Odorized fluids and methods

Abstract

Odorants and odorant compositions that include a sulfur-containing compound and / or a sulfur-free compound are disclosed. Methods of odorizing a material, such as a fluid are provided. The fluid can be an ether, such as dimethyl ether. Odorized fluids that include a fluid and an odorant or odorant composition are disclosed. Methods of generating energy are disclosed. Systems and kits that include an odorant or odorant composition, and a sensor are provided.

Description

ODORIZED FLUIDS AND METHODSREFERENCE TO RELATED APPLICATION

[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 No. 63 / 631,521, filed on April 9, 2024, the disclosure of which is incorporated herein by reference in its entirety.TECHNICAL FIELD

[0002] This disclosure relates to odorants for fluids, such as a dialkyl ether, odorized fluids, and methods for odorizing fluids, such as a dialkyl ether.BACKGROUND

[0003] 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.

[0004] There remains a need for improved methods of odorizing fluids, and odorants for fluids, including odorants for fuel gases, such as dialkyl ethers, particularly dimethyl ether. There also remains a need for odorants that are compatible with energy producing devices, engines, and removal technologies. There also remains a need for odorants having a very low odor perception, a distinctive smell profile, an alarming character, or a combination thereof.SUMMARY

[0005] 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.

[0006] In one aspect, odorized fluids are provided. In some embodiments, the odorized fluids include a fluid and an odorant. The odorant can be dispersed in the fluid. The fluid can include any of those described herein, such as dimethyl ether. The odorant can include any of those described herein. In some embodiments, the odorant includes a thiol moiety, a thioether moiety, a cycloalkene moiety, an acrylate moiety, an alcohol moiety, an alkynyl moiety, hydrogen sulfide, or a combination thereof.

[0007] In another aspect, odorant compositions are provided. In some embodiments, the odorant compositions include an odorant and an additive. The additive can be dispersed in the odorant, or the odorant can be dispersed in the additive. The odorant can include any of those described herein.

[0008] In yet another aspect, methods of odorizing a fluid are provided. In some embodiments, the methods include contacting (i) a fluid and (ii) an odorant or an odorant composition, as described herein, to form an odorized fluid. The fluid can include any of those described herein, such as dimethyl ether. The odorant an include any of those described herein.

[0009] In a still further aspect, methods of removal are provided, such as methods of removal of an odorant, such as any of the odorants described herein. In some embodiments, the methods include providing an odorized fluid, such as any of those described herein; and contacting the odorized fluid and a removal substrate or scrubber. The removal substrate or scrubber can reduce an amount of the odorant in the odorized fluid by adsorption, absorption, chemical reaction, or a combination thereof. The removal substrate or scrubber can rely on, at least in part, and / or include catalytic decomposition, an adsorption or absorption media, a water trap, or a solvent trap.

[0010] 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.DEFINITIONS

[0011] 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 any definition 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.

[0012] As the various features of the subject matter of this disclosure are described, within particular aspect, a combination or combinations of the different features may 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 may be combined to describe and disclose the inventive designs, compositions, systems, processes, or methods consistent with the entire disclosure.

[0013] 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.

[0014] The terms “including,” “with,” and “having,” as used herein, are defined as comprising (i.e., open language), unless specified otherwise.

[0015] 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.

[0016] 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 20mg / 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 °C to 75 °C, this range should be interpreted as encompassing temperatures in a range from “about” 10 °C to “about” 75 °C unless otherwise stated.

[0017] Values or ranges may 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.

[0018] 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.

[0019] 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-dimethylbutane, and 2, 3 -dimethylbutane; and a general reference to a “C4 alkyl” or “butyl group” includes an / / -butyl group, a ec-butyl group, an Ao-butyl group, and a / -butyl group.

[0020] 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 hydrogen 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.

[0021] 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.

[0022] 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 may be linear or branched unless otherwise specified.

[0023] 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 may 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).

[0024] 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.

[0025] 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 may be the same or different.

[0026] 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.

[0027] 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.

[0028] Those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments disclosed herein without materially departing from thenovel 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, may 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

[0029] The present disclosure is directed to odorants, odorant compositions, methods of removing odorants, and methods of odorizing materials, such as fluids, which can include a fuel gas.ODORANTS

[0030] Odorants are provided herein, such as odorants for a fluid. The odorants can be non-toxic (e.g., to humans or mammals), or have a detectable odor below a toxicity level. The odorants can be environmentally benign, such as by not posing health or toxicity concerns to human or biological species. Combustion products of the odorants also can be environmentally benign. The odorants can be benign to the components of a device system, such as a combustion system or any other system or device. For example, the odorant cannot impact, or impacts by less than 1%, or less than 0.1 %, the performance (e.g., energy output) of a device, e.g., an engine.

[0031] In some embodiments, the odorants for a fluid include a sulfur-containing compound, a sulfur-free compound, or a combination thereof.Sulfur -Containing Compounds

[0032] The sulfur-containing compounds generally can include any number of carbon atoms. In some embodiments, the sulfur-containing compounds include a C1-C20 sulfur- containing compound, a C1-C15 sulfur-containing compound, a C1-C10 sulfur-containing compound, a Ci-Cs sulfur-containing compound, a C1-C5 sulfur-containing compound, a C1-C3 sulfur-containing compound, a C2-C20 sulfur-containing compound, a C2-C15 sulfur-containing compound, a C2-C10 sulfur-containing compound, a C2-C8 sulfur-containing compound, a C2-C5 sulfur-containing compound, or a C2-C3 sulfur-containing compound. The carbon atoms can bepresent in any arrangement or configuration (e.g., linear, branched, cyclic, aryl, etc.), and can include any of the hydrocarbyl groups described herein. In some embodiments, the sulfur- containing compound is a non-cyclic compound. In some embodiments, the sulfur-containing compound is a cyclic compound, such as a non-aryl cyclic compound. In some embodiments, the sulfur-containing compound does not include any carbon atoms, e.g., hydrogen sulfide (H2S).

[0033] A sulfur-containing compound can include one or more sulfur atoms, such as one sulfur atom, two sulfur atoms, etc. The sulfur atoms can be present at any position within a sulfur-containing compounds. For example, a sulfur-containing compound can include a thiol moiety (C-S-H), a thioether moiety (C-S-C), or a combination thereof. In some embodiments, the sulfur-containing compound includes an alkyl mercaptan, an alkenyl mercaptan, an alkynyl mercaptan, or a combination thereof. In some embodiments, the sulfur-containing compound includes a dialkyl sulfide, a dialkenyl sulfide, a dialkynyl sulfide, any asymmetric version thereof, or a combination thereof. An “asymmetric version” of a dialkyl sulfide, a dialkenyl sulfide, or a dialkynyl sulfide includes an alkyl-alkenyl sulfide, an alkyl-alkynyl sulfide, and an alkenyl-alkynyl sulfide. In some embodiments, the sulfur-containing compound includes a cyclic alkyl sulfide (e.g., tetrahydrothiophene), a cyclic alkenyl sulfide (e.g., thiophene), or a combination thereof.

[0034] The following table includes a non-limiting listing of sulfur-containing compounds:Sulfur-Free Compounds

[0035] The sulfur-free compounds generally can include any number of carbon atoms. For example, the sulfur-free compounds can include a C1-C20 sulfur-free compound, a C 1-C15 sulfur-free compound, a C1-C10 sulfur-free compound, or a C1-C5 sulfur-free compound. The carbon atoms can be present in any arrangement or configuration (e.g., linear, branched, cyclic, aryl, etc.), and can include any of the hydrocarbyl groups described herein. In some embodiments, the sulfur-free compound is a non-cyclic compound. In some embodiments, the sulfur-free compound is a cyclic compound, such as a non-aryl cyclic compound. For example, the sulfur-free compound can include a cyclic hydrocarbyl moiety, such as a cycloalkane moiety or a cycloalkene moiety.

[0036] The sulfur-free compounds generally can include one or more functional groups, such as a functional group formed from one or more carbon atoms and one or more non-carbon atoms, such as nitrogen and / or oxygen. In some embodiments, the sulfur-free compound includes an acrylate moiety (C=C-C(O)-O). The sulfur-free compound can include an alkyl acrylate, such as a C1-C5 alkyl acrylate, wherein the alkyl is straight or branched. In some embodiments, the sulfur-free compound includes an alcohol moiety (C-O-H). The sulfur-freecompound can include a C1-C10 alcohol, a C3-C6 alcohol, or a C4 alcohol. The sulfur-free compound can include an alkanol, an alkenol, an alkynol, or a combination thereof, wherein the alkanol, the alkenol, and the alkynol is linear, branched, or cyclic. In some embodiments, the sulfur-free compound includes an alkynyl moiety (C=C). The sulfur-free compound can include an alkyne, such as a 2-alkyne. The alkyne can be a C5-C8 alkyne, a C6-C7 alkyne, or a Ce alkyne, which can be linear or branched.

[0037] The following table includes a non-limiting listing of sulfur-free compounds:

[0038] In some embodiments, the sulfur-free compound includes a terminal alkyne. The phrase “terminal alkyne” generally refers to organic compounds, including substitutedderivatives of organic compounds and / or heteroatom-containing organic compounds, that include a terminal triple bond, as depicted in the following moiety:

[0039] 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.

[0040] In some embodiments, the terminal alkyne includes 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.

[0041] 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).

[0042] 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.

[0043] 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.

[0044] In some embodiments, the sulfur-free compound includes a hexyne or a substituted derivative thereof, a heptyne or a substituted derivative thereof, an octyne or a substituted derivative thereof, or a combination thereof. In some embodiments, the odorants include a heptyne, an octyne, or a combination thereof. The term “heptyne” refers to acompound 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:

[0045] 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.

[0046] In some embodiments, a terminal alkyne includes a compound of formula (I): R'-(CH2)„-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-Ce alkyl, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc. Alternatively, R1can be selected from a C3-Ci2cycloalkyl, a C3-C10 cycloalkyl, or a C3-C7 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0047] 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.

[0048] In some embodiments, the terminal alkyne includes 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.

[0049] In some embodiments, the terminal alkyne includes a compound of formula (IV): H-C C-(CH2)11-O-(CH2)n1-CVC-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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] In some embodiments, an alkyne, such as an odorant or a terminal alkyne whenR5or R6is hydrogen, includes a compound of formula (VIII):R'-C=C-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.

[0054] The following table provides a non-limiting listing of terminal alkynes:

[0055] In some embodiments, the heptyne and / or the octyne includes a compound of formula (DC):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).

[0056] 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).

[0057] 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).

[0058] The following table includes a non-limiting listing of heptynes and octynes:ODORANT COMPOSITIONS

[0059] Also provided herein are odorant compositions. In some embodiments, the odorant compositions include any one or more odorants provided herein, and an additive. Theadditive can be dispersed in the odorant, or vice versa, depending, for example, on whether the additive or the odorant, respectively, is the majority component.

[0060] The additive of an odorant composition can include an odoriferous additive, a non-odoriferous additive, or both an odoriferous additive and a non-odoriferous additive.

[0061] The additive, in some embodiments, does not include methacrylic acid, an acrylic acid Ci-Ce alkyl ester, or a combination thereof. In some embodiments, the additive includes methacrylic acid, an acrylic acid Ci-Ce alkyl ester, or a combination thereof.

[0062] In some embodiments, the additive is a stabilizer. The additive can include an antioxidant, a radical inhibitor, or a combination thereof. The additive can include, but is not limited to, vitamin C or a derivative thereof (ascorbyl palmitate, ascorbyl acetate, etc ), a tocopherol or a derivative thereof (vitamin E, vitamin E acetate, etc.), vitamin A or a derivative thereof (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 hydroxy anisole, 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), orthobenzoquinone (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.

[0063] The additive can be a diluent, such as a diluent for the odorant. 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, PFC218, or PFC-318).

[0064] An odorant generally can be present in an odorant composition at any desirable amount. In some embodiments, the odorant is present in an odorant composition at a totalamount 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 odorant composition. If an odorant includes two or more compounds, such as (i) two sulfur-free compounds, (ii) two sulfur-containing compounds, (iii) a sulfur-free compound and a sulfur-containing compound, etc., then the (i) two sulfur-free compounds, (ii) two sulfur-containing compounds, (iii) a sulfur-free compound and a sulfur- containing compound, etc. can be present in the odorant 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 odorant composition. For example, if 20 g of a first sulfur-free compound and 30 g of a second sulfur-free compound are present in an odorant composition having a total weight of 100 g, then the first and second sulfur-free compounds are present in the odorant composition at a “total amount” of 50 wt%.

[0065] An odorant composition generally can be in any phase, e.g., a liquid or gas. An odorant composition can be stored and / or used in any desirable phase.ODORIZED FLUIDS

[0066] Also provided herein are odorized fluids (or compositions). In some embodiments, the odorized fluids generally include (i) a fluid, such as a gas, and (ii) any of the odorants or the odorant compositions disclosed herein. An odorant or an odorant composition can be dispersed, evenly or unevenly, in the fluid.

[0067] An odorant can be present in an odorized fluid at any desired amount. When an odorant composition is present in an odorized fluid, the odorant composition can be present at an amount that is effective to achieve in the odorized fluid a desirable concentration of the odorant. In some embodiments, an odorant is present in an odorized 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, an odorant is present in an odorized fluid at a concentration of 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 5mg / 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, an odorant is present in an odorized 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, an odorant is present in an odorized fluid at a concentration of 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. As used herein, the units “mg / m3n” indicate a concentration (“mg / m3”) at normal (“n”) atmospheric pressure at a location, which, at sea level, is typically 1 bar or 14.7 psi.

[0068] An odorized fluid can be an odorized fluid that is suitable for a particular use, depending on the character of a fluid that is present in an odorized fluid. For example, an odorized fluid can be a fuel for a device or system, such as a heat-generating device (a heater, such as a space heater, water heater, etc., a cooking appliance, etc.), an engine or motor, etc. The engine can be a compression ignition engine.METHODS OF ODORIZING FLUIDS

[0069] Also provided herein are methods of odorizing fluids. In some embodiments, the methods include providing a fluid, and contacting the fluid and an odorant or an odorant composition as provided herein to form an odorized fluid.

[0070] Before, during, or after any one or more of the limitations of the methods provided herein is / are performed, the fluid and / or the odorized 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 odorizing a fluid also include disposing the fluid and / or the odorized fluid in a fuel distribution system, such as any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.).

[0071] 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 odorized fluid, storing the odorized fluid, or a combination thereof. The odorant or the odorant 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 odorant. The providing of the fluid can include providing a container in which the fluid is disposed, and the contacting of the fluid and the odorant or the odorant composition can include disposing the odorant or the odorant 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 odorant or the odorant composition can include contacting the first stream and a second stream that includes the odorant or the odorant composition.

[0072] The contacting of the fluid and the odorant or the odorant composition can be achieved using any technique. For example, the contacting of the fluid and the odorant or odorant composition can include dispensing the odorant or the odorant composition with a liquid meter. As a further example, the contacting of the fluid and the odorant or the odorant composition can include nebulizing the odorant or the odorant composition.FLUIDS

[0073] The odorants or odorant compositions provided herein can be used to odorize any fluid, and the odorized fluids can include any fluid. The fluids generally can be in any phase, e g., liquid or gas. In some embodiments, the fluid is a gas at atmospheric pressure and room temperature (i.e., 20 °C).

[0074] In some embodiments, the fluid is a fuel gas.

[0075] In some embodiments, the fluid is an ether, such as a dialkyl ether, which can be of the formula R^O-R2, wherein R1and R2are independently selected from a C1-C5 alkyl, a Ci- C4 alkyl, a C1-C3 alkyl, a C1-C2 alkyl, or a Ci alkyl, wherein, optionally, 100 wt%, at least 99 wt%, at least 95 wt%, at least 90 wt%, at least 80 wt%, at least 70 wt%, at least 60 wt%, at least 50 wt%, at least 40 wt%, or at least 30 wt% of the fluid is the ether. In some embodiments, the fluid includes dimethyl ether.SENSORS AND SYSTEMS

[0076] The odorants or odorant compositions provided herein can be used in combination with a sensor, such as a sensor designed to indicate the presence of an odorant and / or other compounds. Therefore, systems are provided herein that include a sensor and an odorant, or a sensor and an odorant composition.

[0077] A sensor can be coupled to any device or apparatus, such as 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 of organic odorants at very low concentrations that are not detectable by humans for special applications or circumstances. Furthermore, the odorant can be selected so that extremely high sensitivity and selectivity of the sensor can be realized to avoid false alarms.METHODS OF GENERATING ENERGY

[0078] Also provided herein are methods of generating energy. The methods generally can include using any of the odorized fluids provided herein as a source of energy. The odorized fluids can be a fuel for an appliance or device, such as any of those described herein. The appliances or devices can consume a fluid and an odorant. The appliances or devices can produce an exhaust, exit gas, offgas, flue gas, etc., which can include an odorant.

[0079] In some embodiments, the methods include providing an engine, such as a compression ignition engine, and disposing an odorized fluid in the compression ignition engine.The disposing of the odorized fluid in the compression ignition engine can produce an exhaust, which can be an odorant-containing exhaust.

[0080] In some embodiments, the methods include providing a fuel cell, the fuel cell comprises an anode, and contacting the anode and an odorized fluid. The contacting of the anode and the odorized fluid can produce an oxidized odorized fluid.

[0081] In some embodiments, the methods also include removing the odorant from the exhaust, exit gas, offgas, or flue gas or the odorized fluid. The removing of the odorant can be performed at least in part with any of the apparatuses or techniques provided herein, including, but not limited to, the use of catalytic decomposition, an adsorption media, an absorption media, a water trap, a solvent trap, etc.

[0082] In some embodiments, the methods include providing an odorized fluid (or an odorant-containing exhaust, exit gas, offgas, or flue gas produced from the odorized fluid) or an oxidized odorized fluid; contacting the odorized fluid (or the odorant-containing exhaust, exit gas, offgas, or flue gas) or the oxidized odorized fluid and a removal substrate or scrubber. The removal substrate or scrubber can reduce an amount of the odorant in the odorized fluid (or the odorant-containing exhaust, exit gas, offgas, or flue gas) or the oxidized odorized fluid by adsorption, absorption, or chemical reaction by the use of catalytic decomposition, an adsorption or absorption media, a water trap, or a solvent trap to produce a deodorized fluid. The removal substrate or scrubber can reduce the amount of the odorant in the odorized fluid (or the odorantcontaining exhaust, exit gas, offgas, or flue gas) or the oxidized odorized fluid by any desired amount, including, but not limited to, at least 90 %, at least 95 %, at least 99 %, at least 99.9 %, or 100 % (e.g., if the amount of odorant is reduced by 90 %, then a hypothetical starting odorant concentration of 10 units in an odorized fluid or oxidized odorized fluid would be reduced to 1 unit in the deodorized fluid).

[0083] In some embodiments, the odorant or the odorant composition is at least partially consumable by an engine, fuel cell, or other device, thereby optionally (i) improving the performance of the engine, fuel cell, or other device, (ii) increasing the energy produced by the fuel cell or engine, or (iii) a combination thereof, relative to a fuel cell or engine operated with the fluid of the odorized fluid in the absence of the odorant or the odorant composition.

[0084] In some embodiments, the methods include removing (e.g., scrubbing) an odorant from the odorized fluid or the exhaust, exit gas, offgas, or flue gas produced by consumption ofthe odorized fluid. The removal of the odorant an occur at any one or more points of the methods provided herein. For example, the methods can include removing an odorant from an odorized fluid prior to the consumption of the odorized fluid. Removal of an odorant from a fuel gas can be necessary or desirable, in some instances, such as (i) when an odorant is detrimental for the end-use of a fuel gas or fuel gas consuming appliance and / or device, and / or (ii) when an odorant is not eliminated during the consumption of the fuel gas, which can result in an environmental release of the odorant, thereby possibly negating the ability of the odorant to indicate leaks.

[0085] In some embodiments, the methods include removing (e.g., scrubbing) an odorant from an exhaust, exit gas, offgas, or flue gas from any of the devices described herein. The odorants provided herein can be removed by any known technique, such as (i) specially designed or commercially available adsorption and / or absorption processes, (ii) a water trap, and / or (iii) a humidifier system based on odorant solubility in water.

[0086] The removal (e.g., scrubbing) of an odorant from an odorized fluid and / or an exhaust, exit gas, offgas, or flue gas 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 (US7780933B2, US8658321B2, JP2018153634A, JP06317909B2, JP05766744B2, JP6306377A, JP04745557B2, US8444945B2, JP04822692B2, US7837964B2, US2008 / 0090115A1, US10889597 B2), or absorption and / or adsorption on activated carbon, zeolites, silica, or other substrates (JP07271867B2, JP05949333B2, JP2012143747A, JP2011201975A, JP05295689B2, JP2001019984A, JP2001157709A, US6875410B2, JP 05051864B2, US8057577B2, EP2337621B1).

[0087] More specifically, an odorant can be removed from a 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 organometallicframework compound (MOF); and a polymer type-absorbent in granular form, powder form, and fibrous form.

[0088] 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) ; and a rare earth metal (for example, oxides of scandium, yttrium, cerium, ytterbium and lanthanum); 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 zirconium. Preferably the alkaline earth metal is magnesium, calcium, barium, or strontium. Preferably the rare earth metal of the rare earth oxide is selected from scandium, yttrium, cerium, ytterbium and 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 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 / AFOs 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.

[0089] 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.

[0090] 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 the at least a portion of the odorant as a liquid.

[0091] 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)), polyvinylidene fluoride (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.

[0092] 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 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.

[0093] An odorant or odorant composition can be at least partially consumable by any of the devices described herein, thereby improving the performance of the device, increasing the energy produced by the device, or a combination thereof relative to a device operated with the fluid in the absence of the odorant or the odorant composition.EXAMPLES

[0094] 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.EXAMPLE 1

[0095] 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.

[0096] The odorant solutions at various concentrations were evaluated by olfactory testing using a method similar those disclosed in literature (see Journal of Applied Toxicology, 3, 272-289, 1983; Perception & Psychophysics, 39, 281-286, 1986) and an olfactory panel of at least 8 panel members.

[0097] The odor characteristic of each odorant 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 represented the lowest concentration at which the panelists could detect the odorant. The odor characteristic score for each compound was 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.** 1 (extremely unpleasant) and 10 (extremely pleasant).EXAMPLE 2

[0098] Dilutions of various odorants were prepared by mixing 50-100 mg / m3n 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.

[0099] 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 adilution 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.

[0100] The nominal concentration^ 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 / m3n; 5.0 ppm mol) of THT.

[0101] 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 a steeper slope, and that a compound has a lower odor detection threshold compared to THT. Preferably, a lower concentration will achieve an alarming level of odor, but the concentration of the odorant should be sufficient to result in an odor similar to that of THT.

[0102] Results of Example 2 are provided in the following table. The data showed that some compounds performed similarly to THT when used as odorants. In the case of Example 2.1 (hept-2-yne), Example 2.2 (hept-3-yne), Comparative Example 2.6 (pent-l-yne), Example 2.5 (hex-l-yne), Example 2.9 (hex-l-en-5-yne), Comparative Example 2.11 (hepta- 1,6-diyne) and Example 2.19 (hex-2 -yne), the compounds provided a comparable or stronger odor than THT at a similar concentration. In other Examples, including Example 2.1 (hept-2-yne) and Example 2.5 (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 the panel members.** Concentration required to match odor strength of THT at 1% v / vADilution equipment reached operational limit

[0103] The data of Examples 1 and 2 demonstrated that the l- / 2-hexynes, the 2- / 3- heptynes, and the 3- / 4-octynes were suitable gas odorants. The odor properties and alarming character of the l- / 2-hexynes, the 2- / 3 -heptynes, and the 3- / 4-octynes were comparable to a typical commercial natural gas odorant, namely tetrahydrothiophene (THT), and other alkynes considered to be suitable gas odorants, for instance, 1 -pentyne.

[0104] The data reveal several surprising and unexpected results. First, l- / 2-hexynes, 2- / 3-heptynes, and 3- / 4-octynes have odor detection thresholds comparable to or lower than previously considered alkynes (e.g.,1 -pentyne) and can serve as a fluid (gas) odorant in hydrogen gas and other fluids despite having a higher number of total aliphatic carbons (which corresponds to a higher boiling point and lower vapor pressure). Second, l- / 2-hexynes, 2- / 3 -heptynes, and 3- / 4-octynes have an odor strength equal to or better than other alkynes (e.g., pent-l-yne) and THT. Third, 2- / 3 -heptynes and 3- / 4-octynes have significantly lower odor detection thresholdscompared to similar shorter alkynes despite having only two carbons as a flexible spacer (e.g., m=l in formula i). Fourth, 2- / 3 -heptynes and 3- / 4-octynes demonstrate a distinct and unique odor compared to equivalent terminal alkynes (namely, hept-l-yne and oct-l-yne). These odor characteristics impart an alarming and unique smell similar to typical commercial natural gas odorants. Hept-2-yne demonstrates characteristic and unique smell properties compared to hex- 1-yne even though both are composed of four carbons as a flexible spacer (e.g., m=3 in formula i).

[0105] The data shown in Examples 1 and 2 also demonstrate that enyne compounds are suitable odorants 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 such as pent-l-yne. Surprisingly and unexpectedly, the enyne compounds do not behave like an alkyne or an alkene, but instead have their own unique set of odor properties. Embodiments of the enyne compounds have odor detection levels equal to or lower than previously considered alkynes (pent-l-yne); odor strengths equal to or better than previously considered alkynes (pent-l-yne) and a typical commercial natural gas odorant (THT); significantly lower odor detection thresholds compared to similar length dienes and alkynes (for example, 1 -heptyne, 1 -octyne and 1,5 -hexadiene); and significantly worse odor characteristics compared to similar alkenes, dienes, and alkynes (for example, 1-hexene, 1- heptyne and 1,5-hexadiene). These are all desirable properties when selecting an odorant compound.EXAMPLE 3

[0106] In this example, a drop of each odorant was placed on a cotton swab, which was then placed inside a glass vial that could be opened and wafted. Each panelist then assessed the odor intensity of each odorant on a scale of 1 (very weak) to 10 (very strong), and provided a brief description of the odor. The results indicated that diethyl sulfide had a relatively high odor intensity, and a different odor description than dimethyl sulfide and tetrahydrothiophene.

[0107] The odor evaluations were performed in random order, and, between the testing of each odorant, the panelists smelled ground coffee in a sealed container to establish an olfactory baseline.

[0108] The results of this example are provided in the following table.

[0109] The following abbreviations appear in the preceding table: tetrahydrothiophene (THT), z-propyl mercaptan (IPM), diethyl sulfide (DES), ethyl mercaptan (EM), zz-propyl mercaptan (NPM), / / -butyl mercaptan (NBM), dimethyl sulfide (DMS), and / -butyl mercaptan(TBM).ASPECTS

[0110] The following is a listing of non-limiting aspects of the disclosure:

[0111] Aspect 1. An odorant for a fluid, such as a dialkyl ether (e.g., dimethyl ether), the odorant comprising, consisting essentially of, or consisting of a sulfur-containing compound, a sulfur-free compound, or a combination thereof.

[0112] Aspect 2. The odorant of Aspect 1, wherein the odorant is non-toxic (e.g., to humans and / or other animals).

[0113] Aspect 3. The odorant of Aspect 1, wherein the odorant has a detectable odor below a toxicity level (e.g., for humans and / or other animals).

[0114] Aspect 4. The odorant of Aspect 1, wherein the odorant is environmentally benign, such as by not posing health, toxicity, or ecological concern to humans or other animals.

[0115] Aspect 5. The odorant of any of the preceding Aspects, wherein the odorant, upon combustion, is environmentally benign as a combustion product, such as by not posing health, toxicity, or ecological concern to humans or other animals.

[0116] Aspect 6. The odorant of any of the preceding Aspects, wherein the odorant does not undesirably impact the components of a device system, such as a combustion system, fuel cell, or any other appliance (for example, the odorant does not impact, or impacts by less than 1%, or less than 0.1 %, the performance (e.g., energy output) of a device).

[0117] Aspect 7. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound comprises, consists essentially of, or consists of a C1-C20 sulfur-containing compound, a C1-C15 sulfur-containing compound, a C1-C10 sulfur-containing compound, a Ci-Cs sulfur-containing compound, a C1-C5 sulfur-containing compound, a C1-C3 sulfur-containing compound, a C2-C20 sulfur-containing compound, a C2-C15 sulfur-containing compound, a C2- C10 sulfur-containing compound, a C2-C8 sulfur-containing compound, a C2-C5 sulfur-containing compound, or a C2-C3 sulfur-containing compound.

[0118] Aspect 8. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound is a non-cyclic compound.

[0119] Aspect 9. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound is a cyclic compound, such as a non-aryl cyclic compound.

[0120] Aspect 10. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound comprises a thiol moiety (C-S-H), a thioether moiety (C-S-C), or a combination thereof.

[0121] Aspect 11. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound comprises, consists essentially of, or consists of an alkyl mercaptan, an alkenyl mercaptan, an alkynyl mercaptan, or a combination thereof.

[0122] Aspect 12. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound comprises, consists essentially of, or consists of a dialkyl sulfide, a dialkenyl sulfide, a dialkynyl sulfide, any asymmetric version thereof, or a combination thereof.

[0123] Aspect 13. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound comprises, consists essentially of, or consists of a cyclic alkyl sulfide (e.g., tetrahydrothiophene), a cyclic alkenyl sulfide (e.g., thiophene), or a combination thereof.

[0124] Aspect 14. The odorant of any of the preceding Aspects, wherein each alkyl (e.g., alkyl of an alkyl mercaptan, each alkyl of a dialkyl sulfide, etc.) is independently selected from the group consisting of a straight alkyl and a branched alkyl, wherein each alkenyl is independently selected from the group consisting of a straight alkenyl and a branched alkenyl, and wherein each alkynyl is independently selected from the group consisting of a straight alkynyl and a branched alkynyl.

[0125] Aspect 15. The odorant of any of the preceding Aspects, wherein the sulfur- containing compound comprises, consists essentially of, or consists of any one or more of the compounds of the following table:

[0126] Aspect 16. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of a C1-C20 sulfur-free compound, a Ci- C15 sulfur-free compound, a C1-C10 sulfur-free compound, or a C1-C5 sulfur-free compound.

[0127] Aspect 17. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of a cyclic compound.

[0128] Aspect 18. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises a cyclic hydrocarbyl moiety, such as a cycloalkane moiety or a cycloalkene moiety.

[0129] Aspect 19. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises an acrylate moiety (C=C-C(O)-O).

[0130] Aspect 20. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of an alkyl acrylate, such as a C1-C5 alkyl acrylate, wherein the alkyl is straight or branched.

[0131] Aspect 21. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises an alcohol moiety (C-O-H).

[0132] Aspect 22. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of a C1-C10 alcohol, a C3-C6 alcohol, or a C4 alcohol.

[0133] Aspect 23. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of an alkanol, an alkenol, an alkynol, or a combination thereof, wherein the alkanol, the alkenol, and the alkynol is linear, branched, or cyclic.

[0134] Aspect 24. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of an alkynyl moiety (C=C).

[0135] Aspect 25. The odorant of any of the preceding Aspects, wherein the sulfur-free compound is an alkyne, such as a 2-alkyne.

[0136] Aspect 26. The odorant of any of the preceding Aspects, wherein the alkyne is a Cs-Cs alkyne, a C6-C7 alkyne, or a Ce alkyne, which can be linear or branched.

[0137] Aspect 27. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of any one or more compounds of the following table:

[0138] Aspect 28. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of a heptyne or a substituted derivative thereof, an octyne or a substituted derivative thereof, or a combination thereof.

[0139] Aspect 29. The odorant of any of the preceding Aspects, wherein the heptyne comprises, consists essentially of, or consists of a 2-heptyne.

[0140] Aspect 30. The odorant of any of the preceding Aspects, wherein the heptyne comprises, consists essentially of, or consists of a 3-heptyne.

[0141] Aspect 31. The odorant of any of the preceding Aspects, wherein the heptyne comprises, consists essentially of, or consists of a 3-octyne.

[0142] Aspect 32. The odorant of any of the preceding Aspects, wherein the heptyne comprises, consists essentially of, or consists of a 4-octyne.

[0143] Aspect 33. The odorant of any of the preceding Aspects, wherein the heptyne and / or the octyne comprises, consists essentially of, or consists of a compound of formula (IX):CH3-(CH2)m-C=C-(CH2)n-CH3formula (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).

[0144] Aspect 34. The odorant of any of the preceding Aspects, wherein the heptyne and / or the octyne comprises, consists essentially of, or consists of a compound of formula (X):(CH3)2CH-(CH2)m-C=C-(CH2)11-CH3formula (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).

[0145] Aspect 35. The odorant of any of the preceding Aspects, wherein the heptyne and / or the octyne comprises, consists essentially of, or consists of a compound of formula (XI):(CH3)3C-CCH2)m-C=C-(CH2)11-CH3formula (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).

[0146] Aspect 36. The odorant of any of the preceding Aspects, wherein the heptyne and / or the octyne comprises, consists essentially of, or consists of at least one of the following compounds:

[0147] Aspect 37. The odorant of any of the preceding Aspects, wherein the sulfur-free compound comprises, consists essentially of, or consists of a terminal alkyne, wherein, as usedherein, the phrase “terminal alkyne” includes substituted and / or heteroatom-containing derivatives thereof.

[0148] Aspect 38. 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.

[0149] Aspect 39. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a linear terminal alkyne.

[0150] Aspect 40. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of a branched terminal alkyne.

[0151] Aspect 41. The compound of any of the preceding Aspects, wherein the terminal alkyne includes two or more triple bonds, one or more double bonds, or a combination thereof (e.g., when the terminal alkyne includes at least one triple bond and at least one double bond, the compound can be referred to as an “enyne”, and, in some embodiments, the enyne includes the terminal triple bond and a terminal double bond; when the terminal alkyne includes two or more triple bonds, the compound can be referred to as a “diyne”, and the diyne can include two terminal triple bonds).

[0152] Aspect 42. The compound of any of the preceding Aspects, wherein the terminal alkyne includes a heteroatom.

[0153] Aspect 43. The compound of any of the preceding Aspects, wherein the heteroatom is oxygen.

[0154] Aspect 44. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises an ether moiety, a ketone moiety, or both an ether moiety and a ketone moiety.

[0155] Aspect 45. 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.

[0156] Aspect 46. 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.

[0157] Aspect 47. 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.

[0158] Aspect 48. 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 from0 to 5, or 0 to 4.

[0159] Aspect 49. 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.

[0160] Aspect 50. 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.

[0161] Aspect 51. 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.

[0162] Aspect 52. The compound of any of the preceding Aspects, wherein the terminal alkyne comprises, consists essentially of, or consists of one or more of the following compounds:

[0163] Aspect 53. An odorant composition comprising, consisting essentially of, or consisting of the odorant of any of the preceding Aspects and an additive.

[0164] Aspect 54. The odorant composition of any of the preceding Aspects, wherein the additive is dispersed in the odorant, or the odorant is dispersed in the additive.

[0165] Aspect 55. The odorant composition of any of the preceding Aspects, wherein the additive is an odoriferous additive.

[0166] Aspect 56. The odorant composition of any of the preceding Aspects, wherein(A) the additive comprises, consists essentially of, or consists of methacrylic acid, an acrylic acid Ci-C6alkyl 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.

[0167] Aspect 57. The odorant composition of any of the preceding Aspects, wherein the additive includes a non-odiferous additive.

[0168] Aspect 58. The odorant 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 an odorant).

[0169] Aspect 59. The odorant 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.

[0170] Aspect 60. The odorant composition of any of the preceding Aspects, wherein the stabilizer comprises, consists essentially of, or consists of 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, hexamethylene tetramine, tert-butyl hydroxytoluene (BHT), 4-tert-butylcatechol (TBC), tert-butyl hydroxyanisole, hydroquinone (HQ), 2,5-di-tert-butyl-phenol (Ionol), a-tocopherol, an a- hydroxy acid (e.g., citric acid, lactic acid, malic acid, etc.), hydroquinone monomethyl ether (4- methoxyphenol, MEHQ), 2-ethyl phenol, 4-ethyl phenol, 2, 2, 6, 6-Tetram ethylpiperidine 1-oxyl (TEMPO), or a combination thereof.

[0171] Aspect 61. The odorant composition of any of the preceding Aspects, wherein the additive is a diluent for the odorant.

[0172] Aspect 62. The odorant 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).

[0173] Aspect 63. The odorant composition of any of the preceding Aspects, wherein the sulfur-containing compound is present is present in the odorant 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 odorant composition.

[0174] Aspect 64. The odorant composition of any of the preceding Aspects, wherein the sulfur-free compound is present is present in the odorant 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 odorant composition.

[0175] Aspect 65. The odorant composition of any of the preceding Aspects, wherein the sulfur-containing compound and the sulfur-free compound are present in the odorant 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 odorant composition (e.g., if 20 g of a sulfur-containing compound and 30 g of an sulfur-free compound are present in an odorantcomposition having a total weight of 100 g, then the sulfur-containing compound and the sulfur- free compound are present in the odorant composition at a “total amount” of 50 wt%).

[0176] Aspect 66. An odorized fluid comprising, consisting essentially of, or consisting of (i) a fluid, such as a gas, and (ii) the odorant of any of the preceding Aspects, or the odorant composition of any of the preceding Aspects, wherein the odorant or the odorant composition is dispersed in the fluid.

[0177] Aspect 67. The odorized fluid of any of the preceding Aspects, wherein the odorant or the odorant composition is evenly or unevenly dispersed in the fluid.

[0178] Aspect 68. The odorized fluid of any of the preceding Aspects, wherein the odorant is present in the odorized 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.

[0179] Aspect 69. The odorized fluid of any of the preceding Aspects, wherein the odorant is present in the odorized fluid at a concentration of 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.

[0180] Aspect 70. The odorized fluid of any of the preceding Aspects, wherein the odorant is present in the odorized 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.

[0181] Aspect 71. The odorized fluid of any of the preceding Aspects, wherein the odorant is present in the odorized fluid at a concentration of 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, about5 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 15 mg / m3n.

[0182] Aspect 72. The odorized fluid of any of the preceding Aspects, wherein the odorized fluid is a fuel for a device or system, such as a heat-generating device (e.g., a heater, such as a space heater, water heater, etc., a cooking appliance, etc.), an engine or motor, etc.

[0183] Aspect 73. The odorized fluid of any of the preceding Aspects, wherein the engine is a compression ignition engine.

[0184] Aspect 74. A method of odorizing 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 odorant of any of the preceding Aspects, or the odorant composition of any of the preceding Aspects to form an odorized fluid.

[0185] Aspect 75. The method or odorized fluid of any of the preceding Aspects, wherein the fluid and / or the odorized fluid is present in a fuel distribution system (such as any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.)).

[0186] Aspect 76. The method of any of the preceding Aspects, further comprising disposing the fluid and / or the odorized fluid in a fuel distribution system (such as any fuel supply infrastructure (e.g., fuel storage, fuel distribution, fuel delivery, etc.)).

[0187] Aspect 77. The method of any of the preceding Aspects, wherein the providing of the fluid comprises capturing the fluid.

[0188] Aspect 78. The method of any of the preceding Aspects, further comprising pressurizing the odorized fluid, storing the odorized fluid, or a combination thereof.

[0189] Aspect 79. The method of any of the preceding Aspects, wherein the odorant or the odorant 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 odorant.

[0190] Aspect 80. The method of any of the preceding Aspects, wherein the contacting of the fluid and the odorant, or the fluid and the odorant composition comprises dispensing the odorant or the odorant composition with a liquid meter.

[0191] Aspect 81. The method of any of the preceding Aspects, wherein the contacting of the fluid and the odorant or the odorant composition comprises nebulizing the odorant or the odorant composition.

[0192] Aspect 82. 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 odorant or the odorant composition comprises disposing the odorant or the odorant composition in the container.

[0193] Aspect 83. 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 odorant or the odorant composition comprises contacting the first stream and a second stream comprising the odorant or the odorant composition.

[0194] Aspect 84. The odorant, odorant composition, odorized fluid, or method of any of the preceding Aspects, wherein the fluid is a gas (at atmospheric pressure and room temperature).

[0195] Aspect 85. The odorant, odorant composition, odorized fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of a fuel gas.

[0196] Aspect 86. The odorant, odorant composition, odorized fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of an ether, such as a dialkyl ether, which can be of the formula R'-O-R2, wherein R1and R2are independently selected from a C1-C5 alkyl, a C1-C4 alkyl, a C1-C3 alkyl, a C1-C2 alkyl, or a Ci alkyl, wherein, optionally, 100 wt%, at least 99 wt%, at least 95 wt%, at least 90 wt%, at least 80 wt%, at least 70 wt%, at least 60 wt%, at least 50 wt%, at least 40 wt%, or at least 30 wt% of the fluid is the ether.

[0197] Aspect 87. The odorant, odorant composition, odorized fluid, or method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of dimethyl ether.

[0198] Aspect 88. A method of generating energy, the method comprising, consisting essentially of, or consisting of (I) providing a fuel cell, the fuel cell comprises an anode, and contacting the anode and the odorized fluid of any of the preceding Aspects; or (II) providing an engine, such as a compression ignition engine, and disposing the odorized fluid of any of the preceding Aspects in the compression ignition engine; (III) disposing the odorized fluid of any of the preceding Aspects in a system or device that consumes the odorized fluid, wherein the system or device consumes the fluid and the odorant, or wherein the system or device consumes the fluid and produces an exhaust, offgas, exit gas, flue gas, etc. that includes the odorant.

[0199] Aspect 89. The method of any of the preceding Aspects, wherein the contacting of the anode and the odorized fluid produces an oxidized odorized fluid; or wherein the disposing of the odorized fluid in the compression ignition engine produces an exhaust, exit gas, offgas, or flue gas, which can be an odorant-containing exhaust, exit gas, offgas, or flue gas.

[0200] Aspect 90. The method of any of the preceding Aspects, further comprising removing the odorant from the odorized fluid, wherein, optionally, the removing of the odorant is performed at least in part with any of the apparatuses or techniques provided herein, including, but not limited to, the use of catalytic decomposition, an adsorption media, an absorption media, a water trap, a solvent trap, etc.

[0201] Aspect 91. The method of any of the preceding Aspects, further comprising removing the odorant from the odorant-containing exhaust, exit gas, offgas, or flue gas or the oxidized odorized fluid, wherein, optionally, the removing of the odorant is performed at least in part with any of the apparatuses or techniques provided herein, including, but not limited to, the use of catalytic decomposition, an adsorption media, an absorption media, a water trap, a solvent trap, etc.

[0202] Aspect 92. A method of removal, the method comprising providing the odorized fluid (or an odorant-containing exhaust, exit gas, offgas, or flue gas produced by the odorized fluid) or the oxidized odorized fluid of any of the preceding Aspects; contacting the odorized fluid (or the odorant-containing exhaust, exit gas, offgas, or flue gas) or the oxidized odorized fluid and a removal substrate or scrubber; wherein the removal substrate or scrubber reduces an amount of the odorant in the odorized fluid (or the odorant-containing exhaust, exit gas, offgas, or flue gas) or the oxidized odorized fluid by adsorption, absorption, or chemical reaction by the use of catalytic decomposition, an adsorption or absorption media, a water trap, or a solvent trapto produce a deodorized fluid; wherein, optionally, the removal substrate or scrubber reduces the amount of the odorant in the odorized fluid (or the odorant-containing exhaust, exit gas, offgas, or flue gas) or the oxidized odorized fluid by at least 90 %, at least 95 %, at least 99 %, at least 99.9 %, or 100 % (e.g., if the amount of odorant is reduced by 90 %, then a hypothetical starting odorant concentration of 10 units in an odorized fluid or oxidized odorized fluid would be reduced to 1 unit in the deodorized fluid).

[0203] Aspect 93. The method of any of the preceding Aspects, wherein the odorant or the odorant composition is at least partially consumable by the fuel cell or engine, thereby optionally improving the performance of the fuel cell or engine, increasing the energy produced by the fuel cell or engine, or a combination thereof relative to a fuel cell or engine operated with the fluid of the odorized fluid in the absence of the odorant or the odorant composition.

[0204] Aspect 94. A system comprising (i) a sensor, and (ii) the odorant or the odorant composition of any of the preceding Aspects.

[0205] Aspect 95. The system of any of the preceding Aspects, wherein the sensor is coupled to — or configured to be coupled to — a fuel supply, a fuel cell, another component of a fuel cell system, any appliance that uses the fluid as fuel, or any component of an appliance that uses the fluid as fuel.

[0206] Aspect 96. The system of any of the preceding Aspects, wherein the sensor comprises circuitry programmed to shut down a fuel cell, an appliance, or other system or component thereof in the event of a leak.

[0207] Aspect 97. The system of any of the preceding Aspects, wherein the sensor is configured to permit the use of any of the odorants of the preceding Aspects at a concentration that is not detectable by an average human.

Claims

CLAIMSWhat is claimed is:

1. An odorized fluid comprising:(i) a fluid comprising dimethyl ether; and(ii) an alkyne odorant dispersed in the fluid.

2. The odorized fluid of claim 1, wherein the alkyne odorant comprises a Cs-Cs alkyne.

3. The odorized fluid of claim 1 or 2, wherein the alkyne odorant is a 2-alkyne.

4. The odorized fluid of claim 1 or 2, wherein the alkyne odorant is a terminal alkyne.

5. The odorized fluid of claim 1 or 2, wherein the alkyne odorant comprises a 1-hexyne, a 2- hexyne, a 2-heptyne, or a combination thereof.

6. The odorized fluid of claim 1 or 2, wherein the alkyne odorant comprises hex-l-yne.

7. The odorized fluid of claim 1 or 2, wherein the alkyne odorant comprises hex-2-yne.

8. The odorized fluid of claim 1 or 2, wherein the alkyne odorant comprises hept-2-yne.

9. The odorized fluid of any one of claims 1-8, wherein the alkyne odorant is present in the odorized 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 toabout 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.

10. The odorized fluid of any one of claims 1-8, wherein the alkyne odorant is present in the odorized fluid at a concentration of 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 15 mg / m3n.

11. The odorized fluid of any one of claims 1-10, further comprising an additive.

12. The odorized fluid of claim 11, wherein the additive does not include methacrylic acid, an acrylic acid Ci-Ce alkyl ester, or a combination thereof.

13. The odorized fluid of claim 11 or 12, wherein the additive comprises a stabilizer, a diluent, or a combination thereof.

14. The odorized fluid of any one of claims 11-13, wherein the additive comprises an antioxidant, a radical inhibitor, or a combination thereof.

15. The odorized fluid of any one of claims 11-14, wherein the additive comprises vitamin C or a derivative thereof, a tocopherol or a derivative thereof, vitamin A or a derivative thereof, a phenolic benzylamine, formic acid, acetic acid, benzoic acid, sorbic acid, butylated hydroxytoluene (tert-butyl hydroxytoluene (BHT)), butylated hydroxyanisole(BOA or BHA), 4 -tert-butyl catechol (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 (0- 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 any combination thereof.

16. The odorized fluid of any one of claims 1-15, wherein at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of the fluid is the dimethyl ether.

17. A method of odorizing a fluid, the method comprising: contacting the fluid, the alkyne odorant, and an optional additive to form the odorized fluid of any one of claims 1-16.

18. The method of claim 17, wherein the fluid or the odorized fluid is present in a fuel distribution system.

19. The method of claim 17, further comprising disposing the fluid or the odorized fluid in a fuel distribution system.

20. A method of generating energy, the method comprising: providing a compression ignition engine; anddisposing the odorized fluid of any one of claims 1-16 in the compression ignition engine.

21. A method of removal, the method comprising: providing the odorized fluid of any one of claims 1-16; contacting the odorized fluid and a removal substrate or scrubber; wherein the removal substrate or scrubber reduces an amount of the alkyne odorant in the odorized fluid by adsorption, absorption, or chemical reaction by the use of catalytic decomposition, an adsorption or absorption media, a water trap, or a solvent trap to produce a deodorized fluid.

22. The method of claim 21, wherein the removal substrate or scrubber reduces the amount of the alkyne odorant in the odorized fluid by at least 90 %, at least 95 %, at least 99 %, or at least 99.9 %.

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