Refrigerant compositions containing propylene and fluorocarbons and uses thereof

Abstract

Disclosed herein are compositions comprising HFC-32, HFO-1234yf, and propylene, and optionally further comprising HFC-125, propane, and / or carbon dioxide. The compositions of the invention are useful as refrigerants in air conditioning, heat pump, and refrigeration systems, providing a GWP of less than 150, a cooling capacity within 10% of R-404A or R-1234yf, and a COP similar to or improved relative to R-404A or R-1234yf.

Description

[Technical field]

[0001] The present invention relates to refrigerant compositions and methods and systems that use such compositions. [Background technology]

[0002] In the past few years, refrigerant blends have been proposed that use new molecules to provide blends with GWPs below 150, thereby improving upon existing fluoroolefin blends. The new molecules proposed are fluoroethylenes, such as HFO-1123, HFO-1132a, and HFO-1132E. However, there are significant concerns regarding the reactivity and safety of these molecules. HFO-1123 and HFO-1132a are known reactive monomers that can form homopolymers and copolymers with other olefins. Additionally, HFO-1123 is treated similarly to tetrafluoroethyene (TFE), which is known to be explosive in the presence of air and / or at pressures above 50 psi. HFO-1132a deflagrates at high pressures, in addition to its potential risk of runaway polymerization (the heat of polymerization for HFO-1132a is 2-3 times higher than TFE). Little data is available on HFO-1132E, but it is a structural isomer of HFO-1132a and is believed to be a more reactive monomer than HFO-1234yf, and thus may pose a potential deflagration hazard. Summary of the Invention [Problem to be solved by the invention]

[0003] The inventors have identified refrigerant blends that provide the required lower GWP, but are also less likely to pose safety risks when used. [Means for solving the problem]

[0004] The inventors have discovered unique compositions that provide a GWP of 150 or less, a capacity within 10% of either R-404A or R-1234yf, and a COP similar to or improved over R-404A or R-1234yf. Also, while the components are flammable or mild compounds, it is possible to produce blends that are only mildly flammable (ASHRAE Class 2L flammability), thus reducing the fire hazard.

[0005] In one embodiment of the invention, the composition comprises HFC-32, HFO-1234yf, and propylene.

[0006] The present invention includes the following aspects and embodiments.

[0007] In one embodiment, disclosed herein are compositions useful as refrigerants and heat transfer fluids. The compositions disclosed herein include 2,3,3,3-tetrafluoropropene (HFO-1234yf), difluoromethane (HFC-32), and propylene.

[0008] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant blend comprising HFC-32, HFO-1234yf, propylene, and further comprising propane.

[0009] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant blend comprising HFC-32, HFO-1234yf, propylene, and further comprising pentafluoroethane (HFC-125).

[0010] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant blend comprising HFC-32, HFO-1234yf, propylene, and further comprising propane and HFC-125.

[0011] According to any of the foregoing embodiments, the process comprises HFC-32, HFO-1234yf, propylene, and further comprises propane and / or HFC-125, and carbon dioxide (CO 2Also disclosed herein are compositions comprising refrigerant blends further comprising:

[0012] According to any of the foregoing embodiments, the mixture may comprise about 0.05 to 22.0 weight percent HFC-32, about 68.0 to 99.9 weight percent HFO-1234yf, and about 0.05 to 10 weight percent propylene, preferably about 3.0 to 22.0 weight percent HFC-32, about 68.0 to 95.0 weight percent HFO-1234yf, and about 2.0 to 10.0 weight percent propylene. Also disclosed herein are compositions comprising about 3.0 to 38.3 weight percent HFC-32, about 56.5 to 82.0 weight percent HFO-1234yf, and about 0.5 to 26.5 weight percent propylene, or about 18.0 to 22.0 weight percent HFC-32, about 75.0 to 79.0 weight percent HFO-1234yf, and about 0.5 to 3.0 weight percent propylene.

[0013] According to any of the foregoing embodiments, the mixture may comprise about 0.03 to 22.0 weight percent HFC-32, about 68.0 to 99.9 weight percent HFO-1234yf, about 0.03 to 9.0 weight percent propylene, and about 0.03 to 10.0 weight percent propane, preferably about 3.0 to 22.0 weight percent HFC-32, about 68.0 to 95.0 weight percent HFO-1234yf, about 2.0 to 9.0 weight percent propylene, and about 2.0 to 9.0 weight percent propane.

[0033] Also disclosed herein are compositions comprising about 18.0 to 22.0 weight percent HFC-32, about 75.0 to 79.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, and about 0.5 to 2.0 weight percent propane, or about 18.0 to 22.0 weight percent HFC-32, about 75.0 to 79.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, and about 0.5 to 2.0 weight percent propane.

[0014] According to any of the foregoing embodiments, the mixture is selected from the group consisting of about 0.03 to 21.0 weight percent HFC-32, about 68.93 to 99.9 weight percent HFO-1234yf, about 0.03 to 10.0 weight percent propylene, and about 0.03 to 4.0 weight percent HFC-125, preferably about 3.0 to 21.0 weight percent HFC-32, about 68.93 to 95.0 weight percent HF Also disclosed herein are compositions comprising about 17.0 to 19.0 weight percent HFC-32, about 77.0 to 79.0 weight percent HFO-1234yf, about 1.0 to 3.0 weight percent propylene, and about 0.5 to 4.0 weight percent HFC-125.

[0015] According to any of the foregoing embodiments, the mixture is about 0.03 to 21.0 weight percent HFC-32, 68.93 to 99.9 weight percent HFO-1234yf, 0.03 to 10.0 weight percent propylene, 0.03 to 10.0 weight percent propane, and 0.03 to 4.0 weight percent HFC-125, preferably about 3.0 to 21.0 weight percent HFC-32, about 68.93 to 95.0 weight percent HFO-1234yf, about 2. Also disclosed herein are compositions comprising 0 to 9.0 weight percent propylene, about 2.0 to 9.0 weight percent propane, and about 2.0 to 4.0 weight percent HFC-125, or about 17.0 to 19.0 weight percent HFC-32, about 17.0 to 19.0 weight percent HFO-1234yf, about 1.0 to 2.0 weight percent propylene, about 1.0 to 2.0 weight percent propane, and about 0.5 to 4.0 weight percent HFC-125.

[0016] According to any of the foregoing embodiments, the mixture may comprise about 0.03 to 22.0 weight percent HFC-32, 61.38 to 99.9 weight percent HFO-1234yf, 0.03 to 10.0 weight percent propylene, 0.03 to 10.0 weight percent propane, and 0.03 to 12.0 weight percent CO 2, preferably about 2.0 to 22.0 weight percent HFC-32, about 67.93 to 95.0 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 10.0 weight percent propane, and about 0.03 to 4.0 weight percent CO 2 or about 0.5 to 22.0 weight percent HFC-32, about 70.0 to 89.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, about 0.5 to 2.0 weight percent propane, and about 0.5 to 13.0 weight percent CO 2 Also disclosed herein are compositions comprising:

[0017] According to any of the foregoing embodiments, the mixture may comprise about 0.03 to 20.0 weight percent HFC-32, 69.93 to 99.9 weight percent HFO-1234yf, 0.03 to 10.0 weight percent propylene, 0.03 to 4.0 weight percent HFC-125, and 0.03 to 6.0 weight percent CO. 2 , preferably about 3 to 20 weight percent HFC-32, about 69.93 to 95 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 4.0 weight percent HFC-125, and about 3.0 to 6.0 weight percent CO 2 or about 2.0 to 19.0 weight percent HFC-32, about 71.0 to 89.0 weight percent HFO-1234yf, about 0.5 to 3.0 weight percent propylene, about 0.5 to 4.0 weight percent HFC-125, and about 0.5 to 14.0 weight percent CO 2 Also disclosed herein are compositions comprising:

[0018] According to any of the foregoing embodiments, the mixture may comprise about 0.03 to 20.0 weight percent HFC-32, about 69.93 to 99.9 weight percent HFO-1234yf, about 0.03 to 10.0 weight percent propylene, about 0.03 to 4.0 weight percent HFC-125, and about 0.03 to 6.0 weight percent CO 2, preferably about 3 to 20 weight percent HFC-32, about 69.93 to 95 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 4.0 weight percent HFC-125, and about 3.0 to 6.0 weight percent CO 2 or about 2.0 to 19.0 weight percent HFC-32, about 71.0 to 89.0 weight percent HFO-1234yf, about 0.5 to 3.0 weight percent propylene, about 0.5 to 4.0 weight percent HFC-125, and about 0.5 to 14.0 weight percent CO 2 Also disclosed herein are compositions comprising:

[0019] According to any of the foregoing embodiments, the mixture may comprise about 0.02 to 20.0 weight percent HFC-32, about 69.93 to 99.9 weight percent HFO-1234yf, about 0.02 to 10.0 weight percent propylene, about 0.02 to 10.0 weight percent propane, about 0.02 to 0.5 weight percent HFC-125, and about 0.02 to 5.0 weight percent CO. 2 , preferably about 2.0 to 20.0 weight percent HFC-32, about 69.93 to 95.0 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 10.0 weight percent propane, about 2.0 to 4.0 weight percent HFC-125, and about 0.5 to 4.0 weight percent CO 2 or about 0.5 to 19.0 weight percent HFC-32, about 71.0 to 88.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, about 0.5 to 2.0 weight percent propane, about 0.5 to 4.0 weight percent HFC-125, and about 0.5 to 13.0 weight percent CO 2 Also disclosed herein are compositions comprising:

[0020] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition further comprising at least one lubricant.

[0021] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein the lubricant is selected from the group consisting of polyalkylene glycols, polyol esters, polyvinyl ethers, poly-alpha-olefins, and combinations thereof.

[0022] According to any of the foregoing embodiments, the amount of lubricant can range from about 1% to about 20% by weight, from about 1% to about 7% by weight, and in some cases from about 1% to about 3% by weight.

[0023] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition further comprising at least one stabilizer.

[0024] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, lactones, and combinations thereof.

[0025] Also disclosed herein, according to any of the preceding embodiments, is a composition, wherein the stabilizer is selected from the group consisting of tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-terbutyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, butylated hydroxytoluene, and combinations thereof.

[0026] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition further comprising a tracer.

[0027] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition, wherein the tracer is selected from hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

[0028] According to any of the foregoing embodiments, there is provided a composition, the tracer being selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-161, HFC-152a, HFC-143a, HFC-227ca, HFC-227ea, HFC-236fa, HFC-236cb, HFC-236ea, HFC-245cb, HFC-245fa, HFC-245eb, HFC-254eb, HFC-263fb, HFC-264b, HFC-264cb, HFC-264fa, HFC-264b ... , HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC-338mf, HFC-338pcc, CFC-12, CFC-11, CFC-1 14, CFC-114a, CFC-115, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC- 244bb, HCC-40, HFO-1141, HCFO-1130E, HCFO-1130Z, HCFO-1130a, HCFO-1131, HCFO-1131a, HCFO-1122, HFO- 1123, HFO-1234ye, HFO-1243zf, HFO-1225yeZ, HFO-1225yeE, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC- Also disclosed herein are compositions selected from the group consisting of C318, PFC-1216, PFC-31-10mc, PFC-31-10my, CFO-1113, HFC-365mfc, HFC-43-10mee, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, hexafluorobutadiene, 3,3,3-trifluoropropyne, and combinations thereof.

[0029] Also disclosed herein, in accordance with any of the aforementioned embodiments, is a process for producing cooling, comprising evaporating any of the aforementioned compositions in the vicinity of a body to be cooled, and then condensing the composition.

[0030] Also disclosed herein, in accordance with any of the aforementioned embodiments, is a process for producing heating, the process comprising condensing any of the aforementioned compositions in the vicinity of a body to be heated and then evaporating the composition.

[0031] Also disclosed herein, in accordance with any of the aforementioned embodiments, is a system for cooling or heating, comprising an evaporator, a compressor, a condenser, and an expansion device, the system comprising any of the aforementioned compositions.

[0032] Also disclosed herein, in accordance with any of the foregoing embodiments, is a method for replacing a first refrigerant composition with a second refrigerant composition in a cooling or heating system, comprising removing the first refrigerant composition from the cooling or heating system and charging the cooling or heating system with the second refrigerant composition, wherein the first refrigerant is selected from any of R-22, R-134a, R-1234yf, R-1234ze, R-407C, R-407F, R-404A, or R-507, and the second refrigerant composition is any of the foregoing compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] definition A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during the cycle used to transfer heat.

[0034] A heat transfer system is a system (or device) used to create a heating or cooling effect in a particular space. Heat transfer systems can be portable or stationary systems.

[0035] Examples of heat transfer systems are any type of refrigeration and air conditioning system, including, but 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.

[0036] Refrigeration capacity (also called cooling capacity) is a term that defines the change in enthalpy of the refrigerant in the evaporator per pound of refrigerant circulating, or the heat removed by the refrigerant in the evaporator per unit volume (volume) of refrigerant vapor leaving the evaporator. Refrigeration capacity is a measure of the ability of a refrigerant or heat transfer composition to produce cooling. Thus, the higher the capacity, the greater the degree of cooling produced. Cooling rate refers to the heat removed per unit time by the refrigerant in the evaporator.

[0037] The coefficient of performance (COP) is the amount of heat removed divided by the energy input required to run the cycle. The higher the COP, the more energy efficient it is. COP is directly related to the energy efficiency ratio (EER), which is a rating of the efficiency of a refrigeration or air conditioning system at a specific combination of internal and external temperatures.

[0038] The term "subcooling" refers to lowering the temperature of a liquid below the saturation point of that liquid at a given pressure. While the saturation point is the temperature at which the vapor is completely condensed into liquid, subcooling continues to cool the liquid to a lower temperature at a given pressure. Cooling the liquid below its saturation temperature (or boiling point temperature) can increase the net refrigeration capacity. Subcooling thereby increases the refrigeration capacity and energy efficiency of the system. The amount of subcooling is the amount of cooling below the saturation temperature (in degrees).

[0039] Superheat is a term that defines how much a vapor composition is heated above its saturated vapor temperature (the temperature at which the first drop of liquid forms when the composition is cooled, also called the "dew point").

[0040] Temperature gradient (sometimes simply referred to as "gradient") is the absolute value of the difference between the start and end temperatures of a phase change process by a refrigerant in a refrigerant system component, excluding any subcooling or superheating. The term can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to the temperature gradient of a refrigeration, air conditioning or heat pump system, it is common to provide the average temperature gradient, which is the average of the evaporator temperature gradient and the condenser temperature gradient.

[0041] Net refrigeration effect is the amount of heat each kilogram of refrigerant absorbs in the evaporator to produce useful cooling.

[0042] Mass flow is the amount of refrigerant (in kilograms) circulating through a refrigeration, heat pump, or air conditioning system at a given time.

[0043] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition in use in any heat transfer system) that provides lubrication to the compressor to help prevent parts from seizing.

[0044] Flammability is a term used to mean 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 lowest concentration of the heat transfer composition in air that can propagate flame through a homogeneous mixture of the composition and air under the test conditions specified in ASTM E-681. The upper flammability limit ("UFL") is the highest concentration of the heat transfer composition in air that can propagate flame through a homogeneous mixture of the composition and air under the same test conditions. Also, testing under the conditions of ASTM E-681 determines whether a refrigerant compound or mixture is flammable or non-flammable.

[0045] When a refrigerant leaks, the lower boiling point components of the mixture may leak preferentially. This can cause the composition of the system and the vapor leak to change over the time of the leak. This can cause a non-flammable mixture to become flammable under potential leak conditions. 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 mixed, but also under leak conditions.

[0046] Global warming potential (GWP) is an index for estimating the relative global warming contribution resulting from the atmospheric emission of one kilogram of a particular greenhouse gas compared to the emission of one kilogram of carbon dioxide. GWP can be calculated for various time horizons and indicates the impact of a given gas's atmospheric lifetime. The GWP for a 100-year time horizon is the commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component.

[0047] Ozone depletion potential (ODP) is a number that indicates the amount of ozone destruction caused by a substance. ODP is the ratio of a chemical's effect on the ozone compared to that of a similar mass of CFC-11 (fluorotrichloromethane). For this reason, 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 do not contain chlorine or other ozone-depleting halogens, so they have an ODP of zero.

[0048] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or device that comprises recited elements is not necessarily limited to only those elements, but may include other elements not expressly recited or that are inherent in such composition, process, method, article, device, etc.

[0049] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase closes the claim to including materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase is intended to limit only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0050] The transitional phrase "consisting essentially of" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of." Typically, the components of the refrigerant mixture and the refrigerant mixture itself may contain small amounts (e.g., less than about 0.5% by weight in total) of impurities and / or by-products (e.g., from production of the refrigerant components or recycling of the refrigerant components from other systems) that do not materially affect the novel and basic characteristics of the refrigerant mixture.

[0051] It should be readily understood that where applicants have defined an invention or portions thereof with open-ended terms such as "comprising," the description should be construed as also describing an invention using the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0052] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that it has a different meaning.

[0053] 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 belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed composition embodiments, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are merely illustrative and are not intended to be limiting.

[0054] composition The present inventors propose a safer alternative to HFO-1123, HFO-1132E, etc., by using small amounts of propylene and / or propane in the refrigerant blend to improve capacity and keep GWP low. Propylene and propane are less reactive and flammable, but can produce desirable refrigerant blends when used in small amounts. Propylene has a molecular weight about 2 / 3 that of HFO-1132E or HFO-1132a, which allows less propylene to be used to achieve the same cooling effect. The key attributes of the refrigerant compositions claimed herein are safety (Class 2 or Class 2L stability and flammability), environmental friendliness (low GWP and zero ODP), and good refrigerant performance. In particular, the compositions provide a GWP of less than 150, cooling capacity within 10% of R-404A or R-1234yf, and a COP similar to or improved over R-404A or R-1234yf.

[0055] The refrigerant blends of the present invention include compositions comprising HFO-1234yf, HFC-32, and propylene; compositions comprising HFO-1234yf, HFC-32, propylene, and propane; compositions comprising HFO-1234yf, HFC-32, propylene, and HFC-125; compositions comprising HFO-1234yf, HFC-32, propylene, propane, and HFC-125; compositions comprising HFO-1234yf, HFC-32, propylene, propane, and HFC-125; 2 A composition comprising HFO-1234yf, HFC-32, propylene, HFC-125, and CO 2 and a composition comprising HFO-1234yf, HFC-32, propylene, propane, HFC-125, and CO 2 The composition includes:

[0056] In one embodiment, the refrigerant blend composition includes HFC-32, HFO-1234yf, and propylene. In another embodiment, the refrigerant blend composition further includes propane. In a different embodiment, the refrigerant blend composition further includes HFC-125. In another embodiment, the refrigerant blend composition further includes propane and HFC-125. In another embodiment, any of the aforementioned refrigerant blend compositions includes carbon dioxide (CO 2 ).

[0057] In one embodiment, the refrigerant blend composition comprises about 0.05 to 22.0 weight percent HFC-32, about 68.0 to 99.9 weight percent HFO-1234yf, and about 0.05 to 10.0 weight percent propylene. In another embodiment, the refrigerant blend composition comprises about 3.0 to 22.0 weight percent HFC-32, about 68.0 to 95.0 weight percent HFO-1234yf, and about 2.0 to 10.0 weight percent propylene. In another embodiment, the refrigerant blend composition comprises about 3.0 to 38.3 weight percent HFC-32, about 56.5 to 82.0 weight percent HFO-1234yf, and about 0.5 to 26.5 weight percent propylene. In another embodiment, the refrigerant blend composition comprises 18.0 to 22.0 weight percent HFC-32, about 75.0 to 79.0 weight percent HFO-1234yf, and about 0.5 to 3.0 weight percent propylene.

[0058] In one embodiment, the refrigerant blend composition comprises about 0.03-22.0 weight percent HFC-32, about 68.0-99.9 weight percent HFO-1234yf, about 0.03-9.0 weight percent propylene, and about 0.03-10.0 weight percent propane. In another embodiment, the refrigerant blend composition comprises about 3.0-22.0 weight percent HFC-32, about 68.0-95.0 weight percent HFO-1234yf, about 2.0-9.0 weight percent propylene, and about 2.0-9.0 weight percent propane. In another embodiment, the refrigerant blend composition comprises about 18.0-22.0 weight percent HFC-32, about 75.0-79.0 weight percent HFO-1234yf, about 0.5-2.0 weight percent propylene, and about 0.5-2.0 weight percent propane. In another embodiment, the refrigerant blend composition comprises about 18.0 to 22.0 weight percent HFC-32, about 75.0 to 79.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, and about 0.5 to 2.0 weight percent propane.

[0059] In one embodiment, the refrigerant blend composition comprises about 0.03 to 21.0 weight percent HFC-32, about 68.93 to 99.9 weight percent HFO-1234yf, about 0.03 to 9.0 weight percent propylene, and about 0.03 to 4.0 weight percent HFC-125. In another embodiment, the refrigerant blend composition comprises about 3.0 to 21.0 weight percent HFC-32, about 68.93 to 95.0 weight percent HFO-1234yf, about 2.0 to 9.0 weight percent propylene, and about 2.0 to 4.0 weight percent HFC-125. In another embodiment, the refrigerant blend composition comprises about 17.0 to 19.0 weight percent HFC-32, about 77.0 to 79.0 weight percent HFO-1234yf, about 1.0 to 3.0 weight percent propylene, and about 0.5 to 4.0 weight percent HFC-125.

[0060] In one embodiment, the refrigerant blend composition is from about 0.03 to 22.0 weight percent HFC-32, from about 61.83 to 99.9 weight percent HFO-1234yf, from about 0.03 to 10.0 weight percent propylene, from about 0.03 to 10.0 weight percent propane, and from about 0.03 to 12.0 weight percent CO 2 In another embodiment, the refrigerant blend composition comprises about 2.0 to 22.0 weight percent HFC-32, about 67.93 to 95.0 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 10.0 weight percent propane, and about 0.03 to 4.0 weight percent CO 2 In another embodiment, the refrigerant blend composition comprises about 0.5 to 22.0 weight percent HFC-32, about 70.0 to 89.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, about 0.5 to 2.0 weight percent propane, and about 0.5 to 13.0 weight percent CO 2 Includes.

[0061] In one embodiment, the refrigerant blend composition comprises about 0.03 to 21.0 weight percent HFC-32, about 68.93 to 99.9 weight percent HFO-1234yf, about 0.03 to 10.0 weight percent propylene, about 0.03 to 10.0 weight percent propane, and about 0.03 to 4.0 weight percent HFC-125. In another embodiment, the refrigerant blend composition comprises about 2.0 to 21.0 weight percent HFC-32, about 68.93 to 95.0 weight percent HFO-1234yf, about 2.0 to 9.0 weight percent propylene, about 2.0 to 9.0 weight percent propane, and about 0.5 to 4.0 weight percent HFC-125. In another embodiment, the refrigerant blend composition comprises about 17.0 to 19.0 weight percent HFC-32, about 17.0 to 19.0 weight percent HFO-1234yf, about 1.0 to 2.0 weight percent propylene, about 1.0 to 2.0 weight percent propane, and about 0.5 to 4.0 weight percent HFC-125.

[0062] In one embodiment, the refrigerant blend composition comprises about 0.03 to 20.0 weight percent HFC-32, about 69.93 to 99.9 weight percent HFO-1234yf, about 0.03 to 10.0 weight percent propylene, about 0.03 to 4.0 weight percent HFC-125, and about 0.03 to 6.0 weight percent CO 2 In another embodiment, the refrigerant blend composition comprises about 3 to 20 weight percent HFC-32, about 69.93 to 95 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 4.0 weight percent HFC-125, and about 3.0 to 6.0 weight percent CO 2 In another embodiment, the refrigerant blend composition comprises about 2.0 to 19.0 weight percent HFC-32, about 71.0 to 89.0 weight percent HFO-1234yf, about 0.5 to 3.0 weight percent propylene, about 0.5 to 4.0 weight percent HFC-125, and about 0.5 to 14.0 weight percent CO 2 Includes.

[0063] In one embodiment, the refrigerant blend composition comprises about 0.02 to 20.0 weight percent HFC-32, about 69.93 to 99.9 weight percent HFO-1234yf, about 0.02 to 10.0 weight percent propylene, about 0.02 to 10.0 weight percent propane, about 0.02 to 0.5 weight percent HFC-125, and about 0.02 to 5.0 weight percent CO 2 In another embodiment, the refrigerant blend composition comprises about 2.0 to 20.0 weight percent HFC-32, about 69.93 to 95.0 weight percent HFO-1234yf, about 2.0 to 10.0 weight percent propylene, about 2.0 to 10.0 weight percent propane, about 2.0 to 4.0 weight percent HFC-125, and about 0.5 to 4.0 weight percent CO 2 In another embodiment, the refrigerant blend composition comprises about 0.5 to 19.0 weight percent HFC-32, about 71.0 to 88.0 weight percent HFO-1234yf, about 0.5 to 2.0 weight percent propylene, about 0.5 to 2.0 weight percent propane, about 0.5 to 4.0 weight percent HFC-125, and about 0.5 to 13.0 weight percent CO 2 Includes.

[0064] In some embodiments, HFC-32, HFO-1234yf, propylene, and optionally propane, HFC-125, and / or CO 2Refrigerants containing have low GWP. In one embodiment, the refrigerant has a GWP of less than 150, or preferably less than 100. The GWP values ​​for the compositions of the present invention are taken from the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report, 2013 (AR5) for HFO-1234yf, HFC-32, and HFC-125. The GWP values ​​for propane and propylene are taken from the California Air Resources Board (see https: / / ww2.arb.ca.gov / resources / documents / high-gwp-refrigerants). Table A provides GWP values ​​for the determination of blend GWP.

[0065] [Table 1]

[0066] In addition to the refrigerant, the composition of the invention may contain other additional compounds. These additional compounds may be chosen from lubricants, stabilizers, tracers, UV dyes, among others.

[0067] In one embodiment, HFC-32, HFO-1234yf, propylene, and optionally, propane, HFC-125, and / or CO 2The compositions disclosed herein containing a refrigerant comprising may further comprise at least one refrigeration lubricant. In one embodiment, the at least one lubricant is selected from the group consisting of polyalkylene glycols (PAGs), polyol esters (POEs), and polyvinyl ethers (PVEs), and combinations thereof. Additionally, the compositions of the present invention may include other lubricants, such as mineral oils, alkylbenzenes, polyalphaolefins, among others. The amount of lubricant included in the compositions of the present invention may vary over a wide range. When the refrigerant is charged into a system for cooling or heating, the amount of lubricant mixed with the refrigerant will vary depending on the location in the system. The amount of lubricant may range from about 1 to about 20% by weight, from about 1 to about 7% by weight, and in some cases from about 1 to about 3% by weight.

[0068] In another embodiment, the stabilizer is selected from the group consisting of HFC-32, HFO-1234yf, propylene, and optionally propane, HFC-125, and / or CO 2 The stabilizer acts to inhibit the decomposition of the refrigerant molecules due to the presence of water or oxygen in the system. Additionally, the stabilizer can prevent polymerization of the HFO components of the refrigerant mixture. Thus, the stabilizer can be added to refrigerants containing HFC-32, HFO-1234yf, propylene, and optionally propane, HFC-125, and / or CO. 2Provided herein is a composition comprising a refrigerant comprising or consisting essentially of, and further comprising at least one stabilizer. In one embodiment, the at least one stabilizer may be selected from nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, lactones, and combinations thereof. In another embodiment, the stabilizer is selected from the group consisting of tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, butylated hydroxytoluene, and combinations thereof.

[0069] Alternatively, the stabilizer included in the composition of the present invention may be selected from the group consisting of hindered phenols, thiophosphates, butylated triphenyl phosphorothioate, organophosphates or phosphites, aryl alkyl ethers, terpenes, terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, amines, nitromethane, alkyl silanes, benzophenone derivatives, aryl sulfides, divinyl terephthalic acid, diphenyl terephthalic acid, ionic liquids, and mixtures thereof.

[0070] Additionally, the composition may further comprise at least one tracer compound or a mixture of tracer compounds. A tracer can be used to identify the process by which the refrigerant or refrigerant mixture is produced. The tracer compound may be specific to the production method or may be added as a single tracer or a mixture of tracers in a specific amount to detect dilution, adulteration, contamination, or other unauthorized activities.

[0071] The tracer may be a single compound, but may also be two or more tracer compounds of the same class of compound or different classes of compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 1 part per million (ppm) to about 5000 ppm by weight based on the weight of the total composition. In other embodiments, the tracer is present at a total concentration of about 1 ppm to about 1000 ppm. In other embodiments, the tracer is present at a total concentration of about 2 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 10 ppm to about 300 ppm.

[0072] The tracer compound may be selected from hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof. In particular, the tracer may be selected from HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-152a (1,1-difluoromethane), HFC-143a (1,1,1-trifluoroethane), HFC-227ca (1,1,1,2,2,3,3-heptafluoropropane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC-227b (1,1,1,2,3,3,3-heptafluoropropane), HFC-227c (1,1,1,2,3,3,3-heptafluoropropane), HFC-227d (1,1,1,2,3,3,3-heptafluoropropane), HFC-227e (1,1,1,2,3,3,3-heptafluoropropane), HFC-227f (1,1,1,2,3,3,3-heptafluoropropane), HFC-227g (1,1,1,2,3,3,3-heptafluoropropane), HFC-227h ... HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236cb (1,1,1,2,2,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-245eb (1,1,1,2,3-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2-fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (2-trifluoromethyl-1,1, 1,3,3,3-Hexafluoropropane), HFC-338mf (1,1,1,2,2,4,4,4-Octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-Octafluorobutane), CFC-12 (Dichlorodifluoromethane), CFC-11 (Trichlorofluoromethane), CFC-114 (1,2-Dichloro-1,1,2,2-tetrafluoroethane), CFC-114a (2,2-Dichloro-1,1,1,2-tetrafluoroethane), CFC-115 (chloropentafluoroethane), HCFC-22 (chlorodifluoromethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), HCFC-124a (1-chloro-1,1,2,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142b (1-chloro-1,1-difluoroethane), HCFC-151a (1-chloro-1-fluoroethane) , HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane), HCC-40 (chloromethane), HFO-1141 (fluoroethylene), HCFO-1130 (1,2-dichloroethylene, E- and / or Z-isomer), HCFO-1130a (1,1-dichloroethylene), HCFO-1131 (1-chloro-2-fluoroethylene, E- and / or Z-isomer), HCFO-1131a (1-chloro-1-fluoroethylene), HCFO-1122 (2-chloro-1,1-difluoroethylene), HFO-1123 (trifluoroethylene), HFO-1234ye (1,2,3,3-tetrafluoropropene), HFO-1243zf (3,3,3-trifluoropropene), HFO-1225yeZ (1,2,3,3,3-pentafluoropropene), HFO-1225yeE (1,2,3,3,3-pentafluoropropene), HFO-1225zc (1,1,3,3,3-pentafluoropropene), PFC-116 (hexafluoroethane), PFC-C216 (hexafluorocyclopropane), PFC-218 (octafluoropropane), PFC-C318 (octafluoropropane), Fluorocyclebutane (octafluorocyclebutane), PFC-1216 (hexafluoropropene), PFC-31-10mc (decafluorobutane), PFC-31-10my (2-trifluoromethyl-1,1,1,2,3,3,3-heptafluoropropane), 2-chloro-1,1,2-trifluoroethylene (CFO-1113), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-10mee), 1,1,1,2,The tracer may include, but is not limited to, compounds selected from 2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, hexafluorobutadiene, 3,3,3-trifluoropropyne, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons, or one hydrofluorocarbon combined with 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.

[0073] In another embodiment, the mixture of HFC-32, HFO-1234yf, propylene, and optionally propane, HFC-125, and / or CO as described herein. 2 Provided herein is a storage vessel for a refrigerant containing a composition comprising:

[0074] The storage container will be appropriately prepared for filling with the composition by evacuation and heating such that there is a limit to the amount of water and / or oxygen to prevent reaction or decomposition of the refrigerant portion of the composition within the container. In one embodiment, water is limited to 0.1-200 ppm by weight, or 0.1-100 ppm by weight, or 0.1-50 ppm by weight, or 0.1-10 ppm by weight. In another embodiment, oxygen is limited to 0.35 volume percent or less. In another embodiment, oxygen is present at about 0.01-0.35 volume percent. In yet another embodiment, oxygen is limited to 0.01-0.25 volume percent. And in yet another embodiment, oxygen is limited to 0.01-0.15 volume percent.

[0075] The container for storing the aforementioned composition can be constructed of any suitable material and design that can seal the composition while maintaining the gas and liquid phases. Examples of suitable containers include pressure vessels such as tanks, filled cylinders, and secondary filled cylinders. The container can be constructed from any suitable material, such as carbon steel, manganese steel, chromium-molybdenum steel, among various low alloy steels, stainless steels, and sometimes aluminum alloys.

[0076] The compositions of the present invention can be prepared by any convenient method for combining the desired amounts of the individual components. A preferred method is to weigh the desired amounts of the components and then combine the components in a suitable vessel. Agitation may be used if desired. In another embodiment, any of the aforementioned refrigerant compositions are selected from HFC-32, HFO-1234yf, propylene, and optionally propane, HFC-125, and / or CO. 2 It can be prepared by blending.

[0077] Additionally, compositions may be prepared from recycled or regenerated refrigerants. One or more of the components may be recycled or regenerated by removing contaminants such as air, water, or residues that may include lubricants or particulate residues from the system components. Means for removing contaminants may vary widely, but may include distillation, decantation, filtration, and / or drying with the use of molecular sieves or other absorbents. The recycled or regenerated components may then be combined with other components as described above.

[0078] Methods, processes and apparatus A vapor compression refrigeration, air conditioning or heat pump system includes an evaporator, a compressor, a condenser and an expansion device. The vapor compression cycle reuses the refrigerant in multiple steps to produce a cooling effect in some steps and a heating effect in other steps. The above cycle can be simply explained as follows: Liquid refrigerant passes through an expansion device and enters an evaporator where it boils and removes heat from the environment, forming a low temperature gas and producing cooling. The low pressure gas enters a compressor where the gas is compressed and its pressure and temperature are increased. The high pressure (compressed) gaseous refrigerant then enters a condenser where the refrigerant is condensed and releases its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from a higher pressure level in the condenser to a lower pressure level in the evaporator, thus repeating the cycle.

[0079] In one embodiment, provided herein is a process for producing cooling comprising evaporating any of the compositions described herein in the vicinity of a body to be cooled and then condensing the composition.

[0080] In another embodiment, provided herein is a process for producing heating, the process comprising condensing any of the compositions described herein in the vicinity of a body to be heated and then evaporating the composition.

[0081] An object to be cooled or heated may be defined as any space, location, object, or object to which it is desirable to provide cooling or heating. Examples include, but are not limited to, spaces (open or enclosed) that require air conditioning, cooling, or heating, such as rooms, apartments, or buildings, such as apartment buildings, college dormitories, townhouses, or other multifamily or single-family homes, hospitals, office buildings, supermarkets, classrooms or administrative buildings of schools, colleges or universities, and passenger compartments of automobiles or trucks. Additionally, objects to be cooled may include electronic equipment, such as computer equipment, central processing units (CPUs), data centers, server banks, and personal computing devices, among others.

[0082] In some cases, such as in chillers, the object being cooled is a secondary fluid that is transferred to the space, location, object, or body for which it is desired to provide cooling. Secondary fluids include, by way of non-limiting example, water, aqueous brine solutions (e.g., CaCl for cooling equipment in manufacturing processes), 2 , MgCl 2 etc.), or a glycol or alcohol-water solution. The same applies to water-heating heat pumps, where the object to be heated is, for example, water to be transported to a home for heating, or water to heat water for use in an appliance.

[0083] By "proximate" it is meant that the evaporator of a system comprising the refrigerant blend of the present invention is located either within or in close proximity to the object to be cooled, such that the air moving through the evaporator moves through or around the object to be cooled. In a process for producing heating, "proximate" means that the condenser of a system comprising the refrigerant is located either within or in close proximity to the object to be heated, such that the air moving through the condenser moves through or around the object to be heated. In some embodiments, with respect to heat transfer, "proximate" can mean, for example, that the object to be cooled is directly immersed in the refrigerant, or that tubing containing the refrigerant flows inside and through electronic equipment and out of electronic equipment.

[0084] In another embodiment, a system for cooling is provided, the system including an evaporator, a compressor, a condenser, and an expansion device, the system including any of the compositions disclosed herein.

[0085] In one embodiment, the system for cooling may be selected from the group consisting of refrigeration and air conditioning systems including, but not limited to, stationary heat transfer systems, air conditioners, freezers, refrigerators, supermarket refrigerated cases, supermarket freezer cases, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, portable refrigerators, transport refrigeration devices, portable heat transfer systems, portable air conditioning units, dehumidifiers, and combinations thereof.

[0086] In one embodiment, the system for cooling may be a chiller. In some embodiments, the chiller is a direct expansion evaporator chiller or a flooded evaporative chiller. In some embodiments, the heat exchanger for the chiller operates in a counter-current mode, which will increase the efficiency of the system. In some embodiments, the chiller includes a compressor selected from a centrifugal, screw, scroll, or reciprocating compressor.

[0087] A chiller is a heat transfer device that cools (or chills) a liquid and then uses that liquid to cool or heat a secondary location. For example, they are often used to air condition buildings such as office buildings, apartment buildings, hospitals, etc. Chillers may be used in manufacturing processes to cool equipment such as distillation columns. Additionally, chillers may be used to refrigerate display cases in supermarkets.

[0088] In another embodiment, a system for heating is provided, the system including an evaporator, a compressor, a condenser, and an expansion device, the system including any of the compositions disclosed herein. In one embodiment, the system for heating may be a heat pump. The heat pump may be a residential heat pump for heating air. In another embodiment, the heat pump may be a high temperature heat pump, which means a heat pump with a condenser temperature above 55°C, or a condenser temperature above 80°C, or even a condenser temperature above 100°C.

[0089] Heat pumps, similar to chillers, can include flooded or direct expansion evaporators. Heat pumps may utilize positive displacement or dynamic compressors (e.g., centrifugal compressors). Positive displacement compressors include reciprocating, screw, or scroll compressors. Of note are heat pumps that use screw compressors. Also of note are heat pumps that use centrifugal compressors.

[0090] Residential heat pumps are used to produce heated air to heat a residence or dwelling (including a single-family home or an attached apartment building) and to produce maximum condenser operating temperatures of about 30°C to about 50°C.

[0091] Of note are high temperature heat pumps that may be used to heat air, water, another heat transfer medium, or some portion of an industrial process such as a piece of equipment, a storage area, or a process stream. In one embodiment, these high temperature heat pumps use a condenser operating temperature above about 55° C. In one embodiment, the condenser operating temperature for a high temperature heat pump is from about 55° C. to about 150° C. In one embodiment, the system for heating may be a water heating heat pump.

[0092] In one embodiment, a method is provided for replacing a first refrigerant composition with a second refrigerant composition in a cooling or heating system, the method comprising removing the first refrigerant composition from the cooling or heating system and charging the cooling or heating system with the second refrigerant composition, the first refrigerant being selected from any of R-22, R-134a, R-1234yf, R-407C, R-407F, R-404A, or R-507, and the second refrigerant composition being a composition according to any one of claims 1 to 11.

[0093] The present invention will be described in more detail below with reference to specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize various non-critical parameters that can be changed or modified to obtain essentially the same results. EXAMPLES

[0094] Refrigerant performance is determined for the compositions of the present invention at typical conditions for medium temperature refrigeration and portable air conditioning. For medium temperature refrigeration, the results are compared to R-404A. For portable air conditioning, the results are compared to R-1234yf. In the results tables for all examples, the Average Temp Glide (average of the temperature gradient in the evaporator and the temperature gradient in the condenser), the cooling capacity (CAP%) relative to R-404A or R-1234yf, and the COP (COP%) relative to R-404A or R-1234yf are calculated from physical property measurements for the compositions of the present invention at the specified conditions.

[0095] About medium temperature refrigeration:

[0096] [Table 2]

[0097] About portable air conditioners:

[0098] [Table 3]

[0099] Example 1 Refrigerant performance in medium temperature refrigeration for 32 / 1234yf / propylene. The results are shown in Table 1.

[0100] [Table 4]

[0101] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-1234yf, and a COP very similar to R-1234yf.

[0102] Example 2 Refrigerant performance in portable air conditioning for 32 / 1234yf / propylene. The results are shown in Table 2.

[0103] [Table 5]

[0104] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-1234yf, and a COP very similar to R-1234yf.

[0105] Example 3 Refrigerant performance in medium temperature refrigeration for 32 / 1234yf / propylene / propane. The results are shown in Table 3.

[0106] [Table 6]

[0107] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that of R-404A, and a COP about 3% higher than R-404A.

[0108] Example 4 Refrigerant performance in portable air conditioning for 32 / 1234yf / propylene / propane. The results are shown in Table 4.

[0109] [Table 7]

[0110] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-1234yf, and a COP very similar to R-1234yf.

[0111] Example 5 Refrigerant performance in medium temperature refrigeration for 1234yf / 32 / propylene / 125. The results are shown in Table 5.

[0112] [Table 8]

[0113] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-404A, and a COP very similar to R-404A.

[0114] Example 6 Refrigerant performance in portable air conditioning for 32 / 1234yf / propylene / 125. The results are shown in Table 6.

[0115] [Table 9]

[0116] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-1234yf, and a COP very similar to R-1234yf.

[0117] Example 7 Refrigerant performance in medium temperature refrigeration for 1234yf / 32 / propylene / propane / 125. The results are shown in Table 7.

[0118] [Table 10]

[0119] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-404A, and a COP very similar to R-404A.

[0120] Example 8 Refrigerant performance in portable air conditioning for 32 / 1234yf / propylene / propane / 125. The results are shown in Table 8.

[0121] [Table 11]

[0122] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-1234yf, and a COP very similar to R-1234yf.

[0123] Example 9 1234yf / 32 / propylene / 125 / CO 2 The refrigerant performance in medium temperature refrigeration is shown in Table 9.

[0124] [Table 12]

[0125] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-404A, and a COP very similar to R-404A.

[0126] Example 10 32 / 1234yf / propylene / 125 / CO 2 Refrigerant performance in portable air conditioners for. The results are in Table 10.

[0127] [Table 13]

[0128] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-1234yf, and a COP very similar to R-1234yf.

[0129] Example 11 1234yf / 32 / propylene / propane / 125 / CO 2 Refrigerant performance in medium temperature refrigeration. The results are in Table 11.

[0130] [Table 14]

[0131] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-404A, and a COP very similar to R-404A.

[0132] Example 12 1234yf / 32 / propylene / propane / CO 2 Refrigerant performance in medium temperature refrigeration. The results are in Table 12.

[0133] [Table 15]

[0134] The results show that the compositions of the present invention have a GWP of 150 or less, a capacity within 10% of that for R-404A, and a COP very similar to R-404A.

Claims

1. A composition comprising HFC-32, HFO-1234yf, and propylene.

2. The composition according to claim 1, further comprising propane.

3. The composition according to claim 1, further comprising HFC-125.

4. The composition according to claim 1, further comprising propane and HFC-125.

5. CO 2 A composition according to any one of claims 1 to 4, further comprising:

6. The composition according to claim 1, comprising about 0.05 to 22.0 weight percent of HFC-32, about 68.0 to 99.9 weight percent of HFO-1234yf, and about 0.05 to 10 weight percent of propylene.

7. The composition according to claim 2, comprising approximately 0.03 to 22.0 weight percent of HFC-32, approximately 68.0 to 99.9 weight percent of HFO-1234yf, approximately 0.03 to 9.0 weight percent of propylene, and approximately 0.03 to 10.0 weight percent of propane.

8. The composition according to claim 3, comprising approximately 0.03 to 21.0 weight percent of HFC-32, approximately 68.93 to 99.9 weight percent of HFO-1234yf, approximately 0.03 to 10.0 weight percent of propylene, and approximately 0.03 to 4.0 weight percent of HFC-125.

9. The composition according to claim 4, comprising approximately 0.03 to 21.0 weight percent of HFC-32, approximately 68.93 to 99.9 weight percent of HFO-1234yf, approximately 0.03 to 10.0 weight percent of propylene, approximately 0.03 to 10.0 weight percent of propane, and approximately 0.03 to 4.0 weight percent of HFC-125.

10. Approximately 0.03 to 22.0 weight percent of HFC-32, approximately 61.38 to 99.9 weight percent of HFO-1234yf, approximately 0.03 to 10.0 weight percent of propylene, approximately 0.03 to 10.0 weight percent of propane, and approximately 0.03 to 12.0 weight percent of CO 2 The composition according to claim 5, comprising:

11. Approximately 0.03 to 20.0 weight percent of HFC-32, approximately 69.93 to 99.9 weight percent of HFO-1234yf, approximately 0.03 to 10.0 weight percent of propylene, approximately 0.03 to 4.0 weight percent of HFC-125, and approximately 0.03 to 6.0 weight percent of CO 2 The composition according to claim 5, comprising:

12. Approximately 0.02–20.0 weight percent HFC-32, approximately 69.93–99.9 weight percent HFO-1234yf, approximately 0.02–10.0 weight percent propylene, approximately 0.02–10.0 weight percent propane, approximately 0.02–0.5 weight percent HFC-125, and approximately 0.02–5.0 weight percent CO 2 The composition according to claim 5, comprising:

13. The composition according to claim 1, further comprising at least one lubricant.

14. The composition according to claim 13, wherein the lubricant is selected from the group consisting of polyalkylene glycol, polyol ester, polyvinyl ether, and combinations thereof.

15. The composition according to claim 1, further comprising at least one stabilizer.

16. The composition according to claim 15, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azole, phenol compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, lactones, and combinations thereof.

17. The composition according to claim 15, wherein the stabilizer is selected from the group consisting of toltriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-diterbutyl-4-methylphenol, fluorinated epoxide, n-butylglycidyl ether, hexanediol diglycidyl ether, allylglycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, butylated hydroxytoluene, and combinations thereof.

18. The composition according to claim 1, further comprising at least one tracer.

19. The composition according to claim 18, wherein the tracer is selected from hydrofluorocarbon, hydrofluoroolefin, hydrochlorocarbon, hydrochloroolefin, hydrochlorofluorocarbon, hydrochlorofluoroolefin, hydrochlorocarbon, hydrochloroolefin, chlorofluorocarbon, chlorofluoroolefin, hydrocarbon, perfluorocarbon, perfluoroolefin, and combinations thereof.

20. The tracer is HFC-23, HCFC-31, HFC-41, HFC-161, HFC-152a, HFC-143a, HFC-227ca, HFC-227ea, HFC-236fa, H FC-236cb, HFC-236ea, HFC-245cb, HFC-245fa, HFC-245eb, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281e a, HFC-281fa, HFC-329p, HFC-329mmz, HFC-338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, CFC -115, HCFC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40 , HFO-1141, HCFO-1130E, HCFO-1130Z, HCFO-1130a, HCFO-1131, HCFO-1131a, HCFO-1122, HFO-1123, HFO- 1234ye, HFO-1243zf, HFO-1225yeZ, HFO-1225yeE, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, The composition according to claim 18, selected from the group consisting of PFC-1216, PFC-31-10mc, PFC-31-10my, CFO-1113, HFC-365mfc, HFC-43-10mee, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, hexafluorobutadiene, 3,3,3-trifluoropropyne, and combinations thereof.

21. A process for causing cooling, comprising evaporating the composition according to claim 1 in the vicinity of an object to be cooled, and then condensing the composition.

22. A process for generating heating, comprising condensing the composition according to claim 1 in the vicinity of an object to be heated, and then evaporating the composition.

23. A system for cooling or heating, comprising an evaporator, a compressor, a condenser, and an expansion device, wherein the system comprises the composition described in claim 1.

24. A method for replacing a first refrigerant composition with a second refrigerant composition in a cooling or heating system, comprising removing the first refrigerant composition from the cooling or heating system and filling the cooling or heating system with the second refrigerant composition, wherein the first refrigerant is selected from R-22, R-134a, R-1234yf, R-407C, R-407F, R-404A, or R-507, and the second refrigerant composition is the composition described in claim 1.