System, facility, and method for stabilizing hydrofluoroolefin in a refrigerant system

Abstract

The present invention relates to a system, facility, and method for preparing and filling a refrigerant circuit with either (1) a fluorolefin refrigerant composition stabilized with an inhibitor that prevents or reduces oligomerization or polymerization of the fluorolefin constituent of the composition, or (2) a fluorolefin refrigerant composition purified by removing the inhibitor, and / or maintaining the integrity of the fluorolefin refrigerant composition in a cooling facility by circulating the fluorolefin refrigerant composition through one or more columns or devices to remove at least one of oxygen and oxygen-containing contaminants, moisture / water, and oligomerization / polymerization by-products.

Description

Technical Field

[0001] The present invention relates to a highly versatile system and method capable of stabilizing and / or purifying a fluorolefin-based refrigerant or a heat transfer composition for a refrigerant or heat transfer equipment used in a cooler and a heat exchanger, in which a fluorolefin is likely to oligomerize or polymerize in the presence of air, oxygen, and / or an oxidizing compound, or a pollutant, and maintaining the stability / completeness of a fluorolefin refrigerant composition or a fluorolefin heat transfer composition used in a cooler or heat transfer equipment. Here, the fluorolefin is likely to oligomerize or polymerize in the presence of air, oxygen, and / or an oxidizing compound or a pollutant.

Background Art

[0002] A heat transfer fluid or refrigerant composed of 2,3,3,3-tetrafluoropropene (HFO-1234yf) contains stable molecules under heat transfer use conditions or cooling use conditions. However, HFO-1234yf can oligomerize or homopolymerize during storage and / or use in the presence of air and oxidizing chemicals. It can also decompose certain fluorolefins and / or produce by-products to be removed when in contact with other compounds (e.g., among various pollutants, especially excess oxygen, oxidizing chemicals, or radical-generating compounds) in a contaminated system that can occur unexpectedly under abnormal conditions such as extreme temperatures or in certain uses and / or applications. It has been observed that this decomposition can occur by any number of different mechanisms.

[0003] One solution was to provide a stabilized composition as disclosed in Japanese Patent No. 2009298918, U.S. Patent Nos. 6,969,701, 8,133,407, U.S. Patent Application Publication Nos. 2006 / 0022166, 2006 / 0043330, 2008 / 0157022, and International Publication No. 2007 / 126760, and European Patent No. 2057245, U.S. Patent Nos. 8101094, 8535555, 8097181, and 8075796 (the entire disclosures of each of which are incorporated herein by reference).

[0004] Another solution has been proposed, as disclosed in each of U.S. Patent Application Publication Nos. 20210108119 and 202100430368, the entire disclosures of each of which are incorporated herein by reference, such that a fluorolefin-containing composition, e.g., 2,3,3,3-tetrafluoropropene, is modified to contain an effective amount of an oligomerization inhibitor / polymerization inhibitor comprising at least one of limonene, α-terpinene, α-tocopherol, butylhydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol. However, these inhibitor compounds effectively react with oxygen and / or function as a chain transfer agent to stop polymer chain growth for fluorolefins, but their presence may also reduce the purity of the refrigerant going to a heat transfer system, e.g., a refrigerant system.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

[0006] Therefore, in order to maintain the integrity of the system and the fluorinated olefin-containing composition, regardless of whether an oligomer / polymer inhibitor is added or present, an alternative approach is needed to inhibit the oligomerization / polymerization of the fluorinated olefin components of the refrigerant / heat transfer composition in heat transfer / cooling systems and equipment. [Means for Solving the Problems]

[0007] The present invention relates to a system, equipment, and method for inhibiting the oligomerization / polymerization of the fluorinated olefin components of a refrigerant / heat transfer composition in a heat transfer / cooling system and equipment, and maintaining the integrity of the system and the fluorinated olefin-containing composition regardless of the presence of an oligomer / polymer inhibitor.

[0008] The present invention relates to a method for preparing and filling a refrigerant circuit with a system, facility, kit, and any fluorolefin refrigerant composition stabilized with an inhibitor that prevents or reduces oligomerization or polymerization of the fluorolefin constituents of the composition, or (2) a method for preparing a fluorolefin refrigerant composition free of an oligomerization inhibitor or a polymerization inhibitor, excluding / removing oxygen or oxidative contamination, excluding / removing moisture, and excluding or removing oligomer / polymer products and by-products, and circulating the fluorolefin refrigerant composition through one or more treatment zones to maintain the integrity of the fluorolefin refrigerant composition and the system, optionally, to a method configured to receive a pressure source for an inhibitor-containing fluorolefin composition charge containing an effective amount of the inhibitor.

[0009] The present invention provides a general-purpose system, retrofit component, and method for excluding or reducing unwanted oligomerization / polymerization of the fluorolefin constituent(s) of a heat transfer / refrigerant composition by optionally adding an oligomerization inhibitor / polymerization inhibitor in an effective amount of 1 weight percent (wt% or mass%) or less, more specifically, 0.02 - 0.5 weight percent, to a refrigerant circuit that includes various treatment steps for removing oxygen and oxygen-containing contaminants, removing moisture, and / or removing any in-situ generated oligomerization or polymerization by-products through which the fluorolefin refrigerant composition passes, wherein the fluorolefin composition contains HFO-1234yf and optionally contains at least one of R-32, R-125, R-152a, R-E-HFO-1234ze, R-134a, R-227ea, R-E / Z-1336mzz, CO2, R-E / Z-1132, R-1132a.

[0010] Disclosed herein is a fluorolefin-containing composition obtained from a storage tank, container, receptacle, or canister containing HFO-1234yf and optionally containing at least one of R-32, R-125, R-E-HFO-1234ze, R-134a, R-227ea, R-E-1336mzz, CO2, R-E / Z-1132, R-1132a, and R-152a, which is passed at a sufficient rate through a cartridge filled with at least one oligomerization inhibitor / polymerization inhibitor such as limonene, terpinene, pinene, etc. to add an effective amount of inhibitor sufficient to prevent at least HFO-1234yf from oligomerizing / polymerizing, and can then be filled into a refrigerant / heat transfer system / facility.

[0011] Disclosed herein is a kit comprising a pressurized canister of a fluorolefin-containing composition comprising HFO-1234yf and optionally at least one of R-32, R-125, R-152a, R-E / Z-HFO-1234ze, R-134a, R-227ea, R-E / Z-1336mzz, CO2, R-E / Z-1132, and R-1132a, and a cartridge filled with an effective amount of an inhibitor for preventing at least HFO-1234yf from oligomerizing / polymerizing, the inhibitor being at least one oligomerization inhibitor / polymerization inhibitor such as limonene, terpinene, pinene, etc., for example, an oxidation product inhibitor.

[0012] Disclosed herein is a kit containing a pressurized canister of a fluorinated olefin-containing composition comprising a lubricant, at least one oligomerization inhibitor / polymerization inhibitor selected from (1) d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, and (2) ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, or para-xylene, alpha-methylstyrene, and α,2-dimethylstyrene, α,3-dimethylstyrene, or α,4-dimethylstyrene (in an amount of about 0.02 to about 0.3 ppm to prevent at least HFO-1234yf from oligomerizing / polymerizing).

[0013] Disclosed herein is an HFO-1234yf fluorinated olefin-containing composition containing one or more of limonene, terpinene, pinene, i.e., oxidation product inhibitors, wherein the inhibitor is removed using a column to produce a pure stream of the HFO-1234yf fluorinated olefin-containing composition, which is then charged to heat transfer / cooling equipment.

[0014] By using one or more oxygen / air / oxygen-containing / oxidation contaminant removal columns, water / moisture removal dryers, and one or more systems for removing and / or reducing oligomerization / polymerization by-products, the oligomerization / homopolymerization product substances and oligomer / polymer by-products in the circulating HFO-1234yf-containing fluorinated olefin composition are reduced, avoided, eliminated, and removed, regardless of whether the refrigerant equipment is filled with a stabilized or purified HFO-1234yf-containing fluorinated olefin composition. General systems, retrofit parts, and methods for maintaining the integrity of the refrigerant circulating in the refrigerant equipment are disclosed herein.

[0015] An effective amount of an oligomer / polymer inhibitor comprising at least one of terpene, terpenoid, terpinene, linear unsaturated hydrocarbon, and a mixture of two or more thereof is added to a fluorinated olefin-containing refrigerant before filling it into a refrigerant facility to prevent and / or reduce undesirable oligomerized / polymerized fluorinated olefin by-products of the fluorinated olefin-containing refrigerant. Systems, components, and methods are disclosed herein. The device is novel, existing, or retrofitted to include one or more systems that remove and / or reduce oligomerized / polymerized by-products in the circulating HFO-1234yf-containing fluorinated olefin composition fluid of the facility or system, such as one or more oxygen / air / oxygen-containing / oxidation contaminant removal columns, water / moisture removal dryers.

[0016] Methods and systems are disclosed herein that include one or more oxygen / air / oxygen-containing / oxidation contaminant removal columns that use a supported or unsupported deoxidizer that reacts with or removes oxygen / air / oxygen-containing / oxidizing compounds to promote oligomerization / polymerization of the fluorinated olefin components of the refrigerant composition circulating within the cooling facility without cleaving the C-F bonds of the fluorinated olefin.

[0017] In this specification, optionally, at room temperature, for example, 20°C to 30°C, a system and method are disclosed that use a device or column filled with a deoxygenating reagent suitable for removing oxygen from a fluoroolefin-containing mixture. The deoxygenating reagents include, but are not limited to, zero-valent or low-valent transition metals and reduced oxides of transition metals. The transition metals are selected from the group including Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd. The zero-valent or low-valent transition metals and reduced oxides of transition metals can be commercially available or can be prepared by heating a transition metal oxide at a high temperature (100°C to 300°C) in the presence of a reducing agent such as hydrogen in a container such as a tube or column. Examples of metal oxides suitable for such reduction include, but are not limited to, CuO, TiO2, V2O5, Mn2O3, Fe2O3, Co3O4, ZnO, NiO, and PdO. Other deoxygenating reagents include solutions of polyhydroxybenzene compounds such as ascorbate, NaHSO4, Na2SO3, Na2S2O5, Na2S2O3, Na2S2O2, pyrogallol, Ti(III) salts, Cr(II) salts, Sn(II) salts, Fe(II) salts, nitrites, and hypophosphites.

[0018] Oxygen removal from the fluoroolefin composition may be carried out by passing the fluoroolefin mixture through a column or bed of the deoxygenating reagent at 20°C to 30°C without cleaving the C-F bonds of at least the HFO-1234yf fluoroolefin constituent of the composition.

[0019] Disclosed herein is a general-purpose system, retrofit component, and method that can (1) eliminate or reduce unwanted oligomerization / polymerization of the fluoroolefin constituent(s) of a refrigerant by adding an effective amount of an oligomer / polymer inhibitor to a source of heat transfer / refrigerant or refrigerant composition or blend, such as a storage container like a vessel, tank, or canister, prior to filling a heat transfer / refrigerant system or heat transfer / refrigerant circuit, or (2) remove an inhibitor from a stabilized heat transfer / refrigerant contained in a storage tank, vessel, or canister to provide a pure, substantially inhibitor-free heat transfer / refrigerant composition (this heat transfer / refrigerant composition includes devices for eliminating, removing, or reducing oxygen / air, moisture, oligomer / polymer by-products in the circulating fluid of a heat transfer / cooling circuit by using one or more filters and / or separators, and optionally, a fresh source of a stabilized refrigerant or refrigerant composition blend is provided and added to a new, existing, or retrofitted heat transfer / refrigerant system or circuit).

[0020] Also disclosed herein are systems and methods for preventing and / or reducing the formation of oligomer and homopolymer products and by-products, the systems and methods being adapted to add at least one oligomerization inhibitor / polymerization inhibitor of an effective amount to a source of a fluoroolefin-containing heat transfer / refrigerant composition or a circulating fluoroolefin heat transfer / refrigerant composition, the inhibitor being selected from one of d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof.

[0021] Also disclosed herein are systems and dispensing techniques with at least one of d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, which are dispensed / metered into a flowing stream of a 2,3,3,4-tetrafluoropropene-containing composition to stabilize the composition against oligomerization and / or polymerization.

[0022] Also disclosed herein are methods and devices for providing a fluidity feed of a fluoroolefin heat transfer / refrigerant composition stabilized with an effective amount of d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, and at least one of inhibitors.

[0023] Also disclosed herein is a system comprising a pre-packaged / built-in feed of a composition comprising at least HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, HFO-1132a, and CO2, and an inhibitor-containing cartridge comprising an oligomer inhibitor carried on or not carried on a carrier such as d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof; or the inhibitor can be added to or formulated with a lubricant for use during an oil change. The lubricant facilitates the addition of a higher concentration of the inhibitor.

[0024] In one embodiment of the invention, the kit comprises a pre-packaged / built-in feed of a lubricant and an inhibitor comprising d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, or para-xylene, and one of α-methylstyrene, α,2-dimethylstyrene, α,3-dimethylstyrene, or α,4-dimethylstyrene.

[0025] In another embodiment of the present invention, the kit includes a lubricant containing d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, and a cartridge filled with an inhibitor, which is a pre-packaged / built-in supply, or ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, meta-xylene, ortho-xylene, or para-xylene, alpha (α)-methylstyrene, α-methylstyrene, α,2-dimethylstyrene, α,3-dimethylstyrene, or α,4-dimethylstyrene, and can be added to the lubricant during oil change in a refrigerant circuit.

[0026] Also disclosed herein is a system comprising a kit including a pre-packaged / built-in supply of a lubricant or a cartridge supply adapted to add an inhibitor comprising an HFO-1234yf-containing composition, a lubricant, and an inhibitor containing d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, or d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, or ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, or para-xylene, α-methylstyrene, α,2-dimethylstyrene, α,3-dimethylstyrene, or α,4-dimethylstyrene during oil change.

[0027] Also disclosed herein is a system facility comprising at least one compressor, at least one evaporator, at least one condenser, at least one expansion device which is an orifice, a capillary tube or an expansion valve, at least one dryer for removing moisture, and optionally at least one of at least one supply valve, a refrigerant circuit for transporting a hydrofluoroolefin refrigerant composition, a filling subsystem or kit for a stabilized refrigerant, a filling subsystem for a purified refrigerant, a subsystem for separating oligomers / polymers, and an oligomer / polymer filter.

[0028] Also disclosed herein is a system comprising a dryer for removing moisture or water, including a compressor, an evaporator, a condenser, a filter section and a dryer section, and a cooling circuit for circulating a hydrofluoroolefin refrigerant composition including a filling subsystem for a stabilized refrigerant.

[0029] Also disclosed herein is a system comprising a compressor, an evaporator, a condenser, a dryer for removing moisture or water, a filling subsystem for a purified refrigerant, and optionally a filling subsystem for a stabilized refrigerant, and a cooling circuit for transporting a hydrofluoroolefin refrigerant composition.

[0030] Also disclosed herein is a system for separating oligomers / polymers including (1) removing oxidizing compounds including oxygen and / or a deoxidizer and / or (2) including an oligomer / polymer filter, wherein an air or oxygen detector or sensor is associated with the vapor space of the refrigerant within a container or part of the cooling circuit to control the use of the deoxidizer, the system comprising a compressor, an evaporator, a condenser, at least one dryer for removing moisture or water, and at least one subsystem, and a refrigerant circuit for transporting a hydrofluoroolefin refrigerant composition.

[0031] Also disclosed herein is any combination with the disclosed device, system, and their use, a transport assembly or supply facility for automobiles, trucks, railway vehicles, or other transport systems, and any moving carrier well-known as an "intermodal" system such as an intermodal system including "container" (a combination of sea transport / land transport) and "swap body" (a combination of road transport and railway transport).

Brief Description of the Drawings

[0032]

Figure 1

Figure 2

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Figure 6

Mode for Carrying Out the Invention

[0033] The above summary and the following "Detailed Description of the Invention" are merely illustrative and explanatory, and do not limit the present invention defined by the appended claims. Any one or more other features and advantages of the embodiments will become apparent from the following "Detailed Description of the Invention" and the claims.

[0034] Refrigerants such as the fluoroolefin HFO-1234yf are stable molecules under normal cooling use conditions. However, 2,3,3,3-tetrafluoropropene (HFO-1234yf, R-1234yf, or 1234yf) may oligomerize or homopolymerize during storage in the presence of air / oxidants, oxidizing chemicals, or radical-generating compounds among various contaminants. Certain fluoroolefins, such as HFO-1234yf, may decompose and / or form oligomer / polymer by-products under abnormal conditions such as extreme temperatures or in contaminated systems under contact with other compounds (such as, among various contaminants, excessive oxygen, oxidizing chemicals, or radical-generating compounds) that can occur unexpectedly in certain uses and / or applications. Preferably, it has been observed that it should be removed using a subsystem containing an oxygen scavenger that can respond to sensor detection of air / oxygen. Such decomposition may occur during storage and transportation or when using the fluoroolefin as a refrigerant and heat transfer fluid. One solution to avoid by-product formation from oligomerization / homopolymerization / polymerization is to use various inhibitors such as terpenes, terpenoids, terpinene, and linear unsaturated hydrocarbons, which stabilize hydrofluoroolefin components such as HFO-1234yf from oligomerization / homopolymerization / polymerization, as disclosed, for example, in U.S. Patent Application Publication Nos. 20210108119 and 2021004036 by the same applicant, the entire disclosures of which are incorporated herein by reference.

[0035] Before referring to the details of the embodiments described herein, some terms are defined or clarified as follows.

[0036] As used herein, a refrigerant is a compound or a mixture or blend of compounds, e.g., a refrigerant composition that functions as a heat transfer fluid in a cycle in which the fluid optionally undergoes a phase change back from a liquid to a gas.

[0037] As used herein, the term fluoroolefin describes a compound containing carbon atoms, fluorine atoms, and optionally chlorine atoms and / or hydrogen atoms. In one embodiment, the fluoroolefins used in the compositions of the present invention include compounds having 2 to 12 carbon atoms. In another embodiment, the fluoroolefins include compounds having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefins include compounds having 3 carbon atoms. Representative fluoroolefins and chlorofluoroolefins include, but are not limited to, the compounds shown in Table 1 below.

[0038] [Table 1]

[0039] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements, and may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or". For example, condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0040] The transitional phrase "consisting of" excludes any unrecited element, step, or ingredient. In the context of a claim, such a phrase closes the claim to the inclusion of materials other than those recited, except for impurities ordinarily associated with the recited materials. When the phrase "consists of" appears in a clause within the body of the claim rather than immediately following the preamble, the phrase limits the claim to only the elements recited in that clause, and other elements are not excluded from the claim as a whole.

[0041] The transitional phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, mechanisms, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, mechanisms, components, or elements do not substantially affect the basic and novel features of the claimed invention, particularly the mechanism of action for achieving any desired result of the process of the present invention. The term "consisting essentially of" has an intermediate meaning between "comprising" and "consisting of".

[0042] It should be readily understood that when the applicant defines the invention or a part thereof in terms of non-limiting terms such as "comprising", the description (unless otherwise specified) should be construed to also include inventions using the terms "consisting essentially of" or "consisting of".

[0043] Also, the use of "a" or "an" is employed to describe the elements and components described herein. This is merely for convenience and is for giving the general meaning of the scope of the present invention. This description should be construed to include one or at least one, and the singular form also includes the plural form unless it is clear that the singular form has a different meaning.

[0044] Also disclosed herein are methods and systems that include one or more steps or components, which may or may not be integrated with each other. In certain embodiments, the components and methods of use are integrated with each other, but in other embodiments, some of the steps or components may be associated with other systems and processes.

[0045] In certain disclosed embodiments, any of the disclosed devices, systems, and their uses are part of, or combined with, an assembly or supply facility for an automobile, truck, railway vehicle, or other transportation system, or any moving carrier known as an "intermodal" system, where the intermodal system includes "containers" (a combination of sea and land transport) as well as "swap bodies" (a combination of road and rail transport).

[0046] Fluoroolefin or blend compositions disclosed herein include, but are not limited to, compositions containing HFO-1234yf alone or in combination with 1,1,1,3-tetrafluoropropene (HFO-1234ze, R-1234ze, or 1234ze), and optionally a) HFO-Z / E-1225ye, b) HFO-Z / E-1225ye, and HFC-32, c) HFO-Z / E-1225ye, and HFC-134a, d) HFO-Z / E-1225ye, HFC-134a, and HFC-32, e) HFO-Z / E-1225ye, and HFO-1234yf, or f) HFO-Z / E-1225ye, and HFC-125, and includes additional compounds selected from these.

[0047] Further fluorolefin compositions include at least one of HFO-1234yf and HFO-1234ze, and i) R-134a, R-32, and R-125, ii) R-134a, iii) R-227ea, iv) R-236fa, and v) commercially available blends including but not limited to one of Opteon™ XL10, XP10, XP20, XP40, XP44, and commercially available HFO-1234ze blends such as R-448A manufactured by Honeywell International and sold by Daikin Global.

[0048] In certain embodiments of the present invention, the refrigerant components and fluorolefin compositions also include those as specified in U.S. Patent Application Publication Nos. 20210108119 and 2021004036 by the same applicant, the entire disclosures of which are incorporated herein by reference, including but not limited to the fluorolefins specified in Tables 1-3 of U.S. Patent Publication Nos. 20210108119 and 2021004036.

[0049] In certain embodiments disclosed herein, the fluorolefin includes at least one of HFO-1234yf and HFO-1234ze and may be blended with at least one hydrofluorocarbon. Examples of suitable hydrofluorocarbons include at least one component selected from HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea. The amount of hydrofluorocarbon(s) can range from about 25 to about 75 mole percent, from about 30 to about 60 mole percent, and in some cases from about 30 to about 50 mole percent. In one particular embodiment, the aforementioned amount of hydrofluorocarbon(s) is blended with HFO-1234yf and HFO-1234ze.

[0050] In other embodiments, the refrigerant composition comprises at least about 99 weight percent of HFO-1234yf and at least one element, in an amount greater than 0 weight percent but less than 1 weight percent, selected from or including HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propylene, HCFO-1233xf, HFC-245cb, HFO-1225zc, and combinations thereof.

[0051] In other embodiments, the refrigerant composition comprises at least about 99.5 weight percent of HFO-1234yf and at least one element, in an amount greater than 0 weight percent but less than 0.5 weight percent, selected from or including HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propylene, HCFO-1233xf, HFC-245cb, and combinations thereof.

[0052] In other embodiments, the refrigerant composition comprises at least about 98 weight percent of HFO-1234yf and at least one element, in an amount greater than 0 weight percent but less than 2 weight percent, selected from or including HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propylene, HCFO-1233xf, HFC-245cb, HFO-1225zc, and combinations thereof.

[0053] In other embodiments of the refrigerant composition, the composition comprises at least about 99 weight percent of HFO-1234ze and at least one element, in an amount greater than 0 weight percent but less than 1 weight percent, selected from or including HFO-1234yf, HFC-245fa, HFC-236fa, HFO-1234ye, and combinations thereof.

[0054] Optionally, the blended composition may further include at least one additional component selected from HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional component can include greater than 0 to about 5 wt%, about 0 to about 2 wt%, and in some cases about 0 to about 0.5 weight percent.

[0055] In a specific embodiment, the aforementioned amount of the additional element is blended with at least one of HFO-1234yf and HFO-1234ze.

[0056] In another specific embodiment, the aforementioned amount of the additional element is blended with at least one of HFO-1234yf and HFO-1234ze, and at least one hydrofluorocarbon selected from HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, and optionally combined with carbon dioxide, where either HFO-1234yf or HFO-1234ze is present in an amount of at least 99 weight percent or at least about 99.5 weight percent.

[0057] To avoid undesirable byproduct formation from oligomerization, homopolymerization, or polymerization of fluoroolefins such as HFO-1234yf, inhibitors such as terpenes, terpenoids, terpinene, linear unsaturated hydrocarbons, for example, those disclosed in U.S. Patent Application Publication Nos. 20210108119 and 2021004036 by the same applicant (the entire disclosures of each are incorporated herein by reference) are added.

[0058] To avoid oligomerization, homopolymerization, or the formation of oligomer / polymer by-products of fluoroolefins such as HFO-1234yf, inhibitors such as terpenes, terpenoids, terpinene, linear unsaturated hydrocarbons, for example, those disclosed in U.S. Patent Application Publication Nos. 20210108119 and 2021004036 by the same applicant (the entire disclosures of each are incorporated herein by reference), or xylene and methylstyrene inhibitors, for example, U.S. Provisional Patent Application Nos. 63 / 321118, titled "HYDROCARBON ADDITIVES FOR 1234 YF AND HFC COMPOSITIONS, METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE", and 63 / 321120, titled "HYDROCARBON ADDITIVES FOR 1234 YF COMPOSITION AND METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE" (each filed on March 18, 2022, the entire disclosures of each are incorporated herein by reference) are included.

[0059] "Inhibitor" means at least one compound according to the present invention that reduces, if not eliminates, the conversion of hydrofluoroolefins to oligomers or polymers. The oligomerization reaction, homopolymerization reaction, or polymerization reaction can be accelerated by relatively high temperatures, but such reactions can also occur under ambient conditions depending on the concentration and type of initiator (e.g., contaminants). The inhibitor can function as a radical inhibitor without affecting the cooling system.

[0060] However, these 1234yf inhibitor-containing compositions or blends react effectively with oxygen and / or function as a chain transfer agent to stop polymer chain growth, but the presence of the inhibitor may also reduce the purity of the refrigerant or refrigerant blend sent to the refrigerant system, depending on the level of inhibitor present. Thus, in certain embodiments, when introducing HFO-1234yf or an HFO-1234yf blend composition into a refrigerant system, the stored HFO-1234yf or HFO-1234yf-stabilized blend composition is passed through an absorbent bed such as silica gel to remove inhibitors and / or stabilizers and ensure that a high-purity HFO-1234yf or HFO-1234yf blend composition is sent to the refrigerant facility or system. An additional advantage is that silica gel can effectively remove water and reduce potential corrosion in the system.

[0061] Furthermore, the refrigerant facility may be provided with an oxygen removal subsystem that includes one or more oxygen removal devices, such as a tube or column filled or containing a material suitable for removing or excluding oxygen or oxidizing compounds by, for example, deoxygenation or other means, and a sensor for determining the presence of air or oxygen. The tube / column may be arranged in parallel or in series and may include a bypass line with a valve associated with or arranged in series with the cooling circuit, and the bypass line with a valve may optionally respond to the air / oxygen sensor alone or in combination with a moisture removal silica bed or drying medium and optionally an ultraviolet dye cartridge.

[0062] The oxygen removal tube / column generally contains a low-valent transition metal such as Cu that is operated at ambient temperature, and without affecting the fluorolefin molecule, preferentially forms a more stable Cu-F bond, for example, without cleaving the C-F bond, effectively reducing the oxygen level in the fluorolefin composition to less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, etc. The oxygen removal column includes a valve adapted to provide a regeneration medium to the column after use when there is a single or multiple columns. When there are multiple oxygen removal columns, an appropriate bypass line is included, whereby the system can remain online and another column can be regenerated while at least one column is operating. Other metal-containing reducing reagents can be used for this purpose, including Ti, V, Mn, Fe, Co, Zn, Ni, and Pd, as well as ascorbate. Other deoxidizers, such as polyhydroxybenzenes such as NaHSO3, Na2SO3, Na2S2O5, Na2S2O3, Na2S2O4, pyrogallol, Cr(II) salts, P(=O)H2OM, M = alkali metal, and alkaline earth metals, etc., may also be used.

[0063] Furthermore, the refrigerant facility described herein may include a system for removing oligomers / by-products from an HFO-1234yf or HFO-1234yf blend composition, with or without lubricating oil, and may include an oil return line so that the lubricating oil can be returned to the compressor. As used herein, oil return may refer to the ability of a heat transfer composition to carry a lubricant through a heat transfer system and return it to the compressor. That is, during use, it is not uncommon for a portion of the compressor lubricant to be carried from the compressor to other parts of the system by the heat transfer composition. In such a system, if the lubricant does not efficiently return to the compressor, ultimately, the compressor may fail due to insufficient lubrication.

[0064] In some embodiments, the lubricant is a mineral lubricant. In some embodiments, the mineral lubricant is selected from paraffin (such as straight-chain carbon-chain saturated hydrocarbons, branched-chain carbon saturated hydrocarbons, and mixtures thereof), naphthene (such as saturated cyclic and ring structures), aromatic compounds (containing unsaturated hydrocarbons containing one or more rings characterized by alternating carbon-carbon double bonds), and non-hydrocarbons (such as molecules containing atoms such as sulfur, nitrogen, oxygen, and mixtures thereof), and mixtures and combinations thereof.

[0065] Some embodiments may contain one or more synthetic lubricating oils. In some embodiments, the synthetic lubricating oil is an alkyl group-substituted aromatic compound (such as benzene or naphthalene substituted with a straight-chain alkyl group, a branched-chain alkyl group, or a mixture of straight-chain alkyl groups, a mixture of branched-chain alkyl groups) (often referred to as alkylbenzene), synthetic paraffin and naphthene, poly(α-olefin), polyglycol (such as polyalkylene glycol), dibasic acid ester, polyester, neopentyl ester, polyvinyl ether (PVE), silicone, silicate ester, fluoride, phosphate ester, polycarbonate, and mixtures thereof (meaning a mixture of any lubricant disclosed in this chapter).

[0066] The lubricants disclosed in this specification may be commercially available lubricants. For example, the lubricant may be paraffinic mineral oil sold by BVA Oil as BVM100N, naphthenic mineral oil sold by Crompton Co. under the trade names Suniso® 1GS, Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trade name Calumet® RO-30, linear alkylbenzene sold by Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150 and Zerol® 500, branched alkylbenzene sold by Nippon Oil as HAB22, polyol ester (POE) sold by Castrol (UK) under the trade name Castrol® 100, polyalkylene glycol (PAG) such as RL-488A of Dow (Dow Chemical, Midland, Michigan), and mixtures thereof (meaning any mixture of the lubricants disclosed in this paragraph).

[0067] The lubricant used with the present invention may be designed for use with hydrofluoroolefin and / or hydrofluorocarbon refrigerants and may also be compatible with the compositions disclosed herein under the operating conditions of compression cooling devices and air conditioning devices. In some embodiments, the lubricant is selected by considering the requirements of a given compressor and the environment to which the lubricant is exposed.

[0068] As used herein, a refrigerant container may be any closed device that maintains the supply of HFO-1234yf or an HFO-1234yf blend composition under pressure, with or without the use of an inhibitor, and examples include, but are not limited to, containers, canisters, tanks, cylinders, cooling devices, air conditioners, or containers later used in the cooling circuit of a heat pump device optionally including an oxygen or air sensor (not shown). Further, the refrigerant container may be a cooling circuit of a cooling device, an air conditioner, or a heat pump device in which a refrigerant or blend is used. Additionally, the refrigerant container may be a storage container or canister for fresh refrigerant, or a storage container or canister for recovering a recycled HFO-1234yf or HFO-1234yf blend composition.

[0069] As used herein, a cooling circuit may be part of any heat transfer system that is fixed in a stationary position during operation. A stationary heat transfer system may be installed within a building, attached to a building, otherwise associated with a building, or an independent device installed outdoors such as a soft drink vending machine. These stationary applications may include, but are not limited to, stationary air conditioning units and heat pumps, cryogenic coolers, high-temperature heat pumps, and residential, commercial, or industrial air conditioning systems (including residential heat pumps). In stationary refrigeration applications, the disclosed stabilized or purified compositions or blends may be useful in various items of equipment including: commercial, industrial, or residential refrigerators and freezers, ice machines, built-in coolers and freezers, flooded evaporator cryogenic coolers, direct expansion cryogenic coolers, walk-in and reach-in coolers and freezers, and combined systems. In some embodiments, the disclosed compositions may be used in supermarket cooling systems. Further, stationary applications may utilize a secondary loop system where a secondary fluid is cooled by a primary refrigerant and then the secondary fluid is pumped to a remote location to provide a cooling effect at that remote location.

[0070] As used herein, a cooling circuit may be part of a mobile heat transfer system and refers to any cooling, air conditioning, or heating device incorporated into a transportation unit for road, rail, marine, or air use, and includes the cooling circuit. Further, the mobile cooling or air conditioning unit is independent of any mobile carrier and includes devices well-known as "intermodal" systems. Such intermodal systems include "containers" (combined with marine / land transportation) and "swap bodies" (combined with road / rail transportation). Such mobile cooling.

[0071] A heat transfer medium (also referred to herein as a heat transfer fluid, heat transfer composition, heat transfer fluid composition, or refrigerant composition) is a working fluid used to transfer heat from a heat source to a heat sink.

[0072] As used herein, the term "lubricant" means a composition or any material added to a compressor (and contacting any heat transfer composition in use within any heat transfer system) that provides lubrication to the compressor to assist in preventing component seizure.

[0073] As used herein, a compatibilizer is a compound that improves the solubility of the hydrofluorocarbons of the disclosed compositions in a heat transfer system lubricant. In some embodiments, the compatibilizer improves oil return to the compressor. In some embodiments, the composition is used with a system lubricant to reduce the viscosity of the oil-rich phase.

[0074] One embodiment of the method of the present invention includes operating a refrigerant system facility as follows: a) providing a pressurized fluoroolefin refrigerant composition comprising at least one of HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, E / Z-R-1132, R-1132a, and HFC-227ea, and optionally carbon dioxide; b) discharging and passing the composition through a device containing a supported or unsupported oligomerization inhibitor selected from limonene, α - terpinene, and α - tocopherol, and mixtures of two or more thereof; c) adding up to 0.5 weight percent of the agent to the refrigerant composition to form a fluorolefin stabilized feedstock stabilized against at least one of oligomerization and polymerization; d) filling the refrigerant equipment with the fluorolefin stabilized feedstock of c).

[0075] One embodiment of another method of the present invention includes operating a refrigerant system equipment as follows: a) providing pressurized HFO - 1234yf; b) discharging the HFO - 1234yf and passing it through a device containing a supported or unsupported feed of an oligomerization inhibitor selected from d - limonene, l - limonene, β - pinene, α - pinene, α - terpinene, β - terpinene, γ - terpinene, and δ - terpinene, and mixtures of two or more thereof; c) adding up to 0.5 weight percent of the agent to the refrigerant composition to form an HFO - 1234yf feedstock stabilized against at least one of oligomerization and polymerization; d) filling the refrigerant equipment with the stabilized feedstock of c).

[0076] One embodiment of another method of the present invention includes operating a refrigerant system equipment as follows: a) providing pressurized HFO - 1234yf; b) discharging the HFO - 1234yf and i. alpha (α) - methylstyrene (C6H5C(CH3)=CH2), ii. α,2-dimethylstyrene (ortho (o)-alpha (α), 2-dimethylstyrene), iii. α,3-dimethylstyrene (meta (m)-, α,3-dimethylstyrene), iv. α,4-dimethylstyrene (p,α-dimethylstyrene), passing through a column containing a supported or unsupported feed of at least one oligomerization inhibitor selected from among these, c) adding up to 0.5 weight percent of said agent to the refrigerant composition to form a stabilized HFO-1234yf feedstock that is stabilized against at least one of oligomerization and polymerization, d) filling the refrigerant equipment with the stabilized feedstock of c).

[0077] Another method embodiment of the present invention involves maintaining the integrity of the refrigerant within a system having at least one cooling circuit by: · (1) providing at least one of a stabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions, or (2) an unstabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions, · (1) purifying by removing stabilizers from HFO-1234yf and HFO-1234ze refrigerant compositions, or (2) stabilizing by adding an effective amount of an oligomerization inhibitor to said unstabilized HFO-1234yf and HFO-1234ze refrigerant compositions, · (1) filling the cooling circuit after the stabilizers of the HFO-1234yf and HFO-1234ze refrigerant compositions have been removed, or (2) after an effective amount of an oligomerization inhibitor has been added to an unstabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions, · circulating the refrigerant in said filling circuit, and optionally, · removing moisture, oxygen, and one of oligomer products and by-products from the filled cooling circuit.

[0078] Another method embodiment of the present invention involves maintaining the integrity of the refrigerant in a system having at least one cooling circuit by: · removing moisture from the fully fluorinated olefin stabilized refrigerant in the circuit; · drying the fully fluorinated olefin stabilized refrigerant in the circuit; · optionally, detecting the presence of at least one of air, oxygen, and moisture; · removing oxygen and oxygen-containing compounds capable of initiating oligomerization and / or polymerization of fluorinated olefins in the fully fluorinated olefin stabilized feedstock in the circuit; · removing one of oligomerization polymerization products and by-products from the fully fluorinated olefin stabilized feedstock in the circuit.

[0079] In certain embodiments, the cooling facility includes at least one compressor, at least one evaporator, at least one condenser, at least one expansion device which can be an orifice, capillary tube or expansion valve, and optionally one or more devices for removing oxygen and / or moisture, such as tubes, columns, housings, and optionally at least one of the following: at least one supply valve for discharging a fluorinated olefin-containing composition to or from the cooling facility, a cooling circuit for transporting the fluorinated olefin-containing composition, a filling subsystem for the stabilized refrigerant and / or kit, a filling subsystem for the purified refrigerant, a subsystem for separating oligomers / polymers, an oligomer / polymer filter, and an oligomer / polymer filter derived from HFO-1234yf.

[0080] Disclosed herein is a filling subsystem for a stabilized refrigerant, including but not limited to, a mounting adapted to connect and fill a refrigerant circuit or cooling facility with a stabilized refrigerant, comprising: 1) a tank filled with HFO-1234yf and a cartridge supply of d-limonene; 2) A tank filled with HFO-1234yf and a cartridge supply of l-limonene, 3) A tank filled with HFO-1234yf and a cartridge supply of β-pinene, 4) A tank filled with HFO-1234yf and a cartridge supply of α-pinene, 5) A tank filled with HFO-1234yf and a cartridge supply of α-terpinene, 6) A tank filled with HFO-1234yf and a cartridge supply of β-terpinene, 7) A tank filled with HFO-1234yf and a cartridge supply of γ-terpinene, 8) A tank filled with HFO-1234yf and a cartridge supply of δ-terpinene, 9) A tank filled with HFO-1234yf and a cartridge supply of ethane, 10) A tank filled with HFO-1234yf and a cartridge supply of propane, 11) A tank filled with HFO-1234yf and a cartridge supply of cyclopropane, 12) A tank filled with HFO-1234yf and a cartridge supply of propylene, 13) A tank filled with HFO-1234yf and a cartridge supply of butane, 14) A tank filled with HFO-1234yf and a cartridge supply of butene, 15) A tank filled with HFO-1234yf and a cartridge supply of isobutane, 16) A tank filled with HFO-1234yf and a cartridge supply of isobutene, 17) A tank filled with HFO-1234yf and a cartridge supply of 2-methylbutane, 18) A tank filled with HFO-1234yf and a cartridge supply of meta-xylene, 19) A tank filled with HFO-1234yf and a cartridge supply of ortho-xylene, or A tank filled with HFO-1234yf, and a cartridge supply of para-xylene, wherein the tank optionally includes a sensor for detecting air and / or oxygen.

[0081] Disclosed herein is a stabilized refrigerant filling subsystem comprising, but not limited to, a mounting adapted to connect and fill a stabilized refrigerant to a refrigerant circuit or cooling facility: 1) A tank filled with HFO-1234ze, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234ze, and a cartridge supply of l-limonene, or 3) A tank filled with HFO-1234ze, and a cartridge supply of β-pinene, or 4) A tank filled with HFO-1234ze, and a cartridge supply of α-pinene, or 5) A tank filled with HFO-1234ze, and a cartridge supply of α-terpinene, or 6) A tank filled with HFO-1234ze, and a cartridge supply of β-terpinene, or 7) A tank filled with HFO-1234ze, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234ze, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234ze, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234ze, and a cartridge supply of propane, or 11) A tank filled with HFO-1234ze, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234ze, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234ze, and a cartridge supply of butane, or 14) A tank filled with HFO-1234ze, and a cartridge supply of butene, or 15) A tank filled with HFO-1234ze, and a cartridge supply of isobutane, or 16) A tank filled with HFO-1234ze, and a cartridge supply of isobutene, or 17) A tank filled with HFO-1234ze, and a cartridge supply of 2-methylbutane, or 18) A tank filled with HFO-1234ze, and a cartridge supply of meta-xylene, or 19) A tank filled with HFO-1234ze, and a cartridge supply of ortho-xylene, or 20) A tank filled with HFO-1234ze, and a cartridge supply of para-xylene, wherein Any one of tanks 1 to 20 optionally includes a sensor for detecting air and / or oxygen.

[0082] Disclosed herein is a filling subsystem for a stabilized refrigerant, which includes, but is not limited to, a mounting part adapted to connect and fill a stabilized refrigerant to a refrigerant circuit or a cooling facility: 1) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of l-limonene, or 3) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of β-pinene, or 4) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of α-pinene, or 5) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of α-terpinene, or 6) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of β-terpinene, or 7) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of propane, or 11) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of butane, or 14) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of butene, or 15) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of isobutene, or 16) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of 2-methylbutane, or 17) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of meta-xylene, or 18) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of ortho-xylene, or 19) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of para-xylene.

[0083] Disclosed herein is a stabilized refrigerant filling subsystem comprising a mounting portion adapted to connect and fill a stabilized refrigerant, including but not limited to the following, to a refrigerant circuit or cooling facility: 1) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of I-limonene, or 3) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of β-pinene, or 4) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of α-pinene, or 5) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of α-terpinene, or 6) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of β-terpinene, or 7) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of propane, or 11) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of butane, or 14) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of butene, or 15) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of isobutene, or 16) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of 2-methylbutane, or 17) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of meta-xylene, or 18) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of ortho-xylene, or 19) A tank filled with HFO-1234yf and HFC-32, and a cartridge supply of para-xylene, wherein the tank optionally includes a sensor for detecting air and / or oxygen.

[0084] Disclosed herein is a filling subsystem for a stabilized refrigerant, including but not limited to, a mounting portion adapted to connect and fill a stabilized refrigerant to a refrigerant circuit or cooling facility: 1) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of l-limonene, or 3) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of β-pinene, or 4) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of α-pinene, or 5) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of α-terpinene, or 6) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of β-terpinene, or 7) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of propane, or 11) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of butane, or 14) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of butene, or 15) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of isobutene, or 16) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of 2-methylbutane, or 17) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of meta-xylene, or 18) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of ortho-xylene, or 19) A tank filled with HFO-1234yf and HFC-125, and a cartridge supply of para-xylene, wherein any one of Tanks 1 to 19 optionally includes a sensor for detecting air and / or oxygen.

[0085] Disclosed herein is a stabilized refrigerant filling subsystem comprising a mounting portion adapted to connect and fill a stabilized refrigerant, including but not limited to the following, to a refrigerant circuit or a cooling facility: 1) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of l-limonene, or 3) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of β-pinene, or 4) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of α-pinene, or 5) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of α-terpinene, or 6) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of β-terpinene, or 7) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of propane, or 11) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of butane, or 14) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of butene, or 15) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of isobutene, or 16) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of 2-methylbutane, or 17) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of meta-xylene, or 18) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of ortho-xylene, or 19) A tank filled with HFO-1234yf, HFC-32, and HFC-125, and a cartridge supply of para-xylene, wherein any one of tanks 1 to 19 optionally includes a sensor for detecting air and / or oxygen.

[0086] Disclosed herein is a stabilized refrigerant filling subsystem comprising, but not limited to, a mounting portion adapted to connect and fill a stabilized refrigerant to a refrigerant circuit or cooling facility: 1) A tank filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of l-limonene, or 3) A tank filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of β-pinene, or 4) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of α-pinene, or 5) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of α-terpinene, or 6) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of β-terpinene, or 7) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of γ-terpinene, or 8) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of δ-terpinene, or 9) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of ethane, or 10) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of propane, or 11) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of cyclopropane, or 12) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of propylene, or 13) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of butane, or 14) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of butene, or 15) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of isobutene, or 16) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of 2-methylbutane, or 17) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of meta-xylene, or 18) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of ortho-xylene, or 19) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a, and a cartridge supply of para-xylene.

[0087] Disclosed herein is a stabilized refrigerant filling subsystem, including but not limited to, having a mounting portion adapted to connect and fill a stabilized refrigerant to a refrigerant circuit or cooling facility: 1) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of d-limonene, or 2) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of l-limonene, or 3) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of β-pinene, or 4) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of α-pinene, or 5) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of α-terpinene, or 6) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of β-terpinene, or 7) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of propane, or 11) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of butane, or 14) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of butene, or 15) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of isobutene, or 16) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of 2-methylbutane, or 17) A tank filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of meta-xylene, or 18) Tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of ortho-xylene, or tanks filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a, and a cartridge supply of para-xylene, wherein Any one of Tanks 1 to 18 optionally includes a sensor for detecting air and / or oxygen.

[0088] Disclosed herein is a stabilized refrigerant filling subsystem comprising, but not limited to, a mounting portion adapted to connect and fill a stabilized refrigerant to a refrigerant circuit or cooling facility: 1) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of d-limonene, or 2) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of l-limonene, or 3) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, HFO-1132a, and a cartridge supply of β-pinene, or 4) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, HFO-1132a, and a cartridge supply of α-pinene, or 5) A tank filled with HFO-1234yf and HFO-1234ze, and a cartridge supply of α-terpinene, or 6) A tank filled with HFO-1234yf and, optionally, at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of β-terpinene, or 7) A tank filled with HFO-1234yf and, optionally, at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of γ-terpinene, or 8) A tank filled with HFO-1234yf and, optionally, at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of δ-terpinene, or 9) A tank filled with HFO-1234yf and, optionally, at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of ethane, or 10) A tank filled with HFO-1234yf and, optionally, at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of propane, or 11) A tank filled with HFO-1234yf and, optionally, at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of cyclopropane, or 12) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of propylene, or 13) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of butane, or 14) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of butene, or 15) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of isobutene, or 16) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of 2-methylbutane, or 17) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of meta-xylene and 18) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of ortho-xylene, or 19) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, and HFO-1132a, and a cartridge supply of para-xylene.

[0089] In one embodiment, the cooling circuit includes a first supply valve and a second supply valve, and a filling subsystem for the stabilized refrigerant. The filling subsystem includes a built-in pressurization source for the fluoroolefin refrigerant composition, a flow-through cartridge, and an oligomerization / polymerization inhibitor for stabilizing the fluoroolefin refrigerant composition. The cartridge has an outlet connected to the high-pressure side of the supply valve for filling the circuit with the stabilized fluoroolefin refrigerant and is in fluid communication therewith. The circuit is a closed loop.

[0090] In one embodiment, the refrigerant line of the cooling facility or the refrigerant line of the refrigerant circuit includes at least one of the following a), b), c), and d) in series or in parallel, or is retrofitted to include them: a) A flow-through treatment zone containing a material for drying the refrigerant composition or blend and / or optionally containing a deoxygenation reagent suitable for removing oxygen from the fluoroolefin-containing mixture at room temperature, for example, 20 °C to 30 °C. Each treatment zone or combination of treatment zones can be regenerated. Reagents that can be used for removing oxygen include, but are not limited to, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd, and ascorbate. b) A tube, capsule, or cartridge of an oligomer-inhibiting stabilizer, where the stabilizer is supported on pellets or other inert media or not supported, for example, a self-standing solid or liquid that is added to the refrigerant composition or blend by a fluorolefin stream. Inhibitors described in U.S. Patent Application Publication Nos. 20210108119 and 202100430368, and various oligomer or polymer-inhibiting stabilizers including, but not limited to, d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more of these. c) A device for removing moisture. d) A separation filter system for removing oligomer / polymer products and / or by-products that may form during the circulation of the refrigerant composition or blend.

[0091] In other embodiments, the refrigerant line of a mobile cooling facility or the refrigerant line of a mobile refrigerant circuit includes at least one of the following a), b), c), and d) in series or in parallel, or is modified to include them. a) A through-flow treatment zone that contains a material for drying the refrigerant composition or blend and / or optionally contains a deoxygenation reagent suitable for removing oxygen from a fluorolefin-containing mixture at room temperature, for example, from 20 °C to 30 °C. Each treatment zone or combination of treatment zones can be regenerated. Reagents that can be used for removing oxygen include, but are not limited to, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd, and ascorbate. b) A tube, capsule, or cartridge of an oligomer-inhibiting stabilizer, wherein the stabilizer is supported on pellets or other inert media or is not supported, for example, a self-standing solid or liquid that is added to a refrigerant composition or blend by a fluorinated olefin stream. Inhibitors described in U.S. Patent Application Publication Nos. 20210108119 and 202100430368, and various oligomer or polymer-inhibiting stabilizers including, but not limited to, d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, c) A device for removing moisture, d) A separation filter system for removing oligomer / polymer products and / or by-products that may form during the circulation of the refrigerant composition or blend.

[0092] In still other embodiments disclosed herein, the transport means mobile cooling system is transported to a supply center having a Recover, Recycling and Recharge machine (RRRM) and (1) adds a stabilizer to a source of filled HFO-1234yf or HFO-1234yf blend, (2) removes the stabilizer from the filled stabilized HFO-1234yf or stabilized HFO-1234yf blend, (3) can be attached to an Opteon™ product, or a stabilizer injection kit for a system operating with R448A, or connected to one or more of the systems for injecting the stabilizer into the system.

[0093] One embodiment of the present invention is a cooling system having a built-in pressure source for a fluoroolefin containing at least 2,3,3,3 - tetrafluoropropene, and a refrigerant circuit through which a refrigerant can circulate. The circuit includes at least a first in-line filling valve, a first flow line that provides a fluid-controlled flow between the refrigerant circuit and the pressurization processing unit, a second flow line that provides a fluid-controlled flow between the processing unit and the first in-line filling valve on the downstream side of the compressor, and at least one or more in-line through-flow oxygen removal tubes / columns, optionally at room temperature, for example, 20°C to 30°C, suitable for removing oxygen and oxidizing compounds from the fluoroolefin-containing mixture, including but not limited to zero-valent or low-valent transition metals and reduced oxides of transition metals, where the transition metal is selected from the group including Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd. The zero-valent or low-valent transition metals and reduced oxides of transition metals may be commercially available or may be prepared by heating transition metal oxides in the presence of a reducing agent such as hydrogen at a high temperature (100°C to 300°C) in a container such as a tube or column. Suitable metal oxides for such reduction include, for example, CuO, TiO2, V2O5, Mn2O3, Fe2O3, Co3O4, ZnO, NiO, PdO. Other oxygen removal reagents include solutions of polyhydroxybenzene compounds such as ascorbate, NaHSO4, Na2SO3, Na2S2O5, Na2S2O3, Na2S2O2, pyrogallol, Ti(III) salts, Cr(II) salts, Sn(II) salts, Fe(II) salts, nitrites, and hypophosphites. The removal of oxygen from the fluoroolefin composition may be carried out by passing the fluoroolefin mixture through the tube / column or bed of the oxygen removal agent(s) at about 20°C to about 30°C.

[0094] Although several metals / metal oxides are well known as oxygen scavengers, generally, these compounds are very reactive towards fluoroolefins based on the technical literature. Surprisingly, certain reduced metal oxides of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd perform the intended function of removing oxygen without cleaving the C-F bond in 2,3,3,3-tetrafluoropropene or other fluoroolefins. The metals / metal oxides present in well-known oxygen scavengers are used to cleave the C-F bond to form a more stable metal fluoride bond and can remove oxygen without the expected C-F bond cleavage. The cleavage of the C-F bond in fluoroolefins (C=C-F) is very common. The metal-fluorine bond (e.g., Cu-F about 431 kJ / mol) is more stable than the metal-oxygen (e.g., Cu-O about 343 kJ / mol) bond, and thus, there is an energy driving force for the reaction between the metal oxide (product of oxygen capture) and the organic fluorine compound. Therefore, it was not expected and not obvious that a material useful for scrubbing oxygen from inert gases (Ar, N2), hydrocarbons, and regular olefins (ethylene, propylene) could remove oxygen contaminants from 2,3,3,3-tetrafluoropropene.

[0095] In other embodiments, a stored fresh HFO-1234yf or HFO-1234yf blend composition containing a stabilizer can be passed through a filter capable of removing the stabilizer from the HFO-1234yf or HFO-1234yf blend composition to provide a high-purity HFO-1234yf or HFO-1234yf blend composition, which can be filled into the refrigerant equipment and systems described herein, and the circulating composition can be passed through an absorbent filter bed such as silica gel that can remove inhibitors, their oxidation derivatives, and water to reduce potential corrosion in the system.

[0096] Another embodiment of the present invention is a refrigerant filling kit including, within a canister, a sealed stabilized fluoroolefin-containing composition including HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea, and optionally carbon dioxide, and a refrigerant filling kit including a sealed refrigerant canister containing a stabilized fluoroolefin composition (the composition including at least HFO-1234yf as a refrigerant component and up to 0.5 weight percent of an oligomer inhibitor including at least one of d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene), and a tube for connecting the discharge end of the refrigerant canister to a valve of a refrigerant circuit. In certain embodiments, any of the lubricants described above can be included in the stabilized refrigerant blend. Thus, the refrigerant filling kit can include any of the disclosed refrigerant blends that are stabilized but do not include a lubricant.

[0097] An embodiment of the injector kit of the present invention includes a fixture (including but not limited to the following) adapted to connect a stabilizer containing a lubricant to a cooling facility. a. A canister filled with a POE lubricant and up to 0.5 weight percent d-limonene. b. A canister filled with a POE lubricant and up to 0.5 weight percent l-limonene. c. A canister filled with a POE lubricant and up to 0.5 weight percent β-pinene. d. A canister filled with a POE lubricant and up to 0.5 weight percent α-pinene. e. A canister filled with a POE lubricant and up to 0.5 weight percent α-terpinene. f. A canister filled with a POE lubricant and up to 0.5 weight percent β-terpinene. g. A canister filled with a POE lubricant and up to 0.5 weight percent γ-terpinene. h. A canister filled with a POE lubricant and up to 0.5 wt% of δ - terpinene i. A canister filled with a POE lubricant and up to 0.5 wt% of ethane j. A canister filled with a POE lubricant and up to 0.5 wt% of propane k. A canister filled with a POE lubricant and up to 0.5 wt% of cyclopropane l. A canister filled with a POE lubricant and up to 0.5 wt% of propylene m. A canister filled with a POE lubricant and up to 0.5 wt% of butane n. A canister filled with a POE lubricant and up to 0.5 wt% of butene o. A canister filled with a POE lubricant and up to 0.5 wt% of isobutene p. A canister filled with a POE lubricant and up to 0.5 wt% of isobutene q. A canister filled with a POE lubricant and up to 0.5 wt% of methylbutane r. A canister filled with a POE lubricant and up to 0.5 wt% of meta - xylene s. A canister filled with a POE lubricant and up to 0.5 wt% of ortho - xylene t. A canister filled with a POE lubricant and up to 0.5 wt% of para - xylene u. A canister filled with a mineral oil lubricant and up to 0.5 wt% of d - limonene v. A canister filled with a mineral oil lubricant and up to 0.5 wt% of l - limonene w. A canister filled with a mineral oil lubricant and up to 0.5 wt% of β - pinene x. A canister filled with a mineral oil lubricant and up to 0.5 wt% of α - pinene y. A canister filled with a mineral oil lubricant and up to 0.5 wt% of α - terpinene z. A canister filled with a mineral oil lubricant and up to 0.5 wt% of β - terpinene aa. A canister filled with a mineral oil lubricant and up to 0.5 wt% of γ - terpinene bb. A canister filled with a mineral oil lubricant and up to 0.5 wt% of δ - terpinene cc. A canister filled with a mineral oil lubricant and up to 0.5 wt% of ethane dd. A canister filled with a mineral oil lubricant and up to 0.5 wt% of propane ee. A canister filled with a mineral oil lubricant and up to 0.5 wt% of cyclopropane ff. A canister filled with a mineral oil lubricant and up to 0.5 wt% of propylene gg. A canister filled with a mineral oil lubricant and up to 0.5 wt% of butane hh. A canister filled with a mineral oil lubricant and up to 0.5 wt% of butene ii. A canister filled with a mineral oil lubricant and up to 0.5 wt% of isobutane jj. A canister filled with a mineral oil lubricant and up to 0.5 wt% of isobutene kk. A canister filled with a mineral oil lubricant and up to 0.5 wt% of 2 - methylbutane ll. A canister filled with a mineral oil lubricant and up to 0.5 wt% of meta - xylene mm. A canister filled with a mineral oil lubricant and up to 0.5 wt% of ortho - xylene nn. A canister filled with a mineral oil lubricant and up to 0.5 wt% of para - xylene oo. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of d - limonene pp. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of l - limonene qq. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of β - pinene rr. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of α - pinene ss. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of α - terpinene tt. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of β - terpinene uu. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of γ - terpinene vv. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of δ - terpinene ww. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of ethane xx. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of propane yy. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of cyclopropane zz. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of propylene aaa. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of butane bbb. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of butene ccc. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of isobutene ddd. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of isobutane eee. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of 2 - methylbutane fff. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of meta - xylene ggg. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of ortho - xylene hhh. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of para - xylene

[0098] Embodiments of the injector kit of the present invention comprise a fixture adapted to connect a stabilizer containing a refrigerant composition (including but not limited to the following). a. A canister filled with a POE lubricant and up to 0.5 wt% of d-limonene b. A canister filled with a POE lubricant and up to 0.5 wt% of l-limonene c. A canister filled with a POE lubricant and up to 0.5 wt% of β-pinene d. A canister filled with a POE lubricant and up to 0.5 wt% of α-pinene e. A canister filled with a POE lubricant and up to 0.5 wt% of α-terpinene f. A canister filled with a POE lubricant and up to 0.5 wt% of β-terpinene g. A canister filled with a POE lubricant and up to 0.5 wt% of γ-terpinene h. A canister filled with a POE lubricant and up to 0.5 wt% of δ-terpinene i. A canister filled with a POE lubricant and up to 0.5 wt% of ethane j. A canister filled with a POE lubricant and up to 0.5 wt% of propane k. A canister filled with a POE lubricant and up to 0.5 wt% of cyclopropane l. A canister filled with a POE lubricant and up to 0.5 wt% of propylene m. A canister filled with a POE lubricant and up to 0.5 wt% of butane n. A canister filled with a POE lubricant and up to 0.5 wt% of butene o. A canister filled with a POE lubricant and up to 0.5 wt% of isobutene p. A canister filled with a POE lubricant and up to 0.5 wt% of methylbutane q. A canister filled with a POE lubricant and up to 0.5 wt% of meta-xylene r. A canister filled with a POE lubricant and up to 0.5 wt% of ortho-xylene s. A canister filled with a POE lubricant and up to 0.5 wt% of para-xylene t. A canister filled with mineral oil lubricant and up to 0.5 wt% of d - limonene u. A canister filled with mineral oil lubricant and up to 0.5 wt% of l - limonene v. A canister filled with mineral oil lubricant and up to 0.5 wt% of β - pinene w. A canister filled with mineral oil lubricant and up to 0.5 wt% of α - pinene x. A canister filled with mineral oil lubricant and up to 0.5 wt% of α - terpinene y. A canister filled with mineral oil lubricant and up to 0.5 wt% of β - terpinene z. A canister filled with mineral oil lubricant and up to 0.5 wt% of γ - terpinene aa. A canister filled with mineral oil lubricant and up to 0.5 wt% of δ - terpinene bb. A canister filled with mineral oil lubricant and up to 0.5 wt% of ethane cc. A canister filled with mineral oil lubricant and up to 0.5 wt% of propane dd. A canister filled with mineral oil lubricant and up to 0.5 wt% of cyclopropane ee. A canister filled with mineral oil lubricant and up to 0.5 wt% of propylene ff. A canister filled with mineral oil lubricant and up to 0.5 wt% of butane gg. A canister filled with mineral oil lubricant and up to 0.5 wt% of butene hh. A canister filled with mineral oil lubricant and up to 0.5 wt% of isobutene ii. A canister filled with mineral oil lubricant and up to 0.5 wt% of 2 - methylbutane jj. A canister filled with mineral oil lubricant and up to 0.5 wt% of meta - xylene kk. A canister filled with mineral oil lubricant and up to 0.5 wt% of ortho - xylene ll. A canister filled with mineral oil lubricant and up to 0.5 wt% of para - xylene Canister filled with mm. alkylbenzene lubricant and up to 0.5 wt% of d-limonene Canister filled with nn. alkylbenzene lubricant and up to 0.5 wt% of l-limonene Canister filled with oo. alkylbenzene lubricant and up to 0.5 wt% of β-pinene Canister filled with pp. alkylbenzene lubricant and up to 0.5 wt% of α-pinene Canister filled with qq. alkylbenzene lubricant and up to 0.5 wt% of α-terpinene Canister filled with rr. alkylbenzene lubricant and up to 0.5 wt% of β-terpinene Canister filled with ss. alkylbenzene lubricant and up to 0.5 wt% of γ-terpinene Canister filled with tt. alkylbenzene lubricant and up to 0.5 wt% of δ-terpinene Canister filled with uu. alkylbenzene lubricant and up to 0.5 wt% of ethane Canister filled with vv. alkylbenzene lubricant and up to 0.5 wt% of propane Canister filled with ww. alkylbenzene lubricant and up to 0.5 wt% of cyclopropane Canister filled with xx. alkylbenzene lubricant and up to 0.5 wt% of propylene Canister filled with yy. alkylbenzene lubricant and up to 0.5 wt% of butane Canister filled with zz. alkylbenzene lubricant and up to 0.5 wt% of butene Canister filled with aaa. alkylbenzene lubricant and up to 0.5 wt% of isobutane Canister filled with bbb. alkylbenzene lubricant and up to 0.5 wt% of isobutene Canister filled with ccc. alkylbenzene lubricant and up to 0.5 wt% of 2-methylbutane ddd. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of meta - xylene, eee. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of ortho - xylene, or fff. A canister filled with an alkylbenzene lubricant and up to 0.5 wt% of para - xylene.

[0099] Here, embodiments of the present invention will be described with reference to non - limiting drawings. FIG. 1 illustrates a first system embodiment 100 for adding a stabilizer to the HFO - 1234yf or HFO - 1234yf blend described herein. The canister 105 with a valve contains the HFO - 1234yf or HFO - 1234yf blend and is in fluid communication with the inlet side of the stabilizer cartridge 110. When the valve 115 is opened, the pressurized HFO - 1234yf or HFO - 1234yf blend flows through the cartridge 110, picks up the inhibitor, and provides an HFO - 1234yf composition containing an inhibitor of 0.5 wt% or less, an inhibitor of 0.001 - 0.1 wt%, an inhibitor of 0.001 - 0.2 wt%, an inhibitor of 0.001 - 0.3 wt%, an inhibitor of 0.001 - 0.4 wt%, an inhibitor of 0.001 - 0.01 wt%, an inhibitor of 0.001 - 0.02 wt%, an inhibitor of 0.001 - 0.03 wt%, an inhibitor of 0.001 - 0.04 wt%, an inhibitor of 0.001 - 0.05 wt%, an inhibitor between 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 and 0.1 weight percent, and an inhibitor between 0.01 - 0.05 weight percent, and all values and ranges therebetween.

[0100] The cooling circuit 101 generally sequentially includes devices such as a high-pressure side supply valve 115, a filter / dryer 120, an expansion valve 125, an evaporator 130, a low-pressure side supply valve 135, a compressor 140, and a condenser 145 when a change in the refrigerant phase is involved. However, if the refrigerant circuit does not rely on changing the phase of the refrigerant to transfer energy, there will be fewer components included. The order of components 115, 120, 125, 135, 140, 145 can be arranged as shown, but may include additional components if necessary. Once stabilized, the 1234yf refrigerant exits the cartridge 110, passes through the high-pressure side supply valve 115, and is metered / filled into the cooling circuit 101. Next, the stabilized refrigerant sequentially flows through a filter / dryer 120, devices such as an expansion valve 125, an evaporator 130, a low-pressure side supply valve 135, and a compressor 140. Then, the compressed and stabilized refrigerant passes through a heat exchanger / condenser 145, then through the valve 115, and is recycled. Alternatively, the liquid refrigerant may be throttled through a low-pressure side supply valve 135 disposed upstream of the compressor. The cartridge 110 includes, but is not limited to, at least one of the various oligomer or polymer inhibitor stabilizers described above, including d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene (including mixtures of two or more). The cooling circuit 101 may be a new, existing, or retrofitted system and requires a fresh fill of refrigerant, additional refrigerant, replacement refrigerant, or an initial supply of refrigerant, etc.

[0101] A single "stabilizer" cartridge 110 or filter / dryer 120 is shown, but multiple cartridges 110 containing the same or different inhibitors, and / or multiple filter / dryers 120 containing different filter media and arranged in series or parallel, may be used. Two stabilization cartridges may be arranged in series / sequentially with a bypass line (not shown) such that the refrigerant flowing from the tank 105 flows through the first cartridge 110 but bypasses the second stabilization cartridge. Alternatively, the refrigerant from the tank 105 may flow through the first cartridge 110 and then bypass the second cartridge.

[0102] Figure 2 shows a second system embodiment 200 for removing stabilizers from a stabilized HFO-1234yf or stabilized HFO-1234yf blend composition refrigerant to provide a high-purity HFO-1234yf or HFO-1234yf blend composition prior to filling the purified refrigerant into the cooling circuit. Here, a refrigerant cylinder / canister filled with liquid refrigerant is shown for the high-pressure side supply valve 215. Alternatively, the liquid refrigerant may be throttled through a low-pressure side supply valve (not shown) disposed upstream of the compressor. In this case, the valve canister 205 optionally contains a stabilized HFO-1234yf with or without HFO-1234ze containing additional refrigerant components and is disposed in fluid communication with the inlet side of a stabilizer removal column / filter 250 described herein, e.g., a silica bed capable of removing the inhibitors described herein. The cooling circuit 201 sequentially includes a supply valve 215, a filter 220, an expansion device 255, e.g., an expansion valve, an evaporator 230, a compressor 240, and a heat exchanger / condenser 245. When the canister valve (not shown) is opened, the liquid HFO-1234yf, or an HFO-1234yf blend refrigerant containing, e.g., HFO-1234ze, flows to and passes through the filter 250 to remove the stabilizer. Although a single filter is shown, multiple filters in series or parallel including a bypass line (not shown) may also be used.

[0103] FIG. 3 illustrates Embodiment 300 that uses a stand-alone filter for O2 removal in the system and / or uses a polymer / filter in the compressor suction line. A bypass line with a valve is shown around both the O2 and polymer filters for actual removal and replacement in the system and to illustrate the concept that they may only be needed in certain situations. Also, the cooling circuit 301 may be provided with a refrigerant cylinder (not shown) for filling the liquid to a high-pressure side supply valve (not shown) downstream of the heat exchanger / condenser 345. Alternatively, liquid HFO-1234yf, or an HFO-1234yf blend containing, for example, HFO-1234ze may also be throttled and a low-pressure side supply valve may be utilized (not shown). Alternatively, integrating the filter / dryer 320 and the O2 filter 316 into one package (not shown), moving the polymer filter 317 upstream of a device such as an expansion valve, e.g., valve 365, or integrating all three filters 320, 316, and 317 into one package and placing it upstream of the expansion device 365 is included. As shown in FIG. 3, the cooling circuit 301 comprises a filter / dryer 320 and an O2 filter 316 with a valve 360 and an optional controller (not shown) for controlling the fluid flow, an expansion device such as valve 365, an evaporator 330, a polymer filter 317 with a valve 361 and an optional controller (not shown) for controlling the fluid flow, a compressor 340, and a heat exchanger / condenser 345, in sequence.

[0104] FIG. 4 shows Embodiment 400 that includes an integrated oil separator / polymer filter 470 for the oil in the return line 471 that returns the oil to the compressor 440. The cooling circuit 401 comprises a filter / dryer 420, a device 465 such as an expansion valve, an evaporator 430, a compressor 440, an integrated oil separator / polymer filter 470 and a return line 471, and a heat exchanger / compressor 445, in sequence.

[0105] FIG. 5 is similar to FIG. 4, but shows Embodiment 500 which uses an integrated oil / polymer filter 575 for the flow of compressor oil from the oil sump of the compressor to the lubricating surfaces of the compressor via a shaft drive or / and an external oil pump. The cooling circuit 501 sequentially includes a filter / dryer 520, an expansion device such as a valve 565, an evaporator 530, a compressor 540, an integrated oil separator / polymer filter 575 and a return line 571, and a heat exchanger / compressor 545.

[0106] FIG. 6 shows Embodiment 600 of an integrated system including a cooling circuit 601 with a stabilizer injection kit 680 for system operation with Opteon® products or R448A, either already filled with refrigerant or with more stabilizer added to the system in some other way. The injection will be into the system via a low-pressure side supply valve 635 or any other suitable location.

[0107] The cooling circuit 601 sequentially includes a filter / dryer 620, a device such as an expansion valve 665, an evaporator 630, a low-pressure side supply valve 635, a stabilizer injection kit 680, a compressor 640, a heat exchanger 645, and a supply valve 615. The kit 680 contains one of a stabilized lubricant, a stabilized HFO-1234yf, or an HFO-1234yf blend containing, for example, HFO-1234ze, a refrigerant, and a stabilized refrigerant / lubricant mixture. The stabilizer is selected from d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, or ethane, propane, cyclopropane, propylene, and a canister filled with an alkylbenzene lubricant, and up to 0.5 wt% of isobutene, 2-methylbutane, ortho-xylene, or para-xylene, α-methylstyrene, and α,2-imethylstyrene, α,3-dimethylstyrene, or α,4-dimethylstyrene in an amount effective to reduce or eliminate oligomerization / polymerization of the HFO-1234yf component of the refrigerant, for example, in an amount of 0.02 to 0.3 weight percent.

[0108] In certain embodiments disclosed herein, at least a) one supply valve adapted to fill a refrigerant circuit with a fluoroolefin refrigerant composition, b) a filling subsystem for a stabilized refrigerant, optionally a filling subsystem for a purified refrigerant including an air / oxygen detector, d) optionally a subsystem for removing oxygen and / or oxidizing compounds including an oxygen scavenger responsive to the air / oxygen detector, e) a subsystem for separating oligomers / polymers, and f) an oligomer / polymer filter may be added to an existing appearance as separate components or as an integrated system.

[0109] Examples 1 - 4 An Inconel tube (registered trademark) (0.5 inch outer diameter, 15 inches long, 0.34 inch wall thickness) was filled with 8 cc of CuO (40 wt%) on Al2O3. The catalyst was reduced in a Lindberg furnace with 50 sccm of H2 / N2 (50% H2) at 175 o °C for 8 hours. After the reactor was cooled to room temperature, CF3CF=CH2 (HFO-1234yf) containing different concentrations of air was fed at 10 - 20 sccm (standard cubic centimeters per minute). During operation, the air concentration was measured by GC, showing that the O2 concentration was less than 5 ppm.

[0110] [Table 2]

[0111] Examples 5 - 10 30 g of HFO-1234yf containing various concentrations of d-limonene was passed through 20 g of silica gel (200 mesh) or 50 mL of mineral oil. GC indicated that the residual inhibitor content was less than 5 ppm.

[0112] [Table 3]

[0113] Although certain aspects, embodiments, and principles have been described above, it is understood that this specification has been made for illustrative purposes only and is not intended to limit the scope of the present invention or the appended claims. The various aspects, embodiments, and principles described above may be used alone and in combination with each other.

Claims

1. A refrigerant system comprising a cooling circuit for transporting a fluoroolefin refrigerant composition, said refrigerant circuit comprising at least one compressor, at least one expansion device, at least one evaporator, at least one condenser, at least one dryer for removing moisture, and optionally, a) at least one supply valve configured to fill the refrigerant circuit with a fluoroolefin refrigerant composition, b) a filling subsystem for a stabilized refrigerant, c) a filling subsystem for a purified refrigerant, optionally including an air / oxygen detector, d) a subsystem for removing oxygen and / or oxidizing compounds, optionally including a deoxidizer that responds to said air / oxygen detector, e) a subsystem for separating oligomers / polymers, f) an oligomer / polymer filter, and comprising at least one component selected from the group consisting of.

2. The cooling circuit is a closed loop, contains the fluoroolefin refrigerant composition, and the fluoroolefin refrigerant composition is at least one of HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, E / Z-R-1132, and HFC-227ea, optionally carbon dioxide, The refrigerant system according to claim 1.

3. The refrigerant system according to claim 1, wherein said at least one dryer for removing moisture is a single filter dryer.

4. The refrigerant system according to claim 1, wherein said at least one dryer is a single dryer containing an absorbent bed for removing moisture.

5. The refrigerant system according to claim 1, wherein said at least one dryer is a single column containing a filter section and a dryer section.

6. The cooling circuit includes a first supply valve and a second supply valve, and a stabilized refrigerant filling subsystem, the filling subsystem including a built-in pressurization source for a fluoroolefin refrigerant composition, a flow-through cartridge, and an oligomerization inhibitor / polymerization inhibitor for stabilizing the fluoroolefin refrigerant composition, the flow-through cartridge having an outlet connected to the high-pressure side of the supply valve for filling the circuit with the stabilized fluoroolefin refrigerant and in fluid communication therewith, the refrigerant system according to claim 1.

7. The cooling circuit includes a first supply valve and a filling subsystem for a purified refrigerant, the filling subsystem including a built-in pressurization source for a stabilizer-containing fluoroolefin refrigerant composition in fluid communication with a separation column for removing the stabilizer and providing a purified stabilizer-free fluoroolefin refrigerant composition, the column having an outlet connected to the high-pressure side of the first supply valve and in fluid communication therewith, the cooling system according to claim 1.

8. There is a single compressor having an outlet, connected to and in fluid communication with a polymer separator, the refrigerant system according to claim 1.

9. The refrigerant system according to claim 7, further comprising a second supply valve and a subsystem for filling the low-pressure side of the second supply valve with a stabilized fluoroolefin refrigerant composition.

10. The refrigerant system according to claim 1, wherein a plurality of moisture removal dryers are arranged in series in fluid communication with the circuit.

11. The refrigerant system according to claim 1, wherein a plurality of moisture removal dryers are arranged in series and in fluid communication with the circuit, and the circuit optionally includes a valved bypass for a second moisture removal dryer.

12. A process for operating a refrigerant facility, a) providing a fluoroolefin refrigerant composition and optionally a lubricant, the fluoroolefin refrigerant composition including at least one of HFO-1234yf and HFO-1234ze, and optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, E / Z-R-1132, R-1132a, and HFC-227ea, and optionally carbon dioxide, in a step. b) A step of discharging the fluorinated olefin refrigerant composition and passing it through a column containing the supported oligomerization inhibitor / polymerization inhibitor, wherein the oligomerization inhibitor / the polymerization inhibitor is selected from the group consisting of limonene, α-terpinene, and α-tocopherol, and at least one element selected from the group consisting of mixtures of two or more of these. c) A step of adding up to 0.5 weight percent of the oligomerization inhibitor / polymerization inhibitor to the fluorinated olefin refrigerant composition to form a fluorinated olefin stabilized feedstock stabilized against oligomerization and / or polymerization. d) A step of filling the refrigerant equipment with the fluorinated olefin stabilized feedstock of c). A process comprising the above steps.

13. The process according to claim 12, wherein the refrigerant equipment includes a refrigerant circuit, and step d) includes a step of directly filling the refrigerant circuit with the fluorinated olefin stabilized feedstock of c).

14. The process according to claim 12, wherein the column is a cartridge.

15. The process according to claim 13, wherein the cartridge contains an inert material that supports the oligomerization inhibitor / polymerization inhibitor.

16. The oligomerization inhibitor / polymerization inhibitor is in liquid form, and the cartridge is configured to allow the fluorinated olefin refrigerant composition to pass through under the transport force of the fluorinated olefin refrigerant composition and add up to 0.5 weight percent of the oligomerization inhibitor / polymerization inhibitor to the fluorinated olefin refrigerant composition. The process according to claim 13.

17. The process according to claim 16, further comprising a step of circulating the filled fluorinated olefin stabilized feedstock within the refrigerant equipment.

18. The cooling equipment includes a cooling circuit in which the fluorinated olefin stabilized feedstock continuously circulates, and the process includes the following steps: a) A step of removing moisture from the fluorinated olefin stabilized feedstock within the circuit. b) A step of drying the fluorinated olefin stabilized feedstock within the circuit. c) A step of removing oxygen and oxidizing compounds capable of initiating fluorolefin oligomerization and / or polymerization in the fluorolefin stabilization feedstock in the circuit, optionally responding to an air / oxygen detector associated with the cooling circuit or the vapor space in the fluorolefin stabilization feedstock; d) A step of removing one of the oligomerization polymerization products and by-products from the fluorolefin stabilization feedstock in the circuit; The process according to any one of claims 16 or 17, further comprising at least one of the above.

19. The process according to claim 18, comprising a step of removing moisture from the fluorolefin stabilization feedstock in the circuit.

20. The process according to claim 12, wherein the oligomerization inhibitor / polymerization inhibitor comprises an element selected from the group consisting of limonene, α-terpinene, and α-tocopherol, and mixtures of two or more thereof.

21. The fluorolefin refrigerant composition i. A fluorolefin containing at least HFO-1234yf; ii. Optionally, an HFC containing at least one of HFC-32, HFC-125, and HFC-134a; The process according to claim 12, comprising the above.

22. A method for maintaining the integrity of a refrigerant in a system having at least a cooling circuit, the method comprising: - (1) Providing at least one of a stabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions, or (2) an unstabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions; - (1) A step of purifying by removing stabilizers from HFO-1234yf and HFO-1234ze refrigerant compositions, or (2) a step of stabilizing by adding an effective amount of an oligomerization inhibitor to the unstabilized HFO-1234yf and HFO-1234ze refrigerant compositions, and subsequently filling the cooling circuit with (1) or (2); - A step of circulating the refrigerant in the filled cooling circuit, optionally - A step of removing moisture, oxygen, and one of the oligomer products and by-products from the filled cooling circuit; A method comprising the above.

23. A method for maintaining the integrity of a refrigerant within a system having at least a cooling circuit, the method comprising: - Continuously circulating a fluorolefin-containing refrigerant composition in the cooling circuit; - Passing the circulating fluorolefin-containing refrigerant composition through at least one moisture removal dryer, at least one oxygen removal column, and at least one oligomer product or polymer product or by-product filter / separator. A method comprising the above steps. **Claim 24** The method according to claim 23, wherein the fluorolefin-containing refrigerant composition comprises at least one of HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, and optionally carbon dioxide. **Claim 25** The method according to claim 23, wherein the system is filled with a stabilized source of HFO-1234yf and HFO-1234ze tetrafluoropropene, and the stabilizer inhibits oligomerization / polymerization of the tetrafluoropropene. **Claim 26** The process according to claim 23, wherein the step of passing the circulating fluorolefin-containing refrigerant composition through the moisture removal dryer and the oxygen removal column is performed upstream of a compressor in the refrigerant circuit. **Claim 27** The process according to claim 26, wherein the discharge from the compressor passes through the oligomer product or polymer product or by-product separator / filter. **Claim 28** a) A pressurized source of fluorolefins comprising at least 2,3,3,3-tetrafluoropropene; b) A refrigerant circuit configured to circulate a refrigerant and comprising a first in-line filling valve; c) A first flow line providing fluid control communication between the pressurized source and a flow-through inhibitor cartridge; d) A second flow line providing fluid control communication between the flow-through inhibitor cartridge and the high-pressure side of the first in-line filling valve; e) Optionally, at least one or more in-line flow-through oxygen removal columns containing a deoxidizer capable of removing oxygen but not cleaving the C-F bonds of the fluorolefins; f) Optionally, an in-line inhibitor removal column in the first flow line. A cooling system comprising the above components. Claim 29 The system of claim 28, wherein the pressurizing source comprises HFO-1234yf and HFO-1234ze, and optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea, and optionally carbon dioxide. Claim 30 a) A sealed fluorolefin-containing refrigerant canister comprising HFO-1234yf and HFO-1234ze, and optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea, and optionally carbon dioxide; b) A packaged cartridge filled with an oligomer inhibitor; c) A first tube configured to connect the discharge end of the refrigerant canister to the inlet end of the packaged cartridge; d) A second tube configured to connect the outlet end of the packaged cartridge to a valve in the refrigerant circuit. A refrigerant filling kit comprising the above components. Claim 31 The cooling system of claim 28, wherein the inhibitor comprises at least one element selected from the group consisting of d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more styrenes, in an effective amount of about 0.02 to about 0.3 ppm. Claim 32 The process of claim 12, wherein the inhibitor comprises at least one element selected from the group consisting of d-limonene, l-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more styrenes, in an amount of about 0.02 to about 0.3 ppm. Claim 33 The cooling system according to claim 28, wherein the inhibitor is present in an effective amount of from about 0.02 to about 0.3 ppm and comprises at least one element selected from the group consisting of ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, or para-xylene, α-methylstyrene, α,2-dimethylstyrene, α,3-dimethylstyrene, and α,4-dimethylstyrene.

34. The process according to claim 12, wherein the inhibitor is present in an amount of from about 0.02 to about 0.3 ppm and comprises at least one element selected from the group consisting of ethane, propane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, or para-xylene, α-methylstyrene, α,2-dimethylstyrene, α,3-dimethylstyrene, and α,4-dimethylstyrene.

35. A refrigerant filling kit comprising a sealed stabilized fluoroolefin composition containing a refrigerant canister containing HFO-1234yf and HFO-1234ze, and optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, R-236fa, and HFC-227ea, and optionally carbon dioxide.

36. A refrigerant canister containing a sealed stabilized fluoroolefin composition, the composition comprising at least HFO-1234yf as a refrigerant component, at least one of d-limonene, l-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, and up to 0.5 weight percent of an oligomer inhibitor; and a tube configured to connect the discharge end of the refrigerant canister to a valve of a refrigerant circuit. A refrigerant filling kit comprising the same.

37. A refrigerant canister containing a sealed and stabilized fluoroolefin composition, wherein the composition comprises at least HFO-1234yf as a refrigerant component, at least one of ethane, propane, cyclopropane, propylene, butane, butene, isobutene, 2-methylbutane, meta-xylene, ortho-xylene, or para-xylene, α,-methylstyrene, α,2-dimethylstyrene, α,3-dimethylstyrene, or α,4-dimethylstyrene, and an oligomer inhibitor of less than 0.5 weight percent. A refrigerant canister. A pipe configured to connect the discharge end of the refrigerant canister to a valve of the refrigerant circuit. A refrigerant filling kit comprising the above.

38. A canister filled with a POE, mineral oil, or alkylbenzene lubricant and less than 0.5 weight percent of ethane, or propane, or cyclopropane, or propylene, or butane, or butene, or isobutene, or isobutylene, or 2-methylbutane, or meta-xylene, or ortho-xylene, or para-xylene, and a pipe configured to connect the discharge end of the refrigerant canister to a valve of the refrigerant circuit. A refrigerant filling kit comprising the above.

39. A refrigerant system including a cooling circuit for transporting a fluoroolefin refrigerant composition, wherein the refrigerant system comprises: a) at least one dryer for removing moisture, and optionally, b) at least one supply valve configured to fill the refrigerant circuit with the fluoroolefin refrigerant composition, c) a filling subsystem for the stabilized refrigerant, d) optionally, a filling subsystem for the purified refrigerant included in an air / oxygen detector, e) optionally, a subsystem for removing oxygen and / or oxidizing compounds including a deoxidizer that responds to the air / oxygen detector, f) a subsystem for separating oligomers / polymers, g) an oligomer / polymer filter, A refrigerant system comprising at least one of the above.

40. Equipment for adding or integrating into a refrigerant system having a refrigerant circuit, wherein the equipment comprises: a) at least one supply valve adapted to fill the refrigerant circuit with a fluoroolefin refrigerant composition, b) a filling subsystem for the stabilized refrigerant, c) optionally, a filling subsystem for the purified refrigerant included in an air / oxygen detector, d) Optionally, a subsystem for removing oxygen and / or oxidizing compounds, comprising a deoxidizer, that responds to the air / oxygen detector; e) A subsystem for separating oligomers / polymers; f) An oligomer / polymer filter; A facility comprising at least one of the above. **Claim 41** A transportation supply center comprising the system according to any one of claims 1, 28, and 39. **Claim 42** A transportation supply center comprising the facility according to claim 40.

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