Odorants for carbon dioxide, odorized carbon dioxide, and methods

Abstract

Odorized fluids that include a fluid and an odorant are disclosed. Odorants can include sulfur, odorized materials, and methods of odorizing a material, such as a fluid. The fluid can be carbon dioxide. The odorant can include a sulfide and / or a mercaptan. The odorant can be effective at relatively low concentrations. The odorant can be distinguishable from other commonly used odorants.

Description

ODORANTS FOR CARBON DIOXIDE, ODORIZED CARBON DIOXIDE, AND METHODSREFERENCE TO RELATED APPLICATION

[0001] This application is being filed on April 3, 2025, as a PCT International Patent Application and claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 631,506, 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 carbon dioxide, odorized fluids, and methods for odorizing fluids, such as carbon dioxide.BACKGROUND

[0003] A number of technologies are directed to capturing and / or storing fluids, such as carbon dioxide. The amount of carbon dioxide that is captured and / or stored has increased in recent years, thereby increasing the risk of exposure, especially as captured and / or stored carbon dioxide is transported through populated areas. Carbon dioxide and other gases can cause one or more hazards, such as asphyxiation.

[0004] Various technologies are used to detect gas (e.g., carbon dioxide) leaks, such as technologies that rely on infrared cameras, manual checks, drone planes, etc.

[0005] There remains a need for improved methods of odorizing fluids, and odorants for fluids, including odorants that are effective at relatively low concentrations, olfactorily distinguishable from other widely used odorants, or a combination thereof.SUMMARY

[0006] 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.

[0007] In one aspect, odorants are provided, such as odorants for a fluid, which can include carbon dioxide. In some embodiments, the odorants include one or more sulfides, one or more mercaptans, or a combination thereof. The one or more sulfides can include diethyl sulfide, dimethyl sulfide, diethyl sulfide, propyl sulfide, tetrahydrothiophene, ethyl methyl sulfide, or a combination thereof. In some embodiments, the one or more mercaptans is selected from / c / 7-butyl mercaptan, ethyl mercaptan, / / -butyl mercaptan, .sec-butyl mercaptan, / / -propyl mercaptan, 2-propyl mercaptan, / ?eto-mercaptoethanol, or a combination thereof.

[0008] In another aspect, odorized materials are provided, such as odorized fluids (also referred to as odorized compositions). The odorized fluids can include odorized carbon dioxide. In some embodiments, the odorized materials include a fluid, and an odorant dispersed in the fluid. The fluid can include carbon dioxide. The odorant can include one or more sulfides, one or more mercaptans, or a combination thereof. The odorant can be present in an odorized material at any effective amount, including, but not limited to, a concentration of about 1 part per trillion to about 0.1 wt%, or about 1 part per trillion to about 100 parts per million.

[0009] In yet another aspect, methods of odorizing are provided, such as a methods of odorizing a fluid, which can include carbon dioxide. In some embodiments, the methods include providing a fluid, and contacting the fluid and an odorant to produce an odorized material. The providing of the fluid can include capturing the fluid, storing the fluid, or a combination thereof.

[0010] Additional aspects will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the aspects described herein. The advantages described herein may 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 renderindefinite 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 sulfide,” and the like, is meant to encompass one, or mixtures or combinations of more than one, fluid, sulfide, 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 ratio of from about 45:55 to about 55:45, Applicant’s intent is to recite individually 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51 :49, 52:48, 53:57, 54:46, and 55:45, 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 beinterpreted 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, and2,3-dimethylbutane; and a general reference to a “C4 alkyl” or “butyl group” includes an / / -butyl group, a .sec-butyl group, an zso-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 the novel teachings and advantages according to this disclosure. Accordingly, all such modifications and equivalents are intended to be included within the scope of this disclosure as defined in the following claims. Therefore, it is to be understood that resort can be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, 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, methods of making odorants, and methods of odorizing materials, such as fluids, which can include carbon dioxide.ODORANTS

[0030] The odorants of the present disclosure can include one or more sulfides, one or more mercaptans, or a combination thereof. For example, the odorants can include (i) one sulfide, (ii) two different sulfides, (iii) one sulfide and one mercaptan, (iv) one sulfide and two different mercaptans, (v) two different sulfides and one mercaptan, (vi) one mercaptan, (vii) two different mercaptans, etc. The one or more sulfides and the one or more mercaptans can include any of those known in the art and / or any of those provided herein.

[0031] The odorants can include any total amount of sulfur. Sulfur, for example, can be present at a total concentration of about 20 % to about 60 %, about 30 % to about 50 %, or about 35 % to about 45 %, by weight, based on the total weight of the odorant, such as the total weight of the one or more sulfides and the one or more mercaptans.SULFIDES AND MERCAPTANS

[0032] In some embodiments, the one or more sulfides of the odorants include one or more compounds of formula (I) and / or formula (II), and the one or more mercaptans include one or more compounds of formula (III): formula (I); formula (II);formula (III); wherein R1, R2, R3, and R4, independently, are selected from an unsubstituted or substituted Ci- Cio hydrocarbyl, wherein the unsubstituted or substituted Ci-Cio hydrocarbyl independently selected for R3is divalent; or wherein R1, R2, R3, and R4, independently, are selected from anunsubstituted or substituted C1-C10 alkyl, wherein the unsubstituted or substituted C1-C10 alkyl independently selected for R3is divalent.

[0033] In some embodiments, at least one of R1, R2, R3, or R4, independently, is a Ci-Cs alkyl, a Ci-Ce alkyl, a C1-C5 alkyl, a C1-C4 alkyl, a C1-C3 alkyl, or a C2 alkyl. At least one of R1, R2, R3, or R4, independently, can be a linear unsubstituted or substituted C1-C10 alkyl, or a branched unsubstituted or substituted C1-C10 alkyl. In some embodiments, at least one of R1, R2, R3, or R4, independently, is substituted with a hydroxyl group.

[0034] Each of the compounds of formula (I), formula (II), and / or formula (III), independently, can be present in an odorant at any effective amount. In some embodiments, each of the compounds of formula (I), formula (II), and / or formula (III) is present in the odorant at an amount of at least 0.1 %, at least 1 %, at least 5 %, at least 10 %, at least 20 %, at least 30 %, at least 40 %, at least 50 %, at least 60 %, at least 70 %, at least 80 %, or at least 90 %, by weight, based on the weight of the odorant.

[0035] The one or more sulfides can include any one or more of the following sulfides:

[0036] The one or more mercaptans can include any one or more of the following mercaptans:

[0037] In some embodiments, the odorant includes diethyl sulfide (DES), beta- mercaptoethanol (BME), or a combination thereof. The DES and the BME can present at any weight ratio in the odorant, such as a weight ratio (DES:BME) of about 10:90 to about 90: 10, about 20:80 to about 80:20, about 30:70 to about 70:30, about 40:60 to about 60:40, about 45:55 to about 55:45, or about 50:50.

[0038] In some embodiments, the odorant includes dimethyl sulfide (DMS), / -butyl mercaptan (TBM), or a combination thereof. The DMS and the TBM can be present at any weight ratio in the odorant, such as a weight ratio (DMS:TBM) of about 10:90 to about 90: 10, about 20:80 to about 80:20, about 25:75 to about 75:25, about 30:70 to about 70:30, about 40:60 to about 60:40, about 45:55 to about 55:45, or about 50:50.ODORIZED MATERIAL

[0039] Odorized materials (or compositions) also are provided by the present disclosure. The odorized materials can include a fluid, such as carbon dioxide, and any odorant as provided herein. An odorant can be dispersed (e.g., evenly dispersed or unevenly dispersed) in the fluid.

[0040] The fluid of the odorized materials can be any fluid, such as carbon dioxide, and in any phase (i.e., liquid, gas, etc.). The fluid can be a supercritical fluid.

[0041] An odorant can be present in an odorized material at any effective amount, such as an amount that is detectable by a human having an average sense of smell. In some embodiments, the odorant is present in the odorized material at a concentration of about 1 part per trillion to about 0.1 wt%, about 1 part per trillion to about 0.08 wt%, about 1 part per trillion to about 0.06 wt%, about 1 part per trillion to about 0.04 wt%, about 1 part per trillion to about 0.02 wt%, about 1 part per trillion to about 100 parts per million, about 100 parts per trillion to about 100 parts per million, about 1,000 parts per trillion to about 100 parts per million, about 10,000 parts per trillion to about 100 parts per million, about 100,000 parts per trillion to about 100 parts per million, about 1 part per million to about 100 parts per million, about 10 parts per million to about 100 parts per million, about 20 parts per million to about 100 parts per million, about 30 parts per million to about 100 parts per million, about 40 parts per million to about 100 parts per million, or about 50 parts per million to about 100 parts per million (by weight).METHODS OF ODORIZING

[0042] Also provided herein are methods of odorizing a material, such as a fluid (e.g., carbon dioxide). The methods can include providing a fluid, and contacting the fluid and an odorant, such as those provided herein, to produce an odorized material.

[0043] The providing of the fluid can include capturing the fluid, storing the fluid, or a combination thereof. The fluid can be captured by any known technique or apparatus, such as those known for capturing carbon. The capturing of the fluid can include a post-combustion carbon capture process, a pre-combustion carbon capture process, or an oxy-fuel combustion process.

[0044] Before, during, and / or after the methods provided herein, a fluid and / or an odorized material can be pressurized, stored, and / or transported.

[0045] The contacting of a fluid and an odorant can be achieved in any manner using any known technique or apparatus. One or both of the fluid and the odorant can be pressurized and / or provided as a stream before, during, and / or after the contacting of the fluid and the odorant. Before, during, and / or after the contacting of the fluid and the odorant, the odorant can be in a liquid phase, a gaseous phase, or a combination thereof. Therefore, the contacting of the fluid and the odorant can include dispensing the odorant with a liquid meter. The liquid meter can achieve a desired concentration of odorant is present in the odorized material. The contacting of the fluid and the odorant can include nebulizing the odorant.

[0046] The providing of the fluid can include providing a container in which the fluid is disposed. When the fluid is present in a container, the contacting of the fluid and the odorant can include disposing the odorant in the container, such as with the aid of a liquid meter or other apparatus.

[0047] In some embodiments, the providing of the fluid comprises providing a first stream comprising the fluid, and the contacting of the fluid and the odorant can include contacting the first stream and a second stream comprising the odorant.EXAMPLES

[0048] 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 1Odor Panel Characterization

[0049] 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 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 compared to dimethyl sulfide and tetrahydrothiophene.

[0050] 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.

[0051] The results of this example are provided in the following table. The odorants in the table are abbreviated as follows: tetrahydrothiophene (THT), z-propyl mercaptan (TPM), diethyl sulfide (DES), ethyl mercaptan (EM), / / -propyl mercaptan (NPM), / / -butyl mercaptan (NBM), dimethyl sulfide (DMS), and / -butyl mercaptan (TBM).EXAMPLE 2Preparation of Odorants

[0052] In this example, a series of odorants was prepared that included the following components and amounts of sulfur:

[0053] A series of odorants was also prepared in which dimethyl sulfide of Sample Nos.1-5 of the previous table was replaced with diethyl sulfide.EXAMPLE 3Odor Detection Threshold Study

[0054] In this example, an odor detection threshold study was performed for diethyl sulfide (DES) in carbon dioxide. This example involved mixing carbon dioxide and DES in air in order to determine the concentration at which DES could be detected by a panel of odor evaluation experts.

[0055] The parameters and results of the studies of this example are provided in the following tables.

[0056] In this example, carbon dioxide was added to air at 1,000 ppm (which was 20% of the 8 hour TWA exposure limit established by OSHA). DES was also introduced into the mixture from zero up to a concentration that could be detected by the panelists. It was found in this example that DES could be detected by all panelists statistically at 500 ppb (0.5 ppm) in the mixture at 1,000 ppm of carbon dioxide in air.

[0057] A calculation was performed to determine what the DES concentration in carbon dioxide (liquid) should be so that, if the mixture were released into the atmosphere and vaporized, the concentration of DES would be 500 ppb when the carbon dioxide reaches 1,000 ppm in air. This calculation was performed because carbon dioxide is typically transported via pipeline under conditions such that it is in the liquid phase.

[0058] When this calculation was performed, it was determined that the DES concentration could be up to about 0.1 wt% in liquid carbon dioxide, which was much higher than the concentration needed for some other odorants, such as a natural gas odorant. This difference is believed to be related to not only the detection threshold, but also the density of carbon dioxide as a liquid.ASPECTS

[0059] The following is a listing of non-limiting aspects:

[0060] Aspect 1. An odorant for a fluid, such as carbon dioxide, the odorant comprising, consisting essentially of, or consisting of one or more sulfides, one or more mercaptans, or a combination thereof.

[0061] Aspect 2. The odorant of Aspect 1, wherein the one or more sulfides comprises, consists essentially of, or consists of one or more compounds of formula (I) and / or formula (II), and the one or more mercaptans comprises, consists essentially of, or consists of one or more compounds of formula (III): formula (I);formula (II);R4- SH formula (III);wherein R1, R2, R3, and R4, independently, are selected from an unsubstituted or substituted C1-C10 hydrocarbyl, wherein the unsubstituted or substituted C1-C10 hydrocarbyl independently selected for R3is divalent; or wherein R1, R2, R3, and R4, independently, are selected from an unsubstituted or substituted C1-C10 alkyl, wherein the unsubstituted or substituted C1-C10 alkyl independently selected for R3is divalent.

[0062] Aspect 3. The odorant of any of the preceding Aspects, wherein sulfur is present at a total concentration of about 20 % to about 60 %, about 30 % to about 50 %, or about 35 % to about 45 %, by weight, based on the total weight of the odorant, such as the total weight of the one or more sulfides and the one or more mercaptans.

[0063] Aspect 4. The odorant of any of the preceding Aspects, wherein at least one of R1, R2, R3, or R4, independently, is a Ci-Cs alkyl, a Ci-Ce alkyl, a C1-C5 alkyl, a C1-C4 alkyl, a C1-C3 alkyl, or a C2 alkyl.

[0064] Aspect 5. The odorant of any of the preceding Aspects, wherein at least one of R1, R2, R3, or R4, independently, is a linear unsubstituted or substituted C1-C10 alkyl.

[0065] Aspect 6. The odorant of any of the preceding Aspects, wherein at least one of R1, R2, R3, or R4, independently, is a branched unsubstituted or substituted C1-C10 alkyl.

[0066] Aspect 7. The odorant of any of the preceding Aspects, wherein at least one of R1, R2, R3, or R4, independently, is substituted with a hydroxyl group.

[0067] Aspect 8. The odorant of any of the preceding Aspects, wherein the one or more sulfides comprises, consists essentially of, or consists of one or more of the following:

[0068] Aspect 9. The odorant of any of the preceding Aspects, wherein the one or more mercaptans comprises, consists essentially of, or consists of one or more of the following:

[0069] Aspect 10. The odorant of any of the preceding Aspects, wherein the odorant comprises, consists essentially of, or consists of diethyl sulfide (DES), Z / eta-mercaptoethanol (BME), or a combination thereof.

[0070] Aspect 1 1 . The odorant of Aspect 10, wherein the DES and the BME are present at a weight ratio (DES:BME) of about 10:90 to about 90:10, about 20:80 to about 80:20, about 30:70 to about 70:30, about 40:60 to about 60:40, about 45:55 to about 55:45, or about 50:50.

[0071] Aspect 12. The odorant of any of the preceding Aspects, wherein the odorant comprises, consists essentially of, or consists of dimethyl sulfide (DMS), / -butyl mercaptan (TBM), or a combination thereof.

[0072] Aspect 13. The odorant of Aspect 12, wherein the dimethyl sulfide and the t- butyl mercaptan are present at a weight ratio (DMS: TBM) of about 10:90 to about 90: 10, about 20:80 to about 80:20, about 25:75 to about 75:25, about 30:70 to about 70:30, about 40:60 to about 60:40, about 45:55 to about 55:45, or about 50:50.

[0073] Aspect 14. The odorant of any of the preceding Aspects, wherein each of the compounds of formula (I), formula (II), and / or formula (III), independently, is present in the odorant at an amount of at least 0.1 %, at least 1 %, at least 5 %, at least 10 %, at least 20 %, at least 30 %, at least 40 %, at least 50 %, at least 60 %, at least 70 %, at least 80 %, or at least 90 %, by weight, based on the weight of the odorant.

[0074] Aspect 15. An odorized material (or composition) comprising, consisting essentially of, or consisting of a fluid, such as carbon dioxide, and the odorant of any one of Aspects 1 to 14.

[0075] Aspect 16. The odorized material of any of the preceding Aspects, wherein the odorant is dispersed (e.g., evenly dispersed or unevenly dispersed) in the fluid.

[0076] Aspect 17. The odorized material of any of the preceding Aspects, wherein the odorant is present in the odorized material at a concentration of about 1 part per trillion to about 0.1 wt%, about 1 part per trillion to about 0.08 wt%, about 1 part per trillion to about 0.06 wt%, about 1 part per trillion to about 0.04 wt%, about 1 part per trillion to about 0.02 wt%, about 1 part per trillion to about 100 parts per million, about 100 parts per trillion to about 100 parts per million, about 1,000 parts per trillion to about 100 parts per million, about 10,000 parts per trillion to about 100 parts per million, about 100,000 parts per trillion to about 100 parts per million, about 1 part per million to about 100 parts per million, about 10 parts per million to about 100 parts per million, about 20 parts per million to about 100 parts per million, about 30 parts per million to about 100 parts per million, about 40 parts per million to about 100 parts per million, or about 50 parts per million to about 100 parts per million (by weight).

[0077] Aspect 18. The odorized material of any of the preceding Aspects, wherein the fluid is a gas.

[0078] Aspect 19. The odorized material of any of the preceding Aspects, wherein the fluid is a supercritical fluid.

[0079] Aspect 20. A method of odorizing, the method comprising, consisting essentially of, or consisting of providing a fluid, and contacting the fluid and the odorant of any of the preceding Aspects to produce an odorized material, such as an odorized material of any of the preceding Aspects.

[0080] Aspect 21. The method of any of the preceding Aspects, wherein the providing of the fluid comprises capturing the fluid.

[0081] Aspect 22. The method of Aspect 21, wherein the capturing of the fluid comprises a post-combustion carbon capture process, a pre-combustion carbon capture process, or an oxy -fuel combustion process.

[0082] Aspect 23. The method of any of the preceding Aspects, wherein the fluid comprises, consists essentially of, or consists of carbon dioxide.

[0083] Aspect 24. The method of any of the preceding Aspects, further comprising pressurizing the fluid and / or the odorized material, storing the fluid and / or odorized material, or a combination thereof.

[0084] Aspect 25. The method of any of the preceding Aspects, wherein the odorant 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.

[0085] Aspect 26. The method of any of the preceding Aspects, wherein the contacting of the fluid and the odorant comprises dispensing the odorant with a liquid meter.

[0086] Aspect 27. The method of any of the preceding Aspects, wherein the contacting of the fluid and the odorant comprises nebulizing the odorant.

[0087] Aspect 28. The method of any of the preceding Aspects, wherein the contacting of the fluid and the odorant disperses (e.g., evenly disperses or unevenly disperses) the odorant in the fluid.

[0088] Aspect 29. The method of any of the preceding Aspects, wherein the providing of the fluid comprises providing a container in which the fluid is disposed.

[0089] Aspect 30. The method of Aspect 29, wherein the contacting of the fluid and the odorant comprises disposing the odorant in the container.

[0090] Aspect 31. The method of any of the preceding Aspects, wherein the providing of the fluid comprises providing a first stream comprising the fluid.

[0091] Aspect 32. The method of Aspect 31, wherein the contacting of the fluid and the odorant comprises contacting the first stream and a second stream comprising the odorant.

Claims

CLAIMSWhat is claimed is:

1. An odorized material comprising: a fluid comprising carbon dioxide; and an odorant dispersed in the fluid, the odorant comprising one or more sulfides, one or more mercaptans, or a combination thereof; wherein: the odorant is present in the odorized material at a concentration of about 1 part per trillion (by weight) to about 0.1 wt%.

2. The odorized material of claim 1, wherein the odorant comprises diethyl sulfide.

3. The odorized material of claim 1, wherein the odorant comprises diethyl sulfide, dimethyl sulfide, propyl sulfide, tetrahydrothiophene, ethyl methyl sulfide, or a combination thereof.

4. The odorized material of claim 1, wherein the odorant comprises a mixture of (a) diethyl sulfide and (b) dimethyl sulfide, propyl sulfide, tetrahydrothiophene, ethyl methyl sulfide, or a combination thereof.

5. The odorized material of claim 1, wherein the one or more sulfides comprises one or more compounds of formula (I) and / or formula (II): formula (I);formula (II); wherein R1, R2, and R3, independently, are selected from an unsubstituted or substituted Ci-Cio alkyl, wherein the unsubstituted or substituted Ci-Cio alkyl independently selected for R3is divalent.

6. The odorized material of claim 1 , wherein the one or more mercaptans comprises one or more compounds of formula (III):formula (III); wherein R4is selected from an unsubstituted or substituted Ci-Cio alkyl.

7. The odorized material of claim 6, wherein R4is substituted with a hydroxyl group.

8. The odorized material of claim 1, wherein the odorant comprises tert-butyl mercaptan, ethyl mercaptan, / / -butyl mercaptan, .sec-butyl mercaptan, / / -propyl mercaptan, 2-propyl mercaptan, Z / eta-mercaptoethanol, or a combination thereof.

9. The odorized material of claim 1, wherein the odorant comprises diethyl sulfide, beta- mercaptoethanol, or a combination thereof.

10. The odorized material of claim 9, wherein the diethyl sulfide and the beta- mercaptoethanol are present at a weight ratio of diethyl sulfide:Z>e -mercaptoethanol of about 10:90 to about 90: 10.

11. The odorized material of claim 1, wherein the odorant comprises dimethyl sulfide, / -butyl mercaptan, or a combination thereof.

12. The odorized material of claim 11, wherein the dimethyl sulfide and the / -butyl mercaptan are present at a weight ratio of dimethyl sulfide: / -butyl mercaptan) of about 10:90 to about 90: 10.

13. The odorized material of any one of claims 1-12, wherein the odorant is present in the odorized material at a concentration of about 1 part per trillion to about 0.08 wt%, about 1 part per trillion to about 0.06 wt%, about 1 part per trillion to about 0.04 wt%, about 1 part per trillion to about 0.02 wt%, about 1 part per trillion to about 100 parts per million, about 100 parts per trillion to about 100 parts per million, about 1,000 parts per trillion to about 100 parts per million, about 10,000 parts per trillion to about 100 parts per million,about 100,000 parts per trillion to about 100 parts per million, about 1 part per million to about 100 parts per million, about 10 parts per million to about 100 parts per million, about 20 parts per million to about 100 parts per million, about 30 parts per million to about 100 parts per million, about 40 parts per million to about 100 parts per million, or about 50 parts per million to about 100 parts per million (by weight).

14. A method of odorizing, the method comprising: providing a fluid comprising carbon dioxide; and contacting the fluid and an odorant to produce an odorized material; wherein the odorant comprises one or more sulfides, one or more mercaptans, or a combination thereof.

15. The method of claim 14, wherein the providing of the fluid comprises capturing the fluid.

16. The method of claim 14 or 15, further comprising pressurizing the odorized material, storing the odorized material, or a combination thereof.

17. The method of any one of claims 14-16, wherein the odorant 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.

18. The method of any one of claims 14-17, wherein the contacting of the fluid and the odorant comprises dispensing the odorant with a liquid meter.

19. The method of any one of claims 14-17, wherein the contacting of the fluid and the odorant comprises nebulizing the odorant.

20. The method of any one of claims 14-19, 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 comprises disposing the odorant in the container.21 . The method of any one of claims 14-19, wherein the providing of the fluid comprises providing a first stream comprising the fluid, and wherein the contacting of the fluid and the odorant comprises contacting the first stream and a second stream comprising the odorant.

22. The method of any one of claims 14-21, wherein the odorized material is the odorized material of any one of claims 1-13.

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