no acid is produced, a corrosion inhibitor may not be necessary. However, a corrosion inhibitor may also be added in accordance with any method disclosed herein.

[0061] An additional component as defined herein, such as a corrosion inhibitor, may be added to the medium before, after, and / or with the additive. 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, about1 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.

[0062] The amount of additive added to the medium when carrying out the methods of the present disclosure is not particularly limited. For example, a method may include adding from about 1 ppm to about 10,000 ppm of the additive to the medium, such as about 1 ppm to about 5,000 ppm, about 1 ppm to about 2,500 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 1 ppm to about 50 ppm, about 1 ppm to about 25 ppm, about 10 ppm to about 10,000 ppm, about 50 ppm to about 10,000 ppm, about 100 ppm to about 10,000 ppm, about 500 ppm to about 10,000 ppm, about 1 ,000 ppm to about 10,000 ppm, or about 5,000 ppm to about 10,000 ppm.

[0063] In certain embodiments, the amount of additive added to the medium depends upon the amount of impurity in the medium. In general, a weight % ratio of additive to impurity may be selected from about 100:1 , about 50:1 , about 25:1 , about 15:1 , about 10:1 , about 9:1 , about 8:1 , about 7:1 , about 6:1 , about 5:1 , about 4:1 , about 3:1 , about 2:1 , or about 1 :1 .

[0064] The presently disclosed compositions, additives, compounds, components, and / or 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, copper, brass, lead, or bronze. 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.

[0065] 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.

[0066] The presently disclosed compositions, additives, compounds, components, and methods are useful for inhibiting corrosion of metal surfaces in contact with any type of corrodent in the medium, such as an acid, 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, 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.

[0067] The compositions, additives, components, and / or compounds disclosed herein may be added to a medium using a variety of different application methods known in the art. In some embodiments, the compositions, additives, components, and / or compounds may be added continuously or intermittently to the medium, either automatically or manually, by using, for example, chemical injection pumps. The addition may involve dripping, pouring, spraying, pumping, injecting, or otherwise adding the composition, additive, compound, and / or component to the medium. In someembodiments, the composition may be heated, such as from about 30QC to 100 -C, prior to addition.

[0068] Additives may be added to the medium at various locations. For example, if a pipeline comprises the medium, a first additive may be added at a first location in the pipeline and a second additive, which may be the same or different than the first additive, may be added at a second location in the pipeline, which may be upstream or downstream of the first location. The order of additive introduction may depend on chemistry compatibility, such as introducing additives that remove byproducts of a first additive downstream where the first additive is introduced.

[0069] The methods, compounds, additives, and / or compositions disclosed herein may be used in any industrial systems that include hydrogencontaining mediums. In some embodiments, the compositions, compounds, additives, and / or methods of the present disclosure may be used to inhibit corrosion of a metal surface present in a pipeline, a storage container, and / or a reaction vessel.

[0070] The compositions, compounds, additives, and / or 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 hydrogen.

[0071] The medium in which the compositions, additives, components, 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 and / or gas from one point to another, such as a pipeline. The device / component may be part of a refinery, such as a separation vessel, a dehydration unit, and / or a gas line.

[0072] In some embodiments, one or more of a pipeline, a heat exchanger, a storage container, a flowline, a downhole tubular, a casing, a tank (e.g., railroad tank car or a tank truck I tanker), a separator, or any combination thereof, comprises the metal surface, which contacts the medium.

[0073] In certain embodiments, a subterranean formation and / or a pipeline comprises the metal surface to be treated by a composition, additive, component, and / or compound of the present disclosure. In some embodiments, the pipeline is intended to transport a liquid and / or gaseous medium I process fluid, such as a medium comprising, consisting essentially of, or consisting of hydrogen. In addition to hydrogen, a medium of the present disclosure may comprise or exclude water, a hydrocarbon, a brine, crude oil, refined oil, a gas, liquefied natural gas, carbon dioxide, and any combination thereof.

[0074] A medium of the present disclosure may comprise or exclude, for example, produced water, fresh water, seawater, municipal water, recycled water, salt water, surface water, condensed water, injection water, ground water, carbon dioxide, hydrogen, or any mixture thereof.

[0075] A medium may comprise, consist of, or consist essentially of hydrogen, such as liquid hydrogen, gaseous hydrogen, supercritical hydrogen, or any combination thereof.

[0076] In certain embodiments, a pipeline, a reaction vessel, and / or a storage container comprises the medium.

[0077] In some embodiments, a pipeline, reaction vessel, and / or storage container as disclosed herein may comprise hydrogen, an impurity and / or an acid, and an additive, wherein the additive is selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof. As described above, the pipeline, storage container, and / or reaction vessel may comprise other components, such as a solvent, an acid, a surfactant, a corrosion inhibitor, a drag reducing agent, a pH control agent, or any combination thereof.

[0078] A medium treated with a composition, additive, component, 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 may be at a temperature of from about 40 °C to about 250 °C. Insome 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.

[0079] Various systems are also provided in the present disclosure. A system of the present disclosure may include, for example, a pipeline (or reaction vessel and / or storage container) containing hydrogen and an impurity. The pipeline comprises an impurity removal unit coupled thereto, wherein the impurity removal unit receives at least a portion of the hydrogen from a first location on the pipeline, removes the impurity and / or converts the impurity to a compound that can be removed by the impurity removal unit, and sends an impurity depleted hydrogen to a second location on the pipeline downstream of the first location.

[0080] In some embodiments, the impurity removal unit comprises a catalyst bed for removal of a nitrogen oxide compound from the hydrogen and / or a sulfur recovery unit for removal of hydrogen sulfide from the hydrogen.

[0081] The catalyst bed can include catalyst particles and / or pellets. The catalyst particles and / or pellets may comprise a metal (e.g., rhodium, palladium, platinum, or combinations thereof) supported on, impregnated into, bonded to the surface of silica, alumina, or silica-alumina particles and / or pellets. The treated hydrogen can be transferred to another location in the pipeline or to another hydrogen-containing pipeline.

[0082] The sulfur recovery unit can be coupled with the hydrogencontaining pipeline for conversion of hydrogen sulfide to elemental sulfur according to the Claus process. Because the Claus process operates at extremely high temperatures, the sulfur recovery unit can include compressors and / or a cooler to compress and cool the treated hydrogen to again form hydrogen that can be transferred to another location in the pipeline or to another hydrogen-containing pipeline.

[0083] 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 differentforms, 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” is intended to include “at least one corrosion inhibitor” or “one or more corrosion inhibitors.”

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] The transitional phrase “consisting of” excludes any element, component, ingredient, and / or method step not specified in the claim.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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

CLAIMSWhat is claimed is:1 . A method of treating a medium, comprising: adding a composition comprising an additive to the medium, wherein the additive is selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof, and wherein the medium comprises hydrogen.

2. The method of claim 1 , wherein the hydrogen comprises gaseous hydrogen, liquid hydrogen, supercritical hydrogen, or any combination thereof.

3. The method of claim 1 or claim 2, wherein the medium comprises an impurity and / or an acid.

4. The method of claim 3, wherein the acid is selected from the group consisting of sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and any combination thereof.

5. The method of claim 3 or claim 4, wherein the impurity comprises water, oxygen, hydrogen sulfide, sulfur dioxide, a nitrogen oxide, carbon dioxide, a metal oxide, or any combination thereof.

6. The method of any one of the preceding claims, wherein the dehydrating agent comprises a member selected from the group consisting of silica gel, calcium chloride, phosphorus pentoxide, sodium sulfate, anhydrous magnesium sulfate, a molecular sieve, sulfuric acid, calcium oxide, activatedalumina, barium oxide, phosphorus oxychloride, thionyl chloride, dimethyl sulfoxide, acetic anhydride, triethyl orthoformate, dimethylformamide, a brine, an alcohol, a glycol, a liquid desiccant, glycerol, acetic acid, sugar syrup, and any combination thereof.

7. The method of any one of the preceding claims, wherein the carbon dioxide scavenger is selected from the group consisting of an amine, an ionic liquid, activated carbon, a zeolite, sodium hydroxide, lithium hydroxide, an amine-containing polymer, a solid amine sorbent, an enzyme-based compound, and any combination thereof.

8. The method of any one of the preceding claims, wherein the oxygen scavenger is selected from the group consisting of hydrazine, ascorbic acid, iron powder, a tannin, glucose oxidase, sodium erythorbate, sulfur dioxide, a sulfite, diethylhydroxylamine, carbohydrazide, methyl ethyl ketoxime, and any combination thereof.

9. The method of any one of the preceding claims, wherein the hydrogen sulfide scavenger is selected from the group consisting of an iron-containing compound, an amine, a sodium-containing compound, a zinc-containing compound, a calcium-containing compound, an oxidizing agent, a triazine, an ammonium-containing compound, formaldehyde, acrolein, and any combination thereof.

10. The method of any one of the preceding claims, wherein the sulfur oxide scavenger is selected from the group consisting of a calcium-containing compound, a sodium-containing compound, ammonia, magnesium hydroxide, iron oxide, zinc oxide, ammonium hydroxide, and any combination thereof.11 . The method of any one of the preceding claims, wherein the nitrogen oxide scavenger is selected from the group consisting of ammonia, urea,hydrazine, iron oxide, activated carbon, a catalytic converter, and any combination thereof.

12. The method of any one of the preceding claims, wherein the composition comprises from about 1 wt. % to about 100 wt. % of the additive.

13. The method of any one of the preceding claims, further comprising adding from about 1 ppm to about 10,000 ppm of the additive to the medium.

14. The method of any one of the preceding claims, wherein the composition comprises a solvent selected from the group consisting of water, an alcohol, an amine, a hydrocarbon, heavy aromatic naphtha, xylene, acetone, an oil, toluene, and any combination thereof.

15. The method of claim 14, wherein the composition comprises from about 1 wt. % to about 99 wt. % of the solvent.

16. The method of any one of the preceding claims, wherein a pipeline, reaction vessel, and / or storage container comprises the medium.

17. A composition, comprising: liquid hydrogen, an acid and / or an impurity, and an additive selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof.

18. The composition of claim 17, wherein the acid is selected from the group consisting of sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and any combination thereof.

19. The composition of claim 17 or claim 18, wherein the impurity comprises water, oxygen, hydrogen sulfide, sulfur dioxide, a nitrogen oxide, carbon dioxide, a metal oxide, or any combination thereof.

20. The composition of any one of the preceding claims, wherein the dehydrating agent comprises a member selected from the group consisting of silica gel, calcium chloride, phosphorus pentoxide, sodium sulfate, anhydrous magnesium sulfate, a molecular sieve, sulfuric acid, calcium oxide, activated alumina, barium oxide, phosphorus oxychloride, thionyl chloride, dimethyl sulfoxide, acetic anhydride, triethyl orthoformate, dimethylformamide, a brine, a glycol, a liquid desiccant, glycerol, ethanol, acetic acid, sugar syrup, and any combination thereof.21 . The composition of any one of the preceding claims, wherein the carbon dioxide scavenger is selected from the group consisting of an amine, an ionic liquid, activated carbon, a zeolite, sodium hydroxide, lithium hydroxide, an amine-containing polymer, a solid amine sorbent, an enzymebased compound, and any combination thereof.

22. The composition of any one of the preceding claims, wherein the oxygen scavenger is selected from the group consisting of hydrazine, ascorbic acid, iron powder, a tannin, glucose oxidase, sodium erythorbate, sulfur dioxide, a sulfite, diethylhydroxylamine, carbohydrazide, methyl ethyl ketoxime, and any combination thereof.

23. The composition of any one of the preceding claims, wherein the hydrogen sulfide scavenger is selected from the group consisting of an iron- containing compound, an amine, a sodium-containing compound, a zinc- containing compound, a calcium-containing compound, an oxidizing agent, a triazine, an ammonium-containing compound, formaldehyde, acrolein, and any combination thereof.

24. The composition of any one of the preceding claims, wherein the sulfur oxide scavenger is selected from the group consisting of a calcium-containing compound, a sodium-containing compound, ammonia, magnesium hydroxide, iron oxide, zinc oxide, ammonium hydroxide, and any combination thereof.

25. The composition of any one of the preceding claims, wherein the nitrogen oxide scavenger is selected from the group consisting of ammonia, urea, hydrazine, iron oxide, activated carbon, a catalytic converter, and any combination thereof.

26. The composition of any one of the preceding claims, wherein the composition comprises from about 1 wt. % to about 100 wt. % of the additive.

27. The composition of any one of the preceding claims, further comprising a solvent selected from the group consisting of water, an alcohol, an amine, a hydrocarbon, heavy aromatic naphtha, xylene, acetone, an oil, toluene, and any combination thereof.

28. A method of inhibiting corrosion of a metal surface in contact with a medium, comprising: adding a composition to the medium, wherein the composition comprises an additive selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof, and wherein the medium comprises hydrogen and an impurity and / or an acid selected from the group consisting of sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and any combination thereof.

29. The method of claim 28, wherein the impurity comprises water, oxygen, hydrogen sulfide, sulfur dioxide, a nitrogen oxide, carbon dioxide, a metal oxide, or any combination thereof.

30. The method of claim 28 or claim 29, wherein a pipeline, a reaction vessel, and / or a storage container comprises the metal surface.31 . A device, comprising: hydrogen; an impurity; and an additive, wherein the additive is selected from the group consisting of a dehydrating agent, a carbon dioxide scavenger, an oxygen scavenger, a hydrogen sulfide scavenger, a sulfur oxide scavenger, a nitrogen oxide scavenger, and any combination thereof.

32. The device of claim 31 , wherein the device comprises a pipeline, a reaction vessel, and / or a storage container.

33. The device of claim 31 or claim 32, further comprising a solvent, an acid, a surfactant, a corrosion inhibitor, a drag reducing agent, a pH control agent, or any combination thereof.

34. A system comprising: a pipeline containing hydrogen and an impurity; and an impurity removal unit coupled to the pipeline; wherein the impurity removal unit receives at least a portion of the hydrogen from a first location on the pipeline, removes the impurity and / or converts the impurity to a compound that can be removed by the impurity removal unit, and sends an impurity depleted hydrogen to a second location on the pipeline downstream of the first location.

35. The system of claim 34, wherein the impurity removal unit is a catalyst bed for removal of a nitrogen oxide compound from the hydrogen, a sulfur recovery unit for removal of hydrogen sulfide from the hydrogen, or a combination thereof.