Compositions containing difluoromethane, tetrafluoropropene, and carbon dioxide and uses thereof

Abstract

According to the present invention, a refrigerant composition is disclosed. The composition comprises a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2. The composition is useful as a refrigerant in methods for generating cooling and heating, in methods for replacing the refrigerant R-410A, and in refrigeration, air conditioning, or heat pump systems. The composition of the present invention has a cooling capacity within ±10% of that of R-410A and has a GWP of less than 400 or less than 300.

Description

Technology Field

[0001] The present invention relates to a composition for use in refrigeration, air conditioning, or heat pump systems. The composition of the present invention is useful in methods for generating cooling and heating and in methods for replacing refrigerants, and in refrigeration, air conditioning, and heat pump devices. Background Technology

[0002] For decades, the refrigeration industry has been researching alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which are being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. In particular, these HFC refrigerants, including the currently widely used HFC-134a, R-32, and R-410A, have an ozone depletion potential of zero and are therefore not affected by the phased-out under current regulations resulting from the original Montreal Protocol. With the implementation of the Kigali Amendment to the Montreal Protocol, alternative refrigerants with even lower GWP are being sought. The problem to be solved

[0003] A certain composition comprising difluoromethane, tetrafluoropropene, and carbon dioxide has been found to have properties suitable for use as a substitute for currently available commercial refrigerants, particularly R-410A, which have a relatively high GWP. Therefore, the inventors have identified a refrigerant gas that does not destroy ozone, has a significantly lower direct global warming potential, and is comparable to the performance of R-410A, and is thus an environmentally sustainable alternative. means of solving the problem

[0004] According to the present invention, a composition comprising a refrigerant mixture is disclosed. The refrigerant mixture essentially consists of difluoromethane, tetrafluoropropene, and carbon dioxide. Effects of the invention

[0005] Refrigerant mixtures are useful as components in compositions that also contain non-refrigerant components (e.g., lubricants) in methods for generating cooling or heating, in methods for replacing refrigerant R-410A, and particularly in air conditioning and heat pump systems. Specific details for implementing the invention

[0006] Before discussing the details of the embodiments described below, some terms are defined or clarified.

[0007] definition

[0008] As used herein, the term 'heat transfer fluid' (also referred to as 'heat transfer medium') means a composition used to transport heat from a heat source to a heat sink.

[0009] A heat source is defined as any space, location, object, or body from which it is desirable to add, transfer, move, or remove heat. Examples of heat sources are (open or closed) spaces requiring refrigeration or cooling, e.g., refrigerator or freezer cases in a supermarket, refrigerated shipping containers, building spaces requiring air conditioning, industrial water chillers, or vehicle cabins requiring air conditioning. In some embodiments, the heat transfer composition may remain in a constant state during the transfer process (i.e., does not evaporate or condense). In other embodiments, an evaporative cooling process may also utilize the heat transfer composition.

[0010] A heat sink is defined as any space, location, object, or thing capable of absorbing heat. A vapor compression refrigeration system is an example of such a heat sink.

[0011] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during a cycle used for heat transfer.

[0012] A heat transfer system is a system (or device) used to generate a heating or cooling effect in a specific space. Heat transfer systems can be mobile or stationary systems.

[0013] Examples of heat transfer systems include, but are not limited to, stationary heat transfer systems, air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, portable refrigerators, portable heat transfer systems, portable air conditioning units, dehumidifiers, and combinations thereof, any type of refrigeration and air conditioning system.

[0014] Refrigeration capacity (also referred to as cooling capacity) is a term that defines the enthalpy change of the refrigerant in the evaporator per pound of circulating refrigerant, or the heat removed by the refrigerant in the evaporator per unit volume of refrigerant vapor exiting the evaporator (volumetric capacity). Refrigeration capacity is a measure of the ability of a refrigerant or heat transfer composition to generate cooling. Therefore, the larger the capacity, the greater the cooling produced. The cooling rate refers to the heat removed by the refrigerant in the evaporator per unit time.

[0015] The coefficient of performance (COP) is the value obtained by dividing the amount of heat removed by the energy input required to operate the cycle. The higher the COP, the higher the energy efficiency. COP is directly related to the energy efficiency ratio (EER), which is the efficiency rating for refrigeration or air conditioning equipment at specific internal and external temperature settings.

[0016] The term "subcooling" refers to the reduction of a liquid's temperature below its saturation point for a given pressure. While the saturation point is the temperature at which vapor completely condenses into a liquid, subcooling continues to cool the liquid to a lower temperature at a given pressure. By cooling the liquid below its saturation temperature (or bubble point temperature), the net cooling capacity can be increased. Consequently, subcooling improves the cooling capacity and energy efficiency of a system. The subcool amount is the amount of cooling below the saturation temperature (in degrees).

[0017] Superheating is a term that defines how much a vapor composition is heated beyond its saturated vapor temperature (the temperature at which the first drop of liquid forms when the composition is cooled, also referred to as the "dew point").

[0018] A temperature glide (sometimes simply referred to as "glide") is the absolute value of the difference between the starting temperature and the ending temperature of a phase change process by a refrigerant within a component of a refrigerant system, excluding any subcooling or superheating. This term may be used to describe the condensation or evaporation of near azeotrope mixtures or non-azeotrope compositions. When referring to a temperature glide in a refrigeration, air conditioning, or heat pump system, it is common to provide an average temperature glide, which is the average of the temperature glide in the evaporator and the temperature glide in the condenser.

[0019] The net cooling effect is the amount of heat absorbed by 1 kilogram of refrigerant in the evaporator to produce useful cooling.

[0020] Mass flow rate is the amount of refrigerant (in kilograms) circulating through a refrigeration, heat pump, or air conditioning system over a given period.

[0021] As used herein, the term “lubricant” means any material added to a composition or compressor (and in contact with any heat transfer composition during use in any heat transfer system) that provides lubrication to the compressor to assist in preventing seizing of parts.

[0022] As used herein, a compatibilizer is a compound that improves the solubility of the hydrofluorocarbon of the disclosed composition in a heat transfer system lubricant. In some embodiments, the compatibilizer improves oil recovery to the compressor. In some embodiments, the composition is used with the system lubricant to reduce oil-rich phase viscosity.

[0023] As used herein, oil recovery refers to the ability of a heat transfer composition to transport lubricant through a heat transfer system and recover it to the compressor. That is, during use, it is not uncommon for a portion of the compressor lubricant to be transported from the compressor to other parts of the system by the heat transfer composition. In such a system, if the lubricant is not efficiently recovered to the compressor, the compressor will eventually fail due to a lack of lubrication.

[0024] As used herein, “ultraviolet” dyes are defined as UV fluorescent or phosphorescent compositions that absorb light in the ultraviolet or “near” ultraviolet region of the electromagnetic spectrum. Fluorescence produced by UV fluorescent dyes can be detected under illumination by UV light emitting at least some radiation having a wavelength in the range of 10 nanometers to about 775 nanometers.

[0025] Flammability is a term used to describe the ability of a composition to ignite and / or propagate a flame. For refrigerants and other heat transfer compositions, the lower flammability limit ("LFL") is the minimum concentration of the heat transfer composition in air capable of propagating a flame through a homogeneous mixture of the composition and air under the test conditions specified in ASTM (American Society of Testing and Materials) E681. The upper flammability limit ("UFL") is the maximum concentration of the heat transfer composition in air capable of propagating a flame through a homogeneous mixture of the composition and air under the same test conditions. Whether a refrigerant compound or mixture is flammable or non-flammable is also determined by testing under the conditions of ASTM-681.

[0026] During a refrigerant leak, the low-boiling component of the mixture may leak preferentially. Therefore, the composition in the system as well as in the vapor leak may change over the duration of the leak. Consequently, a non-flammable mixture may become flammable under a leak scenario. Furthermore, to be classified as non-flammable by ASHRAE (American Society of Heating, Refrigeration and Air-conditioning Engineers), a refrigerant or heat transfer composition must be non-flammable not only when formulated but also under leak conditions.

[0027] The Global Warming Potential (GWP) is an index used to assess the relative contribution to global warming caused by one kilogram of atmospheric release of a specific greenhouse gas compared to the release of one kilogram of carbon dioxide. GWP can be calculated for different time horizons representing the atmospheric lifetime effect for a given gas. The GWP for a 100-year time horizon is typically the standard value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component.

[0028] The Ozone Depletion Potential (ODP) is a numerical value that designates the amount of ozone depletion caused by a substance. ODP is the ratio of a chemical's effect on ozone to the effect of a similar mass of CFC-11 (fluorotrichloromethane). In other words, CFC-11 is defined as having an ODP of 1.0. Other CFCs and HCFCs have ODPs in the range of 0.01 to 1.0. HFCs and HFOs have an ODP of 0 because they do not contain chlorine or other ozone-depleting halogens.

[0029] As used herein, the terms “comprising,” “comprising,” “comprising,” “having,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusions. For example, a composition, process, method, article, or device comprising a list of elements is not necessarily limited to such elements alone and may include other elements not explicitly listed or inherent to such composition, process, method, article, or device.

[0030] The connecting phrase “consisting of” excludes any unspecified elements, steps, or components. In the context of a claim, this would typically close the claim for the inclusion of materials other than those mentioned, with the exception of related impurities. Where the phrase “consisting of” appears in a section of the claim body rather than immediately after a preamble, it limits only the elements indicated in that section; other elements are not excluded from the claim in their entirety.

[0031] The connecting phrase “essentially consisting of” is used to define a composition, method, or apparatus comprising materials, steps, features, components, or elements in addition to those literally disclosed, provided that such additionally included materials, steps, features, components, or elements do not substantially affect the basic and novel features(s) of the claimed invention. The term “essentially consisting of” occupies an intermediate position between “comprising” and “consisting of.” Typically, the components of a refrigerant mixture and the refrigerant mixture itself may contain trace amounts (e.g., less than about 0.5 weight percent total) of impurities and / or by-products (e.g., by the manufacture of the refrigerant components or by-product reclamation from other systems) that do not substantially affect the novel and basic features of the refrigerant mixture.

[0032] Where the applicant has defined an invention or part thereof in an open-ended term such as “comprising”, it will be readily understood that (unless otherwise noted) such description should also be interpreted as describing such invention using the terms “essentially consisting of” or “consisting of”.

[0033] Additionally, the use of indefinite articles (“a” or “an”) is employed to describe the elements and components described herein. This is done merely for convenience and to provide a general meaning of the scope of the invention. Such descriptions should be understood as comprising one or at least one, and the singular form also includes the plural form unless the number is explicitly singular.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. Methods and materials similar or equivalent to those described herein may be used to practice or test embodiments of the disclosed compositions, but suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety unless specific passages are cited. In the event of a conflict, the present specification, including definitions, shall prevail. Furthermore, materials, methods, and examples are merely illustrative and are not intended to be limiting.

[0035] 2,3,3,3-tetrafluoropropene may also be referred to as HFO-1234yf, HFC-1234yf, or R-1234yf. HFO-1234yf may be produced by methods known in the art, for example, by dehydrofluorination of 1,1,1,2,3-pentafluoropropane (HFC-245eb) or 1,1,1,2,2-pentafluoropropane (HFC-245cb).

[0036] Difluoromethane (HFC-32 or R-32) is available for purchase or can be produced by methods known in the art, for example, by dechlorofluorination of methylene chloride.

[0037] Carbon dioxide (CO2) can be purchased from a number of gas suppliers or generated by any of a number of well-known methods.

[0038] composition

[0039] The refrigerant industry has been striving to develop new refrigerant products that provide acceptable performance and environmental sustainability. New global warming regulations may place caps on the Global Warming Potential (GWP) of new refrigerant compositions. Therefore, the industry must seek compositions with low GWP, low toxicity, and low Ozone Depletion Potential (ODP) that also provide good performance for cooling and heating. For many years, R-410A (a blend of 50 wt% HFC-32 and 50 wt% HFC-125) has been used as a substitute for R-22 in air conditioning and heat pumps, but it must be replaced due to its excessively high GWP. Compositions as described herein provide such a substitute that has a lower GWP than previously proposed alternative refrigerants.

[0040] In one embodiment, the refrigerant mixture has a GWP of 400 or less based on AR4 data. In another embodiment, the refrigerant mixture has a GWP of 300 or less based on AR4 data.

[0041] The inventors have identified compositions that provide performance characteristics serving as substitutes for R-410A in refrigeration, air conditioning, and heat pump devices. These compositions comprise refrigerant mixtures essentially consisting of difluoromethane, 2,3,3,3-tetrafluoropropene, and carbon dioxide. In one embodiment, the composition comprising the refrigerant mixture consists of difluoromethane, 2,3,3,3-tetrafluoropropene, and carbon dioxide.

[0042] Identifying an alternative refrigerant that has the appropriate balance of characteristics required for a given application is no trivial matter. The industry has struggled to find a high-capacity refrigerant with a reasonable temperature gradient. In particular, there has been a demand for a refrigerant to replace R-410A that has an acceptable temperature gradient and a GWP of 400 or less, or even 300 or less, and can match the cooling capacity of R-410A.

[0043] A composition comprising a refrigerant mixture for replacing R-410A is disclosed herein, said refrigerant mixture essentially consists of about 42 to about 59 weight percent difluoromethane (HFC-32), about 33 to about 53 weight percent 2,3,3,3-tetrafluoropropene (HFO-1234yf), and about 1 to about 9 weight percent carbon dioxide (CO2).

[0044] In another embodiment, the refrigerant mixture essentially consists of about 42 to about 59 weight% of HFC-32, about 35 to about 51 weight% of 2,3,3,3-tetrafluoropropene, and about 2 to about 9 weight% of CO2.

[0045] In another embodiment, the refrigerant mixture essentially consists of about 42 to 59 weight% of HFC-32, about 37 to 48 weight% of 2,3,3,3-tetrafluoropropene, and about 3 to 9 weight% of CO2.

[0046] In another embodiment, the refrigerant mixture essentially consists of about 42 to 47 weight% of HFC-32, about 40 to 49 weight% of 2,3,3,3-tetrafluoropropene, and about 3 to 9 weight% of CO2.

[0047] In another embodiment, the refrigerant mixture essentially consists of about 44 to 47 weight% of HFC-32, about 40 to 49 weight% of 2,3,3,3-tetrafluoropropene, and about 5 to 9 weight% of CO2.

[0048] In another embodiment, the refrigerant mixture essentially consists of about 42 to 45 weight% difluoromethane, about 46 to 49 weight% 2,3,3,3-tetrafluoropropene, and about 6 to 9 weight% CO2.

[0049] In another embodiment, the refrigerant mixture essentially consists of about 42 to 44 weight% of HFC-32, about 48 to 51 weight% of 2,3,3,3-tetrafluoropropene, and about 7 to 9 weight% of CO2.

[0050] In another embodiment, the refrigerant mixture essentially consists of about 43 to 44 weight% of HFC-32, about 48 to 50 weight% of 2,3,3,3-tetrafluoropropene, and about 7 to 8 weight% of CO2.

[0051] In another embodiment, the refrigerant mixture essentially consists of about 44 weight% HFC-32, about 49 weight% 2,3,3,3-tetrafluoropropene, and about 7 weight% CO2.

[0052] In another embodiment, the refrigerant mixture essentially consists of about 47 to about 59 weight percent difluoromethane, about 37 to about 49 weight percent 2,3,3,3-tetrafluoropropene, and about 3 to about 8 weight percent carbon dioxide.

[0053] In another embodiment, the refrigerant mixture essentially consists of about 52 to about 59 weight percent difluoromethane, about 37 to about 42 weight percent 2,3,3,3-tetrafluoropropene, and about 3 to about 6 weight percent carbon dioxide.

[0054] In another embodiment, the refrigerant mixture essentially consists of about 57 to about 59 weight percent difluoromethane, about 37 to about 39 weight percent 2,3,3,3-tetrafluoropropene, and about 3 to about 5 weight percent carbon dioxide.

[0055] In another embodiment, the refrigerant mixture essentially consists of about 58 weight% difluoromethane, about 38 weight% 2,3,3,3-tetrafluoropropene, and about 4 weight% carbon dioxide.

[0056] In any of the above embodiments, the total amount of the refrigerant mixture must, of course, be 100%.

[0057] In one embodiment, the refrigerant mixture provides a substitute for R-410A having a cooling capacity within 10% of the cooling capacity of R-410A. In another embodiment, the refrigerant mixture provides a substitute for R-410A having a cooling capacity within 5% of the cooling capacity of R-410A. In another embodiment, the refrigerant mixture provides a substitute for R-410A having a cooling capacity within 2% of the cooling capacity of R-410A. In another embodiment, the refrigerant mixture provides a substitute for R-410A having a cooling capacity that matches or is improved upon the cooling capacity of R-410A.

[0058] In one embodiment, the refrigerant mixture provides a substitute for R-410A, wherein the average temperature gradient within the heat exchanger is less than 8.0°C. In another embodiment, the refrigerant mixture provides a substitute for R-410A, wherein the average temperature gradient within the heat exchanger is less than 7.5°C.

[0059] Compositions as listed in Table A are particularly interesting as substitutes for R-410A.

[0060] [Table A]

[0061]

[0062] In some embodiments, in addition to difluoromethane, 2,3,3,3-tetrafluoropropene, and carbon dioxide, the disclosed composition may include an optional non-refrigerant component. Accordingly, a composition comprising a refrigerant mixture essentially consisting of difluoromethane, 2,3,3,3-tetrafluoropropene, and carbon dioxide, and further comprising one or more optional non-refrigerant components selected from the group consisting of lubricants, dyes (including UV dyes), solubilizers, compatibilizers, stabilizers, tracers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof is disclosed herein. In some embodiments, the optional non-refrigerant component may be referred to as an additive. In fact, many of these selective non-refrigerant components fit into one or more of these categories and may have qualities suitable for achieving one or more performance characteristics.

[0063] In some embodiments, one or more non-refrigerant components are present in small amounts relative to the total composition. In some embodiments, the amount of the concentration of the additive(s) in the disclosed composition is less than about 0.1 weight% to a maximum of about 5 weight% of the total composition. In some embodiments of the invention, the additive is present in the disclosed composition in an amount of about 0.1 weight% to about 5 weight% of the total composition, or in an amount of about 0.1 weight% to about 3.5 weight%. The additive component(s) selected for the disclosed composition are selected based on utility and / or individual equipment component or system requirements.

[0064] In one embodiment, the lubricant is selected from the group consisting of mineral oil, alkylbenzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, perfluoropolyether, silicone, silicate ester, phosphate ester, paraffin, naphthene, polyalpha-olefin, and combinations thereof.

[0065] The lubricant disclosed in this specification may be a commercially available lubricant. For example, the lubricants include paraffin mineral oil sold by BVA Oils as BVM 100 N, naphthenic mineral oil sold by Crompton Co. under the trade names Suniso (registered trademark) 1GS, Suniso (registered trademark) 3GS, and Suniso (registered trademark) 5GS, naphthenic mineral oil sold by Pennzoil under the trade name Sontex (registered trademark) 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trade name Calumet (registered trademark) RO-30, and Zerol (registered trademark) 75, Zerol (registered trademark) 150, and Zerol (registered trademark) by Shrieve Chemicals It may be linear alkylbenzene sold as 500 and branched alkylbenzene sold as HAB 22 by Nippon Oil, polyol ester (POE) sold as trade name Castrol (registered trademark) 100 by Castrol, UK, polyalkylene glycol (PAG) such as RL-488A from Dow (Dow Chemical, Midland, Michigan, USA), and mixtures thereof—meaning mixtures of any lubricants disclosed in this paragraph.

[0066] In the composition of the present invention comprising a lubricant, the lubricant is present in an amount of less than 40.0 weight% with respect to the total composition. In another embodiment, the amount of lubricant is less than 20 weight% of the total composition. In another embodiment, the amount of lubricant is less than 10 weight% of the total composition. In another embodiment, the amount of lubricant is about 0.1 to 5.0 weight% of the total composition.

[0067] Notwithstanding the weight ratios for the compositions disclosed herein, it is understood that in some heat transfer systems, additional lubricant may be obtained from one or more equipment components of such heat transfer systems while the composition is in use. For example, in some refrigeration, air conditioning, and heat pump systems, lubricant may be filled into the compressor and / or compressor lubricant sump. Such lubricant will be present in the refrigerant of such systems in addition to any lubricant additive. During use, the refrigerant composition may absorb a certain amount of equipment lubricant while inside the compressor, causing the refrigerant-lubricant composition to change from the starting ratio.

[0068] A non-refrigerant component used with the composition of the present invention may include at least one dye. The dye may be at least one ultraviolet (UV) dye. The UV dye may be a fluorescent dye. The fluorescent dye may be selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthen, thioxanthen, naphthoxanthen, fluorescein, and derivatives of said dyes, and combinations thereof—meaning a mixture of any of the aforementioned dyes or their derivatives disclosed in this paragraph.

[0069] In some embodiments, the disclosed composition contains about 0.001 weight% to about 1.0 weight% of a UV dye. In other embodiments, the UV dye is present in an amount of about 0.005 weight% to about 0.5 weight%; and in other embodiments, the UV dye is present in an amount of 0.01 weight% to about 0.25 weight% of the total composition.

[0070] UV dyes are useful components for detecting leaks of a composition by enabling the observation of fluorescence of the dye at or near the leak point of a device (e.g., a refrigeration unit, an air conditioner, or a heat pump). UV emission from the dye, for example, fluorescence, can be observed under ultraviolet light. Therefore, if a composition containing such UV dye is leaking from a specific point of the device, fluorescence can be detected at or near the leak point.

[0071] Other non-refrigerant components that may be used with the composition of the present invention may include at least one solubilizing agent selected to improve the solubility of one or more dyes in the disclosed composition. In some embodiments, the weight ratio of dye to solubilizing agent is in the range of about 99:1 to about 1:1. The solubilizing agent comprises at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes, and mixtures thereof—meaning a mixture of any solubilizing agents disclosed in this paragraph.

[0072] In some embodiments, the non-refrigerant component comprises at least one compatibilizer to improve compatibility between one or more lubricants and the disclosed composition. The compatibilizer may be selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof—meaning a mixture of any compatibilizers disclosed in this paragraph.

[0073] The solubilizer and / or compatibilizer may be selected from the group consisting of hydrocarbon ethers containing only carbon, hydrogen and oxygen, e.g., dimethyl ether (DME) and mixtures thereof—meaning mixtures of any hydrocarbon ethers disclosed in this paragraph.

[0074] The compatibilizer may be a linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing 3 to 15 carbon atoms. The compatibilizer may be at least one hydrocarbon selected from the group consisting of propanes, particularly at least propylene and propane; butanes, including n-butane and isobutene; pentanes, including n-pentane, isopentane, neopentane and cyclopentane; hexanes; octanes; nonanes; and decanes. Commercially available hydrocarbon compatibilizers include those sold by Exxon Chemical (USA) under the trade name Isopar (registered trademark) H, and undecane (C 11 ) and dodecane (C 12 A mixture of ) (high-purity C 11 to C 12 Iso-paraffin), Aromatic 150 (C9 to C 11 Aromatic), Aromatic 200 (C9 to C 15Aromatic) and Naphtha 140 (C5 to C 11 Mixtures of paraffin, naphthene, and aromatic hydrocarbons), and mixtures thereof—meaning mixtures of any hydrocarbons disclosed in this paragraph—are included but not limited thereto.

[0075] The compatibilizer may alternatively be at least one polymer compatibilizer. The polymer compatibilizer may be a random copolymer of fluorinated and non-fluorinated acrylates, wherein the polymer has the chemical formula CH2=C(R 1 )CO2R 2 , CH2=C(R 3 )C6H4R 4 , and CH2=C(R 5 )C6H4XR 6 It comprises at least one repeating unit of a monomer represented by; wherein, in the above formula, X is oxygen or sulfur; and R 1 , R 3 , and R 5 is independently selected from the group consisting of H and C1-C4 alkyl radicals; R 2 , R 4 , and R 6 is independently selected from the group consisting of carbon-chain-based radicals containing F and C, and may additionally contain H, Cl, ether oxygen, or sulfur in the form of thioethers, sulfoxides, or sulfone groups and mixtures thereof. Examples of such polymer compatibilizers include those available for purchase under the trade name Zonyl (registered trademark) PHS from E. I. DuPont de Nemours and Company (E. I. du Pont de Nemours and Company; Wilmington, Delaware, 19898, USA). Zonyl (registered trademark) PHS contains 40 wt% CH2=C(CH3)CO2CH2CH2(CF2CF2) mF (also referred to as Zonyl (trademark) fluoromethacrylate or ZFM) (wherein m is 1 to 12, mainly 2 to 8) and 60 wt% of lauryl methacrylate (CH2=C(CH3)CO2(CH2) 11 It is a random copolymer produced by polymerizing CH3 (also referred to as LMA).

[0076] In some embodiments, the compatibilizer component contains about 0.01 to 30 weight percent (based on the total amount of compatibilizer) of an additive that reduces the surface energy of metallic copper, aluminum, steel, or other metals and their metal alloys found in heat exchangers in a manner that reduces the adhesion of the lubricant to the metal. Examples of metal surface energy reducing additives include those available from DuPont under the trade names Zonyl (registered trademark) FSA, Zonyl (registered trademark) FSP, and Zonyl (registered trademark) FSJ.

[0077] Other optional non-refrigerant components that can be used with the composition of the present invention may be metal surface inerts. The metal surface inert is from the group consisting of areoxalyl bis(benzylidene) hydrazide (CAS No.: 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS No.: 32687-78-8), 2,2'-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CAS No.: 70331-94-1), N,N'-(disalicyclidene)-1,2-diaminopropane (CAS No.: 94-91-7), and ethylenediaminetetraacetic acid (CAS No.: 60-00-4) and their salts, and mixtures thereof—meaning mixtures of any metal surface inerts disclosed in this paragraph. It is selected.

[0078] An optional non-refrigerant component used with the composition of the present invention may alternatively be a stabilizer, which is selected from the group consisting of hindered phenol, thiophosphate, butylated triphenylphosphorothionate, organophosphate, or phosphite, aryl alkyl ether, terpene, terpenoid, epoxide, fluorinated epoxide, oxetane, ascorbic acid, thiol, lactone, thioether, amine, nitromethane, alkylsilane, benzophenone derivative, aryl sulfide, divinyl terephthalic acid, diphenyl terephthalic acid, ionic liquid, and mixtures thereof—meaning a mixture of any stabilizers disclosed in this paragraph.

[0079] The stabilizers are tocopherol; hydroquinone; t-butyl hydroquinone; monothiophosphate; and dithiophosphate available from Ciba Specialty Chemicals (Basel, Switzerland, hereinafter "Ciba") under the trade name Irgalube (registered trademark) 63; dialkylthiophosphate esters available from Ciba under the trade names Irgalube (registered trademark) 353 and Irgalube (registered trademark) 350, respectively; butylated triphenylphosphorothionate available from Ciba under the trade name Irgalube (registered trademark) 232; and amine phosphate available from Ciba under the trade name Irgalube (registered trademark) 349 (Ciba). Impaired phosphite available from Ciba for Irgafos (registered trademark) 168, and tris-(di-tert-butylphenyl)phosphite available from Ciba for the trade name Irgafos (registered trademark) OPH; (di-n-octyl phosphite); and iso-decyl diphenyl phosphite available from Ciba under the trade name Yirgafos (registered trademark) DDPP; trialkyl phosphates, e.g., trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, and tri(2-ethylhexyl)phosphate; triaryl phosphates comprising triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate; and mixed alkyl-aryl phosphates comprising isopropylphenyl phosphate (IPPP) and bis(t-butylphenyl)phenyl phosphate (TBPP); butylated triphenyl phosphate, e.g., available under the trade name Syn-O-Ad (registered trademark) comprising Syn-O-Ad (registered trademark) 8784; Tert-butylated triphenyl phosphate, available, e.g., under the trade name Durad (registered trademark) 620; isopropylated triphenyl phosphate, available, e.g., under the trade names Durad (registered trademark) 220 and Durad (registered trademark) 110; anisole; 1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene; myrcene, allocymene, limonene (particularly, d-limonene); retinal; pinene; menthol; geraniol; farnesol; phytol; vitamin A; terpinene; delta-3-carene; terpinolene; phellandrene; fenchene; dipentene; caratenoids, e.g., lycopene, beta-carotene, and xanthophyll, e.g., zeaxanthin; Retinoids, e.g., hepaxanthin and isotretinoin; bornan; 1,2-propylene oxide; 1,2-butylene oxide; n-butyl glycidyl ether; trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane; 3-ethyl-3-hydroxymethyl-oxetane, e.g., OXT-101 (Toagosei Company, Limited, Ltd); 3-ethyl-3-((phenoxy)methyl)-oxetane, e.g., OXT-211 (Toagosei Company, Limited); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, e.g., OXT-212 (Toagosei Company, Limited); ascorbic acid; methanethiol (methyl mercaptan); ethanethiol (ethyl mercaptan); coenzyme A; dimercaptosuccinic acid (DMSA); grapefruit mercaptan ((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine ​​((R)-2-amino-3-sulfanyl-propanoic acid); lipoamide (1,2-dithiolan-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3(or 3,4)-dimethylphenyl]-2(3H)-benzofuranone, available from Ciba under the trade name Irganox (registered trademark) HP-136; benzylphenyl sulfide; diphenyl sulfide; diisopropylamine; dioctadecyl 3,3'-thiodipropionate, available from Ciba under the trade name Irganox (registered trademark) PS 802 (Ciba); didodecyl 3,3'-thiopropionate, available from Ciba under the trade name Irganox (registered trademark) PS 800; di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, available from Ciba under the trade name Tinuvin (registered trademark) 770; Poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate) methyl bis-tallowamine; bis-tallowamine; phenol-alpha-naphthylamine; bis(dimethylamino)methylsilane (DMAMS); tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane; vinyltrimethoxysilane; 2,5-difluorobenzophenone; 2'5'-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone; benzylphenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionic liquids; and mixtures and combinations thereof may be selected from the group consisting of

[0080] An optional non-refrigerant component used with the composition of the present invention may alternatively be an ionic liquid stabilizer. The ionic liquid stabilizer may be selected from the group consisting of an organic salt that is liquid at room temperature (approximately 25°C); a cation selected from the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, and triazolium, and mixtures thereof, and an anion selected from the group consisting of [BF4]-, [PF6]-, [SbF6]-, [CF3SO3]-, [HCF2CF2SO3]-, [CF3HFCCF2SO3]-, [HCClFCF2SO3]-, [(CF3SO2)2N]-, [(CF3CF2SO2)2N]-, [(CF3SO2)3C]-, [CF3CO2]-, and F-, and a mixture thereof. In some embodiments, the ionic liquid stabilizer is selected from the group consisting of emim BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF4 (1-butyl-3-methylimidazolium tetraborate); emim PF6 (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), all of which are available from Fluka (Sigma-Aldrich).

[0081] In some embodiments, the stabilizer comprises: any substituted phenol compound comprising a phenol comprising one or more substituted, or cyclic, straight-chain, or branched aliphatic substituents, such as an obstructed phenol, e.g., 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, tocopherol, etc.; alkylated monophenols comprising t-butyl hydroquinone, other derivatives of hydroquinone, etc.; and hydroxylated thiodiphenyl ethers comprising 4,4'-thio-bis(2-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), etc. 4,4'-Methylenebis(2,6-di-tert-butylphenol), 4,4'-Bis(2,6-di-tert-butylphenol), derivatives of 2,2'- or 4,4-biphenoldiol, 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 4,4-Butylidenebis(3-methyl-6-tert-butylphenol), 4,4-Isopropylidenebis(2,6-di-tert-butylphenol), 2,2'-Methylenebis(4-methyl-6-nonylphenol), 2,2'-Isobutylidenebis(4,6-dimethylphenol), 2,2'-Methylenebis(4-methyl-6-cyclohexylphenol), Alkylidene-bisphenol comprising 2,2- or 4,4-biphenyldiol including 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); butylated hydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol); bisphenol containing heteroatoms including 2,6-di-tert-alpha-dimethylamino-p-cresol, 4,4-thiobis(6-tert-butyl-m-cresol), etc.; acylaminophenol; 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); sulfides including bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide;and mixtures thereof - meaning mixtures of any phenols disclosed in this paragraph - may be.;

[0082] In some embodiments, the stabilizer may be a single stabilizing compound as described in detail above. In other embodiments, the stabilizer may be a mixture of two or more stabilizing compounds from the same class of compounds or different classes of compounds, said classes of compounds as described in detail above.

[0083] An optional non-refrigerant component used with the composition of the present invention may alternatively be a tracer. The tracer may be a single compound or two or more tracer compounds from the same or different classes of compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 1 ppm (part per million) to about 5000 ppm based on the weight of the total composition. In other embodiments, the tracer is present at a total concentration of about 10 ppm to about 1000 ppm. In other embodiments, the tracer is present at a total concentration of about 20 ppm to about 500 ppm. In other embodiments, the tracer is present at a total concentration of about 25 ppm to about 500 ppm. In other embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0084] The tracer may be selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, chlorofluorocarbons (CFCs), hydrofluorochlorocarbons (HCFCs), chlorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof. Alternatively, the tracers are trifluoromethane (HFC-23), dichlorodifluoromethane (CFC-12), chlorodifluoromethane (HCFC-22), methyl chloride (R-40), chlorofluoromethane (HCFC-31), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), chloropentafluoroethane (CFC-115), 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), and pentafluoroethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa), 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea), 1,1,1,2,2,3,3-Heptafluoropropane (HFC-227ea), 1,1,1,3,3-Pentafluoropropane (HFC-245fa), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 1,1,1,2,3-Pentafluoropropane (HFC-245eb), 1,1,2,2-Tetrafluoropropane (HFC-254cb), 1,1,1,2-Tetrafluoropropane (HFC-254eb), 1,1,1-Trifluoropropane (HFC-263fb), 1,1-Difluoro-2-Chloroethylene (HCFC-1122), 2-Chloro-1,1,2-Trifluoroethylene (CFC-1113), 1,1,1,3,3-Pentafluorobutane (HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-Decafluoropentane (HFC-43-10mee), 1,It may be selected from the group consisting of 1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, hexafluorobutadiene, 3,3,3-trifluoropropine, iodotrifluoromethane, deuterium hydrocarbons, deuterium hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O), and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons, or a combination of one hydrofluorocarbon and one or more perfluorocarbons. In other embodiments, the tracer is a blend of at least one CFC and at least one HCFC, HFC, or PFC.

[0085] A tracer may be added to the composition in a predetermined amount to enable the detection of any dilution, contamination, or other changes to the composition of the present invention. Additionally, the tracer may enable the detection of products infringing on existing patent rights by identifying the patent holder's product against competing infringing products. Furthermore, in one embodiment, the tracer compound may enable the detection of the manufacturing process in which the product is manufactured, thereby enabling the detection of patent infringement regarding specific manufacturing process chemistry.

[0086] An additive that can be used with the composition of the present invention may alternatively be a perfluoropolyether as described in detail in U.S. Patent Application Publication No. 2007-0284555, incorporated herein by reference.

[0087] It will be known that some of the additives mentioned above, suitable for non-refrigerant components, have been identified as potential refrigerants. However, according to the present invention, when these additives are used, they are not present in amounts that affect the novel and fundamental features of the refrigerant mixture of the present invention. Preferably, the refrigerant mixture and composition of the present invention containing them contain refrigerants other than HFC-32, HFO-1234yf, and CO2 in an amount of about 0.5 weight% or less.

[0088] In one embodiment, the composition disclosed herein may be prepared by any convenient method for combining desired amounts of individual components. A preferred method is to weigh the desired amount of component and then combine the components in a suitable container. If desired, stirring may be used.

[0089] The composition of the present invention has an ozone depletion potential of 0 and a low global warming potential (GWP). Additionally, the composition of the present invention will have a global warming potential lower than many hydrofluorocarbon refrigerants currently in use and even lower than many proposed alternative products.

[0090] Device and usage method

[0091] The compositions disclosed herein are useful as heat transfer compositions or refrigerants. In particular, compositions comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 are useful as refrigerants. Additionally, compositions comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 are useful as substitutes for R-410A in refrigeration, air conditioning, or heat pump systems. In particular, compositions comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 are useful as substitutes for R-410A in air conditioning and heat pump systems and devices. Alternatively, compositions comprising a refrigerant mixture consisting of HFC-32, HFO-1234yf, and CO2 are useful as substitutes for R-410A in air conditioning and heat pump systems and devices. Additionally, a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 is useful as a substitute for R-410A in refrigeration systems and devices. Furthermore, a composition comprising a refrigerant mixture consisting of HFC-32, HFO-1234yf, and CO2 is useful as a substitute for R-410A in refrigeration systems and devices. And the use of the composition of the present invention in refrigeration systems and devices applies to use in low-temperature refrigeration and medium-temperature refrigeration.

[0092] Accordingly, a method for generating cooling is disclosed herein, comprising the steps of: evaporating a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 near an object to be cooled; and then condensing said composition. Alternatively, the method for generating cooling comprises the steps of: evaporating a composition comprising a refrigerant mixture consisting of HFC-32, HFO-1234yf, and CO2 near an object to be cooled; and then condensing said composition. In one embodiment, this method may be used for refrigeration, air conditioning, and heat pumps. In another embodiment, the cooling method may be used for refrigeration. In another embodiment, the cooling method may be used for low-temperature refrigeration. In another embodiment, the cooling method may be used for medium-temperature refrigeration. In another embodiment, the cooling method may be used for air conditioning. In another embodiment, the cooling method may be used for heat pumps.

[0093] In another embodiment, a method for generating heat is disclosed herein, comprising the steps of: evaporating a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2; and then condensing said composition near an object to be heated. Alternatively, the method for generating heat comprises the steps of: evaporating a composition comprising a refrigerant mixture consisting of HFC-32, HFO-1234yf, and CO2; and then condensing said composition near an object to be heated. In one embodiment, this method is used in a heat pump.

[0094] Vapor-compression refrigeration, air conditioning, and heat pump systems include an evaporator, a compressor, a condenser, and an expansion unit. The refrigeration cycle reuses the refrigerant in multiple stages to produce a cooling effect in one stage and a heating effect in another. The cycle can be simply described as follows: Liquid refrigerant enters the evaporator through the expansion unit; at a low temperature, the liquid refrigerant boils in the evaporator to form a gas by absorbing heat from the external environment, thereby producing cooling. Often, air or a heat transfer fluid flows over or around the evaporator to transfer the cooling effect caused by the evaporation of the refrigerant within the evaporator to the object to be cooled. The low-pressure gas enters the compressor and is compressed, causing its pressure and temperature to rise. Subsequently, the high-pressure (compressed) gaseous refrigerant enters the condenser, where it condenses and releases its heat to the external environment. The refrigerant returns to the expansion unit, through which the liquid expands from the high-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.

[0095] An object to be cooled or heated may be defined as any space, location, object, or thing where providing cooling or heating is desirable. Examples include (open or enclosed) spaces requiring air conditioning, cooling, or heating, e.g., rooms, apartments or buildings, e.g., apartment buildings, university dormitories, townhouses, or other row houses or detached houses, hospitals, office buildings, supermarkets, university classrooms or government buildings, and car or truck cabins.

[0096] "Nearby" means that the evaporator of a system containing a refrigerant composition is positioned within or adjacent to the object to be cooled so that air moving over the evaporator moves into or around the object to be cooled. In a method for generating heat, "nearby" means that the condenser of a system containing a refrigerant composition is positioned within or adjacent to the object to be heated so that air moving over the evaporator moves into or around the object to be heated.

[0097] A method for replacing R-410A in an air conditioning or heat pump system is provided, comprising the step of replacing R-410A in the air conditioning or heat pump system with a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2. Alternatively, a method for replacing R-410A in an air conditioning or heat pump system comprises the step of replacing R-410A in the air conditioning or heat pump system with a composition comprising a refrigerant mixture consisting of HFC-32, HFO-1234yf, and CO2.

[0098] Often, alternative refrigerants are most useful when they can be used in the original refrigeration equipment designed for a different refrigerant. Additionally, compositions as disclosed herein may be useful as a substitute for R-410A in equipment designed for R-410A with minimal or no system modifications. Furthermore, compositions may be useful for replacing R-410A in equipment specifically modified or entirely manufactured for these new compositions, including HFC-32, HFO-1234yf, and CO2.

[0099] In many applications, some embodiments of the disclosed composition are useful as a refrigerant and provide cooling performance (meaning cooling capacity) at least comparable to that of a refrigerant to be replaced.

[0100] In one embodiment, a method for replacing R-410A is provided, the method comprising the step of charging an air conditioning or heat pump system with a composition comprising a refrigerant mixture consisting of HFC-32, HFO-1234yf, and CO2 as a substitute for said R-410A.

[0101] In one embodiment of this method, the cooling capacity provided by a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 is within about ±10% of the cooling capacity produced by R-410A under the same operating conditions. In another embodiment of this method, the cooling capacity provided by a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 is within about ±5% of the cooling capacity produced by R-410A under the same operating conditions. In another embodiment of this method, the cooling capacity provided by a composition comprising a refrigerant mixture essentially consisting of HFC-32, HFO-1234yf, and CO2 is within about ±2% of the cooling capacity produced by R-410A under the same operating conditions.

[0102] Additionally, an air conditioning or heat pump system comprising an evaporator, a compressor, a condenser, and an expansion device, characterized by containing a composition comprising HFC-32, HFO-1234yf, and CO2, is disclosed herein.

[0103] In another embodiment, a refrigeration system comprising an evaporator, a compressor, a condenser, and an expansion device is disclosed herein, characterized by containing a composition comprising HFC-32, HFO-1234yf, and CO2. The device may be intended for low-temperature refrigeration or medium-temperature refrigeration.

[0104] The composition of the present invention has been found to have some temperature gradient in the heat exchanger. Accordingly, the system will operate more efficiently when the heat exchanger operates in a counter-current mode or a cross-current mode with a counter-current trend. A counter-current trend means that the closer the heat exchanger is to the counter-current mode, the more efficient the heat transfer is. Accordingly, an air conditioning heat exchanger, in particular an evaporator, is designed to provide some aspect of a counter-current trend. Accordingly, an air conditioning or heat pump system is provided herein, wherein the system comprises one or more heat exchangers (evaporators, condensers, or both) operating in a counter-current mode or a cross-current mode with a counter-current trend.

[0105] Additionally, the composition of the present invention can be used in a system having a heat exchanger operating in a cross-flow mode.

[0106] In other embodiments, a refrigeration, air conditioning, or heat pump system is provided herein, wherein the system comprises one or more heat exchangers (evaporators, condensers, or both) operating in a countercurrent mode, a crosscurrent mode, or a crosscurrent mode having a countercurrent trend.

[0107] In one embodiment, the refrigeration, air conditioning, or heat pump system is a stationary refrigeration, air conditioning, or heat pump system. In another embodiment, the refrigeration, air conditioning, or heat pump system is a mobile refrigeration, air conditioning, or heat pump system.

[0108] Additionally, in some embodiments, the disclosed composition may function as a primary refrigerant in a secondary loop system providing cooling to a remote location using a secondary heat transfer fluid that may comprise water, an aqueous salt solution (e.g., calcium chloride), glycol, carbon dioxide, or a fluorinated hydrocarbon fluid. In such cases, the secondary heat transfer fluid is the object to be cooled, because the fluid is adjacent to the evaporator and is cooled before moving to a second remote object to be cooled.

[0109] Examples of air conditioning or heat pump systems include, but are not limited to, residential air conditioners, residential heat pumps, coolers including flooded evaporative coolers and direct expansion coolers, portable air conditioning units, dehumidifiers, and combinations thereof.

[0110] As used herein, a mobile refrigeration, air conditioning, or heat pump system refers to any refrigeration, air conditioning, or heat pump unit included in a transport unit for road, rail, sea, or air transport. A mobile air conditioning or heat pump system may be used in automobiles, trucks, railway vehicles, or other transport systems. Mobile refrigeration may include transport refrigeration in trucks, aircraft, or railway vehicles. Additionally, the invention includes a device intended to provide refrigeration for any system independent of a moving carrier—which is known as an "intermodal system." Such intermodal systems include "containers" (sea / land transport) as well as "swap bodies" (road and rail transport).

[0111] As used herein, a stationary air conditioning or heat pump system is a system that is fixed in place during operation. A stationary air conditioning or heat pump system may be combined or attached within any various building. Such stationary applications may include, but are not limited to, heat pumps including chillers, residential and high-temperature heat pumps, residential, commercial, or industrial air conditioning systems, window-type, ductless, ducted, packaged terminals, and external but connected to a building, e.g., rooftop systems, stationary air conditioning and heat pumps.

[0112] Examples of refrigeration systems to which the disclosed composition may be useful include commercial, industrial, or residential refrigerators and freezers, ice makers, self-contained coolers and freezers, flooded evaporative coolers, direct expansion coolers, walk-in and reach-in coolers and freezers, and equipment comprising combination systems. In some embodiments, the disclosed composition may be used in supermarket refrigeration systems. Additionally, stationary applications may utilize a secondary loop system that uses a primary refrigerant to generate cooling at one location and transfers it to a remote location via a secondary heat transfer fluid.

[0113] In the refrigeration, air conditioning, and heat pump system of the present invention, the heat exchanger will operate within a predetermined temperature limit. In the case of air conditioning, in one embodiment, the evaporator will operate at an intermediate temperature of about 0°C to about 20°C. In another embodiment, the evaporator will operate at an intermediate temperature of about 0°C to about 15°C. In yet another embodiment, the evaporator will operate at an intermediate temperature of about 5°C to about 10°C.

[0114] In the case of medium temperature refrigeration, in one embodiment, the evaporator will operate at an intermediate temperature of about -25°C to about 0°C. In another embodiment, the evaporator will operate at an intermediate temperature of about -18°C to about -1°C.

[0115] In the case of low-temperature refrigeration, in one embodiment, the evaporator will operate at an intermediate temperature of about -45°C to about -10°C. In another embodiment, the evaporator will operate at an intermediate temperature of about -40°C to about -18°C.

[0116] In one embodiment, the condenser will operate at an average temperature of about 15°C to about 60°C. In another embodiment, the condenser will operate at an intermediate temperature of about 20°C to about 60°C. In another embodiment, the condenser will operate at an intermediate temperature of about 20°C to about 50°C.

[0117] Examples

[0118] The concepts disclosed in this specification will be further described in the following examples, which do not limit the scope of the invention as described in the claims.

[0119] Examples

[0120] Cooling performance

[0121] The cooling performance under typical conditions for air conditioning and heat pump devices for the compositions of the present invention was determined and compared with R-410A, as shown in Table 1. The GWP values ​​are from the literature [Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report, Working Group I, 2007] (AR4). The mean temperature gradient (the average of the temperature gradient in the evaporator and the temperature gradient in the condenser), cooling capacity, and compressor discharge temperature are calculated from measurements of physical properties for the compositions of the present invention under the following specific conditions:

[0122] Evaporator temperature 50℉ (10℃)

[0123] Condenser temperature 115℉ (46.1℃)

[0124] Amount of superheating 20℉ (11.1 K)

[0125] Amount of subcooling 15℉ (8.3 K)

[0126] Compressor efficiency 70%

[0127] [Table 1]

[0128]

[0129]

[0130] All compositions of the present invention provided in Table 1 provide an average temperature gradient of less than 8°C and have a reasonable compressor discharge temperature compared to R-410A, while providing a volumetric capacity within ±10% of the volumetric capacity for R-410A. Many of the compositions in Table 1 provide a volumetric capacity within ±5% of the volumetric capacity for R-410A. Additionally, some of the compositions in Table 1 provide a volumetric capacity within ±2% of the volumetric capacity for R-410A. Furthermore, all compositions exhibit excellent energy efficiency (as a COP compared to R-410A), which is an improvement over R-410A for many of the compositions of the present invention.

[0131] Selected embodiment

[0132] Embodiment A1 : A composition comprising a refrigerant mixture for replacing R-410A, essentially consisting of difluoromethane, 2,3,3,3-tetrafluoropropene, and carbon dioxide.

[0133] Embodiment A2: A composition of embodiment A1 comprising a refrigerant mixture for replacing R-410A, wherein the refrigerant mixture essentially consists of about 42 to about 59 weight% difluoromethane, about 33 to about 53 weight% 2,3,3,3-tetrafluoropropene, and about 1 to about 9 weight% carbon dioxide.

[0134] Embodiment A3 : A composition of any of embodiments A1 and A2, wherein the refrigerant mixture essentially consists of about 42 to about 59 weight% difluoromethane, about 35 to about 51 weight% 2,3,3,3-tetrafluoropropene, and about 2 to about 9 weight% carbon dioxide.

[0135] Embodiment A4 : A composition of any of embodiments A1 to A3, wherein the refrigerant mixture essentially consists of about 42 to 59 weight% difluoromethane, about 37 to 48 weight% 2,3,3,3-tetrafluoropropene, and about 3 to 9 weight% carbon dioxide.

[0136] Embodiment A5 : A composition of any of embodiments A1 to A4, wherein the refrigerant mixture essentially consists of about 42 to 47 weight% difluoromethane, about 40 to 49 weight% 2,3,3,3-tetrafluoropropene, and about 3 to 9 weight% carbon dioxide.

[0137] Embodiment A6 : A composition of any of embodiments A1 to A5, wherein the refrigerant mixture essentially consists of about 44 to 47 weight% of HFC-32, about 40 to 49 weight% of 2,3,3,3-tetrafluoropropene, and about 5 to 9 weight% of CO2.

[0138] Embodiment A7: A composition of any of embodiments A1 to A6, wherein the refrigerant mixture essentially consists of about 42 to 45 weight% difluoromethane, about 46 to 49 weight% 2,3,3,3-tetrafluoropropene, and about 6 to 9 weight% carbon dioxide.

[0139] Embodiment A8 : A composition of any of embodiments A1 to A7, wherein the refrigerant mixture essentially consists of about 42 to 44 weight% difluoromethane, about 48 to 51 weight% 2,3,3,3-tetrafluoropropene, and about 7 to 9 weight% carbon dioxide.

[0140] Embodiment A9 : A composition of any of embodiments A1 to A8, wherein the refrigerant mixture essentially consists of about 44 weight% difluoromethane, about 49 weight% 2,3,3,3-tetrafluoropropene, and about 7 weight% carbon dioxide.

[0141] Embodiment A10 : The composition of Example A1, wherein the refrigerant mixture essentially consists of about 47 to about 59 weight% difluoromethane, about 37 to about 49 weight% 2,3,3,3-tetrafluoropropene, and about 3 to about 8 weight% carbon dioxide.

[0142] Embodiment A11 : A composition of any embodiment of embodiment A1 and embodiment A10, wherein the refrigerant mixture essentially consists of about 52 to about 59 weight% difluoromethane, about 37 to about 42 weight% 2,3,3,3-tetrafluoropropene, and about 3 to about 6 weight% carbon dioxide.

[0143] Embodiment A12: A composition of any of embodiments A1, A10 and A11, wherein the refrigerant mixture essentially consists of about 58 weight% difluoromethane, about 38 weight% 2,3,3,3-tetrafluoropropene, and about 4 weight% carbon dioxide.

[0144] Embodiment A13 : A composition of any of Embodiment A1 and Embodiments A10 to A12, wherein the refrigerant mixture essentially consists of about 58 weight% difluoromethane, about 38 weight% 2,3,3,3-tetrafluoropropene, and about 4 weight% carbon dioxide.

[0145] Embodiment A14 A composition of any of embodiments A1 to A13, further comprising one or more components selected from the group consisting of lubricants, dyes, solubilizers, compatibilizers, stabilizers, tracers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface inerts, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof.

[0146] Embodiment A15 A composition of any of embodiments A1 to A13, further comprising a lubricant selected from the group consisting of mineral oil, alkylbenzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, perfluoropolyether, synthetic paraffin, synthetic naphthene, polyalpha-olefin, and combinations thereof.

[0147] Embodiment A16 : The above lubricant is selected from the group consisting of mineral oil, alkylbenzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, perfluoropolyether, synthetic paraffin, synthetic naphthene, polyalpha-olefin, and combinations thereof, the composition of Example A14.

[0148] Embodiment B1 A method for generating cooling, comprising the step of condensing a composition of any of embodiments A1 to A12, and then the step of evaporating said composition near an object to be cooled.

[0149] Embodiment B2 A method for generating heat, comprising the step of evaporating a composition of any of embodiments A1 to A12, and then the step of condensing said composition near an object to be heated.

[0150] Embodiment C1 : A method for replacing R-410A in an air conditioning or heat pump system, comprising the step of providing a composition of any of embodiments A1 to A12 to the system as a substitute for R-410A in the air conditioning or heat pump system.

[0151] Embodiment C2 : A method for replacing R-410A in a refrigeration system, comprising the step of providing a composition of any of embodiments A1 to A12 to a system as a substitute for R-410A in the air conditioning or heat pump system.

[0152] Embodiment C3 : The method of embodiment C1, wherein the above system includes an evaporator, and the evaporator operates at an intermediate temperature of about 0°C to about 20°C.

[0153] Embodiment C4 : The above system includes an evaporator, and the evaporator operates at an intermediate temperature of about -45°C to about -10°C, the method of embodiment C2.

[0154] Embodiment C5 : The above system includes an evaporator, and the evaporator operates at an intermediate temperature of about -25°C to about 0°C, the method of embodiment C2.

[0155] Embodiment D1: An air conditioning or heat pump system comprising an evaporator, a compressor, a condenser, and an expansion device, characterized by accommodating a composition of any of embodiments A1 to A12.

[0156] Embodiment D2 : An air conditioning or heat pump system of embodiment D1 comprising one or more heat exchangers operating in a counter-flow mode, a cross-flow mode, or a cross-flow mode having a counter-flow trend.

[0157] Embodiment D3 : A refrigeration system comprising an evaporator, a compressor, a condenser, and an expansion device, characterized by accommodating a composition of any of embodiments A1 to A12.

[0158] Embodiment D4 : A refrigeration system of embodiment D3 comprising one or more heat exchangers operating in a counter-flow mode, a cross-flow mode, or a cross-flow mode having a counter-flow trend.

[0159] Embodiment D5 : The above system includes a low-temperature refrigeration system, and the evaporator operates at an intermediate temperature of about -45°C to about -10°C, a refrigeration system of embodiment D3 or embodiment D4.

[0160] Embodiment D6 : The above system includes a medium-temperature refrigeration system, and the evaporator operates at an intermediate temperature of about -25°C to about 0°C, a refrigeration system of embodiment D3 or embodiment D4.

[0161] Embodiment D7 : An air conditioning or heat pump system of embodiment D1 or embodiment D2, wherein the above evaporator operates at an intermediate temperature of about 0°C to about 20°C.

[0162] Embodiment E1: The refrigerant mixture is a composition of any of embodiments A1 to A12 having a GWP of 400 or less, a method of embodiment B1 or B2, a method of embodiment C1 to C5, or a system of any of embodiments D1 to D7.

[0163] Embodiment E2 : The refrigerant mixture is a composition of any of embodiments A1 to A12 having a GWP of 300 or less, a method of embodiment B1 or B2, a method of embodiment C1 to C5, or a system of any of embodiments D1 to D7.

Claims

Claim 1 A composition comprising a refrigerant mixture for replacing R-410A, wherein the refrigerant mixture essentially consists of 47 to 59 weight% difluoromethane, 37 to 49 weight% 2,3,3,3-tetrafluoropropene, and 3 to 8 weight% carbon dioxide, and exhibits a global warming potential (GWP) of 400 or less, an average temperature gradient of less than 8.0°C, and a cooling capacity within ±10% of the cooling capacity of R-410. Claim 2 A composition according to claim 1, wherein the refrigerant mixture essentially comprises 52 to 59 weight% difluoromethane, 37 to 42 weight% 2,3,3,3-tetrafluoropropene, and 3 to 6 weight% carbon dioxide. Claim 3 A composition according to claim 1, wherein the refrigerant mixture essentially comprises 57 to 59 weight% difluoromethane, 37 to 39 weight% 2,3,3,3-tetrafluoropropene, and 3 to 5 weight% carbon dioxide. Claim 4 A composition according to claim 1, wherein the refrigerant mixture essentially consists of 58 weight% difluoromethane, 38 weight% 2,3,3,3-tetrafluoropropene, and 4 weight% carbon dioxide. Claim 5 A composition according to claim 1, further comprising one or more components selected from the group consisting of lubricants, dyes, solubilizers, compatibilizers, stabilizers, tracers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof. Claim 6 In claim 5, the lubricant is a composition selected from the group consisting of mineral oil, alkylbenzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, perfluoropolyether, synthetic paraffin, synthetic naphthene, polyalpha-olefin, and combinations thereof. Claim 7 A method for generating cooling, comprising the step of condensing the composition of claim 1, and then the step of evaporating the composition near an object to be cooled. Claim 8 A method for generating heat, comprising the step of evaporating the composition of claim 1, and then the step of condensing the composition near an object to be heated. Claim 9 A method for replacing R-410A in an air conditioning or heat pump system, comprising the step of providing the composition of claim 1 as a substitute for said R-410A in said air conditioning or heat pump system. Claim 10 An air conditioning or heat pump system comprising an evaporator, a compressor, a condenser, and an expansion device, characterized by accommodating the composition of claim 1. Claim 11 An air conditioning or heat pump system according to claim 10, comprising one or more heat exchangers operating in a counter-current mode, a cross-current mode, or a cross-current mode having a counter-current trend. Claim 12 A method for replacing R-410A in a refrigeration system, comprising the step of providing the composition of claim 1 as a substitute for said R-410A in said refrigeration system. Claim 13 A refrigeration system comprising an evaporator, a compressor, a condenser, and an expansion device, characterized by accommodating the composition of claim 1. Claim 14 A refrigeration system according to claim 13, comprising one or more heat exchangers operating in a reverse flow mode, a cross flow mode, or a cross flow mode having a reverse flow trend.

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