Inhibitors for hydrogen embrittlement and methods

Abstract

Inhibitors of hydrogen embrittlement, which can include a terminal alkene or a terminal alkyne, such as an enyne are described. Compositions, such as treated fluid compositions, that include an inhibitor of hydrogen embrittlement, such as a terminal alkyne or a terminal alkene are described herein. Methods of treating a fluid, generating energy, transporting, or storing a treated fluid are also provided.

Description

INHIBITORS FOR HYDROGEN EMBRITTLEMENT AND METHODSREFERENCE TO RELATED APPLICATIONS

[0001] This application is being filed on April 8, 2025, as a PCT International Patent Application and claims the benefit of and priority to U.S. Provisional Patent Application Nos. 63 / 631,544 and 63 / 631,556, filed on April 9, 2024, the disclosures of which are incorporated herein by reference in their entirety.TECHNICAL FIELD

[0002] This disclosure relates to compounds, such as terminal alkynes and terminal alkenes, that can be used as an odorant and / or inhibitor of hydrogen embrittlement, compositions including an odorant and / or inhibitor of hydrogen embrittlement, and methods of transporting or storing a fluid comprising an odorant / and or inhibitor of hydrogen embrittlement.BACKGROUND

[0003] Hydrogen embrittlement (HE), also known as hydrogen-assisted cracking or hydrogen-induced cracking (HIC), can cause a reduction in the ductility of a metal, typically due to absorbed hydrogen. Hydrogen atoms are small and can permeate solid metals. Once absorbed, hydrogen can lower the stress required for cracks in the metal to initiate and propagate, which can result in embrittlement. Hydrogen embrittlement can occur in a number of metals or metalcontaining materials, including, but not limited to, aluminum, cobalt, copper, iron, nickel, titanium, and alloys thereof, such as steel, stainless steel, carbon steel, X80 / L555 steel, X70 / L485 steel, X65 / L450 steel, X52 / L360 steel, X42 / L290 steel, J55 and J55N steel, N80-P110 steel, L80 steel, K55 steel, API55T steel, A 606-T4 steel and ANSI 4130 steel, alloy steel, such as nickel steel, nickel-chromium steel, nickel (case-hardening) steel, chromium-vanadium steel, austenitic chromium-nickel steel, silicon steel, and silico-manganese spring steel, high-strength 7xxx series (Al-Zn-Mg-Cu alloy) aluminum -based alloys, alpha / beta titanium alloys, alloy 716, alloy 725, alloy 625 grade 1, alloy 718, Udimet® 700, Rene® 41, Hastelloy® X, and TD-NiCr nickel-based alloys, L-605 and Zimaloy cobalt-based alloys, MP35N nickel -cobalt based alloy, and iron-based alloys (A-286). Inhibition of hydrogen embrittlement can be important for the transport of hydrogen in pipelines.

[0004] Inhibition of hydrogen embrittlement has been studied (“Hydrogen Embrittlement and Its Control in Hydrogen-Fueled Engine Systems,” Conference Paper, NASA, January 1, 1978; Int. J. Hydrogen Energy, 10(7 / 8), 551-554, 1985). It has been reported that oxygen (O2), carbon monoxide (CO), nitrogen protoxide (N2O), sulfur dioxide (SO2), and carbon disulfide (CS2) have inhibition properties toward hydrogen embrittlement. However, the concentration of these gases needed for effective inhibition of embrittlement is not compatible with various hydrogen fuel quality standards such as ISO 14687:2019. Furthermore, these compounds can impose risks with regard to safety when used as embrittlement inhibitors (e.g., they can be explosive, corrosive, toxic to humans, etc.). One or more of these disadvantages has limited the use of these materials outside of extremely controlled environments and / or mission critical applications.

[0005] Some organic compounds have been proposed as inhibitors of hydrogen embrittlement. For example, US3345298 discloses the use of a chlorinated acetylenic alcohol in a sulfuric acid solution, but this reference does not disclose or suggest the use of chlorinated acetylenic alcohols in a gas phase. Furthermore, the permissible concentration of halogenated compounds provided in the hydrogen fuel quality standard (ISO 14687:2019) is only 0.05 pm / mol of H2, which would likely be exceeded if chlorinated compounds were used as embrittlement inhibitors in H2 gas applications. The high-water solubility of these compounds also is not compatible with the ISO 13734:2013 standard for the odorization of natural gas.

[0006] The use of ethyl mercaptan as an inhibitor of hydrogen embrittlement in a gas phase has been reported (Gaseous Hydrogen Embrittlement of Materials in Energy Technologies Mechanisms, Modelling and Future Developments, Vol. 1 in Woodhead Publishing Series in Metals and Surface Engineering, 2012, 129-153). However, the concentration required is not compatible with the sulfur specification for hydrogen fuel as defined in the ISO 14687:2019 standard (total sulfur below 0.004 pm / mol H2).

[0007] The use of propargyl alcohol as an inhibitor of hydrogen embrittlement in a hydrochloric acid solution, but not in a gas phase, has been reported (Corrosion, 46(5), 354-359, 1990). The reported toxicity of propargyl alcohol, makes it generally undesirable for this application, and the high-water solubility is not compatible with certain standards such as ISO 13734:2013.

[0008] Other organic molecules have been reported to reduce or prevent hydrogenembrittlement in various aqueous media (see Corrosion Science, 37(1), 1739-1750, 1995; Corrosion, 54(3), 187-193, 1998; British Corrosion Journal, 35(3), 204-209 (2000); Corrosion Engineering, Science and Technology, 49(2), 130-135, 2014). The use of these organic molecules in a gas phase, however, has not been disclosed or suggested, likely because the molecular weight and physicochemical properties of these compounds would make it difficult, if not impossible, to inject and / or maintain these compounds in a gas phase at sufficient concentrations to inhibit embrittlement.

[0009] Odorants have been added to fluids, including various dangerous gases, for decades. Odorants can allow for the detection of a leak without external equipment. Odorants can also allow for leak detection in locations where it can be difficult or impossible to place detectors, such as outdoor locations. Since odorants that are easily detectable by the human olfactory system can be used, small fluid leaks can be easily detected. It would be advantageous to provide a compound, such as an organic compound, that is capable of functioning as an inhibitor of hydrogen embrittlement and as an odorant.

[0010] A promising application for hydrogen includes hydrogen powered fuel cells. Hydrogen fuel cells typically use a precious metal to oxidize hydrogen electrochemically at the anode of a cell. If the active sites of the precious metal are occupied by a molecule other than hydrogen, the activity of the catalyst and the efficiency and performance of the fuel cell can decrease dramatically. This is commonly referred to as poisoning or deactivation of the catalyst, and it can be particularly problematic when sulfur-based odorants such as tetrahydrothiophene (THT) and Zc77-butyl-mcrcaptan (TBM) are used (see International Journal of Hydrogen Energy, 41(28), 12231-12241, 2016; Journal of Power Sources, 152, 226-232, 2005). It would be advantageous to provide a compound, such as an organic compound, that can act as an inhibitor of hydrogen embrittlement and does not undesirably impact the performance of a fuel cell and / or deactivate the catalyst.

[0011] In some instances, it can be necessary to remove odorants from a hydrogen energy system in order to avoid release of the odorant in the environment. If the exhaust from a fuel cell remains unfiltered, odorant can be released in the environment, thereby negating the ability to detect a possible hydrogen leak or resulting in a false leak warning. Similarly, applications that require ultra-pure hydrogen can mandate the removal of the odorant from the hydrogen. It would be advantageous to provide a compound, such as an organic compound, that is capable of actingas an inhibitor of hydrogen embrittlement and can be easily removed from a fluid such as hydrogen.

[0012] There remains a need for improved methods of inhibiting hydrogen embrittlement including identifying and utilizing compounds that (i) can serve as an odorant (e.g., have a very low odor perception, a distinctive smell profile, and / or an alarming character) for a fluid, such as hydrogen, (ii) do not undesirably impact the performance of various devices, such as fuel cells, (iii) can be easily removed from a fluid, such as hydrogen, (iv) are non-toxic to humans and / or the environment, and / or (v) a combination thereof.SUMMARY

[0013] This summary is provided to introduce various concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter, nor is the summary intended to limit the scope of the claimed subject matter.

[0014] In one aspect, compounds are provided, including compounds that are inhibitors of hydrogen embrittlement. Additionally or alternatively, the compounds can be an odorant for a fluid, such as a gas. The compounds can include a terminal alkyne and a terminal alkene, such as a substituted derivative thereof.

[0015] In another aspect, compositions are provided, which can include compositions that are inhibitors of hydrogen embrittlement, odorants, or a combination thereof. In some embodiments, the compositions include any one of more of the compounds provided herein, such as a terminal alkyne or a terminal alkene, and an additive. The additive can include an odiferous compound, a stabilizer, a diluent, or a combination thereof.

[0016] In yet another aspect, treated fluid compositions are provided, which can include a fluid, such as a gas, and any one or more of the compounds or compositions provided herein.The compound or composition can be dispersed in the fluid.

[0017] In a further aspect, methods of treating a fluid are provided. In some embodiments, the methods include providing a fluid, and contacting the (i) fluid, such as a gas, and (ii) any one or more of the compounds (such as a terminal alkyne and a terminal alkene) or compositions provided herein to form a treated fluid.

[0018] In a further aspect, methods of generating energy are provided. In someembodiments, the methods include providing a fuel cell that includes an anode and contacting the anode and a treated fluid composition as provided herein. The contacting of the anode and the treated fluid composition can produce an oxidized treated fluid composition. The methods also can include removing a compound, such as a terminal alkyne and / or a terminal alkene, from the treated fluid composition, the oxidized treated fluid composition, or both the treated fluid composition and the oxidized treated fluid composition.

[0019] In an additional aspect, methods of transporting or storing a treated fluid composition are provided. The methods can include providing any one or more of the treated fluid compositions provided herein and disposing the treated fluid composition in an apparatus formed at least in part of a metal. The apparatus can include a pipeline. A compound, such as a terminal alkyne, or composition that is present in the treated fluid composition can prevent or delay the hydrogen embrittlement of the metal.

[0020] In another additional aspect, systems are provided. In some embodiments, the systems include (i) a sensor, and (ii) a compound, such as a terminal alkyne, or composition provided herein. A sensor can be configured to permit the use of any of the compounds, such as a terminal alkyne, provided herein at a concentration that is not detectable by an average human.

[0021] Additional aspects will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the aspects described herein. The advantages described herein can be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1 depicts a plot of 1,6-heptadiyne concentration (ppm) versus time in hydrogen during a stability test performed at 90 °C.

[0023] FIG. 2 depicts a plot of cis-2-pentene concentration (ppm) versus time in hydrogen during a stability test performed at 90 °C.

[0024] FIG. 3 depicts a plot of 2-pentyne concentration (ppm) versus time in hydrogen during a stability test performed at 90 °C.

[0025] FIG. 4 depicts the results of a durability test of an embodiment of a proton-exchange membrane fuel cell (PEMFC) using hept-2-yne as a hydrogen odorant.

[0026] FIG. 5 depicts the results of a durability test of an embodiment of a PEMFC using hept-3-yne as a hydrogen odorant.

[0027] FIG. 6 depicts the results of a durability test of an embodiment of a PEMFC using oct-4-yne as a hydrogen odorant.

[0028] FIG. 7 depicts the results of a durability test of an embodiment of a PEMFC using hex-l-yne as a hydrogen odorant.

[0029] FIG. 8 depicts the results of a durability test of an embodiment of a PEMFC using l-hexen-5-yne as a hydrogen odorant.

[0030] FIG. 9 depicts the results of a durability test of an embodiment of a PEMFC using hept-l-en-6-yne as a hydrogen odorant.

[0031] FIG. 10 depicts the results of a durability test of an embodiment of a PEMFC using 3,3-dimethyl-but-l-yne as a hydrogen odorant.

[0032] FIG. 11 depicts the results of a durability test of an embodiment of a PEMFC using hexa-l,5-diene as a hydrogen odorant.

[0033] FIG. 12 depicts the results of a durability test of an embodiment of a PEMFC using hex-l-ene as a hydrogen odorant.

[0034] FIG. 13 depicts the results of a durability test of an embodiment of a PEMFC using hex-2-yne as a hydrogen odorant.

[0035] FIG. 14 depicts the results of a durability test of an embodiment of a PEMFC using butyraldehyde as a hydrogen odorant.

[0036] FIG. 15 depicts the results of a durability test of an embodiment of a PEMFC using tetrahydrothiophene (THT) as a hydrogen odorant.DEFINITIONS

[0037] To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2ndEd (1997) can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein or render indefinite or non-enabled any claim to which that definition is applied. To the extent that anydefinition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.

[0038] As the various features of the subject matter of this disclosure are described, within particular aspect, a combination or combinations of the different features can be envisioned. For every aspect of every feature disclosed herein, all combinations that do not detrimentally affect the designs, compositions, systems, processes, or methods described herein are contemplated with or without the express description of that particular combination. Therefore, unless explicitly stated to the contrary, any aspect of feature disclosed here can be combined to describe and disclose the inventive designs, compositions, systems, processes, or methods consistent with the entire disclosure.

[0039] While compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components or steps, unless stated otherwise.

[0040] The terms “including,” “with,” and “having,” as used herein, are defined as comprising (i.e., open language), unless specified otherwise.

[0041] The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one. For instance, the disclosure of “a fluid,” “a sensor,” and the like, is meant to encompass one, or mixtures or combinations of more than one, fluid, sensor, and the like, unless otherwise specified.

[0042] Various numerical ranges are disclosed herein. When Applicants disclose or claim a range of any type, Applicants’ intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. For example, by disclosing a concentration range of about 5 mg / m3n to about 20 mg / m3n, Applicant’s intent is to recite individually 5 mg / m3n, 6 mg / m3n, 7 mg / m3n, 8 mg / m3n, 9 mg / m3n, 10 mg / m3n, 11 mg / m3n, 12 mg / m3n, 13 mg / m3n, 14 mg / m3n, 15 mg / m3n, 16 mg / m3n, 17 mg / m3n, 18 mg / m3n, 19 mg / m3n, and 20 mg / m3n, including any sub-ranges and combinations of sub-ranges encompassed therein, and these methods of describing such ranges are interchangeable. Moreover, all numerical end points of ranges disclosed herein are approximate, unless excluded by proviso. As a representative example, if Applicants state that one or more steps in the processes disclosed herein can be conducted at a temperature in a range from 10 °Cto 75 °C, this range should be interpreted as encompassing temperatures in a range from “about” 10 °C to “about” 75 °C unless otherwise stated.

[0043] Values or ranges can be expressed herein as “about,” from “about” one particular value, and / or to “about” another particular value. When such values or ranges are expressed, other embodiments disclosed include the specific value recited, from the one particular value, and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that there are a number of values disclosed therein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. In another aspect, each use of the term “about” can, independently, mean +20% of the stated value, ±15% of the stated value, ±10% of the stated value, ±5% of the stated value, or ±3% of the stated value.

[0044] Applicants reserve the right to proviso out or exclude any individual members of any such group of values or ranges, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants can be unaware of at the time of the filing of the application. Further, Applicants reserve the right to proviso out or exclude any individual substituents, analogs, compounds, ligands, structures, or groups thereof, or any members of a claimed group, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference or prior disclosure that Applicants can be unaware of at the time of the filing of the application.

[0045] For any particular compound or group disclosed herein, any name or structure (general or specific) presented is intended to encompass all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that can arise from a particular set of substituents, unless otherwise specified. The name or structure also encompasses all enantiomers, diastereomers, and other optical isomers (if there are any) whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan, unless otherwise specified. For example, a general reference to a “Ce alkane,” “hexane” or “hexanes” includes n-hexane, 2-methylpentane, 3 -methylpentane, 2, 2-di methylbutane, and2,3-dimethylbutane; and a general reference to a “C4 alkyl” or “butyl group” includes an / / -butyl group, a sec-butyl group, an / . w-butyl group, and a / -butyl group.

[0046] The term “substituted” when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe the compound or group wherein any non-hydrogen moiety formally replaces one or more hydrogens in that group or compound and is intended to be non-limiting. A compound or group can also be referred to herein as “unsubstituted” or by equivalent terms such as “non-substituted,” which refers to the original group or compound. “Substituted” is intended to be non-limiting and include inorganic substituents or organic substituents as specified and as understood by one of ordinary skill in the art.

[0047] The terms “contact product,” “contacting,” and the like, are used herein to describe compositions and methods wherein the components are contacted together in any order, in any manner, and for any length of time, unless specified otherwise. For example, the components can be contacted by blending or mixing. Further, unless otherwise specified, the contacting of any component can occur in the presence or absence of any other component of the compositions and methods described herein. Combining additional materials or components can be done by any suitable method. Further, the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Although “contact product” can, and often does, include reaction products, it is not required for the respective components to react with one another. Similarly, “contacting” two or more components can result in a reaction product or a reaction mixture. Consequently, depending upon the circumstances, a “contact product” can be a mixture, a reaction mixture, or a reaction product.

[0048] The term “alkyl group” is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from an alkane. The alkyl group can be linear or branched unless otherwise specified.

[0049] A “cycloalkane” is used herein to refer to a saturated cyclic hydrocarbon, with or without side chains, for example, cyclobutane, cyclopentane, cyclohexane, methyl cyclopentane, and methyl cyclohexane. Other identifiers can be utilized to indicate the presence of particular groups, if any, in the cycloalkane (for example, halogenated cycloalkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the cycloalkane).

[0050] The term “hydrocarbyl group” is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (that is, a group containing only carbon and hydrogen). Thus, a hydrocarbyl group includes alkyl groups (linear or branched), cycloalkyl groups, alkenyl groups, aryl groups, and the like. Non-limiting examples of hydrocarbyl groups include methyl, ethyl, butyl, hexyl, phenyl, tolyl, propenyl, and the like.

[0051] When used herein with regard to the selection of a substituent, the term “independently” indicates that two differently labeled substituents, e.g., R1and R2, selected from the same pool of substituents can be the same or different.

[0052] The Abstract of this application is not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein, but rather to satisfy the requirements of 37 C.F.R. § 1.72(b), to enable the United States Patent and Trademark Office and the public generally to determine quickly from a cursory inspection the nature and gist of the technical disclosure. Moreover, any headings that are employed herein are also not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein.

[0053] All publications and patents mentioned herein are incorporated herein by reference in their entireties for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. The publications discussed throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

[0054] Those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments disclosed herein without materially departing from the novel teachings and advantages according to this disclosure. Accordingly, all such modifications and equivalents are intended to be included within the scope of this disclosure as defined in the following claims. Therefore, it is to be understood that resort can be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, can suggest themselves to one of ordinary skill in the art without departing from the spirit of the present disclosure or the scope of the appended claims.DETAILED DESCRIPTION

[0055] The present disclosure is directed to odorants, inhibitors of hydrogen embrittlement, compositions, and methods of treating and / or transporting or storing materials such as fluids, which can include a fuel gas.

[0056] ODORANTS / INHIBITORS OF HYDROGEN EMBRITTLEMENT

[0057] Compounds are provided herein, such as compounds that can function as an inhibitor of hydrogen embrittlement, an odorant for a fluid, or a combination thereof. A compound is an inhibitor of hydrogen embrittlement when the compound has a positive displacement efficacy. A compound functions as an embrittlement inhibitor when the presence of the compound improves the fracture toughness of a metal or alloy in contact with hydrogen.

[0058] The compounds can be non-toxic (e.g., to humans or mammals) or have a detectable odor below a toxicity level. The compounds can be environmentally benign by not posing health or toxicity concerns to human or biological species. Combustion products of the compounds also can be environmentally benign. The compounds can be benign to the components of a device system or apparatus, such as a pipeline, combustion system, fuel cell, or any other system, apparatus, or process.

[0059] In some embodiments, the compound includes a terminal alkene. The phrase “terminal alkene” generally refers to organic compounds, including substituted derivatives of organic compounds and / or heteroatom-containing organic compounds, that include a terminal double bond, as depicted in the following moiety:

[0060] The term “substituted derivatives” of organic compounds, including terminal alkenes, can include compounds with organic or inorganic substituents. In some embodiments, the substituted derivatives of organic compounds include an oxygen substituent.

[0061] A terminal alkene can include a heteroatom, such as oxygen, nitrogen, etc. When a terminal alkene includes oxygen as a heteroatom, the oxygen can be present as part of an ether moiety.

[0062] In some embodiments, the terminal alkene includes a terminal C3-C20 alkene, a terminal C3-C19 alkene, a terminal C3-C18 alkene, a terminal C3-C17 alkene, a terminal C3-C16 alkene, a terminal C3-C15 alkene, a terminal C3-C14 alkene, a terminal C3-C13 alkene, a terminal C3-C12 alkene, a terminal C3-C11 alkene, a terminal C3-C10 alkene, a terminal C3-C9 alkene, a terminal C3-C alkene, or a terminal C3-C7 alkene. In some embodiments, the terminal alkene is hep-l-tene (1-heptene), hex-l-ene (1-hexene), or oct-l-ene (1-octene).

[0063] In some embodiments, the compound can include a hexene, a heptene, an octene, or a combination thereof. The term “heptene” refers to a compound that includes at least one double bond and a linear chain of seven carbon atoms, wherein at least two of the seven carbon atoms are bonded to each other via a double bond, and includes substituted derivatives thereof. The term “octene” refers to a compound that includes at least one double bond and a linear chain of eight carbon atoms, wherein at least two of the eight carbon atoms are bonded to each other via a double bond, and includes substituted derivatives thereof. The substituted derivatives of heptene and octene can include, but are not limited to, a C1-C2 substituted heptene or a C1-C2 substituted octene. The substituted derivatives of the heptene and octene can include, but are not limited to, a C1-C2 substituted heptene or a C1-C2 substituted octene. As an example, the following table shows a generic schematic of a linear chain of seven carbon atoms, an embodiment of a heptene, and an embodiment of a Ci substituted heptene.

[0064] A terminal alkene can include one or more double bonds. When a terminal alkene includes two double bonds, the compound can be referred to as a “diene.” In some embodiments the diene includes a hexadiene or an octadiene. The term “hexadiene” refers to a compound that includes at least two double bonds and a linear chain of six carbon atoms, wherein at least four of the seven carbon atoms are bonded to each other via a triple bond, and includes substituted derivatives thereof. In some embodiments, the hexadiene includes hexa-l,5-diene, where 1,5 refers to the first and second and fifth and sixth carbons, respectively, of the linear chain of seven carbon atoms that are bonded to each other via a double bond. In some embodiments, the octadiene includes octa-l,7-diene, where 1,7 refers to the first and second and seventh and eighth carbons, respectively, of the linear chain of eight carbon atoms that are bonded to each other via a double bond. Substituted derivatives of hexadiene or octadiene can include, but are not limited to, a C1-C2 substituted heptadiene or a C1-C2 substituted octadiene.

[0065] In some embodiments, the terminal alkene includes buta-l,3-diene (1,3- butadiene). In some embodiments, the terminal alkene includes hexa-l,5-diene (1,5 -hexadiene). In some embodiments, the terminal alkene includes hepta-l,6-diene (1,6-heptadiene). In some embodiments, the terminal alkene includes octa-1, 7-diene (1,7-octadiene).

[0066] In some embodiments, the terminal alkene includes a compound of formula (A): CH2=CH(CH2)mCH=CH2formula (A); wherein m is an integer selected from 0 to 4.

[0067] In some embodiments, the heptadiene and / or the octadiene includes a compound of formula (B):CH3CH=CH(CH2)mCH=CH2 formula (B); wherein m is an integer selected from 0 to 4, such as 2 or 3 (e.g., m is 2 for a heptadiene and 3 for an octadiene).

[0068] In some embodiments, the heptadiene and / or the octadiene includes a compound of formula (C):CH3(CH2)mCH=CH(CH2)nCH=CH3 formula (C); wherein m and n, independently, are an integer from 0 to 4; wherein, in some embodiments, m is 0, 1, 2, or 3, and n is 0, 1, 2, or 3; wherein, for example, m + n = 2 for heptadienes, and m + n = 3 for octadienes.

[0069] In some embodiments, a terminal alkene includes a compound of formula (D):R1-(CH2)n-C=CH2; formula (D); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R1is selected from hydrogen, a Ci-C6alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc. Alternatively, R1can be selected from a Cs-Ci2cycloalkyl, a C3-C10 cycloalkyl, or a C3-C7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0070] In some embodiments, the compound includes a terminal alkyne. The phrase “terminal alkyne” generally refers to organic compounds, including substituted derivatives of organic compounds and / or heteroatom-containing organic compounds, that include a terminal triple bond, as depicted in the following moiety:

[0071] The term “substituted derivatives” of organic compounds, including terminal alkynes, can include compounds with organic or inorganic substituents. In some embodiments, the substituted derivatives of organic compounds include an oxygen substituent.

[0072] In some embodiments, the terminal alkyne includes a terminal Cs-C2o alkyne, a terminal C3-C19 alkyne, a terminal C3-C18 alkyne, a terminal C3-C17 alkyne, a terminal C3-C16 alkyne, a terminal C3-C15 alkyne, a terminal C3-C14 alkyne, a terminal C3-C13 alkyne, a terminal C3-Ci2alkyne, a terminal C3-C11 alkyne, a terminal C3-C10 alkyne, a terminal C3-C9 alkyne, a terminal C3-C8 alkyne, or a terminal C3-C7 alkyne.

[0073] A terminal alkyne can be referred to as a “1 -alkyne”. For example, a “heptyne” can include a 1-heptyne (e.g., hept-l-yne), a 2-heptyne (e.g., hept-2-yne), a 3-heptyne (e.g., hept- 3-yne), or combinations thereof. A terminal alkyne can be a linear terminal alkyne (e.g., but-1- yne), or a branched (e.g., bulky) terminal alkyne, which contains a branched terminal alkyne (e.g., 4-methylpent-l-yne) or a cycloalkane terminal alkyne (e.g., cyclopropylacetylene).

[0074] A terminal alkyne can include two or more triple bonds, one or more double bonds, or a combination thereof. When a terminal alkyne includes at least one triple bond and at least one double bond, the compound can be referred to as an “enyne.” A number of enynes are provided herein, such as but-l-en-3-yne. A double bond of an enyne can be a terminal double bond or a non-terminal double bond. When a terminal alkyne includes two triple bonds, the compound can be referred to as a “diyne.” A diyne can include two terminal triple bonds, or one terminal triple bond and one non-terminal triple bond.

[0075] A terminal alkyne can include a heteroatom, such as oxygen, nitrogen, etc. When a terminal alkyne includes oxygen as a heteroatom, the oxygen can be present as part of an ether moiety.

[0076] In some embodiments, the compound can include a hexyne, a heptyne, an octyne, or a combination thereof. The term “heptyne” refers to a compound that includes at least one triple bond and a linear chain of seven carbon atoms, wherein at least two of the seven carbon atoms are bonded to each other via a triple bond, and includes substituted derivatives thereof. The term “octyne” refers to a compound that includes at least one triple bond and a linear chain of eight carbon atoms, wherein at least two of the eight carbon atoms are bonded to each other via a triple bond, and includes substituted derivatives thereof. The substituted derivatives of the heptyne and octyne can include, but are not limited to, a C1-C2 substituted heptyne or a C1-C2 substituted octyne. As an example, the following table shows a generic schematic of a linear chain of seven carbon atoms, an embodiment of a heptyne, and an embodiment of a Ci substituted heptyne.

[0077] In some embodiments, the heptyne includes a 2-heptyne, a 3 -heptyne, or a combination thereof. The terms “2-heptyne” and “3-heptyne”, as used herein, refer to heptynes in which the (i) second and third carbons, or (ii) the third and fourth carbons, respectively, of the linear chain of seven carbon atoms are bonded to each other via a triple bond. In some embodiments, the octyne includes a 3-octyne, a 4-octyne, or a combination thereof. The terms“3-octyne” and “4-octyne”, as used herein, refer to octynes in which (i) the third and fourth carbons, or (ii) the fourth and fifth carbons, respectively, of the linear chain of eight carbon atoms are bonded to each other via a triple bond.

[0078] In some embodiments, a terminal alkyne includes a compound of formula (I): R1-(CH2)n-C=C-H; formula (I); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R1is selected from hydrogen, a Ci-C6alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc. Alternatively, R1can be selected from a C3-C12 cycloalkyl, a C3-C10 cycloalkyl, or a C3-C7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0079] In some embodiments, the terminal alkyne includes a compound of formula (II): R2-(CH2)n-O-(CH2)m-C=C-H; formula (II); wherein n is an integer selected from 0 to 5, or 0 to 4; wherein m is an integer selected from 0 to 5, or 0 to 4; and wherein R2is selected from hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0080] In some embodiments, the terminal alkyne includes a compound of formula (III): H-CVC-(CH2)11-C =C-H; formula (III); wherein n is an integer selected from 0 to 5, or 0 to 4.

[0081] In some embodiments, the terminal alkyne includes a compound of formula (IV): H-C=C-(CH2)n-O-(CH2)m-C=C-H; formula (IV); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein m is an integer selected from 0 to 5, or 0 to 4.

[0082] In some embodiments, the terminal alkyne includes a compound of formula (V): H-CH=CH-(CH2)n-C=C-H; formula (V); wherein n is an integer selected from 0 to 5, 0 to 4, or 1 to 4.

[0083] In some embodiments, the terminal alkyne includes a compound of formula (VI):formula (VI); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R3is hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0084] In some embodiments, the terminal alkyne includes a compound of formula (VII): R4-CH=CH-(CH2)n-C=C-H; formula (VII);wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R4is hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0085] In some embodiments, an alkyne, such as an odorant or a terminal alkyne whenR5or R6is hydrogen, includes a compound of formula (VIII):R5-CVC-R6; formula (VIII); wherein R5and R6, independently, are hydrogen, a Ci-Ce alkyl, or a Ci-Ce cycloalkyl. The Ci-Ce alkyl can include methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0086] In some embodiments, the heptyne and / or the octyne includes a compound of formula (IX):CH3-(CH2)m-C=C-(CH2)n-CH3; formula (IX); wherein m is 2 or 3; n is 0 or 1; and m + n = 3 or 4 (e.g., m + n = 3 for heptynes, and m + n = 4 for octynes).

[0087] In some embodiments, the heptyne and / or the octyne includes a compound of formula (X):(CH3)2CH-(CH2)m-C=C-(CH2)n-CH3; formula (X); wherein m is 1 or 2; n is 0 or 1; and m + n = 2 or 3 (e g., m + n = 2 for heptynes, and m + n = 3 for octynes).

[0088] In some embodiments, the heptyne and / or the octyne includes a compound of formula (XI):(CH3)3C-(CH2)m-C=C-(CH2)n-CH3; formula (XI); wherein m is 1 or 2; n is 0 or 1; and m + n = 2 or 3 (e g., m + n = 2 for heptynes, and m + n = 3 for octynes).

[0089] In some embodiments, the terminal alkyne, terminal alkene, or non-terminal alkyne (such as a compound of formula (VIII) when R5or R6is hydrogen) includes any one or more of the following compounds:

[0090] INHffilTOR / ODORANT COMPOSITIONS

[0091] Also provided herein are compositions, which can be compositions that comprise compounds that function as inhibitors of hydrogen embrittlement, odorants, or a combination thereof. In some embodiments, the composition can comprise a compound that functions as an embrittlement inhibitor and also functions as an odorant. In alternative embodiments, the composition can comprise a compound that functions as an embrittlement inhibitor and a compound (different from the embrittlement inhibitor) that functions as an odorant. In embodiments, the embrittlement inhibitor and the odorant can be the same compound. In alternative embodiments, the embrittlement inhibitor and the odorant can be different compounds. In some embodiments, the compositions include any one or more compounds provided herein and an additive. The additive can be dispersed in the compound(s), or the compound(s) can be dispersed in the additive, depending on whether the additive or the compound(s) is the majority component.

[0092] The additives for the compositions provided herein can include a stabilizer, an antioxidant, a radical inhibitor, or a combination thereof. In some embodiments, the additive is capable of reacting with an odorant poison (such as oxygen (O2), ozone, superoxide anion (Ch'), organic peroxide (ROOR’), organic peroxy radical (ROO*), organic hydroperoxide (ROOH), hydroxyl radical (RO»), inorganic peroxide, hydrogen peroxide, metal oxide, peroxynitrite (ONOO ), nitric oxide (’NO), etc.), thereby avoiding or reducing the likelihood of the (i) formation of one or more undesired products, (ii) polymerization of the odorant, (iii) decomposition of the odorant, or (iv) a combination thereof. The additive, such as a radical inhibitor, can have a reactivity towards the odorant poison that is greater than its reactivity towards the odorant. For example, phenolic derivatives exhibit antioxidant properties through two key mechanisms. In Hydrogen Atom Transfer (HAT), phenolic antioxidants can donate a hydrogen atom to free radicals, neutralizing them and preventing oxidative damage of alkynes. This process stabilizes the free radicals by converting them into less reactive species. In Single Electron Transfer (SET), phenolic compounds transfer an electron to free radicals, reducing them and stopping the chain reaction of oxidation. This helps reduce the autocatalytical nature of the alkyne oxidation process. Amine derivatives act as antioxidants primarily by neutralizing free radicals, which are highly reactive molecules that can cause oxidative damage to alkynes through three key mechanisms. By free radical scavenging, amines, particularly aromatic amines, are effective at scavenging free radicals. They donate hydrogen atoms to free radicals, therebyneutralizing them and preventing further oxidative reactions. Some amines can also decompose hydroperoxides, which are intermediates in the oxidation process. This helps to break down potentially harmful compounds before they can cause damage to alkynes. Hindered amines, such as those derived from 2,2,6,6-tetramethylpiperidine, are particularly effective in protecting materials against UV light degradation. They work by neutralizing free radicals formed during UV exposure. Organic acids, such as citric acid, malic acid, and tartaric acid, can act as antioxidants and protect organic compounds from oxidation through two key mechanisms. Organic acids can neutralize free radicals, which are unstable molecules that can cause oxidative damage organic compounds. By donating an electron to these free radicals, organic acids stabilize them and prevent them from causing further damage to alkynes. Some organic acids can bind to metal ions impurities like iron and copper, which catalyze oxidative reactions. This reduces the availability of the metal ions to participate in oxidation reactions, thereby protecting other organic compounds such as alkynes. Other compounds are chemically converted, such as for example, isopropanol which can react with oxidative species to form acetone, thus avoiding the oxidation of the alkyne moiety. Other mechanisms and properties of the additives are envisioned. This can include for example the reaction of the odorant with an odorant poison catalyzed by the equipment surfaces such as storage tank (e.g. metal or alloy and corresponding oxides surfaces), seals (e.g. organic elastomers), and plastic parts (e.g. resin or processing additives included in the plastic parts).

[0093] The additive can improve the stability of an odorant, such as any of those described herein. For example, an odorant composition or odorized fluid provided herein can be stored (i) for at least 1 month, 6 months, 12 months, 18 months, 24 months, 30 months, 36 months, 42 months, 48 months, 54 months, or 60 months, (ii) at a temperature of at least -40 °C, at least -30 °C, at least -20 °C, at least -10 °C, at least 0 °C, at least 10 °C, at least 15 °C, at least 20 °C, at least 25 °C, at least 35 °C, at least 45 °C, at least 50 °C, at least 55 °C, at least 60 °C, at least 65 °C, at least 70 °C, at least 75 °C, at least 80 °C, at least 85 °C, or at least 90 °C, or (iii) a combination thereof, and during the storing of the odorant composition or the odorized fluid less than 10 mol%, less than 5 mol%, less than 1 mol%, or less than 0.1 mol% of the odorant polymerizes. As a further example, an odorant composition or odorized fluid provided herein can be stored (i) for at least 1 month, 6 months, 12 months, 18 months, 24 months, 30 months, 36 months, 42 months, 48 months, 54 months, or 60 months, (ii) at a temperature of at least -40 °C,at least -30 °C, at least -20 °C, at least -10 °C, at least 0 °C, at least 10 °C, at least 15 °C, at least 20 °C, at least 25 °C, at least 35 °C, at least 45 °C, at least 50 °C, at least 55 °C, at least 60 °C, at least 65 °C, at least 70 °C, at least 75 °C, at least 80 °C, at least 85 °C, or at least 90 °C, or (iii) a combination thereof, and during the storing of the odorant composition or the odorized fluid less than 10 mol%, less than 5 mol%, less than 1 mol%, or less than 0.1 mol% of the odorant reacts with oxygen, ozone, a peroxide, a hydroxyl, a hydroxyl radical, a metal oxide, a superoxide anion (O2 ) to form an oxygenated product.

[0094] The additive can be a non-odiferous compound or an odiferous compound.Examples of odiferous additives include but are not limited to cyclobutanol, 2,4-dimethylpentan- 3-one, 2-methyl-l -pentanol, 4-methyl-2-pentanol, isopropyl ether, 2,2-dimethylbutanol, isoamyl alcohol (isopentanol), 2-methyl-l -butanol, (S)-(+)-4-methyl-2-pentanol, (2R)-2,3-dimethylbutan- l-ol, (2R)-2-methylpentan-l-ol, 2,3-dimethylbutan-l-ol, 3-methylhexan-2-ol, 2,3-dimethyl-2- pentanol, 3-methylpentan-2-ol, 2-methylpentan-3-ol, 3 -methyl-(R)-3 -hexanol, 3 -pentanol, 2- methylpentan-2-ol, 2,3-dimethylbutan-2-ol, 3-methyl-3-hexanol, 2,4-dimethyl-3-pentanol, 2- pentanol, 3-ethyl-2-pentanol, 4,4-dimethylpentan-2-ol, 4-methylhexan-3-ol, 2-methylhexan-3-ol, 3-hexanol, 3,3-dimethyl-l-butanol, 2,4-dimethylpentan-2-ol, 2-methylhexan-2-ol, isopropyl alcohol, 2-methyl-(3S)-3-pentanol, propanol, 1-butanol, 1-pentanol, 2-methyl-2-butanol, 2- methyl-1 -propanol (isobutanol), 2-butanol, (2R)-4,4-dimethylpentan-2-ol, 2- methyltetrahydrofuran, cis-2-penten-l-ol, l-hexen-3-ol, 3-methyl-2-buten-l-ol, 3-buten-2-ol, 3- (1 -methylethoxy)- 1 -propene, l-penten-3-ol, 2-ethyl -5 -methylfuran, 2-ethylfuran, 2-methylfuran, acetal, butyl ether, methyl tert-butyl ether, 1,1 -dimethoxy ethane, 1 -methoxy-cyclohexene, 4- methoxy-2-methyl-l -butene, 3 -methoxy- 1 -propene, pentanal (valeraldehyde), cyclobutanone, 2- methylpentanal, propanal (propionaldehyde), butanal (butyraldehyde), 2,2- dimethylvaleraldehyde, 3 -methylvaleraldehyde, (3S)-3-methylpentanal, 2-ethylpentanal, 2- methyl-(R)-pentanal, 3 -methylbutanal (isovaleraldehyde), hexanal (n-hexylaldehyde), 2- methylpropanal (isobutyraldehyde), (2S)-2-methylpentanal, 2-ethylbutanal, butyl formate, cyclopentyl formate, 3-methyl-2-butenal, tiglic aldehyde, trans-2-butenal, 2-pentenal, 4-pentenal, (4E)-4-hexenal, 3-hexenal, hexenal, 4-methyl-2-pentenal, 2-methyl-2-pentenal, (2E)-2-hexenal, (3Z)-3-hexenal, 1-butene, 2,4,4- trimethyl- 1 -pentene, 2,4,4- trimethyl-2-pentene, 1-pentene, 1- octene, 2-octene, 1-nonene, (E)-2-octene, 1,3 -pentadiene, 2,3 -dimethyl- 1, 3-butadiene, 2,3,4- trimethyl-2-pentene, 1-hexene, 1,5-hexadiene, 1,4-hexadiene, 3-methyl-l, 2-butadiene, 1,5-hexadien-3-ol, cyclohexene, cyclopentene, 5-ethylidene-2-norbomene, ethyl propionate, ethyl butyrate, propyl butyrate, propyl propionate, methyl hexanoate (methyl caproate), ethyl isovalerate, methyl 3 -methylvalerate, ethylpivalate, ethyl valerate, isobutyl propionate, tert-butyl acetate, methyl isobutyrate (methyl 2-methyl propanoate), methyl propionate, methyl isovalerate, butyl propionate, methyl butyrate, methyl valerate, isopropyl propionate, isopropyl butyrate, propyl isobutyrate, propan-2-yl, (2S)-2-methylbutanoate, ethyl 2-methylbutyrate, methyl 2- methylbutyrate, ethyl isobutyrate, isobutyl isobutyrate, butan-2-yl propanoate, isopropyl isobutyrate, vinyl propionate, iso-butyl acrylate, n-butyl acrylate, 4-pentenyl acetate, allyl propionate, 3-butenoic acid, methyl ester, methyl methacrylate, ethyl methacrylate, (E)-2- butenoic acid methyl ester, 4-methylhexan-2-one, 2-pentanone, 5-methyl-2-hexanone (methyl isoamyl ketone), 2-heptanone (methyl n-amyl ketone), 4-heptanone, 3-methylhexan-2-one, 2,2- dimethyl-3 -hexanone, 3-methyl-2-butanone, 2, 2-dimethyl-3 -pentanone, 3-hexanone, 4,4- dimethyl-2-pentanone, 2-hexanone, 3-ethyl-2-pentanone, 5-methylhexan-3-one, 2-methyl-3- hexanone, 2-butanone, 3 -pentanone, sec-butyl acetate, isopropyl acetate, sec-amyl acetate, 1- Methoxy-2-propyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate (isoamyl acetate), ethyl acetate, methyl butyl acetate, (2S)-2-methylbutyl acetate, isopropenyl acetate, mesityl oxide, l-penten-3-one (ethyl vinyl ketone), l-hexen-3-one (vinyl propyl ketone), 2-Hexen-4-one, l-hepten-3-one (vinyl butyl ketone), 4-methyl-4-penten-2-one, 3-methyl-3- penten-2-one,3-penten-2-one, 2-methylphenol (o-cresol), 3 -methylphenol (m-cresol), 4- methylphenol (p-cresol), 2-ethylphenol, 3 -ethylphenol, 4-ethylphenol, 2-propylphenol, 3- propylphenol, 4-propylphenol, 2-butylphenol, 3 -butylphenol, 4-butylphenol, 2-methoxyphenol (guaiacol), 3-methoxyphenol, 4-methoxyphenol or 4-Hydroxyanisole or hydroquinone monomethyl ether also known as MeHQ, 2 -ethoxy phenol, 3 -ethoxyphenol, 4-ethoxyphenol, 2- m ethoxy-3 -methylphenol, 4-methoxy-3 -methylphenol, 2-methoxy-4-m ethylphenol (creosol), 3- methoxy-4-methylphenol, 2-methoxy-5-methylphenol (isocreosol), 3-methoxy-5-methylphenol, 2-hydroxybenzoic acid or salicylic acid, 3 -hydroxybenzoic acid, 4-hydroxybenzoic acid, 2- hydroxybenzoic acid methyl ester or methyl salicylate or wintergreen oil, 3-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester, 2-hydroxybenzoic acid ethyl ester or ethyl salicylate, 3-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acid ethyl ester, 2,3- dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4- dimethylphenol, 3,5-dimethylphenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-fluorophenol, 3 -fluorophenol, 4-fluorophenol, 2-(trifluoromethyl)phenol, 3- (trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,4-dinitrophenol (DNP), 2,4-dinitro-6-sec- butyl-phenol (DNBP) and 2,6-dinitro-p-cresol, benzene- 1 ,2-diol (pyrocatechol), benzene- 1,3- diol (resorcinol), benzene- 1,4-diol (hydroquinone, HQ), 3,4,5-trihydroxybenzoic acid or gallic acid, 3,4,5-trihydroxybenzoic acid methyl ester or methyl gallate, 3,4,5-trihydroxybenzoic acid ethyl ester or ethyl gallate, 3,4,5-trihydroxybenzoic acid propyl ester or propyl gallate, 3,4,5- trihydroxybenzoic acid octyl ester or octyl gallate, dimethylhydroxylamine, trimethylamine, trimethylamine N-oxide, diethylamine, diethylhydroxylamine, triethylamine, triethylamine N- oxide, dipropylamine, dipropylhydroxylamine, tripropylamine, tripropylamine N-oxide, diisopropylamine, diisopropylhydroxylamine, triisopropylamine, triisopropylamine N-oxide, dibutylamine, dibutylhydroxylamine, tributylamine, tributylamine N-oxide, diisobutylamine, diisobutylhydroxylamine, tri-iso-butylamine, tri-iso-butylamine N-oxide, di-tert-butylamine, di- tert-butylhydroxylamine, tri-tert-butylamine, tri-tert-butylamine N-oxide, diethylmethylamine, dipropylmethylamine, diisopropylmethylamine, dipropylethylamine, diisopropylethylamine, ethanolamine, diethanolamine, triethanolamine, N,N-dimethylisopropanolamine (DMPA), 2,2,6,6-tetramethylpiperidine, aniline, N,N-dimethyl aniline, and N,N-diethylaniline.

[0095] An odiferous additive can contribute to the alarming scent of an odorized fluid. As a result, when an additive is an odiferous additive, a concentration of odorant that is used in an odorized fluid or an odorant composition can be reduced without undesirably impacting the detectability of the odorized fluid.

[0096] The additive generally can be any compound that is capable of acting as a stabilizer, an antioxidant, and / or a radical inhibitor, especially for an odorant that includes an alkynyl moiety. As used herein, the term “stabilizer, antioxidant, and / or radical inhibitor” refers to a compound or material that prevents or delays the chemical degradation of a fluid and / or an odorant compound, such as an alkyne.

[0097] When the treated fluid compositions disclosed herein contain an additive, and the additive comprises a stabilizer, an antioxidant, and / or a radical inhibitor, the additive can be present in the composition in any suitable amount. In some embodiments, the additive (stabilizer, antioxidant, and / or radical inhibitor) is present in the composition at a concentration of about 10 ppmw (ppm by weight) to about 10 wt%, about 10 ppmw to about 8 wt%, about 10 ppmw to about 6 wt%, about 10 ppmw to about 4 wt%, about 10 ppmw to about 2 wt%, about 10ppmw to about 1 wt%, about 10 ppmw to about 5,000 ppmw, about 50 ppmw to about 10 wt%, about 50 ppmw to about 8 wt%, about 50 ppmw to about 6 wt%, about 50 ppmw to about 4 wt%, about 50 ppmw to about 2 wt%, about 50 ppmw to about 1 wt%, about 50 ppmw to about 5,000 ppmw, about 50 ppmw to about 1,000 ppmw, about 200 ppmw to about 10 wt%, about 200 ppmw to about 8 wt%, about 200 ppmw to about 6 wt%, about 200 ppmw to about 4 wt%, about 200 ppmw to about 2 wt%, about 200 ppmw to about 1 wt%, about 200 ppmw to about 5,000 ppmw, or about 200 ppmw to about 2,000 ppmw, based on the weight of the inhibitor of hydrogen embrittlement in the composition (or based on the weight of the odorant in the composition). More often, the additive (stabilizer, antioxidant, and / or radical inhibitor) is present in the composition at a concentration of about 10 ppmw (ppm by weight) to about 1,000 ppmw, about 10 ppmw to about 900 ppmw, about 10 ppmw to 750 ppmw, about 10 ppmw to about 500 ppmw, about 50 ppmw to about 1,000 ppmw, about 50 ppmw to 750 ppmw, about 50 ppmw to about 500 ppmw, about 200 ppmw to about 1,000 ppmw, about 200 ppmw to about 900 ppmw, about 200 ppmw to 750 ppmw, or about 200 ppmw to about 500 ppmw.

[0098] Examples of stabilizers, antioxidants, and radical inhibitors include phenolic derivatives including but not limited to, 2-methylphenol (o-cresol), 3 -methylphenol (m-cresol), 4-methylphenol (p-cresol), 2-ethylphenol, 3 -ethylphenol, 4-ethylphenol, 2-propylphenol, 3- propylphenol, 4-propylphenol, 2-butylphenol, 3 -butylphenol, 4-butylphenol, 2-methoxyphenol (guaiacol), 3-methoxyphenol, 4-methoxyphenol or 4-hydroxyanisole or hydroquinone monomethyl ether (also known as MeHQ), 2-ethoxyphenol, 3 -ethoxyphenol, 4-ethoxyphenol, 2- m ethoxy-3 -methylphenol, 4-methoxy-3 -methylphenol, 2-methoxy-4-m ethylphenol (creosol), 3- methoxy -4-methylphenol, 2-methoxy-5-methylphenol (isocreosol), 3-methoxy-5-methylphenol, 2,6-di-tert-butyl-4-methylphenol or butylated hydroxytoluene or tert-butyl hydroxytoluene (also known as BHT), a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol, (l,l-dimethylethyl)-4-methoxyphenol or butylated hydroxyanisole or tert-butylhydroxyanisole (also known as BOA or BHA), 2,5-di-tert-butyl-phenol, 2,6-di-tert-butyl phenol, 2-(l , 1 - dimethylethyl)- 1,4-benzenediol or mono-tert-butylhydroquinone or tert-butyl hydroquinone (also known as MTBHQ or TBHQ), 2-hydroxybenzoic acid or salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-hydroxybenzoic acid methyl ester or methyl salicylate or wintergreen oil, 3-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester, 2-hydroxybenzoic acid ethyl ester or ethyl salicylate, 3-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acidethyl ester, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3, 5 -dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5- trimethylphenol, 2,4,6-trimethylphenol, 3,4,5-trimethylphenol, 2-chlorophenol, 3 -chlorophenol, 4-chlorophenol, 2-fluorophenol, 3 -fluorophenol, 4-fluorophenol, 2-(trifluoromethyl)phenol, 3- (trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,4-dinitrophenol (DNP), 2,4-dinitro-6-sec- butyl-phenol (DNBP) and 2, 6-dinitro-p-cresol, catechol derivatives, including but not limited to, benzene- 1,2-diol (pyrocatechol), benzene- 1,3 -diol (resorcinol), benzene-l,4-diol (hydroquinone, HQ), 4-tert-butylcatechol (TBC), 2,5-Bis(l,l-dimethylethyl)-l,4-benzenediol or 2,5-di-tert- butylhydroquinone (also known as DBHQ or DTBHQ), 2-methyl-l,4-benzenediol or tolyhydroquinone or methylhydroquinone (also known as THQ or M-HQ), 3,4,5- trihydroxybenzoic acid or gallic acid, 3,4,5-trihydroxybenzoic acid methyl ester or methyl gallate, 3,4,5-trihydroxybenzoic acid ethyl ester or ethyl gallate, 3,4,5-trihydroxybenzoic acid propyl ester or propyl gallate and 3,4,5-trihydroxybenzoic acid octyl ester or octyl gallate, amine derivatives, including but not limited to, dimethylhydroxylamine, trimethylamine, tri methyl amine N-oxide, diethylamine, diethylhydroxylamine, triethylamine, triethylamine N- oxide, dipropylamine, dipropylhydroxylamine, tripropylamine, tripropylamine N-oxide, diisopropylamine, diisopropylhydroxylamine, triisopropylamine, triisopropylamine N-oxide, dibutylamine, dibutylhydroxylamine, tributylamine, tributylamine N-oxide, diisobutylamine, diisobutylhydroxylamine, triisobutylamine, triisobutylamine N-oxide, di-tert-butylamine, di-tert- butylhydroxylamine, tri-tert-butylamine, tri-tert-butylamine N-oxide, diethylmethylamine, dipropylmethylamine, diisopropylmethylamine, dipropylethylamine, diisopropylethylamine, ethanolamine, diethanolamine, triethanolamine, N,N-dimethylisopropanolamine (DMPA), 2,2,6,6-tetramethylpiperidine, 2,2,6,6-Tetramethylpiperidine N-oxide (TEMPO) and derivatives, pyridine N-oxide, N-methylmorpholine N-oxide (NMMO), lauryldimethylamine N-oxide, N,N- dimethyldodecylamine N-oxide, N,N-dimethyloctylamine N-oxide, N,N- dimethylhexadecylamine N-oxide, N-palmitoylethanolamine (PEA), N-acetylethanolamine (AEA), N-myristoylethanolamine (MEA), diphenylamine, phenyl-a-naphthylamine (PANA), N,N'-di-2-butyl-l,4-phenylenediamine (DBPDA), N,N-dibenzylhydroxyl amine (DBHA), 1,4- phenylenediamine, aniline, N,N-dimethylaniline and N,N-diethylaniline, organic acids, including but not limited to, formic acid, acetic acid, benzoic acid, sorbic acid, citric acid, malic acid, tartaric acid, succinic acid, lactic acid and oxalic acid, inorganic acids and salts, including but notlimited to, hypophosphorous acid, sodium metabisulfite, sodium bisulfite, sodium sulfite, sodium nitrite, sodium thiosulfate, sodium selenite, sodium hypophosphite, sodium selenate, sodium selenite, sodium hypochlorite, sodium persulfate and equivalent potassium salts, natural product derivatives, including but not limited to, ascorbic acid (vitamin C) or a derivative thereof (e.g., ascorbyl palmitate, ascorbyl acetate, etc.), a tocopherol and tocotrienols (vitamin E) or a derivative thereof (e.g., alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, tocopheryl acetate, etc.), retinol (vitamin A) or a derivative thereof (e.g., retinoid acid, retinyl acetate, retinyl palmitate, etc.), hydroxy cinnamates or a derivative thereof (e.g. caffeic acid, chlorogenic acid, ferulic acid, p-coumaric acid, etc.), flavonoids or a derivative thereof (taxifolin, luteolin, apigenin, tangeritin, quercetin, kaempferol, myricetin, fisetin, galangin, isorhamnetin, pachypodol, rhamnazin, pyranoflavonols, furanoflavonols, hesperetin, naringenin, eriodictyol, homoeriodictyol, cyanidin, delphinidin, malvidin, pelargonidin, peonidin, petunidin, catechin, gallocatechin, catechin 3 -gallate, gallocatechin 3 -gallate, epicatechins, epigallocatechin, epicatechin 3-gallate, epigallocatechin 3 -gallate, etc), glutathione, melatonin and uric acid.

[0099] In some embodiments, the additive has a boiling point that is about 300 °C or less, about 270 °C or less, about 250 °C or less, about 220 °C or less, about 190 °C or less, about 160 °C or less, about 130 °C or less, about 120 °C or less, about 110 °C or less, or about 100 °C or less. In some embodiments, the additive has a freezing point that is about 100 °C or less, about 50 °C or less, about 0 °C or less, about -80 °C or less, about -70 °C or less, about -60 °C or less, about -50 °C or less, about -40 °C or less, about -30 °C or less, about -20 °C or less, or about -10 °C or less.

[0100] The additive can be a non-toxic compound. The additive also can be environmentally benign. In some embodiments, the additive has an acute oral toxicity of at least 100 mg / kg, at least 200 mg / kg, at least 300 mg / kg, at least 500 mg / kg, at least 1,000 mg / kg, at least 2,000 mg / kg, at least 3,000 mg / kg, at least 4,000 mg / kg, or at least 5,000 mg / kg.

[0101] The additive can have any volatility. The additive can be relatively volatile. In some embodiments, the additive has a vapor pressure (at 20 °C) of at least 0.001 kPa, at least 0.01 kPa, at least 0.1 kPa, or at least 1 kPa.

[0102] The additive can be a compound that includes an aldehyde moiety, such as a compound selected from ethanal, propanal, 1 -butanal, isobutanal (2-methylpropanal), pentanal (valeraldehyde), isopentanal (isovaleraldehyde or 3 -methylbutanal), 2-methylbutanal,pivaldehyde (2,2-dimethylpropanal), hexanal, 4-methylpentanal, 3-methylpentanal, 2- methylpentanal, 3, 3 -dimethylbutanal, 1 -octanal, furfural, glyoxal, or a combination thereof. In some embodiments, the additive is a C3-C10 alkyl aldehyde, a C3-C6 alkyl aldehyde, or a derivative thereof, such as a derivative comprising an alkenyl moiety, an alkynyl moiety, or a combination thereof, wherein the alkyl aldehyde is a cyclic or non-cyclic aldehyde.

[0103] The additive can be a compound that includes a ketone moiety (for example, one ketone moiety, two ketone moieties, three ketone moieties, etc.). For example, the additive can include a compound selected from acetone, butanone, 2-pentanone, 3-pentanone, 3-methyl-2- butanone, 2-hexanone, 3 -hexanone, 3-methyl-2-pentanone, 2-methyl-3 -pentanone, 4- methylpentanone, 3,3-dimethyl-2-butanone, 2,3-butadione, 2,3 -pentadione, 2,4-pentadione, 3- methyl-penta-2, 4-dione, cyclobutanone, cyclopentanone, cyclohexanone, methyl isobutyl ketone, or a combination thereof. In some embodiments, the compound is a C3-C10 alkyl ketone, a C3- C10 alkyl diketone, a C4-C8 alkyl ketone, a C4-C8 alkyl diketone, a C3-C6 alkyl ketone, a C3-C6 alkyl diketone, or a derivative thereof, such as a derivative comprising an alkenyl moiety, an alkynyl moiety, or a combination thereof, wherein the alkyl ketone is a cyclic alkyl ketone or a non-cyclic alkyl ketone.

[0104] The additive can be a compound that includes an alcohol moiety (e.g., one alcohol moiety, two alcohol moieties, etc.). For example, the additive can include a compound selected from methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, tert-butanol, 3-methyl-2- butanol, 2-pentanol, 3-pentanol, 2-methyl-3-pentanol, butane-2,3-diol, 1-octanol, 2,3-pentadiol, 2,4-pentadiol, benzyl alcohol, or a combination thereof. In some embodiments, the additive includes a C1-C10 alkyl alcohol, a C1-C10 alkyl di-alcohol, a C2-C10 alkyl alcohol, a C2-C10 alkyl di-alcohol, a Ci-Cg alkyl alcohol, a Ci-Ce alkyl di-alcohol, or a derivative thereof, such as a derivative comprising an alkenyl moiety, an alkynyl moiety, or a combination thereof.

[0105] The additive can be a compound that includes an ester moiety. For example, the additive can include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl sorbate, ethyl sorbate, propyl sorbate, isopropyl sorbate, ethyl 2- butynoate, or a combination thereof. In some embodiments, the compound is a C2 to C10 alkyl ester, a C2-C6 alkyl ester, or a derivative thereof, such as a derivative comprising an alkenyl moiety, an alkynyl moiety, or a combination thereof.

[0106] The additive can be a compound that includes an ether moiety. For example, the additive can include dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, methyl propyl ether, ether propyl ether, diisopropyl ether, methyl isopropyl ether, ethyl isopropyl ether, propyl isopropyl ether, methyl butyl ether, ethyl butyl ether, methyl isobutyl ether, ethyl isobutyl ether, or a combination thereof. In some embodiments, the additive includes a C1-C10 dialkyl ether, a Ci-Ce dialkyl ether, a C1-C2 dialkyl ether, or a derivative thereof, such as a derivative comprising an alkenyl moiety, an alkynyl moiety, or a combination thereof.

[0107] The additive can be an unsubstituted or substituted diphenyl ether, or an unsubstituted or substituted C1-C10 alkylphenyl ether (which can have the following structure: C1-C10 alkyl-O-Ph, wherein, optionally, the phenyl moiety is substituted).

[0108] In some embodiments, the additive is a compound that includes a cycloalkanol moiety, such as a compound selected from cyclopropanol, cyclobutanol, cyclopentanol, or a combination thereof. In some embodiments, the additive is a C3-C8 cycloalkanol, or a C3-C4 cycloalkanol.

[0109] In some embodiments, the additive is an unsubstituted or substituted phenol, such as 2-methylphenol (o-cresol), 3 -methylphenol (m-cresol), 4-m ethylphenol (p-cresol), 2- ethylphenol, 3 -ethylphenol, 4-ethylphenol, 2-propylphenol, 3 -propylphenol, 4-propylphenol, 2- butylphenol, 3 -butylphenol, 4-butylphenol, 2-methoxyphenol (guaiacol), 3 -methoxyphenol, 4- methoxyphenol or 4-Hydroxyanisole or hydroquinone monomethyl ether (also known as MeHQ), 2-ethoxyphenol, 3 -ethoxyphenol, 4-ethoxyphenol, 2-methoxy-3-methylphenol, 4- m ethoxy-3 -methylphenol, 2-methoxy-4-methylphenol (creosol), 3-methoxy-4-methylphenol, 2- methoxy-5-methylphenol (isocreosol), 3-methoxy-5-methylphenol, 2,6-di-tert-butyl-4- methylphenol or butylated hydroxytoluene or tert-butyl hydroxytoluene (also known as BHT), a mixture of 2-tert-butyl-4-methoxyphenol and 3 -tert-butyl-4-m ethoxyphenol, (1,1-dimethylethyl)- 4-methoxyphenol or butylated hydroxyanisole or tert-butylhydroxyanisole (also known as BOA or BHA), 2, 5-di -tert -butyl -phenol, 2,6-di-tert-butyl phenol, 2-(l, 1 -dimethylethyl)- 1,4- benzenediol or mono-tert-butylhydroquinone or tert-butyl hydroquinone (also known as MTBHQ or TBHQ), 2-hydroxybenzoic acid or salicylic acid, 3 -hydroxybenzoic acid, 4- hydroxybenzoic acid, 2-hydroxybenzoic acid methyl ester or methyl salicylate or wintergreen oil, 3 -hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester, 2-hydroxybenzoic acid ethyl ester or ethyl salicylate, 3 -hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acidethyl ester, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 3,4,5-trimethylphenol, 2- chlorophenol, 3 -chlorophenol, 4-chlorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,4- dinitrophenol (DNP), 2,4-dinitro-6-sec-butyl-phenol (DNBP) and 2,6-dinitro-p-cresol, benzene- 1,2-diol (pyrocatechol), benzene-l,3-diol (resorcinol), benzene-l,4-diol (hydroquinone, HQ), 4- tert-butyl catechol (TBC), 2,5-bis(l,l-dimethylethyl)-l,4-benzenediol or 2,5-di-tert- butylhydroquinone (also known as DBHQ or DTBHQ), 2-methyl-l,4-benzenediol or tolyhydroquinone or methylhydroquinone (also known as THQ or M-HQ), 3,4,5- trihydroxybenzoic acid or gallic acid, 3,4,5-trihydroxybenzoic acid methyl ester or methyl gallate, 3,4,5-trihydroxybenzoic acid ethyl ester or ethyl gallate, 3,4,5-trihydroxybenzoic acid propyl ester or propyl gallate and 3,4,5-trihydroxybenzoic acid octyl ester or octyl gallate, or a combination thereof.

[0110] In some embodiments, the additive is a compound that includes a carboxylic acid moiety, such as a compound selected from formic acid, acetic acid, benzoic acid, sorbic acid, citric acid, malic acid, tartaric acid, succinic acid, lactic acid, oxalic acid, or a combination thereof. In some embodiments, the additive is a C2-C10 alkyl carboxylic acid, or a derivative thereof, such as a derivative comprising an alkenyl moiety, an alkynyl moiety, or a combination thereof.

[0111] In some embodiments, the additive is an unsubstituted or substituted quinoline.

[0112] The treated fluid composition containing the additive can be prepared in any suitable manner, but generally, involved a process that comprises contacting the fluid, the inhibitor of hydrogen embrittlement, the additive, and optionally the odorant in any order or sequence. It is important that odor leaks or odor releases be avoided in the preparation of the treated fluid composition.

[0113] In one embodiment, for instance, the treated fluid composition is prepared by a process that comprises introducing the additive in solid form or liquid form through a first leak- tight inlet port into an odorant vessel; introducing the odorant and the inhibitor of hydrogen embrittlement through the first leak-tight inlet port or a second leak-tight inlet port into the odorant vessel and mixing with the additive to form an odorant composition; and discharging at least a portion of the odorant composition from the odorant vessel through a leak-tight outlet portand contacting with the fluid to form the treated fluid composition. Mixing can be simply allowing sufficient time for the materials to combine and form a uniform composition, or a suitable agitation technique can be used. The odorant vessel can be any suitable storage tank, isotainer, Schmidt drum, and the like.

[0114] In another embodiment, the treated fluid composition can be prepared by a process that comprises introducing the additive in liquid form into a multiport vessel; connecting the multiport vessel to an odorant vessel containing the odorant and the inhibitor of hydrogen embrittlement and transferring the additive to the odorant vessel through a leak-tight inlet port and mixing the additive with the odorant and the inhibitor of hydrogen embrittlement to form an odorant composition; disconnecting the multiport vessel from the odorant vessel; and discharging at least a portion of the odorant composition from the odorant vessel through a leak- tight outlet port and contacting with the fluid to form the treated fluid composition. The transfer of the additive from the multiport vessel to the odorant vessel can be accomplished by any suitable means, such as pumping, gravity driven flow, pressure driven flow, and the like. If the additive is in solid form, a concentrated solution can be prepared by combining the additive in solid form with a small amount of the odorant or inhibitor and introducing the concentrated solution (in liquid form) into the multiport vessel.

[0115] In other embodiments, the additive can comprise a diluent, such as a diluent for a compound such as an alkyne or a terminal alkene. The additive can include a Cs-Cs saturated hydrocarbon (e.g., a pentane, a cyclopentane, a hexane, a cyclohexane, a heptane, a cycloheptane, an octane, and / or a fluorinated hydrocarbon, such as, for example, PFC-116, PFC- c216, PFC-218, or PFC-318).

[0116] A compound, such as an alkyne or a terminal alkene, generally can be present in a composition at any desirable amount. In some embodiments, the compound is present in a composition at an amount of at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the composition. If two or more compounds are present, such as a first and a second terminal alkyne, then the first and the second alkynes can be present in the odorant composition at a total amount of at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the composition. For example, if 20 g of a firstterminal alkyne and 30 g of a second terminal alkyne are present in a composition having a total weight of 100 g, then the first and the second alkyne are present in the odorant composition at a total amount of 50 wt%.

[0117] A composition generally can be in any phase, e.g., a liquid or gas. A composition can be stored and / or used in any desirable phase.

[0118] TREATED FLUID C OMPO SITIONS

[0119] Also provided herein are treated fluid compositions. The phrases “treated fluid composition” and “treated fluid” can be used interchangeably herein. In some embodiments, the treated fluids generally comprise (i) a fluid, such as a gas, and (ii) any of the compounds, such as terminal alkynes and terminal alkenes as disclosed herein. A compound or composition can be dispersed, evenly or unevenly, in the fluid.

[0120] A compound, such as a terminal alkyne and terminal alkene, can be present in a treated fluid at any desired amount. When a composition is present in a treated fluid, the composition can be present at an amount that is effective to achieve a desired concentration of the compound in the treated fluid. In some embodiments, a compound, such as a terminal alkyne or terminal alkene, is present in a treated fluid at a concentration of 1,000 mg / m3n or less, 900 mg / m3n or less, 800 mg / m3n or less, 700 mg / m3n or less, 600 mg / m3n or less, 500 mg / m3n or less, 400 mg / m3n or less, 300 mg / m3n or less, 200 mg / m3n or less, 100 mg / m3n or less, 90 mg / m3n or less, 80 mg / m3n or less, 70 mg / m3n or less, 60 mg / m3n or less, 50 mg / m3n or less, 40 mg / m3n or less, 30 mg / m3n or less, 20 mg / m3n or less, or 10 mg / m3n or less. In some embodiments, a compound, such as a terminal alkyne or terminal alkene, is present in a treated fluid at a concentration of at least 0.1 mg / m3n, at least 0.5 mg / m3n, at least 1 mg / m3n, at least 2 mg / m3n, at least 3 mg / m3n, at least 4 mg / m3n, at least 5 mg / m3n, at least 6 mg / m3n, at least 7 mg / m3n, at least 8 mg / m3n, at least 9 mg / m3n, or at least 10 mg / m3n. In some embodiments, a compound, such as a terminal alkyne or terminal alkene, is present in a treated fluid at a concentration of about 1 mg / m3n to about 1,000 mg / m3n, about 1 mg / m3n to about 900 mg / m3n, about 1 mg / m3n to about 800 mg / m3n, about 1 mg / m3n to about 700 mg / m3n, about 1 mg / m3n to about 600 mg / m3n, about 1 mg / m3n to about 500 mg / m3n, about 1 mg / m3n to about 400 mg / m3n, about 1 mg / m3n to about 300 mg / m3n, about 1 mg / m3n to about 200 mg / m3n, about 1 mg / m3n to about 100 mg / m3n, about 1 mg / m3n to about 90 mg / m3n, about 1 mg / m3n to about 80 mg / m3n,about 1 mg / m3n to about 70 mg / m3n, about 1 mg / m3n to about 60 mg / m3n, about 1 mg / m3n to about 50 mg / m3n, about 1 mg / m3n to about 40 mg / m3n, about 1 mg / m3n to about 30 mg / m3n, about 1 mg / m3n to about 20 mg / m3n, or about 1 mg / m3n to about 10 mg / m3n. In some embodiments, a compound, such as a terminal alkyne or terminal alkene, is present in a treated fluid at a concentration of about 5 mg / m3n to about 8,000 mg / m3n, about 5 mg / m3n to about 5,000 mg / m3n, about 5 mg / m3n to about 2,500 mg / m3n, about 5 mg / m3n to about 1,000 mg / m3n, about 5 mg / m3n to about 900 mg / m3n, about 5 mg / m3n to about 800 mg / m3n, about 5 mg / m3n to about 700 mg / m3n, about 5 mg / m3n to about 600 mg / m3n, about 5 mg / m3n to about 500 mg / m3n, about 5 mg / m3n to about 400 mg / m3n, about 5 mg / m3n to about 300 mg / m3n, about 5 mg / m3n to about 200 mg / m3n, about 5 mg / m3n to about 100 mg / m3n, about 5 mg / m3n to about 90 mg / m3n, about 5 mg / m3n to about 80 mg / m3n, about 5 mg / m3n to about 70 mg / m3n, about 5 mg / m3n to about 60 mg / m3n, about 5 mg / m3n to about 50 mg / m3n, about 5 mg / m3n to about 40 mg / m3n, about 5 mg / m3n to about 30 mg / m3n, about 5 mg / m3n to about 20 mg / m3n, or about 5 mg / m3n to about 10 mg / m3n. Yet, in other embodiments, a compound, such as a terminal alkyne or terminal alkene, is present in a treated fluid at a concentration of about 1,000 mg / m3n to about 8,000 mg / m3n, about 2,000 mg / m3n to about 8,000 mg / m3n, about 3,000 mg / m3n to about 8,000 mg / m3n, about 4,000 mg / m3n to about 8,000 mg / m3n, about 1,000 mg / m3n to about 6,000 mg / m3n, about 2,000 mg / m3n to about 6,000 mg / m3n, about 3,000 mg / m3n to about 6,000 mg / m3n, about 4,000 mg / m3n to about 6,000 mg / m3n, about 1,000 mg / m3n to about 5,000 mg / m3n, about 2,000 mg / m3n to about 5,000 mg / m3n, or about 3,000 mg / m3n to about 5,000 mg / m3n. As used herein, the “n” in the unit “mg / m3” indicates that the concentration is at “normal” atmospheric pressure (1 bar, 101.325 kPa, or 14.7 psi).

[0121] A treated fluid can be a treated fluid that is suitable for a particular use, depending on the character of a fluid that is present in a treated fluid. For example, a treated fluid can be a fuel for a fuel cell, as described herein.

[0122] METHODS OF TREATING A FLUID

[0123] Also provided herein are methods of treating fluids. In some embodiments, the methods include providing a fluid, and contacting the fluid and a compound, such as a terminal alkyne or terminal alkene, or a composition as provided herein to form a treated fluid.

[0124] Before, during, or after any one or more of the limitations of the methods provided herein is / are performed, the fluid and / or the treated fluid can be present in a fuel distribution system. The fuel distribution system can include any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.). In some embodiments, the methods of treating a fluid also include disposing the fluid and / or the treated fluid in a fuel distribution system, such as any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.).

[0125] The providing of a fluid can include capturing the fluid. The fluid can be captured using any technique known in the art. In some embodiments, the methods also include pressurizing the treated fluid, storing the treated fluid, or a combination thereof. The compound, such as a terminal alkyne or an alkene, or composition can be in any phase, such as a liquid phase, a gaseous phase, or a combination thereof before, during, and / or after the contacting of the fluid and the compound or composition. The providing of the fluid can include providing a container in which the fluid is disposed, the contacting of the fluid and the compound or composition can include disposing the compound or the composition in the container. The providing of the fluid can include providing a first stream that includes the fluid. When a first stream that includes the fluid is provided, the contacting of the fluid and the compound or the composition can include contacting the first stream and a second stream that includes the compound or the composition.

[0126] The contacting of the fluid and the compound, such as a terminal alkyne or terminal alkene, or a composition can be achieved using any known technique. For example, the contacting of the fluid and the compound or the composition can include dispensing the compound or the composition with a liquid meter. As a further example, the contacting of the fluid and the compound or the composition can include nebulizing the compound or the composition.

[0127] FLUIDS

[0128] The compounds, such as terminal alkynes and terminal alkenes, or compositions provided herein can be used to treat any fluid, and the treated fluids can include any fluid. The fluids generally can be in any phase, e.g., liquid or gas. In some embodiments, the fluid includes a fuel gas. The fluid can include hydrogen gas (FL) or a hydrogen gas blend. The fluid caninclude a natural or synthetic combustion gas. The fluid can include natural gas, liquified natural gas (LNG), liquefied petroleum gas (LPG), municipal gas, town gas (16-20% carbon dioxide (CO2), 1-4% carbon monoxide (CO), 28-31% methane (CH4), 46-52% H2, nitrogen (N2), and 0- 4% oxygen (O2)), heating gas, or a combination thereof. The fluid can include H2, CH4, ethane (C2H6), ethene (C2H4), acetylene (C2H2), propane (CsHg), propene (C3H6), butane (C4H10), isobutane (C4H10), butene (C4H8), pentane (C5H12), or a combination thereof. The fluid can include water gas, synthesis gas or syngas (30-60% CO, 25-30% H2, 0-5% CH4, and 5-15% CO2), reform gas, generator gas, coke gas, or a combination thereof. The fluid can include a non-combustible gas. The fluid can include CO, CO2, industrial gases, such as nitrogen (N2), oxygen (O2), and / or helium, or a combination thereof. In a particular embodiment, the fluid comprises hydrogen gas (H2) and at least 10 mol%, at least 20 mol%, at least 30 mol, at least 50 mol%, at least 75 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 97 mol%, at least 98 mol%, or at least 99 mol% of the fluid is the hydrogen gas. In another embodiment, the fluid comprises hydrogen gas (H2) and from 10 mol% to 40 mol%, from 10 mol% to 30 mol%, from 10 mol% to 25 mol%, from 15 mol% to 30 mol%, or from 15 mol% to 25 mol% of the fluid is the hydrogen gas.

[0129] SENSORS

[0130] The compounds, such as terminal alkynes or terminal alkenes, or compositions provided herein can be used in combination with a sensor, such as a sensor designed to indicate the presence of a compound that is an odorant. Therefore, systems are provided herein that include a sensor and a compound, such as a terminal alkyne or terminal alkene, that is an odorant, or a sensor and a composition that includes a compound, such as a terminal alkyne or terminal alkene, that is an odorant.

[0131] A sensor can be coupled to any device or apparatus, such as a pipeline, a fuel supply, a fuel cell, or some other component of the fuel cell system, or any appliance using hydrogen as fuel, or any component of an appliance using hydrogen as fuel. The sensor can be located in proximity to a self-contained fuel supply, a fuel consumption unit, or both, which can permit the sensor to detect any leaks quickly and / or effectively. A sensor also can include circuitry programmed to shut down a fuel cell, other appliance or system, or any other components in the event of a detected leak. The addition of the sensor can facilitate use oforganic odorants at very low concentrations that are not detectable by humans for special applications or circumstances. Furthermore, an odorant, which can be a terminal alkyne or a terminal alkene, can be selected so that extremely high sensitivity and selectivity of the sensor can be realized to avoid false alarms.

[0132] METHODS OF GENERATING ENERGY

[0133] Also provided herein are methods of generating energy. The methods generally can include using any of the treated fluids provided herein as a source of energy. The treated fluids can be a fuel for an appliance or device, such as a fuel cell. In some embodiments, the methods include providing a fuel cell having an anode and contacting the anode and any of the treated fluids provided herein, such as treated hydrogen gas. The contacting of an anode and a treated fluid can produce an oxidized treated fluid.

[0134] The methods of generating energy can include providing an odorized fluid, providing a fuel cell comprising an anode, and contacting the anode and the odorized fluid. The contacting of an anode and an odorized fluid can produce an oxidized odorized fluid. In some embodiments, the methods include removing (e g., scrubbing, adsorbing, absorbing or decomposing) a compound, such as a terminal alkyne, terminal alkene and / or additive, from a treated fluid or an oxidized treated fluid. The removal of the compound can occur at any one or more points of the methods provided herein. For example, the methods can include removing a compound from an oxidized treated fluid or removing a compound from a treated fluid prior to contacting an anode and the treated fluid. Removal of a compound from a fuel gas can be necessary or desirable in some instances, such as (i) when a compound, such as a terminal alkyne, terminal alkene, additive, etc., is detrimental for the end-use of a fuel gas or fuel gas consuming appliance and / or device, and / or (ii) when a compound, such as a terminal alkyne, terminal alkene, additive, etc., is not eliminated during the consumption of the fuel gas, which can result in an environmental release of the compound, thereby possibly negating the ability of an odorant to indicate leaks.

[0135] In some embodiments, the methods include removing (e.g., scrubbing, adsorbing, absorbing or decomposing) a compound, such as a terminal alkyne, alkene, additive, odorant, etc., from an exhaust gas, offgas, or flue gas from a fuel cell or any appliance using hydrogen. The compounds, such as a terminal alkyne or alkene, additive, odorant, etc., provided herein canbe removed by any known technique, such as (i) specially designed or commercially available adsorption or absorption processes, (ii) a water trap, and / or (iii) a humidifier system based on a compound’s solubility in water.

[0136] The removal (e.g., scrubbing, adsorbing, absorbing or decomposing) of a compound, such as a terminal alkyne, terminal alkene, additive, etc., from a treated fluid and / or an oxidized treated fluid can be achieved by any known technique. These techniques can include, but are not limited to, catalytic decomposition on metal, metal oxide, zeolite, or other substrates (see US7780933B2, US8658321B2, JP2018153634A, JP06317909B2, JP05766744B2, JP6306377A, JP04745557B2, US8444945B2, JP04822692B2, US7837964B2, US20080090115A1, US10889597 B2); absorption or adsorption on activated carbon, zeolites, silica, or other substrates (see JP07271867B2, JP05949333B2, JP2012143747A, JP2011201975A, JP05295689B2, JP2001019984A, JP2001157709A, US6875410B2, JP05051864B2, US805777B2, EP2337621B1); condensation; concentration; evaporation; filtration; membrane separation; or a combination thereof. In some embodiments, the removal of an odorant can include contacting an odorized fluid or an exhaust gas and an adsorption and / or absorption media, or membrane separation media.

[0137] More specifically, a compound can be removed from a fluid, such as a treated fluid or an oxidized treated fluid, by an adsorption or absorption media using one or more materials, such as a porous carrier. Non-limiting examples of such materials include silica- alumina; silica; alumina; zeolite, preferably a zeolite containing Ag, Cu, Zn, Ni, Fe, Ce, La, Zr, and Ti metallic element(s), titania, zirconia, magnesia, silica-magnesia, or zinc oxide; a porous inorganic oxide, such as one selected from the group consisting of Ag, Cu, Ni, Zn, Mn, Fe, Co, Al, Si, Ce, an alkali metal, an alkaline earth metal, or a rare earth metal; terra alba; clay; diatomaceous earth; activated carbon; activated carbon oxide; activated carbon formed by activated carbon processing with nitric acid; an organometallic framework compound (MOF); and a polymer type-absorbent in granular form, powder form, and fibrous form.

[0138] A compound can be removed from a treated fluid by catalytic conversion to one or more compounds having a lower odor detection threshold using one or more materials, such as porous inorganic oxide selected from the group consisting of Ag, Cu, Ni, Zn, Mn, Fe, Co, Al, Si, B, P; an alkali metal; an alkaline earth metal (for example, oxides of magnesium, calcium, strontium and barium); a rare earth metal (for example, oxides of scandium, yttrium, cerium,ytterbium and lanthanum); and a transition metal (for example, oxides of nickel, cobalt, vanadium, chromium, manganese, molybdenum, tungsten, copper, silver, zinc, iron, titanium and zirconium). Alternatively, the porous inorganic oxide can be selected from the group consisting of alumina, silica, silica-alumina, and cerium oxide; a transition metal oxide; a transition metal compound; an alkaline earth metal oxide; and a rare earth metal oxide. Preferably the transition metal is nickel, cobalt, vanadium, chromium, manganese, molybdenum, tungsten, copper, silver, zinc, iron, titanium, and / or zirconium. Preferably the alkaline earth metal is magnesium, calcium, barium, and / or strontium. Preferably the rare earth metal of the rare earth oxide is selected from scandium, yttrium, cerium, ytterbium, and / or lanthanum. Alternatively, a porous inorganic oxide can be selected from a group 13-14 oxide where the group 13-14 element is selected from boron, aluminum, gallium, silicon, germanium, and / or tin. Alternatively, a compound can be removed from a treated fluid using a precious metal catalyst such as Pt / Pd / Rh catalyst, Pt / Pd catalyst, Pt / Rh catalyst, Pd / Rh catalyst, Pt catalyst, Pd catalyst, Au catalyst, Pt / AhCh catalyst; an oxide catalyst such a zeolite, silica-alumina, silica, alumina, zeolite, titania, zirconia, magnesia, silica-magnesia, zinc oxide; a Cu-ZSM-5 catalyst; an organometallic framework compound (MOF) catalyst; and a perovskite type-catalyst in a granular form, a powder form, or fibrous form.

[0139] Alternatively, a compound can be removed from a treated fluid by scrubbing in a water trap or solvent trap containing alkali metal hydroxides, alkali metal Ci to C4 alkyl acid, inorganic peroxide, organic peroxide, perchlorate, ionic or nonionic emulsifier, or a combination thereof.

[0140] The removal of at least a portion of the odorant from the odorized fluid or the exhaust gas can include subjecting the odorized fluid or the exhaust gas to condensation. The condensation can include cooling, pressurizing, or a combination thereof the odorized fluid or the exhaust gas to recover at least a portion of the odorant as a liquid.

[0141] The removal of at least a portion of the odorant from an odorized fluid or an exhaust gas can include contacting the odorized fluid or the exhaust gas and a membrane or filter, wherein the membrane or the filter is configured to retain the odorant or the non-odorant components of the odorized fluid or the exhaust gas. The membrane can include a polymer such as polyethylene, polypropylene, a polyamide, a polyimide, a cellulose acetate, a polysulphone, a polydimethylsiloxane, a fluoropolymer (such as polytetrafluoroethylene (PTFE)), polyvinylidenefluoride (PVDF), ethylene and chlorotrifluoroethylene copolymer (ECTFE), perfluoro sulfonic acid polymer, (such as Nafion and Aquivion), a nanoporous material, a silica mesoporous material, a zeolite, a metal-organic framework (MOF), a perovskite, a metal, or a combination thereof.

[0142] An odorant removal unit can be inserted prior to the storage unit or fuel delivery system to an appliance, such as a fuel cell, to consume the fuel gas. Alternatively, an odorant removal unit can be inserted after the storage unit or the appliance that consumes the fuel gas. After removal, the odorant should be below the critical concentration that negatively impacts the performance of the fuel cell (e.g., below the concentration that reduces efficiency). Other processes in which a treated fluid can require removal of an odorant, embrittlement inhibitor, and / or additive include chemical processes (e.g., hydrogenation and reduction reactions, metal hydride synthesis); petrochemical processes (e.g. hydrocracking, reforming, desulfurization); steel production (for example, using direct reduced iron (DRI)); glass production; semiconductor and electronic production processes (including cleaning, annealing, epitaxy, doping, ion implantation, passivation, chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), plasma etching, atomic layer etching (ALE), diborane and digermane stabilization, and generating EUV light sources); cement production or processing; and other emerging technologies. Odorant removal should also be sufficient to allow dilution of a treated fluid in ambient air without causing false detection or warning of a leak.

[0143] A compound (or combination of compounds), such as a terminal alkyne or terminal alkene, within a treated fluid composition can be at least partially consumable by the fuel cell, thereby improving the performance of the fuel cell, increasing the energy produced by the fuel cell, or a combination thereof, relative to a fuel cell operated with a fluid composition that does not the compounds or compositions described herein.

[0144] METHODS OF TRANSPORTING OR STORING TREATED FLUIDS

[0145] Also provided herein are methods of transporting or storing a material such as a treated fluid composition. In some embodiments, the methods include (i) providing any one or more of the treated fluids provided herein, and (ii) disposing the treated fluid in an apparatus formed, at least in part, of a metal. The apparatus can be formed entirely of a metal. The metalcan include any metal or alloy that is susceptible to hydrogen embrittlement. Tn some embodiments, the apparatus includes a pipeline, tank, storage container, etc.

[0146] In some embodiments, the compound (or combination of compounds), such as a terminal alkyne or terminal alkene, or composition including a compound (or combination of compounds), as provided herein, prevents, delays, reduces, or inhibits the hydrogen embrittlement of the metal. As used herein, the phrase “hydrogen embrittlement” refers to the mechanical damage that occurs in a metal due to hydrogen binding with and penetrating into a metal which causes loss in ductility and tensile strength. The loss of ductility and tensile strength can subsequently cause the initiation and propagation of cracks in the metal. As one of skill in the art would recognize, cracks in a metal used for the storage of a fluid such as hydrogen in a storage apparatus such as a pipeline or tank would cause undesirable leaks and possibly catastrophic failure of the storage apparatus. As used herein, the phrase “prevents, delays, reduces, or inhibits the hydrogen embrittlement of the metal” indicates that a compound or a composition has a positive displacement efficacy. Positive displacement efficacy is a quantitative prediction of the ability of a compound to prevent the binding of hydrogen to a metal or metal surface. Effectively, the compound binds to the surface of the metal and prevents or reduces the ability of hydrogen to bind to the metal surface (i.e., the compound displaces the hydrogen). A larger value (greater than 0 eV) of positive displacement efficacy indicates that the compound has a higher affinity for binding with the metal surface and hydrogen is being displaced by the compound. In embodiments, the treated fluid comprises a compound that has a positive displacement efficacy of greater than 0 eV, at least 0.1 eV, at least 0.5 eV, at least 0.75 eV, at least 1 eV, at least 1.5 eV, at least 2 eV, at least 2.5 eV, at least 3 eV, at least 3.5 eV, or at least 4 eV. In a preferred embodiment, the treated fluid comprises a compound that has a positive displacement efficacy of greater than or equal to 0.1 eV.

[0147] Fracture toughness is a measurement indicating the amount of stress required to propagate a preexisting flaw, such as a flaw in the surface or bulk of a metal or alloy. Flaws can be, but are not limited to, cracks, voids, metallurgical inclusions, weld defects, and design discontinuities, and defects in the bulk of the material. Defects in the bulk of the material can be transgranular or intergranular, and defects can or may not be caused by embrittlement. Fracture toughness is represented by K (stress intensity factor) and J (J-Integral), and fracture toughness tests are performed on materials to quantify the resistance to failure by cracking and theresistance to crack initiation and propagation. The value of K represents the highest value of stress intensity factor that a material under a certain load or work withstand at the crack initiation. The value of J represents the work (energy) per unit fracture surface area that a material can withstand at the crack initiation. K and J can have multiple definitions as described in ASTM El 823 and can be measured using different test methods such as defined in ASTM E647, ASTM E1820, ASTM E1681, and ASTM E399. Other standard measurement methods for K and J include, but are not limited to, ASTM, ISO, JIS, and CEN. Embodiments of this invention describe a treated fluid that comprises a compound that improves the fracture toughness of a metal or alloy (as measured by K) and the work (as measured by J) required to grow a crack in the material when that material is also exposed to hydrogen (EE) gas. Embodiments of this invention also describe a treated fluid composition that comprises one or more compounds and hydrogen gas wherein the fracture toughness of a metal or alloy is improved when contacted when this treated fluid composition as compared to when the metal or alloy is contacted with hydrogen gas only (i.e., in the absence of the compound).

[0148] In a preferred embodiment, the treated fluid comprises a compound that increases the fracture toughness of a metal or metal alloy by at least 5% compared to the fracture toughness measured when the treated fluid does not contain the compound. Alternatively, the treated fluid comprises a compound that increases the fracture toughness of a metal by at least 10%, by at least 25%, or by at least 50%. In an embodiment, the treated fluid is preferably hydrogen. In an embodiment, the treated fluid comprises hydrogen and a compound wherein the presence of the compound increases the fracture toughness of a metal by at least 5%, at least 10%, at least 25%, or at least 50% compared to a treated fluid comprising only hydrogen.EXAMPLES

[0149] The disclosure is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this technology. Various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, can suggest themselves to one of ordinary skill in the art without departing from the spirit of the present disclosure or the scope of the appended claims.

[0150] EXAMPLE 1

[0151] Modeling was completed to predict the positive displacement efficacy of various compounds in hydrogen. For the purpose of these calculations, iron in the Fe(100) surface configuration (as defined by the Miller indices) is used for simplicity as a proxy representation of a steel surface. The computations of this example were performed according to the following process: (i) obtain the chemical structure of the compounds of interest in SMILES format using a molecule editor (i.e., ChemDraw from PerkinElmer); (ii) import the molecular structures in SMILES format into the VASP (Vienna Ab initio Simulation Package) software to perform calculations using high performance computing resources; (iii) optimize the molecular geometry of each compound; (iv) import the optimized geometry at the surface of the Fe(100) slab model; (v) perform Ab initio molecular calculations for the optimized conformer (as determined in (iii)) and search for an optimal docking position which minimizes the energy at the surface of the Fe(100) slab; (vi) optimize the geometry of the molecule docked at the surface of the Fe(100) slab; (vii) assess the final docking configuration (e.g. viability and stability of the optimized compound geometry at the Fe(100) surface); (viii) finalize the calculation of the binding energies (Eb, moi) for the docked molecule at the Fe(100) slab surface; and (ix) calculate H2 displacement efficacy (Eb,H2 - Eb,Moi).

[0152] Using this method, H2 dissociative chemisorption (Eb,H2) on Fe(100) was predicted to be -1.7 eV. Compounds with binding energies lower than the binding energy for H2 dissociative chemisorption have a preference for binding at the Fe(100) surface and, by extension, a preference for binding to a steel surface. Compounds with lower binding energies compared to hydrogen interact more favorably at the Fe(100) surface, thus reducing the hydrogen concentration at the surface. By proxy, this reduces the probability of hydrogen entering the bulk of the metal, which causes embrittlement of a metal or alloy such as steel.

[0153] H2 displacement efficacy of 0 eV is equal to hydrogen dissociative chemisorption (e.g. Eb,H2 - Eb, Moi where -1.7eV - (-1.7eV) = 0 eV). For all other compounds, a positive value of displacement efficacy denotes a displacement of hydrogen by the compound at the surface of Fe(100), meaning that there is a positive Gibbs free energy ( AG) which favors the chemisorption reaction at the surface. This suggests that hydrogen diffusion into the bulk material (metal) is reduced, thereby also reducing (or inhibiting) embrittlement. A negative value of displacement efficacy denotes a preference for hydrogen at the surface of Fe(100) compared to the compound, meaning that there is a negative Gibbs free energy (AG) which favors thechemisorption of hydrogen. A negative value of displacement efficacy suggests hydrogen diffusion into the bulk material is not reduced by the presence of the compound, thereby causing embrittlement.

[0154] Calculations were performed to compare the H2 displacement efficacy of known inhibitors of hydrogen embrittlement with other compounds, including compounds utilized in the invention disclosed herein. The results of these calculations are presented in the following table.

[0155] The results in Example 1 show that, compared to known inhibitors of hydrogen embrittlement (Comparative Examples 1.7-1.9), the terminal alkyne compounds (Examples 1.1- 1.6) disclosed herein surprisingly demonstrate similar or better hydrogen displacement efficacy. This suggests that these compounds will be effective for inhibiting or preventing hydrogen embrittlement by limiting hydrogen binding at the material surface. These compounds have a high affinity for chemisorption at the metal surface compared to hydrogen, thus blocking hydrogen interaction with the surface and reducing the probability of hydrogen intake and migration of the hydrogen into the bulk of the metal which causes embrittlement. In comparison, non-terminal alkenes and alkynes (Comparative Examples 1.10-1.14 and Example 1.15) have significantly less tendency to displace hydrogen at the surface. These compounds have a lower affinity for chemisorption at the metal surface compared to hydrogen, which favors hydrogeninteraction with the surface and increases the probability embrittlement due to of hydrogen intake and migration into the bulk of the metal. Surprisingly, compared to other compounds used as embrittlement inhibitors, diynes (such as 1,5 -hexadiyne) are more effective at displacing hydrogen, suggesting these compounds are more likely to bind with metal surfaces, thus inhibiting or preventing hydrogen embrittlement by limiting the hydrogen intake into the metal. Without wishing to be bound by theory, this result is likely at least in part due to a chelate effect of the two terminal alkynes bonds interacting with one metal center.

[0156] EXAMPLE 2

[0157] A stability test at 90 °C was performed using a 6 meter long stainless steel (alloy 316) seamless tube having diameter of 14 inch and a wall thickness of 0.035 inch. A heated water bath was used to control temperature. A treated (e.g., odorized) hydrogen gas was passed through the tubing at a flow rate 0.8 mL / min, which resulted in a residence time of the gas inside the tubing of about 2 hours. The gas flow was analysed using a VARIAN™ CP-4900 Pro micro gas chromatograph (Varian, Inc., USA), and sampling was performed at 3-minute intervals.

[0158] Dilutions of various odorants were prepared by mixing 50-100 mg / m3n of organic compound in hydrogen gas in a gas cylinder having a pressure of about 100 bar. The hydrogen cylinders were prepared by a gravimetric method as defined in ISO 6142.

[0159] The results of these tests are depicted in FIG. 1, FIG. 2, and FIG. 3. FIG. 1 shows a plot of 1,6-heptadiyne concentration in ppm (mol) versus time in hydrogen during a stability test performed at 90 °C. FIG. 2 depicts a plot of cis-2-pentene concentration in ppm (mol) versus time in hydrogen during a stability test performed at 90 °C. FIG. 3 depicts a plot of 2-pentyne concentration in ppm(mol) versus time in hydrogen during a stability test performed at 90 °C. The data from Example 2 confirm the results of the computational model used in Example 1. Embodiments with the terminal unsaturated bond (e.g. alkyne and alkene), such as 1,6-heptadiyne, surprisingly exhibit good chemisorption properties on a steel surface, whereas non-terminal alkenes (e.g., cis-2-pentene) and non-terminal alkynes (e.g., 2-pentyne) do not interact with the steel surface. As shown in FIG. 1, there is a rapid increase of 1,6-heptadiyne concentration in the hydrogen gas when the steel pipe is heated to 90 °C, confirming the desorption of the compound from the steel surface. Upon cooling, the 1,6-heptadiyne concentration slowly decreases, confirming the chemisorption of the compound on the steelsurface. The chemisorption properties (concentration increase and concentration loss as function of temperature) is further confirmed by the absence of degradation products, suggesting that the concentration changes are due to chemisorption. Such behavior is not observed for cis-2-pentene (FIG. 2) and 2-pentyne (FIG. 3). The data suggest that compounds with a terminal unsaturated bond (e g. alkyne and alkene) as described herein are likely to be suitable inhibitors of hydrogen embrittlement due to their strong chemisorption to steel. Without wishing to be bound by theory, it appears that terminal alkynes form a layer at the metal surface which reduces both the binding of hydrogen at the metal surface and the intake and migration of hydrogen into the bulk metal, thereby preventing or reducing embrittlement.

[0160] EXAMPLE 3

[0161] Dilutions of various odorants were prepared by mixing an organic compound in pure hydrogen gas (class 5.0) in a 1500 psi gas cylinder. The hydrogen cylinders were prepared by a gravimetric method, as defined in ISO 6142.

[0162] The embrittlement of steel was evaluated under ASTM El 820 test conditions. The autoclave chamber was loaded with 1500 psi hydrogen or odorized hydrogen. Steel embrittlement properties were measured using coupons made of AISI 4617 carbon steel having the following dimensions:

[0163] Test results for fracture toughness as expressed by J (J-integral) and K (stress intensity factor) were determined under the following test conditions: modulus of elasticity (Young’s modulus) = 29000 KSI; Poisson’s ratio = 0.32, and dK / dt = 0.005N / mm3 / 2s.

[0164] For the purposes of this invention, K and J were determined from the J-R curves measured in accordance with the guidelines in ASTM El 820 and measured at different crack extension positions: 0 mm crack extension (representing the toughness at the onset of crack growth / crack initiation (Ko and Jo)), 0.2 mm crack extension (Kjo.2mm and Jo.2mm), 1.0 mm crack extension (an indication of the slope of the J-R curve (Kjimmand Jimm)), and at the maximal load (KMAXLOAD and JMAXIOAD) under the Pmax conditions defined in ASTM El 820. The effect of the presence of various embrittlement inhibitors are shown for the J and Kj values at different crack extension and maximum load (maxload) in the following tables.

[0165] The data shown in Example 3 demonstrate that terminal alkyne and alkene compounds can function as embrittlement inhibitors when added to hydrogen gas. The J and K values are higher for hex-l-yne, hexa- 1,5 -diene and 1,7-octadiene compared to pure hydrogen, demonstrating that susceptibility of steel to hydrogen embrittlement is reduced when using these compounds as inhibitors. Hex-l-yne also provides similar embrittlement protection for crack initiation (Ko, Jo) compared to known embrittlement inhibitors, namely, ethyl mercaptan and oxygen, further demonstrating the suitability of this compound for this purpose. Hexa-l,5-diene significantly outperforms ethyl mercaptan as a hydrogen embrittlement inhibitor at crackextension greater than 0 mm and maximum load, demonstrating a surprising increase in effectiveness. Unexpectedly, hexa- 1,5 -diene also performs similarly to oxygen, which is considered to be one of the best hydrogen embrittlement inhibitors, at crack extension greater than 0 mm and maximum load. It also unexpectedly performed much better compared to 1,7- octadiene. Non-terminal alkynes (e.g., hex-2-yne) show fracture toughness values similar to pure hydrogen, indicating that these compounds do not inhibit embrittlement, as suggested by the results for Examples 1 and 2. Of the compounds tested, surprisingly and unexpectedly, only terminal alkynes and alkenes are suitable hydrogen embrittlement inhibitors.

[0166] Comparative Example 3.10 utilized oxygen at 40 ppm and can be used to compare all 40 ppm data. Surprisingly, 1-hexene was less efficient than both 1-hexyne and 1,5 -hexadiene, and unexpectedly, 3, 3 -dimethyl- 1 -butyne had similar performance to 1,5-hexadiene as one of the best hydrogen embrittlement inhibitors. Beneficially, 3, 3 -dimethyl- 1 -butyne also had nearly no smell, which is an advantage at high concentration (no odor masking) if blended with an odorant compound. THF and propanol illustrate other non-effective inhibitors with poor performance similar to ethyl mercaptan and pure hydrogen (no effect).

[0167] EXAMPLE 4

[0168] Dilutions of various odorants were prepared by mixing an organic compound in water to prepare a concentrated solution based on the water solubility of the organic compound. The concentrated solution was then dissolved in water to reach a desired concentration. The actual concentration in the vial headspace and concentration exposure to the panelist varied based on the vapor pressure of the compounds tested and the diffusion of the compounds in air.

[0169] The odorant solutions at various concentrations were evaluated by olfactory testing using a method similar those disclosed in literature (Journal of Applied Toxicology, 3, 272-289, 1983; Perception & Psychophysics, 39, 281-286, 1986) and an olfactory panel of at least 8 panel members.

[0170] In this example, the odor characteristic of each odorant of was ranked from 1 (extremely unpleasant) to 10 (extremely pleasant). Each participant also gave a description of the odorant. Participants were exposed to 10-fold changes in concentration to determine the odor detection threshold from 0.001 mg / L to 10 mg / L. The odor detection threshold represents the lowest concentration at which the panelists could detect the odorant. The odor characteristic score for each compound is calculated by averaging the score (1-10) reported by each of the panel members for each dilution, and the lowest of these scores for each compound (independent of dilution) is reported in the following table.* As determined by panel members** 1 (extremely unpleasant) and 10 (extremely pleasant)

[0171] The data show that some compounds perform similarly to THT when used as odorants (e.g. similar odor detection threshold and / or odor characteristic score). In the case of hex-l-en-5-yne (Example 4.5), hept-l-en-6-yne (Example 4.6), pent-l-yne (Example 4.7), hex- 1-yne (Example 4.8), hepta- 1,6-diyne (Example 4.15), octa- 1,7-diyne (Example 4.16), methyl propargyl ether (Example 4.17), 3 -ethoxy prop- l-yne (Example 4.18) and 3 -(propan-2 -yloxy)- prop-l-yne (Example 4.19), hex-2-yne (Example 4.25), the compounds provide a comparable or stronger odor than THT at a similar concentration.

[0172] EXAMPLE 5

[0173] Dilutions of various odorants were prepared by mixing 50-100 mg / m’n of each compound in pure hydrogen gas (class 5.0) in a gas cylinder at 100 bar. The hydrogen cylinders were prepared by a gravimetric method, as defined in ISO 6142.

[0174] Odorized hydrogen samples were blended with air at ratios from about 50: 1 to 2000: 1 . Olfactory panel members were asked to give their impression of the smell character and indicate whether they found the odorant to be unpleasant (e.g., would the odor cause serious concerns if smelled in a real-world application). The odor threshold was determined by stepwise increases of the concentration. The concentration was doubled every step, starting from a dilution rate of 1:2000. In some cases, even at the highest dilution (lowest concentration tested), the odorant could still be detected. In other cases, even at the highest concentration tested, the odorant could not be detected. For odorants in which this occurred, the odor detection threshold and nominal odor concentration are reported as less than (<) or greater than (>) the known concentration.

[0175] The nominal concentration of the odor strength was established by comparing the odor strength of each compound to a set concentration of the odorant tetrahydrothiophene (THT). This permitted quantification of the concentration of the test compound that matched the odor strength of THT. The THT concentration was set at about 1% v / v of nominal concentration, thereby simulating a typical detection concentration at 20% of the lower explosive limit of hydrogen (LEL = 4% v / v in air; ca. 0.8% v / v in air) and natural gas (LEL = 5% v / v; ca. 1% v / v in air) using a typical gas odorization concentration (18 mg / m’n; 5.0 ppm mol) of THT.

[0176] It is preferred to use a lower concentration of odorant to achieve the same odor strength as THT, indicating that the odor intensity curve as defined in ISO / DTS 18222 has asteeper slope, and that a compound has a lower odor detection threshold compared to THT. Preferably, a lower concentration can achieve an alarming level of odor, but the concentration of the odorant should at least result in an odor similar to that of THT.

[0177] Results of Example 5 are provided in the following table. The data show that some compounds perform similarly to THT when used as odorants. In the case of hept-2-yne (Example 5.1), hex-l-yne (Example 5.6), hex-l-en-5-yne (Example 5.9), hepta- 1,6-diyne (Example 5.11) and hex-2-yne (Example 5.16), the compounds provide a comparable or stronger odor than THT at a similar concentration. In other examples, including Example 5.1 (hept-2- yne) and Example 5.6 (hex-l-yne), the compounds provided a comparable or stronger odor than THT at a lower concentration. In terms of selecting a suitable odorant, both of these are desirable traits.* As determined by panel members.** Concentration required to match odor strength of THT at 1% v / v Dilution equipment reached operational limit

[0178] The data shown in Examples 1 to 5 demonstrate that terminal alkyne compounds can be dual-purpose compounds, acting as both odorants and embrittlement inhibitors. The odor properties, including an alarming smell at relatively low concentrations, are comparable to or better than other typical commercial natural gas odorants such as THT. This is particularly true for short terminal alkynes such as pent-l-yne and hex-l-yne, enynes such as hex-l-en-5-yne, and dynes such as hepta- 1,6-diyne. Surprisingly, in addition to functioning as odorants, these compounds may form a layer at the steel surface that protects against hydrogen embrittlement, likely due to chemisorption of the compound to steel.

[0179] Surprisingly and unexpectedly, the data shown in Examples 1 to 5 demonstrate that some terminal alkyne compounds can inhibit embrittlement without interacting with the alarming smell of another compound acting as an odorant (e.g. odor masking of the odorant). This is particularly true for bulky terminal alkynes such as 3,3-dimethyl-but-l-yne, 4-methyl- pent-l-yne, and 5-methyl-hex-l-yne, very long alkynes such as oct-l-yne and hept-l-yne and cyclic terminal alkynes, such as ethynyl-cyclopropane. Bulky terminal alkynes require a significantly higher concentration for their odor to be detected and provide an odor strength equivalent to THT. It is expected that the odor profile of the fluid will be dominated by another compound acting as an odorant and not the bulky terminal alkyne acting as an embrittlement inhibitor. Alternatively, the concentration of the bulky terminal alkynes in the fluid can be increased to match the odor strength equivalent to THT, allowing the terminal alkyne to function both as an effective embrittlement inhibitor and odorant.

[0180] Surprisingly and unexpectedly, the data shown in Examples 1 to 5 demonstrate that terminal alkene compounds can inhibit embrittlement without interacting with the alarming smell of another compound acting as an odorant (e.g. odor masking of the odorant). This is true, for example, for terminal alkenes, such as 1 -hexene and 1 -octene, and terminal dienes, such as 1,5-hexadiene and 1,7-octadiene. The terminal alkenes can require a significantly higherconcentration to be detected and provide an odor strength equivalent to THT. It is expected that the odor profile of the fluid likely will be dominated by another compound acting as an odorant and not the terminal alkene acting as an embrittlement inhibitor. Alternatively, the concentration of the terminal alkenes in the fluid can be increased to match the odor strength equivalent to THT, allowing the terminal alkene to function both as an effective embrittlement inhibitor and odorant.

[0181] The data shown in Examples 4 and 5 demonstrate that enyne compounds are a suitable odorant for fluids, particularly gases. The odor properties and alarming odor character of enyne compounds are comparable to a typical commercial natural gas odorant (THT) and other alkynes considered to be gas odorants, e.g., pent-l-yne. Surprisingly, embodiments of the enyne compounds have odor detection levels equal to or better than certain alkynes (e g., pent-l- yne); odor strengths that are equal to or better than certain alkynes and a typical commercial natural gas odorant (THT); significantly lower odor detection thresholds compared to similar dienes and alkynes (e.g., 1 -heptyne, 1-octyne and 1,5 -hexadiene); and significantly worse odor characteristics compared to similar alkenes, dienes and alkynes (e.g., 1 -hexene, 1-heptyne and 1,5 -hexadiene). These are all desirable properties when selecting an odorant compound.

[0182] EXAMPLE 6

[0183] Dilutions of various odorants were prepared by mixing an organic compound in hydrogen gas (hydrogen class 5.0) to reach a concentration of about 120 mg / m3n in a gas cylinder at 100 bar. The hydrogen cylinders were prepared by a gravimetric method as defined in ISO 6142

[0184] The Proton-Exchange Membrane Fuel Cell (PEMFC) system was manufactured by Proton Technologies in the Netherlands. The tests were performed using an 8 cm2cell from Proton Technologies. The membrane electrode assemblies (MEA) were Proton Technologies Ames ME As composed of 0.075 mg Pt per cm2(HyPer Pt / C 40%wt) for the anode and 0.3 mg Pt per cm2(HyPer Pt / C 40%wt) for the cathode on a Nafion 211 support.

[0185] The following parameters were used to perform the PEMFC tests:

[0186] Prior to testing the odorant, the PEMFC cell was purged with pure hydrogen. The T=0 value is defined as the time when the odorized hydrogen is injected into the PEMFC and the PEMFC is put into operation. The change of potential (e.g., voltage) at a constant 1 A / cm2current output correlates with the impact of the odorant on the fuel-cell performance during exposure to the odorant. For each batch of MEAs, a reference load is measured using pure hydrogen (class 5.0) without odorant to determine the baseline performance of the MEA batch and allow comparison of the degradation effect for each odorant. Results are shown in the table below.

[0187] The evolution of potential (V) over the duration of the durability test in the PEMFC under a 1 A / cm2current load are shown in FIG. 4, FIG. 5, FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, FIG. 12, and FIG. 13. As shown in the figures, PEMFC performance with hex-l-yne (Example 6.4) (FIG. 7), hex-l-en-5-yne (Example 6.5) (FIG. 8), hept-l-en-6- yne (Example 6.6) (FIG. 9), 3, 3 -dimethyl -but- 1-yne (Example 6.7) (FIG. 10), hexa- 1,5 -diene (Example 6.8) (FIG. 11), hex-l-ene (Example 6.9) (FIG. 12), and hex-2-yne (Example 6.10) (FIG. 13) all follow a similar trend as the reference. The absolute difference in performance between the reference and hydrogen odorized with these compounds can likely be attributed to variability in MEA fabrication.

[0188] As shown in FIG. 14, PEMFC performance with butyraldehyde (Comparative Example 6.11) shows a rapid decline in performance (as indicated by a 120 mV decrease in electrical potential) in the first 15-30 minutes, followed by a slower performance loss (100 mV decrease in electrical potential) over the remaining duration of the test period as compared to the reference test using pure hydrogen.

[0189] As shown in FIG. 15, PEMFC performance with THT (Comparative Example 6.12) shows a rapid decline after 5 minutes of operation.

[0190] It can be concluded from the durability tests at high odorant concentrations in Example 6 that alkenes and alkynes according to this invention are suitable for stable PEMFC operation. Surprisingly and unexpectedly, despite having strong interaction with metal and alloys such as iron and steel, terminal alkenes and alkynes according to this invention do not interact negatively with the metal used as catalyst in the PEMFC (the platinum catalyst used in Example 6). The potential (voltage) is maintained or improved over about 20-24 hours under a constant 1 A / cm2cell current despite the very high concentration (about 10 times higher than the normal gas odorization level). Additionally, the alkynes according to this invention exhibit similar effects on PEMFC performance over time when compared to known hydrogen odorants based on alkyne moieties (e.g., pentyne), which have been shown to have no or very weak interactionswith metal surfaces in Examples 1-3. Furthermore, the alkenes and alkynes according to this invention have significantly better performance compared to known poisonous substances for PEMFC such as aldehydes (e.g. butyraldehyde, Comparative Example 6.11) and sulfur containing compounds (e.g., THT, Comparative Example 6.12) which are known to interact with metal surfaces via sulfur-metal or oxygen-metal dative or Van Der Waals chemical interactions causing a poisonous effect. This data demonstrates the viability of using the alkenes and alkynes according to this invention as hydrogen odorants in fuel-cell operations.

[0191] EXAMPLE 7

[0192] The performance of various antioxidants was tested in a 100 mL 316L stainless steel autoclave equipped with a single bottom impeller mixing at 500 rotations per minute. To the autoclave, 20 g of 2-hexyne or 1 -hexyne was added, followed by the corresponding amount of antioxidant to be tested (ppm by weight). The mixture was then placed under air at 500 psig for 24 hours at 50 °C. The product was tested before and after exposure to air by gas chromatography analysis to determine its purity. An Agilent 8890 system equipped with a J&W HP-5 column was used for the analysis.

[0193] In a 250 mL Erlenmeyer was added successively 50 mL of 2-propanol (CAS #67- 63-0, 99.999% purity), 1 mL of an aqueous potassium iodide solution (CAS #7681-11-0, 99% purity) at 16.67 wt%, and 1 mL of glacial acetic acid (CAS #64-19-7, >99% purity). The Erlenmeyer was equipped with a magnetic stir bar and stirred at 200 rpm. The alkyne to be tested was added at a mass from 0.05 to 1 gram depending on the peroxide concentration. The reaction mixture was brought to a boil for one minute where it developed a yellow color. If the reaction mixture stayed colorless then a larger amount of the alkyne to be tested was used. If the reaction mixture became orange, a smaller amount of the alkyne to be tested was used. After the reaction mixture was cooled to room temperature, an aqueous solution of sodium thiosulfate (CAS #7772-98-7, 99% purity) at 0.0 IN concentration was added to titrate the solution until complete disappearance of color was observed. The amount of aqueous solution of sodium thiosulfate used was recorded as “volume equivalent.” The amount of peroxide in the alkyne was calculated using the following equation: Peroxide concentration in ppmw = 8000 * ((volume equivalents.01 ( / sample mass).

[0194] The following compounds were tested for their antioxidant propertiesThese compounds have the following physicochemical propertiesn.d. = no data foundThe table below lists the olfactory properties of these compounds from various literature sourcesn d. = no data found

[0195] The following table shows the GC purity before and after exposure to oxygen and the peroxide level post ageing as determined by titration using the procedure defined above for the alkynes sample with or without the compounds listed in the tables above. The delta between the initial and final purity by GC may be reflective of the efficiency and ability of the compounds to suppress oxidation and degradation. Alkynes tested (Comparative Example 7.1-4) without antioxidant show significant degradation over the duration of the test as demonstrated by the lower purity post ageing and the increase in peroxide content. Similarly, THT (Comparative Example 7.5), a commonly used gas odorant, also shows a purity loss over the duration of the test. This loss is indicative of the acceptable purity losses for the alkynes if used as gas odorant. For the purposes of this test, any added compounds resulting in a reduction of purity of less than 1% after the ageing and / or a peroxide level below 400 ppmw are considered effective.* Compound visually not fully dissolved at the end of the experiment

[0196] Based on the data above, acetic acid (Example 7.16-7.17), diisopropylcarbinol (Example 7.26-7.29), diisopropyl ketone (Example 7.30-7.32), DMSO (Example 7.38), amyl acetate (Example 7.40), methyl sorbate (Example 7.44), carbohydrazine (Example 7.45), methyl salicylate (Example 7.52), and benzyl alcohol (Example 7.53) are not considered effective stabilizers to protect alkynes again oxidation. The results obtained with carbohydrazine (Example 7.45) highlight the critical importance of antioxidant solubility in alkynes to avoid degradation by oxidation.

[0197] Surprisingly, amine-based compounds such as DABCO (Example 7.34), triethylamine (Example 7.35) and DEHA (Example 7.39) have similar or better antioxidant properties to diphenylamine (Example 7.22-7.25), a well-known antioxidant. Considering their respective physicochemical properties and reported toxicity, DEHA and tri ethylamine are preferred compared to diphenylamine. Nonetheless, the concentration of amine-based antioxidant should be limited to a maximum of ca. 0.05 ppm (by mol) in the hydrogen gas phase to avoid performance issues in fuel-cell operation according the ISO 14687:2019 specifications which limit the ammonia (NH3) concentration to 0.1 ppm (by mol). Assuming a concentration of 5 ppm (by mol) alkynes desired for use as odorant, the alkyne odorant composition can contain a maximum of ca. 1000 ppmw amine-based antioxidant.

[0198] Surprisingly, amyl acetate (example 7.40) and methyl salicylate (Example 7.52) are not effective as stabilizers or antioxidants for alkynes despite being reported as additives in gas odorant formulation based on acrylates (W02006067111 Al and W02006067115A1). Similarly, methyl sorbate (example 7.44) is not an effective stabilizer or antioxidant for alkynesdespite equivalent sodium, calcium, and potassium sorbate and sorbic acid being used as food preservatives. The same conclusion applies for benzyl alcohol (Example 7.53). It is a known antioxidant used in food and cosmetic applications but is not an effective stabilizer or antioxidant for alkynes. These results highlight that careful selection of the antioxidant compound is required, and it is not obvious that previously reported stabilizers and antioxidants will be effective for alkynes.

[0199] Surprisingly, not all the phenolic derivatives performed equally. TBHQ (Example 7.36) and methyl salicylate (Example 7.52) show worse oxidant protection considering the decrease in purity and / or peroxide concentration compared to all other phenolic derivatives.These results highlight once again that careful selection of the antioxidant compound is required, and it is not obvious that previously reported stabilizers and antioxidants will be effective for alkynes.

[0200] Surprisingly, isopropanol (Examples 7.10-7.15 & 7.42-7.43) and acetone (Examples 7.17-7.22) are as effective as well-known antioxidants such as BHT and BHA particularly at concentrations above 10000 ppmw. These results are even more surprising when compared to the results obtained for diisopropylcarbinol (Examples 7.26-7.29) and diisopropyl ketone (Examples 7.30-7.32) which have similar chemical structures but do not perform as effectively as antioxidants.

[0201] Based on these results, triethylamine, DEHA, cresols, ethylphenols, 2-methoxy-4- methyl-phenol, and 2-methoxyphenol are desirable candidates considering their physicochemical properties, e.g., low melting point and / or boiling point and reasonable vapor pressure.Considering the toxicity and olfactory properties, triethylamine, DEHA, 2-ethylphenol, 3- ethylphenol, 2-methoxy-4-methyl-phenol, and 2-methoxyphenol are preferred antioxidants among those tested.

[0202] For compounds having a high melting point (greater than 50 °C) and boiling point (greater than 200 °C), BHA is preferred over BHT, TBHQ, resorcinol, diphenylamine, and DABCO based on the lack of color formation after the oxidant test, low peroxide content, low byproduct formation, lower toxicity, and predicted better compatibility with fuel-cell due to absence of nitrogen atoms. For high melting point (greater than 50 °C) and boiling point (greater than 200 °C) compounds, the maximum concentration in the odorant formulation should not exceed 1000 ppmw, and preferably be equal to or lower than 200 ppmw to comply with technicalguidelines defined in IS013734:2013 which require that the mass fraction of odorant residues after evaporation should be less than 0.2 wt%. Above 1000 ppmw, the odorant composition comprising the compound antioxidant may not be fully vaporized during the gas odorization process, leading to precipitation, deposition on the pipeline walls, and / or blockage or plugging of the odorant injection system.

[0203] EXAMPLE 8

[0204] Gaseous blends of 1 -hexyne and various antioxidants were prepared in multiple steps. First, the mass equivalent to 1000 + / - 150 ppmw of antioxidants was added to pure 1- hexyne to form solution A and allowed to fully dissolved. Secondly, 1 pL of the 1 -hexyne and antioxidant solution A was injected using a liquid syringe into a Tedlar® gas bag filled with 5 dm3of pure hydrogen gas (class 5.0) to form gas mixture B. Thirdly, 0.4 dm3of the gas mixture B was injected using a gas syringe into second Tedlar® gas bag filled with 4.6 dm3of pure hydrogen gas (class 5.0) to form gas mixture C. The resulting mixture C was analyzed by gas chromatography to confirm that the 1 -hexyne concentration was approximately 10 mg / Nm3. Due to its very low concentration in gas mixture C, the antioxidant concentration could not be accurately quantified by gas chromatography. For these tests, the antioxidant concentration in the gas mixture C should be considered equivalent to the weight ratio to its original concentration in solution A, corresponding to 0.0100 + / - 0.0015 mg / Nm3.

[0205] An olfactory panel composed of 5 panelists was used to determine the impact of the antioxidant on the olfactory properties of 1 -hexyne. The panelists were exposed to a reference gas mixture made of pure 1 -hexyne and a test gas mixture including a specific antioxidant and 1 -hexyne mixture undisclosed to the panelists via two separate smelling ports. During the test, the panelists could go back and forth between both ports to determine if the antioxidant containing samples had different olfactory properties as compared to the pure 1- hexyne reference. The pure 1 -hexyne reference gas mixture was composed of a 10 mg / Nm31- hexyne gas mixture in hydrogen diluted with clean air to reach about 1% v / v of nominal concentration, or a concentration of 0.1 mg / Nm31 -hexyne, thereby simulating a typical detection concentration at 20% of the lower explosive limit of hydrogen (LEL = 4% v / v in air; ca. 0.8% v / v in air) and natural gas (LEL = 5% v / v; ca. 1% v / v in air). The test gas mixture was prepared by adjusting the dilution factor of each gas mixture C based on the nominal 1 -hexyneconcentration as determined by gas chromatography analysis to achieve the same final concentration of 0.1 mg / m31-hexyne and ca. 0.0001 mg / Nm3antioxidant concentration in the gas phase.

[0206] Each olfactory panel member was asked to give their impression of the odor character and odor strength for a test gas mixture including an undisclosed antioxidant in comparison to the pure 1-hexyne reference. The panelists were asked to indicate whether they found the test gas sample to be unpleasant (e.g., would the odor cause serious concerns if smelled in a real-world application) and if the odor character and odor strength was equivalent to the pure 1-hexyne reference. If a panelist concluded that the test gas sample had equivalent odor character and strength equivalent to the pure 1-hexyne reference, the smell character of the 1- hexyne and antioxidant gas mixture C was considered equivalent to pure 1-hexyne. If a panelist concluded that the test gas sample had either different odor character (smell was different than the pure 1-hexyne reference sample), the odor character of the 1-hexyne and antioxidant gas mixture C was considered different as compared to pure 1-hexyne. If a panelist concluded that the test gas sample had different odor strength (higher or lower odor intensity), the antioxidant was considered to have synergistic effects (higher odor strength) or antagonistic effects (lower odor strength, odor masking) compared to pure 1-hexyne.

[0207] Results are provided in the following table. In this table, A, B, C, D and E denote the feedback for each of the five individual panelists. The data shows that some antioxidants had an impact on the 1-hexyne odor characteristic. In the case of Example 8.1 (3 -ethylphenol), Example 8.2 (p-cresol), Example 8.4 (2-ethylphenol), and Example 8.5 (DEHA) different olfactory characteristics were observed by some of the panelists. For the other examples, both the 1-hexyne and antioxidant blends and pure 1-hexyne had equivalent olfactive characteristics.

[0208] Surprisingly, in all examples, the presence of an antioxidant in 1 -hexyne did not impact the alarming nature of 1 -hexyne compared to the reference pure 1 -hexyne despite some panelists identifying olfactory differences. Certain panelists identified a difference in odor characteristics for Example 8.1 (3 -ethylphenol) and Example 8.4 (2-ethylphenol). This is very surprising for Example 8.4 (2-ethylphenol) considering that the antioxidant concentration (about 0.0001 mg / m3) is significantly lower compared to the odor detection threshold reported in the literature. For both compounds, the unpleasantness of the smell is preserved and therefore, one can conclude that the presence of either 2- or 3-ethylphenol is not detrimental to the performance of 1 -hexyne as odorant. Their presence actually enhances the alarming and unpleasant olfactive properties based on the feedback from some of the panelists. Certain panelists also identified a difference in odor intensity for Example 8.1 (3-ethylphenol), Example 8.2 (p-cresol), and Example 8.5 (DEHA). Since an equal amount of panelists reported either lower or high odor strength for Example 8.1 (3-ethylphenol), and Example 8.5 (DEHA), both antioxidants can be considered as having no impact on 1 -hexyne olfactory properties. Surprisingly, data collected forExample 8.2 (p-cresol) suggest that p-cresol can enhance the odor strength of 1 -hexyne even if a difference in odor character was not identified by the panelists.

[0209] For some applications, it is beneficial that the effective concentration of the antioxidant in the odorant results in an effective concentration in air below the odor detection threshold to avoid odor masking or fading phenomena. For example, 10 mg / Nm3alkynes containing 1000 ppmw antioxidant would result, at a concentration in air of 20 % of the hydrogen LEL (i.e. 1% in air), in a concentration of 0.0001 mg / Nm3of antioxidant in air during a leak. To avoid odor masking or fading phenomena, the odor detection threshold of the antioxidant should be significantly greater than this value to avoid its presence being detected and impacting the smell properties of the odorant. Data for example 5.3 and 5.5 to 5.8 clearly highlights such behavior. In this regard, compounds such as 3-ethylphenol (Example 5.1) are not desirable antioxidant candidates due to the very low odor detection threshold. The reported odor detection threshold in the literature is lower than 0.0001 mg / Nm3, and it is reasonable to expect that the odorant olfactive properties would be affected by such compounds as demonstrated in Example 5.1. Phenolic compounds such as BHT, BHA, 2-ethylphenol, 4-ethylphenol, m-cresol, 2-methoxy-4-methylphenol, methyl salicylate, and 2-methoxyphenol are preferred considering the odor detection threshold reported in the literature. Similarly, amine-based compounds such as DEHA and diphenylamine are ideal candidates considering the very high odor detection threshold reported in the literature, ensuring that the odorant olfactive properties are not impacted by the presence of the antioxidant at a concentration where the antioxidant is effective. In comparison, one could use a significantly higher concentration of acetone and IPA as antioxidant due to their much higher odor detection. One of reasonable skill in the art would expect that the olfactory properties of the odorant will not be impacted even if concentrations as high as 50,000 ppmw IPA or acetone are used as antioxidant.

[0210] For some applications, it is beneficial that the antioxidant enhances the alarming smell of the odorant. This is particularly true if the antioxidant has an unpleasant smell which can synergistically work with the antioxidant. In this regard, 3-ethylphenol (Example 5.1), p- cresol (Example 5.2), and 2-ethylphenol (Example 5.4) are ideal antioxidant candidates due to their very low odor detection threshold and highly unpleasant odor character profiles which positively impact the performance of the odorant. Similarly, despite having high odor detection thresholds, antioxidants such as DEHA, DABCO, triethylamine, 2-methoxyphenol and 4-ethylphenol enhance the alarming characteristics of the odorant due to their highly unpleasant odor character profiles.

[0211] CONSTRUCTIVE EXAMPLE 9

[0212] Based on the experimental data shown in EXAMPLE 7 and 8, the compounds listed in the below table are antioxidants that would be suitable to protect alkynes against oxidation when used as gas odorants. These compounds have the following properties:ASPECTS

[0213] The following is a listing of non-limiting aspects of the disclosure:

[0214] Aspect 1. A compound, such as a compound that is an inhibitor of hydrogen embrittlement and / or an odorant for a fluid, such as a gas, the compound comprising, consisting essentially of, or consisting of a terminal alkyne and / or a terminal alkene, wherein, as used herein, the phrases “terminal alkyne” and “terminal alkene” include substituted and / or heteroatom-containing derivatives thereof.

[0215] Aspect 2. The compound of Aspect 1, wherein the compound is non-toxic (e.g., to humans and / or other animals).

[0216] Aspect 3. The compound of Aspect 1 , wherein the compound has a detectable odor below a toxicity level (e.g., for humans and / or other animals).

[0217] Aspect 4. The compound of Aspect 1, wherein the compound is environmentally benign, such as by not posing health, toxicity, or ecological concern to humans or other animals.

[0218] Aspect 5. The compound of any of the preceding Aspects, wherein the compound, upon combustion, is environmentally benign as a combustion product, such as by not posing health, toxicity, or ecological concern to humans or other animals.

[0219] Aspect 6. The compound of any of the preceding Aspects, wherein the compound does not undesirably impact the components of a device system, such as a combustion system, fuel cell, or any other appliance (for example, the compound does not impact, or impacts by less than 1%, or less than 0.1 %, the performance (e.g., energy output) of a device).

[0220] Aspect 7. The compound of any of the preceding Aspects, wherein the compound has a positive displacement efficacy with respect to hydrogen of greater than 0 eV, at least 0.1 eV, at least 0.2 eV, at least 0.3 eV, at least 0.4 eV, or at least 0.5 eV.

[0221] Aspect 8. The compound of any of the preceding Aspects, wherein the compound functions as an embrittlement inhibitor in any of the methods, compositions, and / or systems kits.

[0222] Aspect 9. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a terminal C3-C20 alkyne, a terminal C3- C19 alkyne, a terminal C3-C18 alkyne, a terminal C3-C17 alkyne, a terminal C3-C16 alkyne, a terminal C3-C15 alkyne, a terminal C3-C14 alkyne, a terminal C3-C13 alkyne, a terminal C3-C12 alkyne, a terminal C3-C11 alkyne, a terminal C3-C10 alkyne, a terminal C3-C9 alkyne, a terminal C3-C8 alkyne, or a terminal C3-C7 alkyne.

[0223] Aspect 10. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a terminal C3-C20 alkene, a terminal C3- C19 alkene, a terminal C3-C18 alkene, a terminal C3-C17 alkene, a terminal C3-C16 alkene, a terminal C3-C15 alkene, a terminal C3-C14 alkene, a terminal C3-C13 alkene, a terminal C3-C12 alkene, a terminal C3-C11 alkene, a terminal C3-C10 alkene, a terminal C3-C9 alkene, a terminal C3-C8 alkene, or a terminal C3-C7 alkene.

[0224] Aspect 11. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a linear terminal alkyne.

[0225] Aspect 12. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a linear terminal alkene.

[0226] Aspect 13. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a branched terminal alkyne.

[0227] Aspect 14. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a branched terminal alkene.

[0228] Aspect 15. The compound of any of the preceding Aspects, wherein the terminal alkyne includes two or more triple bonds, one or more double bonds (e.g., an enyne), or a combination thereof.

[0229] Aspect 16. The compound of any of the preceding Aspects, wherein the terminal alkene includes two or more double bonds.

[0230] Aspect 17. The compound of any of the preceding Aspects, wherein the terminal alkyne and / or the terminal alkene includes a heteroatom.

[0231] Aspect 18. The compound of any of the preceding Aspects, wherein the heteroatom is oxygen.

[0232] Aspect 19. The compound of any of the preceding Aspects, wherein the terminal alkyne and / or the terminal alkene comprises an ether moiety, a ketone moiety, or both an ether moiety and a ketone moiety, wherein, optionally, the terminal alkene does not include acrylate or an acrylate group (C=C-COOR).

[0233] Aspect 20. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (I):R1-(CH2)n-C=C-H; formula (I); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R1is selected from hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc. Alternatively, R1can be selected from a C3-C12 cycloalkyl, a C3-C10 cycloalkyl, or a C3-C7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0234] Aspect 21. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (II): R2-(CH2)n-O-(CH2)m-C=C-H; formula (II);wherein n is an integer selected from 0 to 5, or 0 to 4; wherein m is an integer selected from 0 to 5, or 0 to 4; and wherein R2is selected from hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0235] Aspect 22. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (III):H-C=C-(CH2)n-C=C-H; formula (III); wherein n is an integer selected from 0 to 5, or 0 to 4.

[0236] Aspect 23. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (IV):H-C=C-(CH2)n-O-(CH2)m-C=C-H; formula (IV); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein m is an integer selected from 0 to 5, or 0 to 4.

[0237] Aspect 24. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (V):H-CH=CH-(CH2)n-C=C-H; formula (V); wherein n is an integer selected from 0 to 5, 0 to 4, or 1 to 4.

[0238] Aspect 25. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (VI):formula (VI); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R3is hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0239] Aspect 26. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a compound of formula (VII):R4-CH=CH-(CH2)n-C=C-H; formula (VII); wherein n is an integer selected from 0 to 5; and wherein R4is hydrogen or a Ci-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0240] Aspect 27. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a compound of formula (A):CH2=CH(CH2)mCH=CH2formula (A);wherein m is an integer selected from 0 to 4, such as 3 or 4 (e.g., m is 3 for a heptadiene and 4 for an octadiene).

[0241] Aspect 28. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a compound of formula (B):CH3CH=CH(CH2)mCH=CH2formula (B); wherein m is an integer selected from 0 to 4, such as 2 or 3 (e.g., m is 2 for a heptadiene and 3 for an octadiene).

[0242] Aspect 29. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a compound of formula (C): CH3(CH2)mCH=CH(CH2)nCH=CH3formula (C); wherein m is 0, 1, 2, or 3, and n is 0, 1, 2, or 3, wherein, optionally, m + n = 2 for heptadienes, and m + n = 3 for octadienes.

[0243] Aspect 30. The compound of any of the preceding Aspects, wherein the terminal alkene comprises, consists essentially of, or consists of a compound of formula (D):formula (D); wherein n is an integer selected from 0 to 5, or 0 to 4; and wherein R1is selected from the group consisting of hydrogen, a Ci-Ce alkyl, or and C3-Ci2cycloalkyl.

[0244] Aspect 31. The compound of any of the preceding Aspects, wherein the terminal alkyne and / or terminal alkene comprises, consists essentially of, or consists of one or more of the following compounds:

[0245] Aspect 32. The compound of any of the preceding Aspects, wherein the terminal alkyne and / or terminal alkene comprises, consists essentially of, or consists of one or more of the following compounds: propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1,3- butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 3 -methyl -1-butene, 4- methyl- 1-pentene, 5-methyl-l-hexene, 6-methyl- 1-heptene, 7-methyl- 1-octene, 3-methyl-l- pentene, 4-methyl- 1-hexene, 5 -methyl- 1-heptene, 6-methyl- 1-octene, 3,3-dimethyl-l-butene,4, 4-dimethyl-l -pentene, 5, 5-dimethyl-l -hexene, 6, 6-dimethyl-l -heptene, 7, 7-dimethyl-l -octene, 3,3-dimethyl-l-pentene, 3,3-dimethyl-l -hexene, 3, 3 -dimethyl -1 -heptene, 3,3-dimethyl-l-octene.

[0246] Aspect 33. The compound of any of the preceding Aspects, wherein the terminal alkyne and / or terminal alkene comprises, consists essentially of, or consists of one or more of the following compounds: 1-butene, 1-hexene, 1-octene, 1,3 -butadiene, 1,4-pentadiene, 1,5- hexadiene, 1,6-heptadiene and 1,7-octadiene.

[0247] Aspect 34. A composition comprising, consisting essentially of, or consisting of the compound of any of the preceding Aspects and an additive.

[0248] Aspect 35. The composition of any of the preceding Aspects, wherein the compound of any of the preceding Aspects functions as both an embrittlement inhibitor and an odorant.

[0249] Aspect 36. The composition of any of the preceding Aspects, further comprising, consisting essentially of, or consisting of an odorant, wherein the odorant and the compound of any of the preceding Aspects are different (for example, a compound of formula (I) and a compound of formula (VIII)).

[0250] Aspect 37. The composition of any of the preceding Aspects, wherein the compound (e.g., a terminal alkyne or a terminal alkene) acts as an embrittlement inhibitor, but not an odorant (e.g., the embrittlement inhibitor is not present at a concentration effective to impart a detectable odor, the embrittlement inhibitor is not an odiferous compound, etc.).

[0251] Aspect 38. The composition of any of the preceding Aspects, wherein the embrittlement inhibitor has an odorant detection threshold (ODT) that is equal to or greater than a value effective to prevent the embrittlement inhibitor from impacting the odorization provided by the odorant.

[0252] Aspect 39. The composition of any of the preceding Aspects, further comprising an alkyne (which can be a non-terminal alkyne), such as an odorant, wherein optionally the alkyne comprises, consists essentially of, or consists of a compound of formula (VIII):R5-OC-R6; formula (VIII); wherein R5and R6, independently, are hydrogen, a Ci-Ce alkyl, or a Ci-Ce cycloalkyl. The Ci-Ce alkyl can include methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc.

[0253] Aspect 40. The composition of any of the preceding Aspects, wherein the compound of formula (VIII) comprises, consists essentially of, or consists of a compound of the following table:

[0254] Aspect 41. The composition of any of the preceding Aspects, wherein the odorant is present in the composition at a concentration less than or equal to a concentration of THT required to produce a comparable or equivalent odor.

[0255] Aspect 42. The composition of any of the preceding Aspects, wherein the odorant is present in the composition at a concentration greater than a concentration of THT required to produce a comparable odor.

[0256] Aspect 43. The composition of any of the preceding Aspects, wherein the additive is dispersed in the odorant, or the odorant is dispersed in the additive.

[0257] Aspect 44. The composition of any of the preceding Aspects, wherein the additive is an odoriferous additive.

[0258] Aspect 45. The composition of any of the preceding Aspects, wherein (A) the additive comprises, consists essentially of, or consists of methacrylic acid, an acrylic acid Ci-Ce alkyl ester, or a combination thereof; or (B) the additive does not include methacrylic acid, an acrylic acid Ci-Ce alkyl ester, or a combination thereof.

[0259] Aspect 46. The composition of any of the preceding Aspects, wherein the additive includes a non-odiferous additive.

[0260] Aspect 47. The composition of any of the preceding Aspects, wherein the additive comprises, consists essentially of, or consists of an agent that is an inhibitor of hydrogen embrittlement.

[0261] Aspect 48. The composition of any of the preceding Aspects, wherein the additive is a stabilizer (i.e., a compound that prevents or delays the chemical degradation of a fluid and / or compound, such as the compound of any of the preceding Aspects).

[0262] Aspect 49. The composition of any of the preceding Aspects, wherein the stabilizer comprises, consists essentially of, or consists of an antioxidant, a radical inhibitor, or a combination thereof.

[0263] Aspect 50. The composition of any of the preceding Aspects, wherein the stabilizer comprises, consists essentially of, or consists of (but are not limited to), vitamin C or a derivative thereof (e.g., ascorbyl palmitate, ascorbyl acetate, etc.), a tocopherol or a derivative thereof (e.g., vitamin E, vitamin E acetate, etc.), vitamin A or a derivative thereof (e.g., vitamin A palmitate, etc.), a phenolic benzylamine, formic acid, acetic acid, benzoic acid, sorbic acid, butylated hydroxytoluene (tert-butyl hydroxytoluene (BHT)), butylated hydroxyanisole (BOA or BHA), 4-tert-butylcatechol (TBC), tert-butyl hydroxyanisole, 4-methoxyphenol (hydroquinone monomethyl ether (MeHQ)), 2-methoxyphenol (guaiacol), 2,6-di-tert-butyl phenol (2,6-DTBP), 2,5-di-tert-butyl-phenol (Ionol), benzene- 1,2-diol (pyrocatechol), benzene- 1,4-diol (hydroquinone, HQ), benzene-l,3-diol (resorcinol), 2-ethyl phenol, 4-ethyl phenol, mono- tertiary-butylhydroquinone (MTBHQ), 2,5-di-tertiary-butylhydroquinone (DTBHQ), tert-butyl hydroquinone (TBHQ), tolyhydroquinone (THQ), (2,2,6,6-tetramethylpiperidin-l-yl)oxyl (TEMPO) and derivatives, N,N-dibenzylhydroxylamine (DBHA), hexamethylenetetramine (Methenamine or HMTA or HMT), para-benzoquinone (p-Bq), ortho-benzoquinone (O-Bq), N-N, dimethylisopropanolamine (DMPA), phenothiazine (PTZ), 2,4-dinitrophenol (DNP), 2,4- dinitro-6-sec-butyl-phenol (DNBP), 2,6-dinitro-p-cresol, 1,4-phenylenediamine, N,N- dimethylaniline, melatonin, uric acid, glutathione or a combination thereof.

[0264] Aspect 51. The composition of any of the preceding Aspects, wherein the additive is a diluent for the compound of any of the preceding Aspects.

[0265] Aspect 52. The composition of any of the preceding Aspects, wherein the additive comprises, consists essentially of, or consists of a Cs-Cs saturated hydrocarbon (e.g., a pentane, a cyclopentane, a hexane, a cyclohexane, a heptane, a cycloheptane, an octane, and / or a fluorinated hydrocarbon, such as, for example, PFC-116, PFC-c216, PFC218, or PFC-318).

[0266] Aspect 53. The composition of any of the preceding Aspects, wherein the additive comprises, consists essentially of, or consists of one or more of the following compounds: 2-methylpropyl methacrylate (isobutyl methacrylate), allyl acrylate, allyl methacrylate, butyl acrylate, butyl methacrylate, ethyl methacrylate, ethyl acrylate, isobutyl acrylate, methyl acrylate, methyl methacrylate, propyl methacrylate, propylacrylate, propargyl alcohol, 1 -cyclohexene- 1-carbaldehyde, 2-methylpropanal (isobutylaldehyde), 3- butenal, 3 -methylbutanal (isopental, isovaleral, isovaleraldehyde), 5-methyl-2-pyrrole aldehyde, butanal (butylaldehyde), cyclohexanal, cyclopent- 1-enecarbaldehyde, cyclopentanecarboxaldehyde (cyclopentaldehyde), ethanone (acetaldehyde), pentanal (valeraldehyde), 2-methyl-2-butene, cis-2-butene, cis-2-pentene, diisobutylene, isobutene, trans-2-butene, trans-2-pentene, vinylacetylene (butenyne), 2-methylpropionic acid, butyric acid, isovaleric acid, lactic acid, pentanoic acid (valeric acid), propionic acid, 1 -butyne, 1 -octyne, 2- butyne, 2-hexyne, 2-octyne, 2-heptyne, 3-heptyne, 3-octyne, 4-methyl-l -pentyne, 4-methyl-2- pentyne, acetylene, vinylacetylene (butenyne), allylmethyl ether, diallylether, cyclohexene, ethylidene, cyclohexane, 1,2-butadiene (methylallene), 1,3 -cyclohexadiene, 1,4-pentadiene, 1,5- cyclooctadiene (cis / trans-l,5-cyclooctadiene), 1,5-cyclooctadiene (cis-l,5-cyclooctadiene), 1,5- cyclooctadiene (trans-l,5-cyclooctadiene), 2,3-dimethyl-l,3-butadiene, 2-methyl- 1,3 -butadiene (isoprene), 3-methyl-l,5-cyclooctadiene, methylallele sulfide, 2,3-butandione (diacetyl), 2,4- pentandione (acetylacetone), hexane-2, 5-dione, pentane-2,3-dione, ethylacetate, methyl acetate,3-methylindole (skatole), 3-hydroxybutan-2-one (acetoin), 5-hydroxyoctan-4-one (butyroin), cyclohexyl mercaptan, ethylmercaptan (EM), isopropylmercaptan (IBM), methylmercaptan (MM), propylmercaptan, sec-butyl mercaptan, tert-butyl mercaptan (TBM), 5-ethenylbicyclo[2.2.1 ]hept-2-ene (5-vinyl-2-norbornene), 5-ethylidenebicyclo[2.2.1 ]hept-2-ene, (5-ethylidene-2-norbomene), bicyclo[2.2.1]hept-2-ene (norbornene), acetic acid, formic acid, di ethyl selenide, diethylselenide, dimethyl selenide, tert-butylselenol, carbonyl sulfide, diethyl disulfide, di ethyl sulfide (DES), diisopropylsulfide, dimethyldisulfide (DMDS), dimethyl sulfide (DMS), methylethyl sulfide (MES), tetrahydrothiophene (THT), tertio-butyl mercaptan (TBM), N-methyl-2-pyrrolidone (NMP), Scentinel® T Gas Odorant, Scentinel® S-50 Gas Odorant, Scentinel® P Gas Odorant, Scentinel® 0-10 Gas Odorant, Scentinel® N Gas Odorant, Scentinel® H-85 Gas Odorant, Scentinel® F-50 Gas Odorant, Scentinel® F-40 Gas Odorant, Scentinel® F-35 Gas Odorant, Scentinel® F-25 Gas Odorant, Scentinel® F-20 Gas Odorant, Scentinel® E Gas Odorant, Scentinel® A Gas Odorant, Scentinel® TB Gas Odorant, Scentinel® S-20 Gas Odorant, Scentinel® T-50 Gas Odorant, and Scentinel® N-4 Gas Odorant.

[0267] Aspect 54. The composition of any of the preceding Aspects, wherein the compound (e.g., the terminal alkyne and / or the terminal alkene) is present in the composition at an amount of at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the composition.

[0268] Aspect 55. The composition of any of the preceding Aspects, wherein the compound includes two or more terminal alkynes, and the two or more terminal alkynes are present in the composition at a total amount of at least 1 wt%, at least 5 wt %, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the composition (e.g., if 20 g of a first terminal alkyne and 30 g of a second terminal alkyne are present in a composition have a total weight of 100 g, then the first and second terminal alkynes are present in the composition at a total amount of 50 wt%).

[0269] Aspect 56. The composition of any of the preceding Aspects, wherein the compound includes two or more terminal alkenes, and the two or more terminal alkenes are present in the composition at a total amount of at least 1 wt%, at least 5 wt %, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the composition (e.g., if 20 g of a first terminal alkene and 30 g of a second terminal alkene are present in a composition have atotal weight of 100 g, then the first and second terminal alkenes are present in the composition at a total amount of 50 wt%).

[0270] Aspect 57. The composition of any of the preceding Aspects, wherein the compound includes one or more terminal alkenes and one or more terminal alkenes, and the one or more terminal alkenes and the one or more terminal alkenes are present in the composition at a total amount of at least 1 wt%, at least 5 wt %, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%, based on the total weight of the composition (e.gf 20 g of a terminal alkene and 30 g of a terminal alkyne are present in a composition have a total weight of 100 g, then the terminal alkene and the terminal alkyne are present in the composition at a total amount of 50 wt%).

[0271] Aspect 58. A treated fluid comprising, consisting essentially of, or consisting of (i) a fluid, such as a gas, and (ii) the compound of any of the preceding Aspects, or the composition of any of the preceding Aspects, wherein the compound or the composition is dispersed in the fluid.

[0272] Aspect 59. The treated fluid of any of the preceding Aspects, wherein the compound or the composition is evenly or unevenly dispersed in the fluid.

[0273] Aspect 60. The treated fluid of any of the preceding Aspects, wherein the compound or the composition of any of the preceding Aspects is an odorant for the fluid.

[0274] Aspect 61. The treated fluid of any of the preceding Aspects, wherein the compound or the composition of any of the preceding Aspects is present in the treated fluid at a concentration of 1,000 mg / m3n or less, 900 mg / m3n or less, 800 mg / m3n or less, 700 mg / m3n or less, 600 mg / m3n or less, 500 mg / m3n or less, 400 mg / m3n or less, 300 mg / m3n or less, 200 mg / m3n or less, 100 mg / m3n or less, 90 mg / m3n or less, 80 mg / m3n or less, 70 mg / m3n or less, 60 mg / m3n or less, 50 mg / m3n or less, 40 mg / m3n or less, 30 mg / m3n or less, 20 mg / m3n or less, or 10 mg / m3n or less.

[0275] Aspect 62. The treated fluid of any of the preceding Aspects, wherein the compound or the composition of any of the preceding Aspects is present in the treated fluid at a concentration of at least 0.1 mg / m3n, at least 0.5 mg / m3n, at least 1 mg / m3n, at least 2 mg / m3n, at least 3 mg / m3n, at least 4 mg / m3n, at least 5 mg / m3n, at least 6 mg / m3n, at least 7 mg / m3n, at least 8 mg / m3n, at least 9 mg / m3n, or at least 10 mg / m3n.

[0276] Aspect 63. The treated fluid of any of the preceding Aspects, wherein the compound or the composition of any of the preceding Aspects is present in the treated fluid at a concentration of about 1 mg / m3n to about 1,000 mg / m3n, about 1 mg / m3n to about 900 mg / m3n, about 1 mg / m3n to about 800 mg / m3n, about 1 mg / m3n to about 700 mg / m3n, about 1 mg / m3n to about 600 mg / m3n, about 1 mg / m3n to about 500 mg / m3n, about 1 mg / m3n to about 400 mg / m3n, about 1 mg / m3n to about 300 mg / m3n, about 1 mg / m3n to about 200 mg / m3n, about 1 mg / m3n to about 100 mg / m3n, about 1 mg / m3n to about 90 mg / m3n, about 1 mg / m3n to about 80 mg / m3n, about 1 mg / m3n to about 70 mg / m3n, about 1 mg / m3n to about 60 mg / m3n, about 1 mg / m3n to about 50 mg / m3n, about 1 mg / m3n to about 40 mg / m3n, about 1 mg / m3n to about 30 mg / m3n, about 1 mg / m3n to about 20 mg / m3n, or about 1 mg / m3n to about 10 mg / m3n.

[0277] Aspect 64. The treated fluid of any of the preceding Aspects, wherein the compound or the composition of any of the preceding Aspects is present in the treated fluid at a concentration of about 1,000 mg / m3n to about 8,000 mg / m3n, about 2,000 mg / m3n to about 8,000 mg / m3n, about 3,000 mg / m3n to about 8,000 mg / m3n, about 4,000 mg / m3n to about 8,000 mg / m3n, about 1,000 mg / m3n to about 6,000 mg / m3n, about 2,000 mg / m3n to about 6,000 mg / m3n, about 3,000 mg / m3n to about 6,000 mg / m3n, about 4,000 mg / m3n to about 6,000 mg / m3n, about 1,000 mg / m3n to about 5,000 mg / m3n, about 2,000 mg / m3n to about 5,000 mg / m3n, or about 3,000 mg / m3n to about 5,000 mg / m3n.

[0278] Aspect 65. The treated fluid of any of the preceding Aspects, wherein the treated fluid is a fuel for a fuel cell or other device or system.

[0279] Aspect 66. A method of treating a fluid, the method comprising, consisting essentially of, or consisting of providing a fluid, and contacting the (i) fluid, such as a gas, and (ii) the compound of any of the preceding Aspects, or the composition of any of the preceding Aspects to form a treated fluid.

[0280] Aspect 67. The method of any of the preceding Aspects, wherein the fluid and / or the treated fluid is present in a fuel distribution system (such as any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.)).

[0281] Aspect 68. The method of any of the preceding Aspects, further comprising disposing the fluid and / or the treated fluid in a fuel distribution system (such as any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.)).

[0282] Aspect 69. The method of any of the preceding Aspects, wherein the providing of the fluid comprises capturing the fluid.

[0283] Aspect 70. The method of any of the preceding Aspects, further comprising pressurizing the treated fluid, storing the treated fluid, or a combination thereof.

[0284] Aspect 71. The method of any of the preceding Aspects, wherein the compound or the composition is in a liquid phase, a gaseous phase, or a combination thereof before, during, and / or after the contacting of the fluid and the compound or the composition.

[0285] Aspect 72. The method of any of the preceding Aspects, wherein the contacting of the fluid and the compound, or the fluid and the composition comprises dispensing the compound or the composition with a liquid meter.

[0286] Aspect 73. The method of any of the preceding Aspects, wherein the contacting of the fluid and the compound or the composition comprises nebulizing the compound or the composition.

[0287] Aspect 74. The method of any of the preceding Aspects, wherein the providing of the fluid comprises providing a container in which the fluid is disposed, and wherein the contacting of the fluid and the compound or the composition comprises disposing the compound or the composition in the container.

[0288] Aspect 75. The method of any of the preceding Aspects, wherein the providing of the fluid comprises providing a first stream comprising the fluid, and wherein the contacting of the fluid and the compound or the composition comprises contacting the first stream and a second stream comprising the compound or the composition.

[0289] Aspect 76. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid is a gas (at atmospheric pressure and room temperature).

[0290] Aspect 77. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of a fuel gas.

[0291] Aspect 78. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of hydrogen gas (H2) or a hydrogen gas blend.

[0292] Aspect 79. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of a natural or synthetic combustion gas.

[0293] Aspect 80. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of natural gas, LNG (liquid natural gas), liquefied petroleum gas (LPG), municipal gas, heating gas, or a combination thereof.

[0294] Aspect 81. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of methane, ethane, ethene, acetylene, propane, propene, butane, isobutane, butene, pentane, or a combination thereof.

[0295] Aspect 82. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises consists essentially of, or consists of water gas, synthesis gas, reform gas, generator gas, coke gas, an industrial gas (e.g., nitrogen, oxygen, argon, helium, etc.) or a combination thereof.

[0296] Aspect 83. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of a noncombustible gas.

[0297] Aspect 84. The compound, composition, treated fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of carbon monoxide, carbon dioxide, or a combination thereof.

[0298] Aspect 85. A method of generating energy, the method comprising, consisting essentially of, or consisting of providing a fuel cell, the fuel cell comprises an anode; and contacting the anode and the treated fluid of any of the preceding Aspects.

[0299] Aspect 86. The method of any of the preceding Aspects, wherein the contacting of the anode and the treated fluid produces an oxidized treated fluid.

[0300] Aspect 87. The method of any of the preceding Aspects, further comprising removing the compound (e.g., one or more terminal alkynes) of any of the preceding Aspects from the treated fluid.

[0301] Aspect 88. The method of any of the preceding Aspects, further comprising removing the compound from the oxidized treated fluid.

[0302] Aspect 89. The method of any of the preceding Aspects, wherein the removing of the compound (e.g., one or more terminal alkynes) of any of the preceding Aspects is performed at least in part with any of the apparatuses or techniques provided herein, including, but notlimited to, the use of catalytic decomposition, an adsorption or absorption media, a water trap, a solvent trap, etc.

[0303] Aspect 90. The method of any of the preceding Aspects, wherein the compound or the composition of any of the preceding Aspects is at least partially consumable by the fuel cell, thereby optionally improving the performance of the fuel cell, increasing the energy produced by the fuel cell, or a combination thereof relative to a fuel cell operated with the fluid of the treated fluid in the absence of the compound or the composition of any of the preceding Aspects.

[0304] Aspect 91. A method of transporting or storing a material, the method comprising, consisting essentially of, or consisting of (i) providing a treated fluid of any of the preceding Aspects, and (ii) disposing the treated fluid in an apparatus formed at least in part of a metal.

[0305] Aspect 92. The method of any of the preceding Aspects, wherein the apparatus comprises, consists essentially of, or consists of a pipeline or a storage container.

[0306] Aspect 93. The composition or method of any of the preceding Aspects, wherein the composition or the compound of any of the preceding Aspects, prevents or delays the hydrogen embrittlement of the metal (the compound or the composition “prevents or delays the hydrogen embrittlement of the metal” when the compound or the composition has a positive displacement efficacy, as defined at Example 1, such as a positive displacement efficacy of at least 0.5 eV, at least 0.75 eV, at least 1 eV, at least 1.5 eV, at least 2 eV, at least 2.5 eV, at least 3 eV, at least 3.5 eV, or at least 4 eV.

[0307] Aspect 94. The composition or method of any of the preceding Aspects, wherein the composition or the compound of any of the preceding Aspects (i) improves the fracture toughness of the metal by at least 3 %, at least 5 %, at least 10 %, at least 15 %, at least 20 %, at least 30 %, at least 40 %, or at least 50 %, relative to a metal contacted by an identical composition that does not include the embrittlement inhibitor, and / or (ii) lengthens a time of service of the apparatus at least 5 %, at least 10 %, at least 15 %, or at least 20 %, relative to an identical apparatus that transports or stores a fluid that does not include the inhibitor of hydrogen embrittlement.

[0308] Aspect 95. A system comprising (i) a sensor, and (ii) the compound or the composition of any of the preceding Aspects.

[0309] Aspect 96. The system of any of the preceding Aspects, wherein the sensor is coupled to — or configured to be coupled to — an apparatus formed at least in part of a metal (such as a pipeline), a fuel supply, a fuel cell, another component of a fuel cell system, any appliance that uses hydrogen as fuel, or any component of an appliance that uses hydrogen as fuel.

[0310] Aspect 97. The system of any of the preceding Aspects, wherein the sensor comprises circuitry programmed to shut down an apparatus, fuel cell, an appliance, or other system or component thereof in the event of a leak.

[0311] Aspect 98. The system of any of the preceding Aspects, wherein the sensor is configured to permit the use of any of the compounds of the preceding Aspects at a concentration that is not detectable by an average human.

Claims

CLAIMSWhat is claimed is:

1. A treated fluid composition comprising:(i) a fluid;(ii) an inhibitor of hydrogen embrittlement dispersed in the fluid, the inhibitor of hydrogen embrittlement comprising a diene and / or a terminal alkyne;(iii) optionally, an additive; and(iv) optionally, an odorant different from the inhibitor.

2. The composition of claim 1, wherein the fluid comprises hydrogen gas (H2) and at least 10 mol%, at least 20 mol%, at least 30 mol%, at least 50 mol%, at least 75 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 97 mol%, at least 98 mol%, or at least 99 mol% of the fluid is the hydrogen gas (H2).

3. The composition of claim 1, wherein the fluid comprises hydrogen gas (H2) and from 10 mol% to 40 mol%, from 10 mol% to 30 mol%, from 10 mol% to 25 mol%, from 15 mol% to 30 mol%, or from 15 mol% to 25 mol% of the fluid is the hydrogen gas (H2).

4. The composition of any one of claims 1-3, wherein the terminal alkyne comprises a mono 1 -alkyne, a diyne, an enyne, or a combination thereof.

5. The composition of any one of claims 1-4, wherein the inhibitor of hydrogen embrittlement has a hydrogen displacement efficacy of at least 0.1 eV.

6. The composition of any one of claims 1-5, wherein the inhibitor of hydrogen embrittlement is present at a concentration sufficient such that the inhibitor of hydrogen embrittlement also functions as an odorant.

7. The composition of any one of claims 1-6, wherein the inhibitor of hydrogen embrittlement comprises hex-l-yne, hept-l-yne, oct-l-yne, hepta- 1,6-diyne, hexa- 1,5 -diyne, and octa- 1,7-diyne, 4-methyl-pent-l-yne, 5-methyl-hex-l-yne, cyclopropyl-acetylene, 3,3-dimethyl- but-l-yne, 1,3 -butadiene, 1,5-hexadiene, 1,7-octadiene, or any combination thereof.

8. The composition of any one of claims 1-7, wherein the inhibitor of hydrogen embrittlement comprises 1,5-hexadiene.

9. The composition of any one of claims 1-8, wherein the inhibitor of hydrogen embrittlement comprises hepta- 1,6-diyne, hexa- 1,5 -diyne, and octa-1, 7-diyne, or a combination thereof.

10. The composition of any one of claims 1-9, wherein the inhibitor of hydrogen embrittlement comprises 3,3-dimethyl-but-l-yne.

11. The composition of any one of claims 1-10, wherein the inhibitor of hydrogen embrittlement is present in the treated fluid composition at a concentration of about 1,000 mg / m3n to about 8,000 mg / m3n, about 2,000 mg / m3n to about 8,000 mg / m3n, about 3,000 mg / m3n to about 8,000 mg / m3n, about 4,000 mg / m3n to about 8,000 mg / m3n, about 1,000 mg / m3n to about 6,000 mg / m3n, about 2,000 mg / m3n to about 6,000 mg / m3n, about 3,000 mg / m3n to about 6,000 mg / m3n, about 4,000 mg / m3n to about 6,000 mg / m3n, about 1,000 mg / m3n to about 5,000 mg / m3n, about 2,000 mg / m3n to about 5,000 mg / m3n, or about 3,000 mg / m3n to about 5,000 mg / m3n.

12. The composition of any one of claims 1-10, wherein the inhibitor of hydrogen embrittlement is present in the treated fluid composition at a concentration of about 100 mg / m3n to about 8,000 mg / m3n, about 100 mg / m3n to about 5,000 mg / m3n, about 100 mg / m3n to about 2,500 mg / m3n, about 100 mg / m3n to about 1,000 mg / m3n, about 500 mg / m3n to about 8,000 mg / m3n, about 500 mg / m3n to about 5,000 mg / m3n, about 500 mg / m3n to about 2,500 mg / m3n, about 500 mg / m3n to about 1,000 mg / m3n, about 1,000 mg / m3n to about 8,000 mg / m3n, about 1,000 mg / m3n to about 5,000 mg / m3n, or about 1,000 mg / m3n to about 2,500 mg / m3n.

13. The composition of any one of claims 1-12, wherein (iv) the odorant is present in the composition.

14. The composition of claim 13, wherein the odorant comprises hex-l-yne, hex-2-yne, hept-1-yne, hept-2-yne, hept-3-yne, oct-l-yne, oct-2-yne, oct-3 -yne, oct-4-yne, 6-methylhept-2-yne, 7-methyloct-3-yne, 2-methyloct-4-yne, hex-l-en-5-yne, hept-l-en-6-yne, 5 -methylhex- 1 -yne, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, cyclohexene, or a combination thereof.

15. The composition of claim 13, wherein the odorant comprises hex-l-yne, hex-2-yne, hept-2 -yne, or a combination thereof.

16. The composition of any one of claims 1-15, wherein (iv) the odorant is present in the treated fluid composition at a concentration of about 1 mg / m3n to about 1,000 mg / m3n, about 1 mg / m3n to about 900 mg / m3n, about 1 mg / m3n to about 800 mg / m3n, about 1 mg / m3n to about 700 mg / m3n, about 1 mg / m3n to about 600 mg / m3n, about 1 mg / m3n to about 500 mg / m3n, about 1 mg / m3n to about 400 mg / m3n, about 1 mg / m3n to about 300 mg / m3n, about 1 mg / m3n to about 200 mg / m3n, about 1 mg / m3n to about 100 mg / m3n, about 1 mg / m3n to about 90 mg / m3n, about 1 mg / m3n to about 80 mg / m3n, about 1 mg / m3n to about 70 mg / m3n, about 1 mg / m3n to about 60 mg / m3n, about 1 mg / m3n to about 50 mg / m3n, about 1 mg / m3n to about 40 mg / m3n, about 1 mg / m3n to about 30 mg / m3n, about 1 mg / m3n to about 20 mg / m3n, or about 1 mg / m3n to about 10 mg / m3n.

17. The composition of any one of claims 1-15, wherein (iv) the odorant is present in the treated fluid composition at a concentration of about 1 mg / m3n to about 50 mg / m3n, about 1 mg / m3n to about 40 mg / m3n, about 1 mg / m3n to about 30 mg / m3n, about 1 mg / m3n to about 20 mg / m3n, about 1 mg / m3n to about 10 mg / m3n, about 2 mg / m3n to about 50 mg / m3n, about 2 mg / m3n to about 40 mg / m3n, about 2 mg / m3n to about 30 mg / m3n, about 2 mg / m3n to about 20 mg / m3n, about 2 mg / m3n to about 15 mg / m’n, about 5 mg / m3n to about 50 mg / m3n, about 5mg / m3n to about 40 mg / m3n, about 5 mg / m3n to about 30 mg / m3n, about 5 mg / m3n to about 20 mg / m3n, or about 5 mg / m3n to about 15 mg / m3n.

18. The composition of any one of claims 1-17, wherein (iii) the additive is present in the composition.

19. The composition of claim 18, wherein the additive comprises a stabilizer, an antioxidant, and / or a radical inhibitor.

20. The composition of claim 18 or 19, wherein the additive comprises a compound having a ketone moiety, a compound having an amine moiety, a compound having an alcohol moiety, a compound having a phenol moiety, or any combination thereof.

21. The composition of any one of claims 18-20, wherein the additive comprises isopropanol (IP A), acetone, triethylamine, diethylhydroxylamine (DEHA), o-cresol, m-cresol, p-cresol, 2- ethylphenol, 3 -ethylphenol, 4-ethylphenol, 2-methoxy-4-methyl -phenol (creosol), 2- methoxyphenol, butylated hydroxyanisole (BHA), 2,6-bis(l,l-dimethylethyl)-4-methylphenol (BHT), resorcinol, diphenylamine, l,4-diazabicyclo[2.2.2]octane (DABCO), 2-butylphenol, 3- methoxylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-(trifluoromethyl)phenol, 3- (trifluoromethyl)phenol, ethanolamine, dimethylaniline, diethylaniline or any combination thereof.

22. The composition of any one of claims 18-21, wherein the additive comprises: tri ethylamine, di ethylhydroxylamine (DEHA), 2-ethylphenol, 3 -ethylphenol, 2-methoxy- 4-methyl -phenol (creosol), 2-methoxyphenol, butylated hydroxyanisole (BHA), or any combination thereof; or triethylamine, diethylhydroxylamine (DEHA), 2-ethylphenol, butylated hydroxyanisole (BHA), or any combination thereof.

23. The composition of any one of claims 1-22, wherein (iii) the additive is present in the treated fluid composition at a concentration of:about 10 ppmw to about 10 wt%, about 10 ppmw to about 8 wt%, about 10 ppmw to about 6 wt%, about 10 ppmw to about 4 wt%, about 10 ppmw to about 2 wt%, about 10 ppmw to about 1 wt%, about 10 ppmw to about 5,000 ppmw, about 50 ppmw to about 10 wt%, about 50 ppmw to about 8 wt%, about 50 ppmw to about 6 wt%, about 50 ppmw to about 4 wt%, about 50 ppmw to about 2 wt%, about 50 ppmw to about 1 wt%, about 50 ppmw to about 5,000 ppmw, about 50 ppmw to about 1,000 ppmw, about 200 ppmw to about 10 wt%, about 200 ppmw to about 8 wt%, about 200 ppmw to about 6 wt%, about 200 ppmw to about 4 wt%, about 200 ppmw to about 2 wt%, about 200 ppmw to about 1 wt%, about 200 ppmw to about 5,000 ppmw, or about 200 ppmw to about 2,000 ppmw, based on a weight of the inhibitor of hydrogen embrittlement in the composition or based on a weight of the odorant in the composition; or about 10 ppmw to about 1,000 ppmw, about 10 ppmw to about 900 ppmw, about 10 ppmw to 750 ppmw, about 10 ppmw to about 500 ppmw, about 50 ppmw to about 1,000 ppmw, about 50 ppmw to 750 ppmw, about 50 ppmw to about 500 ppmw, about 200 ppmw to about 1,000 ppmw, about 200 ppmw to about 900 ppmw, about 200 ppmw to 750 ppmw, or about 200 ppmw to about 500 ppmw, based on a weight of the inhibitor of hydrogen embrittlement in the composition or based on a weight of the odorant in the composition.

24. The composition of any one of claims 1-23, wherein the treated fluid composition is prepared by a process that comprises contacting the fluid, the inhibitor of hydrogen embrittlement, the additive, and optionally the odorant in any order or sequence.

25. The composition of any one of claims 1-24, wherein the treated fluid composition is prepared by a process that comprises: introducing the additive in solid form or liquid form through a first leak-tight inlet port into an odorant vessel; introducing the odorant and the inhibitor of hydrogen embrittlement through the first leak-tight inlet port or a second leak-tight inlet port into the odorant vessel and mixing with the additive to form an odorant composition; and discharging at least a portion of the odorant composition from the odorant vessel through a leak-tight outlet port and contacting with the fluid to form the treated fluid composition.

26. The composition of any one of claims 1-24, wherein the treated fluid composition is prepared by a process that comprises: introducing the additive in liquid form into a multiport vessel; connecting the multiport vessel to an odorant vessel containing the odorant the inhibitor of hydrogen embrittlement and transferring the additive to the odorant vessel through a leak-tight inlet port and mixing the additive with the odorant and the inhibitor of hydrogen embrittlement to form an odorant composition; disconnecting the multiport vessel from the odorant vessel; and discharging at least a portion of the odorant composition from the odorant vessel through a leak-tight outlet port and contacting with the fluid to form the treated fluid composition.

27. The composition of any one of claims 1-26, wherein the fluid or the treated fluid composition is present in a fuel distribution system.

28. A method of transporting or storing a material, the method comprising:(i) providing the treated fluid composition of any one of claims 1-27; and(ii) disposing the treated fluid composition in an apparatus formed at least in part of a metal.

29. The method of claim 28, wherein the apparatus comprises a pipeline.

30. The method of claim 28 or 29, wherein the inhibitor of hydrogen embrittlement prevents or delays hydrogen embrittlement of the metal.

31. The method of any one of claims 28-30, wherein the apparatus has a time of service at least 10 % greater than a time of service of an identical apparatus that transports or stores a fluid that does not include the inhibitor of hydrogen embrittlement.

32. A method of generating energy, the method comprising: providing a fuel cell, wherein the fuel cell comprises an anode; and contacting the anode and the treated fluid composition of any one of claims 1-27;wherein the contacting of the anode and the treated fluid composition produces an oxidized treated fluid composition.

33. The method of claim 32, further comprising removing the inhibitor of hydrogen embrittlement from the treated fluid composition or from the oxidized treated fluid composition.

34. The method of claim 32 or 33, wherein the inhibitor of hydrogen embrittlement is at least partially consumable by the fuel cell, thereby improving performance of the fuel cell, increasing energy produced by the fuel cell, or a combination thereof, relative to a fuel cell operated with the fluid of the treated fluid composition in the absence of the inhibitor of hydrogen embrittlement.

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