Refrigerants having low GWP and systems and methods for providing refrigeration

Abstract

A refrigerant comprising about 15% to about 22% by weight of R-32, about 61% to about 71.5% by weight of HFO-1234yf, about 4% to about 14.5% by weight of HFO-1132(E), and 1% to 4% by weight of CO2.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This invention is related to and claims the benefit of priority to U.S. Provisional Patent Application Nos. 63 / 436,574 and 63 / 436,575, each filed December 13, 2022, each of which is incorporated herein by reference.

[0002] The present invention relates to low global warming potential ("low GWP") refrigerants and heat transfer compositions, heat transfer methods, and heat transfer systems that are particularly useful in medium and low temperature refrigeration systems, cascade refrigeration systems, transport refrigeration systems, and heat pumps. In certain aspects, the present invention relates to walk-in refrigeration and / or freezing units sized 3000 square feet or less, and beverage and food coolers located in hallways and corridors that provide cooling at medium and low refrigeration temperatures. The present invention also provides refrigerants and heat transfer compositions, heat transfer methods, and heat transfer systems that can provide low GWP solutions as an alternative to the use of relatively high GWP refrigerants, including R448A, particularly in walk-in refrigeration and / or freezing units sized 3000 square feet or less and beverage and food coolers located in hallways and corridors. [Background technology]

[0003] Certain single-component fluorocarbons, including chlorofluorocarbons ("CFCs"), hydrochlorofluorocarbons ("HCFCs"), and hydrofluoroolefins ("HFOs"), have been used in many heat transfer applications. One advantage that single-component fluids have as refrigerants is that they have a constant boiling point for a given pressure. This is highly desirable because it allows for the design of a refrigeration system or method with a refrigerant temperature along the evaporator that has small, acceptable variations during the evaporation process, assuming little or no pressure drop as the refrigerant flows through the evaporator.

[0004] Those skilled in the art have primarily utilized single-component refrigerants, such as HFC-134a, in many refrigeration applications and have avoided refrigerant blends because blends generally exhibit a significant change in boiling point temperature upon evaporation, which has been recognized as a major obstacle to the ability to identify blends with the correct balance of properties to be useful in such systems. This change in boiling point temperature is generally reflected in a blend characteristic known as the blend's "glide." Generally, the greater the glide, the greater the boiling point differences experienced within various refrigeration equipment. In many critical applications, this parameter is considered critical to the success of the refrigerant and / or the refrigeration system in which the refrigerant is used, and a relatively low glide characteristic provides a significant advantage in many critical applications.

[0005] Another refrigerant characteristic that has become increasingly important in recent years, to the point that it is now critical for many applications, is the environmental compatibility of the refrigerant. This environmental compatibility can be measured, at least in part, by the predicted impact that releasing the refrigerant into the atmosphere would have on global warming. This predicted impact is often measured as the refrigerant's global warming potential (GWP), and refrigerants with a GWP are highly desirable and / or legally required for use in many applications.

[0006] Flammability is another important concern for refrigerants used in applications. Currently, it is most preferred for refrigerants to be non-flammable up to a Class 1 classification by ASHRAE. The second most preferred grade of non-flammable is a Class 2L classification by ASHRAE. Applicants and others in the art have come to recognize that it is extremely difficult to develop new refrigerants that are simultaneously environmentally compatible, have a GWP preferably less than 150, have a low glide, preferably less than 3°C, and are non-flammable, preferably having a 2L or 1 rating. Applicants have particularly realized that in many applications, it is extremely difficult to identify a single-component fluid that has the complete set of properties that make it particularly advantageous in the types of applications discussed herein, much less identify a refrigerant that is a blend of components that has such a complete set. For example, in many critical applications, it is necessary to identify a refrigerant that simultaneously (1) has a usable glide, (2) has a low global warming potential (GWP) (i.e., less than about 150), (3) is nonflammable (i.e., Class 1 or Class 2L according to ASHRAE), (4) has low or virtually no toxicity, and (5) has heat transfer and other properties (such as chemical stability) that meet the needs of the particular application, particularly in medium-temperature heat transfer systems. While the use of single-component refrigerants can often satisfy one or two of these criteria, those skilled in the art have found it difficult (if not impossible) to find a refrigerant (whether single-component or not) that can satisfy all five criteria, i.e., achieves each of criteria (1) through (5). Here, low-toxicity materials are classified as Class "A" by ASHRAE Standard 34-2016. Materials that are both nonflammable and low-toxic are classified as "A1" or A2L by ASHRAE Standard 34-2016.

[0007] It is also highly desirable to provide refrigerants and heat transfer compositions that can be used in a variety of cooling applications. Applicants have come to recognize that to meet this need, as well as many other important needs noted above, refrigerants and heat transfer compositions must operate within industry and / or government requirements in the most restrictive applications. In this regard, it is noted that the U.S. Department of Energy (DOE) and Natural Resources Canada (NRCAN) are implementing new energy efficiency rules, commonly referred to as "AWEF," that apply to walk-in coolers and refrigeration (hereinafter sometimes referred to as "WICF") of 3,000 square feet or less. These rules include specifications for the Annual Walk-In Energy Factor (AWEF), developed by the Air-Conditioning, Heating, and Refrigeration Institute (AHR1). In such applications, refrigerant glide is particularly important because refrigerants with glide tend to operate at lower evaporating temperatures to meet AWEF dew point standards, which impacts performance under AWEF. The refrigerant that has been used to meet these stringent requirements is R448A, but R448A has the serious drawback of having a GWP of over 150.

[0008] Therefore, efforts to find low-GWP alternative refrigerants, particularly for use in WICFs of 3,000 square feet or less and / or for refrigeration systems used in confined spaces, present a significant and challenging technical challenge. This challenge is particularly difficult because, given the requirement to meet safety concerns when using A2L refrigerants, there may be limitations on the refrigerant charge that can be used in such systems. For example, ANSI / ASHRAE 15, the standard for refrigeration systems, has typically been used by regulatory agencies for on-site installations of refrigeration equipment, including vending machines. However, prior to this regulatory revision, the ANSI / ASHRAE 15 requirements did not allow refrigeration systems (which may include refrigerated vending machines) to be installed in public corridors or lobbies if the systems used refrigerants that were not Class A1. The rationale for this requirement was related to the need for building occupants to have free and unimpeded access to exits in the event of a fire within the building. At the time, it seemed reasonable to assume that vending machines located in public corridors, lobbies, or similar areas could release flammable refrigerants during a fire, potentially restricting occupants' ability to escape the building and preventing firefighters' entry. However, a 2020 study resulted in a change to the ANSI / ASHRAE 15 requirements to allow A2L refrigerants to be used in such systems, provided that the flammable refrigerant charge in the system is no more than three times the refrigerant's lower flammability limit (LFL), expressed in kilograms per cubic meter (kg / m3) (or expressed in imperial units, no more than 106 times the LFL, expressed in pounds per cubic foot). This change was based on the conclusion that such refrigerants, if identified for use in such systems, do not substantially increase the risk to occupants who need to escape the building during a fire.

[0009] Applicants have come to realize that a mosaic of difficult-to-achieve properties can be unexpectedly met by use of the refrigerants of the present invention, as described in detail below. Summary of the Invention

[0010] Applicants have unexpectedly and advantageously discovered that with certain refrigerants based on carefully selected amounts of a combination of R-32, HFO-1234yf, HFO-1132(E) and CO, as described in detail below, it is possible to achieve a refrigerant that meets many, preferably all, of the requirements discussed above, as well as additional requirements and / or advantages as described below.

[0011] Applicants have discovered refrigeration methods and systems that utilize one or more of the refrigerants, heat transfer compositions, and compositions of the present invention as the refrigerant, particularly for WICFs of 3000 square feet or less, and vending machines located in public hallways, lobbies, or similar areas.

[0012] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. More than 15% by weight and less than 22% by weight of R-32; b. greater than 60.5 wt.% to about 71.5 wt.% HFO-1234yf; c. 4% by weight to less than 14.5% by weight of HFO-1132(E); d. A refrigerant comprising greater than 1.5% to 3.5% by weight of CO2.

[0013] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 1A.

[0014] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 15% by weight to about 22% by weight of R-32; b. about 61% by weight to about 71.5% by weight of HFO-1234yf; c. about 4% to about 14.5% by weight of HFO-1132(E); d. 1 wt% to 4 wt% CO2; provided, however, that such refrigerants include refrigerants having a GWP of 150 or less and a lower flammability limit of 0.25 or greater. Refrigerants according to this paragraph may be referred to herein for convenience as Refrigerant 1B.

[0015] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 15.5 wt% to 21.5 wt% R-32; b. 61 wt% to about 71.5 wt% HFO-1234yf; c. 4 wt% to 14 wt% HFO-1132(E); d. Contains a refrigerant containing 2% to 3.5% by weight of CO2.

[0016] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 1C.

[0017] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 19% by weight to less than 22% by weight of R-32; b. 61 wt% to less than 65 wt% HFO-1234yf; c. about 11% to less than 14.5% by weight of HFO-1132(E); d. Contains a refrigerant containing 2% to 3.5% by weight of CO2.

[0018] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 2A.

[0019] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 19% by weight to less than 22% by weight of R-32; b. 61 wt% to less than 65 wt% HFO-1234yf; c. about 11% to less than 14.5% by weight of HFO-1132(E); d. 2% to 3.5% by weight of CO2, and d. 2% to 3.5% by weight of CO2, wherein the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more.

[0020] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 2B.

[0021] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 19% by weight to 21.5% by weight of R-32; b. 61 wt% to 64.5 wt% HFO-1234yf; c. about 11% to 14% by weight of HFO-1132(E); d. 2.5% to 3% by weight of CO2, and a refrigerant.

[0022] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 3A.

[0023] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 19% by weight to 21.5% by weight of R-32; b. 61 wt% to 64.5 wt% HFO-1234yf; c. about 11% to 14% by weight of HFO-1132(E); d. 2.5% to 3% by weight of CO2, and d. 2.5% to 3% by weight of CO2, wherein the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.

[0024] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 3B.

[0025] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 21.5 wt. % R-32; and b. 63 wt% to 64.5 wt% HFO-1234yf; c. about 11% by weight of HFO-1132(E); d. Contains a refrigerant containing 2% to 4% CO2 by weight.

[0026] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 4A.

[0027] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 21.5 wt. % R-32; and b. 63 wt% to 64.5 wt% HFO-1234yf; c. about 11% by weight of HFO-1132(E); d. 2% to 4% CO2 by weight, wherein the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more.

[0028] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 4B.

[0029] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 21.5 wt. % R-32; and b. 61 wt% to 63 wt% HFO-1234yf; c. about 14% by weight of HFO-1132(E); d. Contains a refrigerant containing 2% to 4% CO2 by weight.

[0030] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 5A.

[0031] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 21.5 wt. % R-32; and b. 61 wt% to 63 wt% HFO-1234yf; c. about 14% by weight of HFO-1132(E); d. 2% to 4% CO2 by weight, and d. 2% to 4% CO2 by weight, wherein the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more.

[0032] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 5B.

[0033] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 21.5 wt. % R-32; and b. about 65.5 wt. % HFO-1234yf; c. about 11% by weight of HFO-1132(E); d. 1.5% to 4% by weight of CO2, and a refrigerant.

[0034] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 6A.

[0035] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. about 21.5 wt. % R-32; and b. about 65.5 wt. % HFO-1234yf; c. about 11% by weight of HFO-1132(E); d. 1.5% to 4% CO2 by weight.

[0036] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 6B.

[0037] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. about 21.5 wt. % R-32; and b. about 65.5 wt. % HFO-1234yf; c. about 11% by weight of HFO-1132(E); d. 1.5% to 4% by weight of CO2 as a refrigerant.

[0038] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 6C.

[0039] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 65.5 wt% + / - 1 wt% HFO-1234yf; c. 11% by weight + / - 1% by weight of HFO-1132(E); d.2% by weight + / - 0.5% by weight CO2, and

[0040] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 7A.

[0041] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 65.5 wt% + / - 1 wt% HFO-1234yf; c. 11% by weight + / - 1% by weight of HFO-1132(E); d.2% by weight + / - 0.5% by weight of CO2.

[0042] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 7B.

[0043] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 65.5 wt% + / - 1 wt% HFO-1234yf; c. 11% by weight + / - 1% by weight of HFO-1132(E); d.2% by weight + / - 0.5% by weight of CO2.

[0044] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 7C.

[0045] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 65 wt% + / - 1 wt% HFO-1234yf; c. 11% by weight + / - 1% by weight of HFO-1132(E); d. 2.5% by weight + / - 0.5% by weight CO2, and

[0046] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 8A.

[0047] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 65 wt% + / - 1 wt% HFO-1234yf; c. 11% by weight + / - 1% by weight of HFO-1132(E); d. 2.5% + / - 0.5% CO2 by weight.

[0048] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 8B.

[0049] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 65 wt% + / - 1 wt% HFO-1234yf; c. 11% by weight + / - 1% by weight of HFO-1132(E); d. 2.5% by weight + / - 0.5% by weight of CO2.

[0050] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 8C.

[0051] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 64 wt% + / - 1 wt% HFO-1234yf; c. 11 wt% HFO-1132(E); d. 3.5% by weight + / - 0.5% by weight CO2, and

[0052] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 9A.

[0053] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 64 wt% + / - 1 wt% HFO-1234yf; c. 11 wt% HFO-1132(E); d. 3.5% + / - 0.5% CO2 by weight.

[0054] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 9B.

[0055] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 64 wt% + / - 1 wt% HFO-1234yf; c. 11 wt% HFO-1132(E); d. 3.5% by weight + / - 0.5% by weight of CO2.

[0056] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 9C.

[0057] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. about 21.5 wt. % R-32; and b. about 62 wt. % HFO-1234yf; c. about 14% by weight of HFO-1132(E); d. 1.5% to 4% by weight of CO2, and a refrigerant.

[0058] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 10A.

[0059] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. about 21.5 wt. % R-32; and b. about 62 wt. % HFO-1234yf; c. about 14% by weight of HFO-1132(E); d. 1.5% to 4% CO2 by weight.

[0060] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 10B.

[0061] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. about 21.5 wt. % R-32; and b. about 62 wt. % HFO-1234yf; c. about 14% by weight of HFO-1132(E); d. 1.5% to 4% by weight of CO2 as a refrigerant.

[0062] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 10C.

[0063] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 62.5 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 2.0% by weight + / - 0.5% by weight CO2, and

[0064] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 11A.

[0065] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 62.5 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 2.0% + / - 0.5% CO2 by weight.

[0066] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 11B.

[0067] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 62.5 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 2.0% by weight + / - 0.5% by weight of CO2.

[0068] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 11C.

[0069] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 62 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 2.5% by weight + / - 0.5% by weight CO2, and

[0070] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 12A.

[0071] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 62 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 2.5% + / - 0.5% CO2 by weight.

[0072] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 12B.

[0073] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 62 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 2.5% by weight + / - 0.5% by weight of CO2.

[0074] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 12C.

[0075] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 61 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 3.5% by weight + / - 0.5% by weight CO2, and

[0076] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 13A.

[0077] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 61 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 3.5% + / - 0.5% CO2 by weight.

[0078] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 13B.

[0079] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 61 wt% + / - 1 wt% HFO-1234yf; c. 14 wt% + / - 1 wt% HFO-1132(E); d. 3.5% by weight + / - 0.5% by weight of CO2.

[0080] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 13C.

[0081] The present invention provides a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total refrigerant: a. 21.5 wt% + / - 0.5 wt% R-32; b. 63.5 wt% + / - 2 wt% HFO-1234yf; c. 13 wt% + / - 2 wt% HFO-1132(E); d. Contains a refrigerant containing 2% to 4% CO2 by weight.

[0082] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 14A.

[0083] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 63.5 wt% + / - 2 wt% HFO-1234yf; c. 13 wt% + / - 2 wt% HFO-1132; d. 2% to 4% CO2 by weight.

[0084] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 14B.

[0085] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 63.5 wt% + / - 2 wt% HFO-1234yf; c. 13 wt% + / - 2 wt% HFO-1132(E); d. 2% to 4% by weight of CO2 as a refrigerant.

[0086] The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 14C.

[0087] The present invention relates to a refrigerant comprising the following four components in the following relative concentrations: a. 21.5 wt% + / - 0.5 wt% R-32; b. 63.5 wt% + / - 2 wt% HFO-1234yf; c. 13 wt% + / - 2 wt% HFO-1132(E); d. 2% to 4% CO2 by weight, wherein the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more.

[0088] The refrigerant according to this paragraph may be referred to herein for convenience as refrigerant 15.

[0089] The present invention also provides a method for providing heat transfer, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. More than 15 wt% to less than 22 wt% R-32; ii. greater than 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. 4% by weight to less than 14.5% by weight of HFO-1132(E); iv. providing a refrigerant comprising greater than 1.5% and up to 3.5% by weight of CO2; b. transferring heat to or from the refrigerant in a heat transfer system.

[0090] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 1.

[0091] The present invention also provides a method for providing heat transfer, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. Providing a refrigerant comprising 1% to 4% by weight of CO2; b. transferring heat to or from the refrigerant in a heat transfer system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. the capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; ii. transferring, wherein the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0092] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 2A.

[0093] The present invention also provides a method for providing heat transfer, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, wherein the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more; and b. transferring heat to or from the refrigerant in a heat transfer system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. the capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; ii. transferring, wherein the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0094] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 2B.

[0095] The present invention also provides a method for providing heat transfer, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 Providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant to a heat transfer system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator, wherein the amount of the refrigerant in the system is less than or equal to three times the lower flammability limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020).

[0096] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 3A.

[0097] The present invention also provides a method for providing heat transfer in a low temperature and / or medium temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 Providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant in a heat transfer system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. The amount of the refrigerant in the system is less than or equal to three times the lower flammability limit (LFL) of the refrigerant, expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020); ii. The capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; iii. the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0098] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 3B.

[0099] The present invention also provides a method for providing heat transfer in a medium temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. Providing a refrigerant comprising 1% to 4% by weight of CO2; b. providing the refrigerant in the medium temperature refrigeration system.

[0100] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 4A.

[0101] The present invention also provides a method for providing heat transfer in a medium temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 Providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant in a medium temperature refrigeration system.

[0102] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 4B.

[0103] The present invention also provides a method for providing heat transfer in a medium temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant to a medium-temperature refrigeration system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator, wherein the amount of the refrigerant in the system is less than or equal to three times the lower flammability limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020).

[0104] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 4C.

[0105] The present invention also provides a method for providing heat transfer in a medium temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant in the medium temperature refrigeration system, the medium temperature refrigeration system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. the capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; ii. the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0106] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 4D.

[0107] The present invention also provides a method for providing heat transfer in a medium temperature refrigeration system, comprising: c. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 providing a refrigerant having a lower flammability limit equal to or greater than the above; d. providing the refrigerant in the medium temperature refrigeration system, the medium temperature refrigeration system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. The amount of the refrigerant in the system is less than or equal to three times the lower flammability limit (LFL) of the refrigerant, expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020); ii. The capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; iii. the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0108] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 4E.

[0109] The present invention also provides a method for providing heat transfer in a low temperature refrigeration system, comprising: c. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. Providing a refrigerant comprising 1% to 4% by weight of CO2; and d. providing the refrigerant in the low temperature refrigeration system.

[0110] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 5A.

[0111] The present invention also provides a method for providing heat transfer in a low temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant in a low temperature refrigeration system.

[0112] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 5B.

[0113] The present invention also provides a method for providing heat transfer in a low temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant to a low-temperature refrigeration system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator, wherein the amount of the refrigerant in the system is less than or equal to three times the lower flammability limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020).

[0114] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 5C.

[0115] The present invention also provides a method for providing heat transfer in a low temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 Providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant in the low temperature refrigeration system, the low temperature refrigeration system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. the capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; ii. the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0116] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 5D.

[0117] The present invention also provides a method for providing heat transfer in a low temperature refrigeration system, comprising: a. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of all refrigerants: i. about 15% by weight to about 22% by weight of R-32; ii. about 61 wt. % to about 71.5 wt. % HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO2, provided that the refrigerant has a GWP of 150 or less and a GWP of 0.25 kg / m 3 providing a refrigerant having a lower flammability limit equal to or greater than the above; b. providing the refrigerant in the low temperature refrigeration system, the low temperature refrigeration system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. The amount of the refrigerant in the system is less than or equal to three times the lower flammability limit (LFL) of the refrigerant, expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020); ii. The capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; iii. the power consumption in the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

[0118] The method according to this paragraph may be referred to herein for convenience as Heat Transfer Method 5E. [Brief explanation of the drawings]

[0119] [Figure 1] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low temperature and medium temperature refrigeration. [Figure 2] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature refrigeration and including an optional steam injector. [Figure 3] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature refrigeration and including an optional liquid injector. [Figure 4] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature refrigeration and including an optional suction line / liquid line heat exchanger. [Figure 5]FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature refrigeration and including an optional steam injector and oil separator.

[0120] Description of Preferred Compositions Definition: The term "about" in reference to amounts expressed as weight percent means that the amount of the ingredient can vary in an amount of + / - 2% by weight.

[0121] The term "about" in reference to temperatures in degrees Celsius (°C) means that the stated temperature can vary by an amount of + / - 5°C.

[0122] The term "capacity" refers to the amount of cooling provided by a refrigerant in a cooling system in BTU / hr. It is determined experimentally by multiplying the change in enthalpy in BTU / lb of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. Enthalpy can be determined from measurements of the refrigerant's pressure and temperature. The capacity of a refrigeration system relates to its ability to maintain a specific temperature in an area to be cooled. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides a measure of the compressor's ability to pump that amount of heat for a given volumetric flow rate of the refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will provide more cooling or heating power.

[0123] The phrase "coefficient of performance" (hereinafter "COP") is a widely accepted measure of refrigerant performance that is particularly useful for expressing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration, this term represents the ratio of useful refrigeration or cooling capacity to the energy applied by the compressor during vapor compression, and thus represents the ability of a given compressor to pump a quantity of heat for a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, given a particular compressor, a refrigerant with a higher COP will deliver more cooling or heating power. One means for estimating the COP of a refrigerant at specific operating conditions is from the refrigerant's thermodynamic properties using standard refrigeration cycle analysis techniques (see, for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, incorporated herein by reference in its entirety).

[0124] The phrase "discharge temperature" refers to the temperature of the refrigerant at the outlet of the compressor. The advantage of a low discharge temperature is that it allows the use of existing equipment without activating the thermal protection aspects of the system, which are preferably designed to protect compressor components and avoid the use of expensive control devices such as liquid injection to reduce the discharge temperature.

[0125] The phrase "global warming potential" (hereafter "GWP") was developed to allow for the comparison of the global warming impact of various gases. It compares the amount of heat trapped by a specific mass of gas with the amount of heat trapped by a similar mass of carbon dioxide over a specific time period. Carbon dioxide was chosen by the Intergovernmental Panel on Climate Change (IPCC) as the standard gas, giving it a GWP of 1. The higher the GWP, the more a given gas will warm the Earth over that time period compared to CO2. A commonly used time period for GWP is 100 years. GWP provides a common measure that allows analysts to add together emission estimates for different gases. See http: / / www.protocolodemontreal.org.br / site / images / publicacoes / setor_manufatura_equipamentos_refrigeracao_arcondicionado / Como_calcular_el_Potencial_de_Calentamiento_Atmosferico_en_las_mezclas_de_refrigerantes.pdf.

[0126] The term "Occupational Exposure Limit (OEL)" is determined in accordance with ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants.

[0127] As used herein, the phrase "acceptable toxicity" means that the composition is classified as Class "A" by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and as described in Appendix B1 of ASHRAE Standard 34-2016, as each standard exists as of the filing date of this application.

[0128] The term "A1" means a material that is non-flammable and of low toxicity and is classified as "A1" by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and is described in Appendix B1 of ASHRAE Standard 34-2016, as each standard exists as of the filing date of this application.

[0129] The term "A2L" means materials that are mildly flammable and of low toxicity and are classified as "A2L" by ASHRAE Standard 34-2019 Designation and Safety Classification of Refrigerants and are described in Appendix B1 of ASHRAE Standard 34-2019, as each standard exists as of the filing date of this application.

[0130] The term "mass flow rate" is the mass of refrigerant passing through a conduit per unit time.

[0131] The term "non-flammable" refers to a compound or composition that is either A1 or A2L as defined herein.

[0132] As used herein, the term "evaporator glide" means the difference between the saturation temperature of the refrigerant at the evaporator inlet and the dew point of the refrigerant at the evaporator outlet, assuming the pressure at the evaporator outlet is the same as the pressure at the inlet. As used herein, the phrase "saturation temperature" means the temperature at which liquid refrigerant boils to a vapor at a given pressure.

[0133] As used herein, the phrase "acceptable toxicity" means that the composition is classified as Class "A" by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and as described in Appendix B1 of ASHRAE Standard 34-2016, as each standard exists as of the filing date of this application. A material that is non-flammable and has low toxicity is classified as "A1" by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and as described in Appendix B1 of ASHRAE Standard 34-2016, as each standard exists as of the filing date of this application.

[0134] As used herein, the term "replacement" refers to the use of the compositions of the present invention in a heat transfer system designed for or suitable for use with another refrigerant. For example, when the refrigerant or heat transfer composition of the present invention is used in a heat transfer system designed for use with R-22, the refrigerant or heat transfer composition of the present invention is a replacement for R-22 in that system. Thus, the term "replacement" will be understood to include the use of the refrigerant and heat transfer compositions of the present invention in both new and existing systems designed for or suitable for use with a specified refrigerant, such as R-22.

[0135] The term "commercial refrigeration" refers to refrigeration equipment used in a commercial environment and includes commercial coolers used to keep items such as food and beverages below average room temperature but above freezing, commercial freezers used to keep perishable goods frozen, and commercial cooler / freezers. Examples of commercial refrigeration include reach-in refrigerators and freezers found in supermarkets, specialty food stores, convenience stores, and grocery stores; walk-in freezers and refrigerators, including those found in restaurants, cafeterias, and the like; plug-in enclosed vending machines, especially those located in areas where egress may be restricted, such as hallways and aisles; drop-in coolers; draft beer systems; undercounter refrigerators; and refrigerated display cases.

[0136] The term "low temperature cooling system / low temperature refrigeration system" refers to a heat transfer system that operates at a condensing temperature of about 20°C to about 60°C and an evaporating temperature of about -45°C up to and including -12°C.

[0137] The term "medium temperature refrigeration system" refers to a heat transfer system that operates at a condensing temperature of about 20°C to about 60°C and an evaporating temperature of about -12°C to about 0°C.

[0138] The term "superheat" or simply "superheat" refers to the temperature rise of the refrigerant at the outlet of the evaporator above the saturated vapor temperature (or dew point temperature) of the refrigerant.

[0139] The terms "HFO-1132(E)" and "transHFO-1132(E)" each refer to the trans isomer of 1,2-difluoroethylene.

[0140] The terms "HFO-1234ze(E)" and transHFO-1234ze refer to the trans isomer of 1,3,3,3-tetrafluoropropene.

[0141] The term "HFO-1234yf" means 2,3,3,3-tetrafluoropropene.

[0142] The terms "HFO-1336mzz(E)" and "transHFO-1336mzz" each referred to the trans isomer of 1,1,1,4,4,4-hexafluorobut-2-ene.

[0143] The terms "HFC-32" and "R-32" each mean difluoromethane.

[0144] The terms "HFC-134a" and "R-134a" each mean 1,1,1,2-tetrafluoroethane.

[0145] The term "R-22" means chlorodifluoromethane.

[0146] The term "R-404A" refers to a blend of refrigerants consisting of 44% ± 2% by weight R-125, 52% ± 2% by weight R-143a, and 4% ± 2% by weight R134a).

[0147] The term "R407F" refers to a blend of refrigerants consisting of 30% ± 2% by weight of R-32, 30% ± 2% by weight of R-125, and 40% ± 2% by weight of R134a).

[0148] The term "R-410A" refers to a blend of refrigerants consisting of 50% + 0.5 / -1% by weight of R-32 and 50% + 1.5 / -0.5% by weight of R125.

[0149] The term "R-448A" refers to a blend of refrigerants consisting of: 26% by weight R-32; 26% by weight R-125; 26% by weight R-125; 21% by weight R134a; 7% by weight transHFO-1234ze; and 20% by weight HFO-1234yf.

[0150] The term "R-449A" refers to a blend of refrigerants consisting of 24.3% by weight R-32, 24.7% by weight R-125, 25.7% by weight R-134a, and 25.3% by weight HFO-1234yf). DETAILED DESCRIPTION OF THE INVENTION

[0151] Refrigerant and Heat Transfer Compositions Applicants have discovered that inventive refrigerants, such as each of Refrigerants 1-15, and inventive methods, such as Heat Transfer Methods 1-5, described herein, can provide distinctively advantageous properties, including heat transfer characteristics and performance, acceptable toxicity and non-flammability (i.e., Class A2L), unexpectedly high lower flammability limits (LFL), zero or near-zero ozone depletion potential (ODP), and lubricant compatibility, including miscibility with POE and / or PVE lubricants, over the entire operating temperature and concentration ranges used in medium and low temperature refrigeration systems, cascade refrigeration systems, transport refrigeration systems, stationary refrigeration, and heat pumps.

[0152] As used herein, references to groups of compositions, methods, etc. defined by a number, such as the reference in the preceding paragraph to "any of Refrigerants 1-15," include all numbered compositions, specifically including all numbered compositions having a suffix. For example, a reference to "any of Refrigerants 13-14" includes each of Refrigerant 13A, Refrigerant 13B, Refrigerant 13C, Refrigerant 14A, Refrigerant 14B, and Refrigerant 14C.

[0153] A particular advantage of the refrigerants of the present invention, particularly each of Refrigerants 1-15, is that they are mildly flammable, have advantageously high LFLs, and have acceptable toxicity, i.e., each is a Class A1 refrigerant. Those skilled in the art will appreciate that refrigerant flammability can be a characteristic of concern in certain critical heat transfer applications, and that refrigerants classified as Class A2L can often be more advantageous than refrigerants that are not Class A2L. Therefore, it is desirable in the art to provide refrigerant compositions that can be used as replacements for conventional refrigerants that do not possess the combination of properties provided by the refrigerants of the present invention, such as R-22, R404A, R407F, R448A, R449A, R-134a, R404A, and R410A (or as replacements or retrofits for R-32 and R454B). This desirable advantage can be achieved and satisfied by the refrigerants of the present invention.

[0154] Applicants have discovered that the refrigerant compositions of the present invention, including each of Refrigerants 1-15, can achieve a difficult-to-achieve combination of properties, including a particularly low GWP. Thus, the compositions of the present invention have a GWP of 150 or less.

[0155] Additionally, inventive refrigerant compositions containing each of Refrigerants 1-15 have an ODP of zero or near zero. Thus, the compositions of the present invention have an ODP of 0.02 or less, and more preferably zero.

[0156] Additionally, the refrigerant compositions of the present invention, including each of Refrigerants 1-15, exhibit acceptable toxicity and preferably have an OEL greater than about 400. As those skilled in the art will recognize, mildly flammable refrigerants having an OEL greater than about 400 are advantageous because they provide refrigerants that are classified as "Class A2L" under ASHRAE Standard 34, which is desirable.

[0157] Preferred refrigerant compositions of the present invention exhibit both acceptable toxicity and mild flammability under ASHRAE Standard 34 and are therefore Class A2L refrigerants. Applicants have discovered that heat transfer compositions of the present invention, such as those comprising each of Refrigerants 1-15 described herein, can provide a remarkably advantageous and unexpected combination of properties, including good heat transfer characteristics, chemical stability under use conditions, acceptable toxicity, non-flammability, a relatively high LFL, a zero or near-zero ozone depletion potential ("ODP"), and lubricant compatibility, including miscibility with POE and / or PVE lubricants, over the entire operating temperature and concentration ranges used in medium and low temperature refrigeration systems, walk-in freezers and refrigerators, vending machines (including vending machines located in hallways and corridors or other confined locations), cascade refrigeration systems, transport refrigeration systems, heat pumps (including residential air-to-water heat pump systems and air-source heat pump water heaters), stationary air conditioning, commercial air conditioning, and mobile air conditioning.

[0158] The heat transfer composition can consist essentially of any refrigerant of the present invention, such as each of Refrigerants 1-15.

[0159] The refrigerants of the present invention can be provided in a heat transfer composition. Thus, the heat transfer composition of the present invention includes a refrigerant of the present invention, such as any of the preferred refrigerant compositions disclosed herein, and particularly each of Refrigerants 1-15. Preferably, the present invention relates to a heat transfer composition comprising a refrigerant, such as each of Refrigerants 1-15, in an amount of at least about 80% by weight of the heat transfer composition, or at least about 90% by weight of the heat transfer composition, or at least about 97% by weight of the heat transfer composition, or at least about 99% by weight of the heat transfer composition. The heat transfer composition can consist essentially of the refrigerant, or can consist of the refrigerant.

[0160] The heat transfer compositions of the present invention can comprise any refrigerant of the present invention, such as each of Refrigerants 1-15.

[0161] The heat transfer compositions of the present invention may contain other components for the purpose of enhancing or providing certain functional properties to the composition. Such other components may include, in addition to the refrigerants of the present invention, such as each of Refrigerants 1-15, one or more of lubricants, passivators, flammability inhibitors, dyes, solubilizers, compatibilizers, stabilizers, antioxidants, corrosion inhibitors, extreme pressure additives, and antiwear additives, as well as other compounds and / or components that adjust specific properties of the heat transfer composition, and the presence of all such compounds and components is within the broad scope of the present invention.

[0162] lubricant The heat transfer compositions of the present invention may comprise a refrigerant described herein, such as each of Refrigerants 1 through 15, and a lubricant. The heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 1 for convenience.

[0163] The heat transfer composition of the present invention may also include a refrigerant described herein, such as each of Refrigerants 1-15, and a polyol ester (POE) lubricant. The heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 2 for convenience.

[0164] The heat transfer composition of the present invention may also include a refrigerant described herein, such as each of Refrigerants 1-15, and a polyol vinyl ether (PVE) lubricant. The heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 3 for convenience.

[0165] Applicants have discovered that the heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-3, can provide distinctively advantageous properties, including excellent refrigerant / lubricant compatibility, including miscibility with POE and / or PVE lubricants, in addition to the advantageous properties identified herein with respect to refrigerants, over the range of operating temperatures and concentrations used in stationary air conditioning systems (including residential, commercial, and VRF air conditioning), chillers (including air-to-water chillers), heat pump systems (including residential air-to-water heat pump systems), and commercial refrigeration (including medium temperature and low temperature refrigeration).

[0166] A lubricant consisting essentially of POE having a viscosity of about 30 to about 70 at 40° C., as measured according to ASTM D445, is referred to herein as Lubricant 1.

[0167] Commercially available POEs suitable for use in the heat transfer compositions of the present invention include neopentyl glycol dipelargonate, available as Emery 2917® and Hatcol 2370®, and pentaerythritol derivatives, including those sold under the trade names Emkarate RL32-3MAF and Emkarate RL68H by CPI Fluid Engineering. Emkarate RL32-3MAF and Emkarate RL68H are preferred POE lubricants having the properties specified below.

[0168] [Table 1]

[0169] A preferred heat transfer composition comprises a refrigerant of the present invention, such as each of Refrigerants 1-15, and Lubricant 1. The heat transfer composition described in this paragraph may be conveniently referred to as Heat Transfer Composition 4.

[0170] A lubricant consisting essentially of POE having a viscosity of about 30 to about 70 at 40°C, measured according to ASTM D445, based on the weight of the heat transfer composition, is referred to herein as Lubricant 2.

[0171] Commercially available polyvinyl ethers suitable for use in the heat transfer compositions of the present invention having a viscosity of about 30 to about 70 at 40°C as measured in accordance with ASTM D445 include lubricants sold by Idemitsu Kosan under the trade names FVC32D and FVC68D.

[0172] A preferred heat transfer composition comprises a refrigerant of the present invention, such as each of Refrigerants 1-15, and Lubricant 2. The heat transfer composition described in this paragraph may be conveniently referred to as Heat Transfer Composition 5.

[0173] The present invention includes heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-5, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 5% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 6.

[0174] The present invention includes heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-6, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 2% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 7.

[0175] The present invention includes heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-7, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 1% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 8.

[0176] The present invention includes heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1 through 8, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 0.5% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 9.

[0177] The present invention includes heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-9, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.2% to about 0.5% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 10.

[0178] Stabilizers and Protectants While it is believed that in many embodiments the present refrigerants and heat transfer compositions can be used without stabilizers and / or protectants, the present invention also includes heat transfer compositions comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and a protectant and / or stabilizer. Preferred protectants and stabilizers are described below:

[0179] stabilizers The heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-10, preferably include a stabilizer. Preferably, one or more of the following stabilizers are included:

[0180] Alkylated Naphthalene Applicants have surprisingly and unexpectedly discovered that alkylated naphthalenes are highly effective as stabilizers for the heat transfer compositions of the present invention. As used herein, the term "alkylated naphthalene" refers to a compound having the following structure:

[0181] [ka] wherein each R1-R8 is independently selected from a straight chain alkyl group, a branched alkyl group, and hydrogen. The specific length of the alkyl chain, as well as mixtures or branched and straight chains and hydrogen, can be varied within the scope of the present invention, and those skilled in the art will recognize and understand that such variations will reflect the physical properties of the alkylated naphthalene, specifically the viscosity of the alkylated compound, and manufacturers of such materials often define their substances by reference to one or more of these properties in lieu of specifying a particular R group.

[0182] Applicants have discovered that unexpected, surprising, and advantageous results result from the use of alkylated naphthalenes as stabilizers in accordance with the present invention, including heat transfer compositions 1-10 each having the following properties; alkylated naphthalene compounds having the indicated properties are conveniently referred to herein as Alkylated Naphthalene 1 (or AN1) through Alkylated Naphthalene 5 (or AN5), as shown in columns 1-5, respectively, of the table below.

[0183] [Table 2]

[0184] As used herein in reference to viscosity at 40°C measured according to ASTM D445, the term "about" means + / - 4 cSt.

[0185] As used herein in reference to viscosity at 100°C measured according to ASTM D445, the term "about" means + / - 0.4 cSt.

[0186] As used herein in reference to pour point as measured according to ASTM D97, the term "about" means + / - 5°C.

[0187] Applicants have also discovered that unexpected, surprising, and advantageous results result from the use of alkylated naphthalenes as stabilizers in accordance with the present invention, including heat transfer compositions 1-27 each having the following properties; the alkylated naphthalene compounds having the indicated properties are conveniently referred to herein as Alkylated Naphthalene 6 (or AN6) through Alkylated Naphthalene 10 (or AN10), as shown in columns 6-10, respectively, of the table below.

[0188] [Table 3]

[0189] Examples of alkylated naphthalenes within the meaning of Alkylated Naphthalene 1 and Alkylated Naphthalene 6 include products sold by King Industries under the following trade names: NA-LUBE, KR-007A, KR-008, KR-009, KR-015, KR-019, KR-005FG, KR-015FG, and KR-029FG.

[0190] Examples of alkylated naphthalenes within the meaning of alkylated naphthalene 2 and alkylated naphthalene 7 include products sold by King Industries under the following trade names: NA-LUBE, KR-007A, KR-008, KR-009, and KR-005FG.

[0191] Examples of alkylated naphthalenes within the meaning of Alkylated Naphthalene 5 and Alkylated Naphthalene 10 include the product sold by King Industries under the trade name NA-LUBE KR-008.

[0192] The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-5, where the alkylated naphthalene is AN1, AN2, or AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9, or AN10.

[0193] Acid Depletable Moiety (ADM) One of ordinary skill in the art would be able to determine, without undue experimentation, a variety of ADMs that are useful in accordance with the present invention, and all such ADMs are within the scope of this specification.

[0194] Epoxide Applicants have found that epoxides, and particularly alkylated epoxides, are effective in providing the enhanced stability described herein, particularly and preferably when used in combination with alkylated naphthalene stabilizers, and, without being bound by theory, Applicants believe that this synergistic enhancement is due, at least in part, to their effective function as ADMs in the heat transfer compositions of the present invention.

[0195] In one preferred embodiment of the present invention, the heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-10, comprise an epoxide selected from the group consisting of epoxides that undergoes a ring-opening reaction with an acid, thereby depleting the acid from the system without otherwise adversely affecting the system.

[0196] Useful epoxides include aromatic epoxides, alkyl epoxides (including alkyl ether epoxides), and alkenyl epoxides.

[0197] Preferred epoxides include those of Formula I:

[0198] [ka] wherein at least one of R1-R4 is selected from a 2-15 carbon (C2-C15) acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. The group of epoxides according to Formula I having R groups defined in this paragraph may be referred to herein for convenience as ADM1A.

[0199] Preferred epoxides also include epoxides of Formula I:

[0200] [ka] wherein each of R1-R4 is independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, provided that at least one of R1-R4 is H and at least one of R1-R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. The group of epoxides according to Formula I having R groups defined in this paragraph may be referred to herein for convenience as ADM1B.

[0201] Preferred epoxides also include epoxides of Formula I:

[0202] [ka] wherein each of R1-R4 is independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, provided that at least two of R1-R4 are H and at least one of R1-R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. The group of epoxides according to Formula I having R groups defined in this paragraph may be referred to herein for convenience as ADM1C.

[0203] Preferred epoxides also include epoxides of Formula I:

[0204] [ka] wherein each of R1-R4 is independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, provided that three of R1-R4 are H and one of R1-R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. The group of epoxides according to Formula I having R groups defined in this paragraph may be referred to herein for convenience as ADM1D.

[0205] In a preferred embodiment, at least one of R1-R4 in Formula I is an ether having the structure:

[0206] [ka] wherein each of R5 and R6 is independently a C1-C14 straight or branched, preferably unsubstituted alkyl group. The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM2A.

[0207] In a preferred embodiment, at least one of R1-R4 in Formula I is an ether having the structure:

[0208] [ka] wherein R5 is a C1-C3 alkyl group, preferably unsubstituted; R6 is a C3-C10 straight or branched, preferably unsubstituted alkyl group.The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM2B.

[0209] In a preferred embodiment, one of R1-R4 in formula I is an ether having the structure:

[0210] [ka] wherein each of R5 and R6 is independently a C1-C14 straight or branched, preferably unsubstituted, alkyl group, and the remaining three of R1-R4 are H. The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM3A.

[0211] In a preferred embodiment, one of R1-R4 in formula I is an ether having the structure:

[0212] [ka] wherein R5 is bonded to the epoxide group and is a C1-C3 straight or branched unsubstituted alkyl group, R6 is a C3-C10 straight or branched unsubstituted alkyl group, and the remaining three of R1-R4 are H. The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM3B.

[0213] In a preferred embodiment, one of R1-R4 in formula I is an ether having the structure:

[0214] [ka] wherein R5 is bonded to the epoxide group and is a C1 unsubstituted alkyl; R6 is a C8 branched unsubstituted alkyl group, and the remaining three of R1-R4 are H. The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM3C.

[0215] In a preferred embodiment, the epoxide comprises, consists essentially of, or consists of the ADM3C compound 2-ethylhexyl glycidyl ether having the following structure:

[0216] [ka]

[0217] The epoxide according to this paragraph may be referred to herein for convenience as ADM4.

[0218] In a preferred embodiment, one of R1-R4 in formula I is an ether having the structure:

[0219] [ka] wherein each of R5 and R6 is independently a C1 to C14 straight or branched, preferably unsubstituted, alkyl group, and the remaining three of R1 to R4 are H. The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM5A.

[0220] In a preferred embodiment, one of R1-R4 of Formula II is an ether having the structure:

[0221] [ka] wherein R5 is bonded to the epoxide group and is a C1-C3 straight or branched unsubstituted alkyl group, R6 is a C3-C10 straight or branched substituted alkyl group, and the remaining three of R1-R4 are H. The group of epoxides defined in this paragraph may be referred to herein for convenience as ADM5B.

[0222] In a preferred embodiment, one of R1-R4 of Formula II is an ether having the structure:

[0223] [ka] wherein R5 is attached to the epoxide group and is a C1 unsubstituted alkyl, R6 is a C8 branched substituted alkyl group, and the remaining three of R1-R4 are H. The group of epoxides according to Formula I having R groups defined in this paragraph may be referred to herein for convenience as ADM5C.

[0224] In a preferred embodiment, one of R1-R4 in formula I is an ether having the structure:

[0225] [ka] wherein R5 is bonded to the epoxide group and is a C1 unsubstituted alkyl, R6 is a C8 branched oxygen-substituted alkyl group, and the remaining three of R1-R4 are H. The group of epoxides according to Formula I having R groups defined in this paragraph may be referred to herein for convenience as ADM5D.

[0226] In a preferred embodiment, the epoxide comprises, consists essentially of, or consists of glycidyl neodecanoate, an ADM5C compound in which the substituent on R6 is O and has the following structure:

[0227] [ka]

[0228] The epoxide according to this paragraph may be referred to herein for convenience as ADM6.

[0229] In another embodiment, the heat transfer composition of the present invention comprises a stabilized epoxy compound according to Formula II:

[0230] [ka] wherein each R1 is independently an epoxy-terminated ethoxy, propoxy, or butoxy group. Epoxides according to this paragraph may be referred to herein for convenience as naphthylepoxy1.

[0231] In another embodiment, the heat transfer composition of the present invention comprises a stabilized epoxy compound according to Formula II:

[0232] [ka] wherein each R1 is independently an epoxy-terminated ethoxy or propoxy group. Epoxides according to this paragraph are sometimes referred to herein for convenience as naphthylepoxy2.

[0233] In another embodiment, the heat transfer composition of the present invention comprises a stabilized epoxy compound according to Formula II:

[0234] [ka] wherein each R is independently an epoxy-terminated ethoxy, propoxy, or butoxy group, provided that at least one R is an epoxy-terminated ethoxy group. Epoxides according to this paragraph may be referred to herein for convenience as naphthylepoxy3.

[0235] In another embodiment, the heat transfer composition of the present invention comprises a stabilized epoxy compound according to Formula II:

[0236] [ka] wherein each R is independently an epoxy-terminated ethoxy, propoxy, or butoxy group, provided that at least one R is an epoxy-terminated ethoxy group. Epoxides according to this paragraph may be referred to herein for convenience as naphthylepoxy3.

[0237] In another embodiment, the heat transfer composition of the present invention comprises a stabilized epoxy compound according to Formula II:

[0238] [ka] wherein each R1 is independently an epoxy-terminated ethoxy group. The epoxide according to this paragraph may be referred to herein for convenience as naphthyl epoxy 4.

[0239] In another embodiment, the heat transfer composition of the present invention comprises a stabilized epoxy compound according to Formula II below, wherein each R 1 is an epoxy-terminated ethoxy group, as shown below:

[0240] [ka] 1,6-diglycidyl naphthalene ether. The epoxide according to this paragraph may be referred to herein for convenience as naphthyl epoxy 5.

[0241] The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-10, wherein the alkylated naphthalene is AN1 or AN2 or AN3 or AN4 or AN5 or AN6 or AN7 or AN8 or AN9 or AN10, and further comprises any one of ADM1-ADM6.

[0242] In the heat transfer compositions of the present invention, such as Heat Transfer Compositions 1-10, the ADM is preferably present in an amount of from about 0.05% to about 2.5%, preferably 0.05% to about 1.5%, or preferably 0.05 to 0.5% by weight, all based on the weight of the lubricant and ADM.

[0243] In the heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-10, the alkylated naphthalene is preferably present in an amount of from 0.01% to about 10%, or from about 1.5% to about 4.5%, or from about 2.5% to about 3.5%, these amounts being weight percents based on the amount of alkylated naphthalene and refrigerant in the system. The amounts specified in this paragraph are especially preferred when ADM is also present.

[0244] In heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1-10, the alkylated naphthalene is preferably present in an amount of 0.1% to about 20%, or 1.5% to about 10%, or 1.5% to about 8%, these amounts being weight percents based on the amount of alkylated naphthalene and lubricant in the system. The amounts specified in this paragraph are particularly preferred when ADM is also present. The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-27, comprising one or more naphthyl epoxies 1-5.

[0245] The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-27, comprising one or more naphthyl epoxies 1-5 and further comprising an alkylated naphthalene.

[0246] The present invention includes heat transfer compositions comprising one or more of naphthyl epoxies 1-5, such as each of heat transfer compositions 1-27, and further comprising AN1 or AN2 or AN3 or AN4 or AN5 or AN6 or AN7 or AN8 or AN9 or AN10.

[0247] The present invention includes heat transfer compositions comprising one or more of naphthyl epoxies 1-5, such as each of heat transfer compositions 1-27, and further comprising any one of AN1 or AN2 or AN3 or AN4 or AN5 or AN6 or AN7 or AN8 or AN9 or AN10, and ADM1-ADM6.

[0248] Carbodiimide ADMs may include carbodiimides. In a preferred embodiment, the carbodiimides include compounds having the following structure:

[0249] [ka]

[0250] Other stabilizers It is contemplated that stabilizers other than alkylated naphthalenes and ADM may be included in the heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1 through 27. Examples of such other stabilizers are described below.

[0251] phenolic compounds In a preferred embodiment, the stabilizer further includes a phenolic compound.

[0252] Phenolic compounds include 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenyldiol including 4,4'-bis(2-methyl-6-tert-butylphenol); derivatives of 2,2- or 4,4-biphenyldiol; 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);2,6-di-tert-butyl-4-methyl The compound may be one or more compounds selected from phenol (BHT); 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-alpha-dimethylamino-p-cresol; 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, tocopherol, hydroquinone, 2,2'6,6'-tetra-tert-butyl-4,4'-methylenediphenol, and t-butylhydroquinone, and preferably BHT.

[0253] The phenolic compound, specifically BHT, may be provided in the heat transfer composition in an amount greater than 0, preferably from 0.0001% to about 5% by weight, preferably from 0.001% to about 2.5% by weight, and more preferably from 0.01% to about 1% by weight. In each case, the weight percentages refer to the weight of the heat transfer composition.

[0254] The phenolic compound, specifically BHT, may be provided in the heat transfer composition in an amount greater than 0, preferably from 0.0001% to about 5% by weight, preferably from 0.001% to about 2.5% by weight, and more preferably from 0.01% to about 1% by weight. In each case, the weight percentages refer to weight based on the weight of the lubricant in the heat transfer composition.

[0255] The present invention also includes a stabilizer comprising about 40% to about 95% by weight of an alkylated naphthalene, such as each of AN1-AN10, and 0.1 to about 10% by weight of BHT, based on the weight of all stabilizer components in the composition.

[0256] The present invention also includes a stabilizer comprising about 40% to about 95% by weight of an alkylated naphthalene, such as each of AN1-AN10, 5% to about 30% by weight of an ADM, such as each of ADM1-ADM6, and 0.1 to about 10% by weight of BHT, based on the weight of all stabilizer components in the composition.

[0257] Diene Compounds The diene compounds include C3-C15 dienes and compounds formed by the reaction of any two or more C3-C4 dienes. Preferably, the diene compounds are selected from the group consisting of allyl ether, propadiene, butadiene, isoprene, and terpenes. The diene compounds are preferably terpenes, including, but not limited to, terbene, retinal, geraniol, terpinene, delta-3 carene, terpinolene, phellandrene, fencene, myrcene, farnesene, pinene, nerol, citral, camphor, menthol, limonene, nerolidol, phytol, carnosic acid, and vitamin A1. Preferably, the stabilizer is farnesene. Preferred terpene stabilizers are disclosed in U.S. Provisional Patent Application No. 60 / 638,003, filed December 12, 2004, published as U.S. Patent No. 2006 / 0167044(A1), which is incorporated herein by reference.

[0258] Additionally, the diene compound may be provided in the heat transfer composition in an amount greater than 0, preferably from 0.0001% to about 5% by weight, preferably from 0.001% to about 2.5% by weight, and more preferably from 0.01% to about 1% by weight, in each case the weight percentages refer to the weight of the heat transfer composition.

[0259] Phosphorus compounds The phosphorus compound may be a phosphite compound or a phosphate compound. For the purposes of the present invention, the phosphite compound may be one or more compounds selected from diaryl, dialkyl, triaryl, and / or trialkyl phosphites and / or mixed aryl / alkyl di- or tri-substituted phosphites, specifically hindered phosphite, tris-(di-tert-butylphenyl)phosphite, di-n-octyl phosphite, iso-octyldiphenyl phosphite, iso-decyldiphenyl phosphite, tri-iso-decyl phosphate, triphenyl phosphite, and diphenyl phosphite, in particular diphenyl phosphite.

[0260] The phosphate compound may be a triaryl phosphate, trialkyl phosphate, alkyl monoacid phosphate, aryl diacid phosphate, amine phosphate, preferably triaryl phosphate and / or trialkyl phosphate, especially tri-n-butyl phosphate.

[0261] The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-10, wherein the composition further comprises a phosphate.

[0262] The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-10, wherein the composition further comprises a triaryl phosphate.

[0263] The present invention includes heat transfer compositions, such as each of Heat Transfer Compositions 1-10, wherein the composition further comprises a trialkyl phosphate.

[0264] The phosphorus compound may be provided in the heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1 through 10, in an amount greater than 0, preferably from 0.0001% to about 5% by weight, preferably from 0.001% to about 2.5% by weight, and more preferably from 0.01% to about 1% by weight. In each case, by weight refers to the weight of the heat transfer composition.

[0265] The phosphorus compound may be provided in the heat transfer compositions of the present invention, such as each of Heat Transfer Compositions 1 through 10, in an amount greater than 0, preferably from 0.0002% to about 10% by weight, preferably from 0.002% to about 5% by weight, and more preferably from 0.02% to about 2% by weight. In each case, the weights in this paragraph refer to the weight of the lubricant and phosphate stabilizer.

[0266] Nitrogen compounds When the stabilizer is a nitrogen compound, it may comprise one or more secondary or tertiary amines selected from diphenylamine, p-phenylenediamine, triethylamine, tributylamine, diisopropylamine, triisopropylamine, and triisobutylamine. The amine compound may be an amine antioxidant, such as a substituted piperidine compound, i.e., an alkyl-substituted piperidyl, piperidinyl, piperazinone, or alkyloxypiperidinyl derivative, in particular, 2,2,6,6-tetramethyl-4-piperidone, 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl)sebacate; di(2,2,6,6-tetramethyl-4-piperidyl)sebacate; poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate; alkylated paraphenylenediamines, such as N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine or N,N'-di-sec-butyl-p-phenylenediamine, and hydroxylamines, such as tallowamine, methylbistallowamine, and bistallowamine, or phenol-alpha-naphthylamine, or Tinuvin® 765 (Ciba), BLS® 1944 (Mayzo). The amine-based compound may be one or more amine antioxidants selected from bis(nonylphenylamine), dialkylamines such as N-(1-methylethyl)-2-propylamine, or one or more of phenyl-alpha-naphthylamine (PANA), alkyl-phenyl-alpha-naphthylamine (APANA), and bis(nonylphenyl)amine. Preferably, the amine-based compound is one or more of phenyl-alpha-naphthylamine (PANA), alkyl-phenyl-alpha-naphthylamine (APANA), and bis(nonylphenyl)amine, more preferably phenyl-alpha-naphthylamine (PANA).

[0267] Alternatively, or in addition to the nitrogen compounds identified above, one or more compounds selected from dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] may be used as stabilizers.

[0268] The nitrogen compound may be provided in the heat transfer composition in an amount greater than 0 and from 0.0001% to about 5% by weight, preferably from 0.001% to about 2.5% by weight, and more preferably from 0.01% to about 1% by weight, in each case the weight percentages refer to the weight of the heat transfer composition.

[0269] Isobutylene Isobutylene may also be used as a stabilizer according to the present invention.

[0270] Protective agent The present invention includes a heat transfer composition comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and a protectant comprising a compound according to Formula I,

[0271] [ka] wherein at least one of R and R1 is a C1-C20 alkylthio, which for convenience is referred to hereinafter as Protecting Agent 1.

[0272] The present invention also includes heat transfer compositions comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and a protectant comprising a compound according to Formula I above, wherein each R and R1 is independently a C1-C20 alkylthio, which for convenience is referred to hereinafter as Protectant 2.

[0273] The present invention also includes heat transfer compositions comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and a protectant comprising a compound according to Formula I above, wherein each R and R is independently a C5-C20 alkylthio, which for convenience is referred to hereinafter as Protectant 3.

[0274] The present invention also includes heat transfer compositions comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and a protectant comprising a compound according to Formula I above, wherein each R and R is independently a C5-C10 alkylthio, which for convenience is referred to hereinafter as Protectant 4.

[0275] The present invention includes a heat transfer composition comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and a protectant comprising a compound according to Formula II,

[0276] [ka] For convenience, this will be referred to below as Protectant 5A.

[0277] The present invention includes a heat transfer composition comprising a refrigerant of the invention, such as each of Refrigerants 1-15, and a protectant comprising a compound according to Formula II above, and further comprising dioctyl disulfide, which for convenience is referred to hereinafter as Protectant 5A.

[0278] Specific heat transfer compositions of the present invention include those identified in Table HTC below, where column 1 of the table includes "HTC" as an abbreviation for the defined heat transfer composition. In Table 1 below, the refrigerant numbers refer to the refrigerant numbers defined above (i.e., number 1 in column 3 below means that the heat transfer composition (HTC) contains a refrigerant according to Refrigerant 1, number 2 in column 3 below means that the heat transfer composition (HTC) contains a refrigerant according to Refrigerant 2 defined above, etc.). "Terp" in the "Other Ingredients" column refers to a terpene-type stabilizer. "Lim" in the "Other Ingredients" column refers to a limonene stabilizer. "NR" means that the component or specific amount is "not required" according to the specified HTC definition, and therefore its presence or absence in any amount is acceptable. "Yes" means that the component is required, but any type or amount is acceptable. "Comp" means that the specified composition contains the item identified in the table. "CEO" means that the specified composition consists essentially of the items specified in the table; "CO" means that the composition consists of the items specified in the table.

[0279] [Table 4-1]

[0280] [Table 4-2]

[0281] [Table 4-3]

[0282] [Table 4-4]

[0283] [Table 4-5]

[0284] [Table 4-6]

[0285] The present invention also includes heat transfer compositions, such as each of Heat Transfer Compositions 1-26, further comprising naphthyl epoxy 1. A heat transfer composition according to this paragraph may be referred to herein for convenience as Heat Transfer Composition 27A.

[0286] The present invention also includes heat transfer compositions, such as each of Heat Transfer Compositions 1-26, further comprising naphthyl epoxy 2. A heat transfer composition according to this paragraph may be referred to herein for convenience as Heat Transfer Composition 27B.

[0287] The present invention also includes heat transfer compositions, such as each of Heat Transfer Compositions 1-26, further comprising naphthyl epoxy 3. A heat transfer composition according to this paragraph may be referred to herein for convenience as Heat Transfer Composition 27C.

[0288] The present invention also includes heat transfer compositions, such as each of Heat Transfer Compositions 1-26, further comprising naphthyl epoxy 4. A heat transfer composition according to this paragraph may be referred to herein for convenience as Heat Transfer Composition 27D.

[0289] The present invention also includes heat transfer compositions, such as each of Heat Transfer Compositions 1-26, further comprising naphthyl epoxy 5. A heat transfer composition according to this paragraph may be referred to herein for convenience as Heat Transfer Composition 27E.

[0290] The present invention also includes heat transfer compositions, such as each of Heat Transfer Compositions 1-26, further comprising naphthyl epoxy 6. A heat transfer composition according to this paragraph may be referred to herein for convenience as Heat Transfer Composition 27F.

[0291] Other additives not mentioned herein may also be included in view of the teachings contained herein without departing from the novel and essential features of the present invention.

[0292] Additionally, a combination of surfactants and solubilizers may be added to the compositions of the present invention to aid oil solubility, as disclosed in U.S. Pat. No. 6,516,837, the disclosure of which is incorporated by reference in its entirety.

[0293] Methods, Uses, and Systems system The present invention includes all types of heat transfer systems comprising a refrigerant of the present invention, such as each of Refrigerants 1 through 15, and / or a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1 through 27. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 1 for convenience.

[0294] The present invention also includes, and provides certain advantages in connection with, low temperature refrigeration systems comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1-27. The heat transfer system described in this paragraph may be conveniently referred to as Heat Transfer System 2.

[0295] The present invention also includes, and provides certain advantages in connection with, medium temperature refrigeration systems comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1-27. The heat transfer system described in this paragraph may be conveniently referred to as Heat Transfer System 3.

[0296] The present invention also includes, and provides certain advantages in connection with, cascade refrigeration systems comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1-27. The heat transfer system described in this paragraph may be conveniently referred to as Heat Transfer System 4.

[0297] The present invention also includes, and provides certain advantages in connection with, coolers (including air-cooled coolers) comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1-27. The heat transfer system described in this paragraph may be conveniently referred to as Heat Transfer System 5.

[0298] The present invention also includes, and provides certain advantages in connection with, heat pump systems comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1-27. The heat transfer system described in this paragraph may be conveniently referred to as Heat Transfer System 6.

[0299] The present invention also includes, and provides certain advantages in connection with, commercial refrigeration (including low temperature commercial refrigeration and medium temperature commercial refrigeration) comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or comprising a heat transfer composition of the present invention, such as each of Heat Transfer Compositions 1-27. The heat transfer system described in this paragraph may be conveniently referred to as Heat Transfer System 7.

[0300] In the case of heat transfer systems of the present invention including a compressor and compressor lubricant within the system, the system can include a lubricant, such as each of Refrigerants 1-15, and a lubricant, such as POE and PVE lubricants, at a lubricant loading of about 5% to 60% by weight, or about 10% to 60% by weight, or about 20% to 50% by weight, or about 20% to 40% by weight, or about 20% to 30% by weight, or about 30% to 50% by weight, or about 30% to 40% by weight. As used herein, the term "lubricant loading" refers to the total weight of lubricant contained within the system as a percentage of the total of the lubricant and refrigerant contained within the system. Such systems can also include a lubricant loading of about 5% to 10% by weight, or about 8% by weight of the heat transfer composition.

[0301] In certain embodiments, the heat transfer compositions of the present invention comprise a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant in a low temperature refrigeration system, as follows:

[0302] [Table 5]

[0303] In certain embodiments, the heat transfer compositions of the present invention comprise a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant in a low temperature refrigeration system, as follows:

[0304] [Table 6]

[0305] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a retail food refrigeration system, as follows:

[0306] [Table 7]

[0307] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a walk-in freezer system, as follows:

[0308] [Table 8]

[0309] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a transport refrigeration system, as follows:

[0310] [Table 9]

[0311] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a transport refrigeration system, as follows:

[0312] [Table 10]

[0313] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a transport refrigeration system, as follows:

[0314] [Table 11]

[0315] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a transport refrigeration system, as follows:

[0316] [Table 12]

[0317] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a transport refrigeration system, as follows:

[0318] [Table 13]

[0319] The heat transfer composition comprises a heat transfer composition comprising Refrigerant 1-15, such as any one of Refrigerants 1-15, and / or each of Heat Transfer Compositions 1-27, and a lubricant, in a transport refrigeration system, as follows:

[0320] [Table 14]

[0321] Exemplary Heat Transfer System As described in detail below, a preferred system of the present invention includes a compressor, a condenser, an expansion device, and an evaporator, all in fluid communication using piping, valves, and a control system so that the refrigerant and associated components of the heat transfer composition can flow through the system in a well-known manner to complete a refrigeration cycle. An exemplary schematic diagram of such a basic system is shown in FIG. 1. In particular, the system shown schematically in FIG. 1 shows a compressor 10, which provides compressed refrigerant vapor to a condenser 20. The compressed refrigerant vapor condenses to produce liquid refrigerant, which is then directed to an expansion device 40, which produces refrigerant at a low pressure, and then provided to an evaporator 50. Within the evaporator 50, the liquid refrigerant absorbs heat from a body or fluid being cooled to produce refrigerant vapor, which is then provided to the suction line of the compressor.

[0322] The refrigeration system illustrated in FIG. 2 is the same as that described above in connection with FIG. 1, except that it includes a vapor injection system including a heat exchanger 30 and a bypass expansion valve 25. The bypass expansion device 25 provides liquid refrigerant to the heat exchanger 30 at a reduced pressure, and therefore at a low temperature, by diverting a portion of the refrigerant flow at the condenser outlet through the device. This relatively cool liquid refrigerant then exchanges heat with the relatively hot remaining liquid from the condenser. This action produces subcooled liquid in the main expansion device 40 and evaporator 50, and relatively cool refrigerant vapor is returned to the compressor 10. Injecting cooled refrigerant vapor into the suction side of the compressor in this manner serves to maintain the compressor discharge temperature within acceptable limits, which may be particularly advantageous in low-temperature systems utilizing high compression ratios.

[0323] The refrigeration system illustrated in Figure 3 is the same as that described above in connection with Figure 1, except that it includes a liquid injection system that includes a bypass valve 26. Bypass valve 26 diverts a portion of the liquid refrigerant exiting the condenser to a liquid injection port in the compressor, preferably compressor 10. Injecting liquid refrigerant into the suction side of the compressor in this manner serves to maintain the compressor discharge temperature within acceptable limits, which may be particularly advantageous in low temperature systems utilizing high compression ratios.

[0324] The refrigeration system illustrated in Figure 4 is the same as that described above in connection with Figure 1, except that it includes a liquid line / suction line heat exchanger 35. The refrigerant flow at the condenser outlet is directed to the liquid line / suction line heat exchanger 35, where heat is transferred from the liquid refrigerant to the refrigerant vapor exiting the evaporator 50 and then introduced into the compressor 10.

[0325] The refrigeration system illustrated in Figure 5 is the same as that described above in connection with Figure 2, except that it includes an oil separator 60 connected to the outlet of the compressor 10. As is well known to those skilled in the art, a certain amount of compressor lubricant is typically carried in the compressor discharge refrigerant vapor, and the oil separator is included to provide a means of separating the lubricant liquid from the refrigerant vapor, with the resulting refrigerant vapor having a reduced lubricant oil content proceeding to a condenser inlet, and the liquid lubricant then being returned to a lubricant reservoir, such as a lubricant receiver, for use in lubricating the compressor. In a preferred embodiment, the oil separator includes a sealing material, as described herein, preferably in the form of a filter or solid core.

[0326] Those skilled in the art will appreciate that the different equipment / configuration options shown individually in each of Figures 2-5 can be combined and used together as deemed advantageous for any application.

[0327] use: General Use The methods and systems of the present invention may include any heat transfer system and / or any heat transfer method that utilizes a refrigerant, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, to either absorb heat, reject heat, or both absorb and reject heat. Thus, the present invention provides uses and methods for heating or cooling a fluid or object using a refrigerant, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0328] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, in medium temperature refrigeration systems and provides certain advantages associated therewith.

[0329] The present invention also includes the use of refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, in low temperature refrigeration systems, and provides certain advantages associated therewith.

[0330] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerant 1-15, such as each of Heat Transfer Compositions 1-27, in a walk-in freezer, and provides certain advantages associated therewith.

[0331] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, in a walk-in refrigerator, and provides certain advantages associated therewith.

[0332] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerant 1-15, such as each of Heat Transfer Compositions 1-27, in a vending machine, and provides certain advantages associated therewith.

[0333] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerant 1-15, such as each of Heat Transfer Compositions 1-27, in a vending machine located in a hallway or corridor, and provides certain advantages associated therewith.

[0334] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, in stationary air conditioning systems, and provides certain advantages associated therewith.

[0335] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, in commercial air conditioning, and provides certain advantages associated therewith.

[0336] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, in a cascade refrigeration system, and provides certain advantages associated therewith.

[0337] The present invention also includes the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, in a heat pump system, and provides certain advantages associated therewith.

[0338] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, in transport refrigeration systems, and provides certain advantages associated therewith.

[0339] alternative use The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-22, and provides certain advantages associated therewith.

[0340] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-404A, and provides certain advantages associated therewith.

[0341] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-407F, and provides certain advantages associated therewith.

[0342] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-448A, and provides certain advantages associated therewith.

[0343] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-449A, and provides certain advantages associated therewith.

[0344] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-134A, and provides certain advantages associated therewith.

[0345] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-410A, and provides certain advantages associated therewith.

[0346] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-22 in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0347] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-22 in low temperature refrigerators, and provides certain advantages associated therewith.

[0348] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-22 in heat pumps, and provides certain advantages associated therewith.

[0349] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-22 in transport refrigeration systems, and provides certain advantages associated therewith.

[0350] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-22 in cascade refrigeration systems, and provides certain advantages associated therewith.

[0351] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-404A in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0352] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-404A in low temperature refrigerators, and provides certain advantages associated therewith.

[0353] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-404A in heat pumps, and provides certain advantages associated therewith.

[0354] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-404A in transport refrigeration systems, and provides certain advantages associated therewith.

[0355] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-404A in cascade refrigeration systems, and provides certain advantages associated therewith.

[0356] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-407F in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0357] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-407F in low temperature refrigeration, and provides certain advantages associated therewith.

[0358] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-407F in heat pumps, and provides certain advantages associated therewith.

[0359] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-407F in transport refrigeration systems, and provides certain advantages associated therewith.

[0360] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-407F in cascade refrigeration systems, and provides certain advantages associated therewith.

[0361] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-448A in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0362] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-448A in low temperature refrigerators, and provides certain advantages associated therewith.

[0363] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-448A in heat pumps, and provides certain advantages associated therewith.

[0364] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-448A in transport refrigeration systems, and provides certain advantages associated therewith.

[0365] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-448A in cascade refrigeration systems, and provides certain advantages associated therewith.

[0366] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-134A in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0367] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-134A in low temperature refrigerators, and provides certain advantages associated therewith.

[0368] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-134A in heat pumps, and provides certain advantages associated therewith.

[0369] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-134A in transport refrigeration systems, and provides certain advantages associated therewith.

[0370] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-134A in cascade refrigeration systems, and provides certain advantages associated therewith.

[0371] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-449A in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0372] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-449A in low temperature refrigerators, and provides certain advantages associated therewith.

[0373] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-449A in heat pumps, and provides certain advantages associated therewith.

[0374] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-449A in transport refrigeration systems, and provides certain advantages associated therewith.

[0375] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-449A in cascade refrigeration systems, and provides certain advantages associated therewith.

[0376] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-410A in medium temperature refrigeration systems, and provides certain advantages associated therewith.

[0377] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-410A in low temperature refrigerators, and provides certain advantages associated therewith.

[0378] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-410A in heat pumps, and provides certain advantages associated therewith.

[0379] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-410A in transport refrigeration systems, and provides certain advantages associated therewith.

[0380] The present invention also includes the use of the refrigerants of the present invention, such as each of Refrigerants 1-15, and / or heat transfer compositions comprising Refrigerants 1-15, such as each of Heat Transfer Compositions 1-27, as a replacement for R-410A in cascade refrigeration systems, and provides certain advantages associated therewith.

[0381] Cooling method The present invention provides a method for providing cooling, comprising: (a) evaporating a refrigerant according to the present invention (including any refrigerant selected from each of Refrigerants 1-15) in the vicinity of a body or article or fluid to be cooled; (b) compressing the refrigerant vapor to produce a refrigerant having a discharge temperature of less than about 150°C; (c) condensing the refrigerant from the compressor. The refrigeration method according to this paragraph is referred to herein as Refrigeration Method 1.

[0382] The present invention provides a method for providing cooling, comprising: (a) evaporating a refrigerant according to the present invention (including any refrigerant selected from each of Refrigerants 1 to 15) in the vicinity of an object or article or fluid to be cooled at a temperature of about -40°C to about +10°C to produce a refrigerant vapor; (b) compressing the refrigerant vapor to produce a refrigerant having a discharge temperature of less than about 150°C; (c) condensing the refrigerant from the compressor at a temperature between about 20° C. and about 70° C. to produce a refrigerant vapor. The refrigeration method according to this paragraph is referred to herein as Refrigeration Method 2.

[0383] The present invention includes carrying out cooling according to any one of cooling methods 1 to 3 in a medium-temperature refrigeration system.

[0384] The present invention includes carrying out cooling according to any one of cooling methods 1 to 3 in a low-temperature refrigeration system.

[0385] The present invention includes carrying out cooling according to any of cooling methods 1 to 3 in a transport refrigeration system.

[0386] The present invention includes carrying out cooling in a cascade refrigeration system according to any of cooling methods 1-3.

[0387] The present invention includes carrying out cooling according to any one of cooling methods 1 to 3 in an electronic cooling system.

[0388] The present invention includes carrying out cooling in a heat pump system according to any one of cooling methods 1 to 3.

[0389] The present invention includes providing cooling in a commercial refrigeration system according to any of cooling methods 1-3.

[0390] The present invention includes carrying out cooling according to any of Cooling Methods 1-3 in a commercial low-temperature refrigeration system.

[0391] The present invention includes carrying out cooling according to any of Cooling Methods 1-3 in a commercial medium temperature refrigeration system.

[0392] The present invention includes carrying out cooling in a walk-in freezer according to any one of cooling methods 1 to 3.

[0393] The present invention includes carrying out cooling in a walk-in refrigerator according to any one of cooling methods 1 to 3.

[0394] The present invention includes performing cooling according to any one of cooling methods 1 to 3 in a stationary air-conditioning system.

[0395] The present invention includes carrying out cooling according to any one of cooling methods 1 to 3 in commercial air conditioning.

[0396] The present invention includes carrying out cooling in a vending machine according to any one of cooling methods 1 to 3.

[0397] Specific cooling methods are described in more detail below.

[0398] Applicants have discovered that substantial advantages can be achieved in connection with heat transfer methods in which refrigerants such as each of Refrigerants 1-15, or heat transfer compositions of the present invention comprising refrigerants of the present invention, such as Heat Transfer Compositions 1-27, are used to absorb heat from a fluid surrounding an item or otherwise in thermal communication with the item itself, such as may occur, for example, to cool produce and / or other refrigerated foods, or in connection with cooling certain electronic devices. In such cases, the fluid may be air or a secondary coolant (e.g., water, glycol, water / glycol mixtures, saline solution, etc.), such as occurs in the case of refrigerants used in evaporators in systems and methods requiring that the temperature of the item or fluid being cooled not be exposed to temperatures below a certain limit.

[0399] Generally, therefore, the methods of the present invention utilize equipment and / or processes that enable the refrigerant or heat transfer composition of the present invention to absorb heat, and equipment and / or processes that subsequently remove the absorbed heat from the refrigerant.

[0400] It will be understood that an evaporator used to absorb heat from an article or fluid being cooled may include, for example, a conduit, such as a cooling coil, through which a refrigerant, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerant 1-15, such as each of Heat Transfer Compositions 1-27, flows while such conduit is exposed (directly or indirectly) to the article or fluid to be cooled. In this manner, heat flows from the fluid being cooled (e.g., air) and / or nearby articles (e.g., fresh produce such as fruits, vegetables, and flowers), through the metal or other thermally conductive material of the conduit, to a refrigerant of the present invention, such as each of Refrigerants 1-15, and / or a heat transfer composition comprising Refrigerant 1-15, such as each of Heat Transfer Compositions 1-27.

[0401] Refrigeration method The present invention also provides a method for cooling a fluid or object using a refrigeration system, comprising the steps of: (a) evaporating, in the vicinity of the fluid or object to be cooled, an inventive refrigerant composition, including each of Refrigerants 1-15 and / or a heat transfer composition comprising Refrigerant 1-15, such as each of Heat Transfer Compositions 1-27; and (b) condensing the refrigerant. Certain preferred operations of the preferred heat transfer methods are described below.

[0402] Medium temperature refrigeration method The refrigerants and heat transfer compositions of the present invention can be used in any refrigeration system. However, applicants have discovered that the refrigerants of the present invention, such as each of Refrigerants 1-15, and heat transfer compositions of the present invention comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, offer particular advantages in medium-temperature refrigeration systems. Accordingly, the present invention provides a method for cooling a fluid or object in a medium-temperature refrigeration system, comprising the steps of: (a) evaporating, in the vicinity of the fluid or object to be cooled, a refrigerant composition of the present invention comprising each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27; and (b) condensing the refrigerant, wherein the evaporator temperature is from about -15°C to about 5°C, more preferably from about -10°C to about 5°C.

[0403] As used herein, a medium temperature refrigeration system refers to a refrigeration system utilizing one or more compressors and operating under or within the following conditions: (a) a condenser temperature of about 15°C to about 60°C, preferably about 25°C to about 45°C; (b) an evaporator temperature of about -15°C to about 5°C, preferably about -10°C to about 5°C; optionally (c) an evaporator outlet superheat of about 0°C to about 10°C, preferably about 1°C to about 6°C; and optionally (d) a superheat in the intake line of about 5°C to about 40°C, preferably about 15°C to about 30°C. The superheat along the intake line may be generated by a heat exchanger.

[0404] Examples of medium temperature refrigeration systems and methods include small refrigeration systems (including vending machines, ice makers, and domestic appliances), commercial refrigeration systems (such as supermarket refrigeration systems and walk-in coolers), residential refrigeration systems, industrial refrigeration systems, and skating rinks.

[0405] For storage of perishable produce such as vegetables and fruits in a medium temperature refrigeration system or using a medium temperature refrigeration method, for example, the fluid to be cooled is air having a desired cooling temperature of about 2°C to about 5°C, preferably about 2°C to about 4°C, and more preferably about 2°C to about 3°C ​​(e.g., cooling fresh-cut fruit, vegetables, and flowers). Furthermore, in many applications, it is preferred that the refrigerant temperature along the evaporator not reach below about 0°C (the freezing point of water) to avoid frost formation. Preferably, at the same time, the superheat at the outlet of the evaporator should be maintained at a typical value of about 3°C ​​to about 5°C, preferably about 4°C.

[0406] Thus, the present invention includes a medium temperature refrigeration method comprising a refrigerant, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, wherein the evaporation temperature of the refrigerant is from about 0°C to about 5°C.

[0407] Cascade refrigeration method The present invention also relates to a cascade refrigeration method comprising the refrigerant or heat transfer composition of the present invention. Generally, a cascade system has two or more stages. When a cascade system has two stages, these are generally referred to as an upper stage and a lower stage. Refrigerants of the present invention, such as each of Refrigerants 1-15, or heat transfer compositions comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, can be used in either the upper or lower stage of a cascade refrigeration system. However, it is preferred that refrigerants of the present invention, such as each of Refrigerants 1-15, or heat transfer compositions comprising a refrigerant of the present invention, such as each of the present heat transfer compositions, be used in the upper stage of a cascade system. Given the teachings contained herein, one skilled in the art will be able to determine suitable refrigerants for use in the lower stage of a cascade system, which can include, for example, CO2, R1234yf, and R455A. R455A is a blend of 75.5% R1234yf, 21.5% R32, and 3% CO2. In a cascade system, the refrigerant of the present invention can replace, for example, R404A.

[0408] Low-temperature refrigeration method The present invention also provides a low temperature refrigeration method comprising a refrigerant, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27. The present invention also provides a method for cooling a fluid or object in a low temperature refrigeration system, comprising the steps of: (a) evaporating a refrigerant composition of the present invention, comprising each of Refrigerants 1-15, in the vicinity of the fluid or object to be cooled; and (b) condensing the refrigerant. Preferably, the temperature of the refrigerant in the evaporator is from about -40°C to less than about -15°C, more preferably from about -40°C to about -25°C.

[0409] As used herein, a low temperature refrigeration system refers to a refrigeration system utilizing one or more compressors and operating under or within the following conditions: (a) a condenser temperature of about 15°C to about 50°C, preferably about 25°C to about 45°C, (b) an evaporator temperature of about -40°C to about -15°C or less than about -15°C, preferably about -40°C to about -25°C, optionally (c) an evaporator outlet superheat of about 0°C to about 10°C, preferably about 1°C to about 6°C, and optionally (d) a superheat in the intake line of about 15°C to about 40°C, preferably about 20°C to about 30°C.

[0410] Examples of low temperature refrigeration systems and methods include supermarket refrigeration systems, commercial freezer systems (including supermarket freezers), residential freezer systems, and industrial freezer systems. Low temperature refrigeration systems can be used, for example, to cool frozen goods.

[0411] Refrigeration method for transportation Transport refrigeration creates a link in the cold chain that allows frozen or chilled produce to reach the end user in the correct temperature environment. The present invention relates to transport refrigeration systems comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27. Examples of transport refrigeration include refrigerated road vehicles (such as trucks and vans), rail cars, and containers that can be transported by road vehicles, trains, and ships / boats.

[0412] Heat Pump Method The present invention relates to heat pump processes comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0413] The present invention also provides a method of heating a fluid or object using a heat pump, comprising the steps of: (a) condensing, in the vicinity of the fluid or object to be heated, an inventive refrigerant composition comprising each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27; and (b) evaporating the refrigerant. Examples of heat pumps include heat pump tumble dryers, reversible heat pumps, high temperature heat pumps, and air-to-air heat pumps.

[0414] Secondary Loop Method A refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, can be used as a secondary fluid in a secondary loop system. A secondary loop system includes a primary vapor compression system loop using a primary refrigerant and an evaporator that cools the secondary loop fluid. The secondary fluid then provides the cooling required for the application. Because the refrigerant in such a loop may be exposed to humans in the vicinity of the cooled space, the secondary fluid must be non-flammable and have low toxicity. In other words, a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, can be used as a "secondary fluid." Primary fluids for use in the primary loop (vapor compression cycle, external / outdoor part of the loop) may include, but are not limited to, the following refrigerants: R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze(E), R1234yf, and R449A.

[0415] Air conditioning system The present invention relates to air conditioning systems comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27. The present invention also provides a method of air conditioning using an air conditioning system, comprising: (a) evaporating a refrigerant composition of the present invention, comprising each of Refrigerants 1-15, in the vicinity of a fluid of a body to be cooled; and (b) condensing the refrigerant. The air can be conditioned directly or indirectly by a refrigerant of the present invention (such as each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (such as each of Heat Transfer Compositions 1-27). Examples of air conditioning systems include chillers, residential, industrial, commercial, and mobile air conditioning, including air conditioning of road vehicles such as automobiles, trucks, and buses, and air conditioning of boats and trains.

[0416] Preferred refrigeration systems of the present invention include chillers comprising a refrigerant of the present invention, particularly each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0417] Preferred refrigeration systems of the present invention include stationary air conditioning systems comprising a refrigerant of the present invention, particularly each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0418] Preferred refrigeration systems of the present invention include commercial air conditioning systems comprising a refrigerant of the present invention, particularly each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0419] Preferred refrigeration systems of the present invention include vending machines, particularly those comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0420] Preferred refrigeration systems of the present invention include walk-in freezers comprising a refrigerant of the present invention, particularly each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0421] Preferred refrigeration systems of the present invention include walk-in refrigerators, particularly comprising a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27.

[0422] It will be understood that any of the above-described refrigeration, air conditioning, or heat pump systems using a refrigerant of the present invention, such as each of Refrigerants 1-14, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, may include a suction line / liquid line heat exchanger (SL-LL HX).

[0423] Organic Rankine Cycle System Refrigerant compositions of the present invention, including each of Refrigerants 1-15, or heat transfer compositions including a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, can be used in Organic Rankine Cycles (ORCs). In the context of ORCs, refrigerants used in these systems may also be classified as "working fluids." Rankine cycle systems are well known to be a simple and reliable means for converting thermal energy into mechanical shaft power.

[0424] In industrial environments, it may be possible to use flammable working fluids such as toluene and pentane, especially if the industrial environment already has large amounts of flammable materials in operation or storage on-site. However, there is a need to use non-flammable and / or non-toxic refrigerants as working fluids when the risks associated with using flammable and / or toxic working fluids are not acceptable, such as for power generation in populated areas or near buildings. There is also a movement within the industry to make these materials environmentally acceptable from a GWP perspective.

[0425] The process for recovering waste heat in an organic Rankine cycle system involves pumping a liquid-phase working fluid through a heat exchanger (boiler) where an external (waste) heat source, such as a process stream, heats the working fluid and vaporizes it into saturated or superheated steam. This steam expands through a turbine, converting the waste heat energy into mechanical energy. The vapor-phase working fluid is then condensed to a liquid and pumped back to the boiler to repeat the heat extraction cycle. Thus, the present invention relates to the use of a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, in an organic Rankine cycle.

[0426] Thus, the present invention provides a process for converting thermal energy to mechanical energy in a Rankine cycle, the method comprising: i) vaporizing a working fluid at a heat source and expanding the resulting vapor, or vaporizing a working fluid at a heat source and expanding the resulting vapor, and then ii) cooling the working fluid at a heat sink to condense the vapor, wherein the working fluid is a refrigerant of the present invention, such as each of Refrigerants 1-15, or a heat transfer composition comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27. The mechanical work can be delivered to an electrical device, such as a generator, to produce electrical power.

[0427] The heat source may be provided by a thermal energy source selected from industrial waste heat, solar energy, geothermal hot water, low pressure steam, distributed power generation equipment utilizing fuel cells, internal combustion engines, or prime movers. Preferably, the low pressure steam is low pressure geothermal steam or provided by a fossil fuel powered power plant.

[0428] It will be appreciated that heat source temperatures can vary widely, for example, from about 90°C to over 800°C, and for certain combustion gases and some fuel cells, can vary depending on myriad factors, such as geography, time of year, etc. For example, systems based on sources such as wastewater or low-pressure steam from plastic manufacturing plants, and / or chemical or other industrial plants, oil refineries, etc., as well as geothermal sources, can have source temperatures of about 100°C or less, in some cases as low as about 90°C, or even as low as about 80°C. Gaseous heat sources, such as exhaust gases from combustion processes or any heat source where subsequent processing to remove particulates and / or corrosive species results in lower temperatures, can also have source temperatures of about 130°C or less, about 120°C or less, about 100°C or less, in some cases as low as about 90°C, or even as low as about 80°C.

[0429] electronic cooling Refrigerant compositions of the present invention comprising any one of Refrigerants 1-15, or heat transfer compositions comprising a refrigerant of the present invention, such as each of Heat Transfer Compositions 1-27, may be used in connection with systems and methods of electronic cooling, such as cooling chips, electronic boards, batteries (including batteries used in automobiles, trucks, buses, and other electronic transportation vehicles), computers, and the like. [Example]

[0430] In the following examples, examples of refrigerant compositions of the present invention are identified as compositions A1-A6 in Table 1 below. Each of refrigerants A1-A6 was subjected to thermodynamic analysis to determine its ability to match the operating characteristics of R-448A in various refrigeration systems. The analysis was performed using experimental data collected on the properties of various binary and ternary sets of components used in the refrigerants. The composition of each set was varied over a range of relative percentages in the experimental evaluation, and the mixture parameters for each set were regressed to the experimentally obtained data. The examples used known vapor / liquid equilibrium behavior data available in the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database software (Refprop 9.1 NIST Standard Database 23 from April 2016). The parameters selected to perform the analysis were the same compressor volume for all refrigerants, the same operating conditions for all refrigerants, and the same compressor isentropic and volumetric efficiencies for all refrigerants. For each example, simulations were performed using measured vapor-liquid equilibrium data. Simulation results are reported for each example.

[0431] The refrigerant compositions identified in Table 1 below as Refrigerants A1, A2, A3, A4, A5, and A6 are A2L refrigerants within the broad scope of the invention as described herein.

[0432] [Table 15]

[0433] Comparative examples C1~C6 The following compositions are prepared, tested and found to have the GWP values ​​shown in Tables C1-6A and C1-6B below.

[0434] [Table 16]

[0435] [Table 17]

[0436] As can be seen from the table above, many compositions containing R32, R1132E, and R1234yf and CO2 have a GWP value of 150 or greater and / or a GWP of 0.25 kg / m 3 Unable to achieve any of the above LFLs.

[0437] Examples 1-14: Refrigerant performance / capacity / compressor output and LFL in medium and low temperature refrigeration Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested in medium and low temperature refrigeration systems, such as those generally disclosed in FIG. 1, under the operating conditions specified below.

[0438] Operating conditions 1. Condensation temperature = 45℃ 2. Condenser subcooling = 5°C 3. Evaporation temperature MT=-3.8℃, Evaporation temperature LT=-28.8℃ 4. Evaporator superheat = 3.8°C 5. Insulation efficiency = 70% 6. Volumetric efficiency = 100%

[0439] The results of this test are reported in Table E1-14 below.

[0440] [Table 18]

[0441] As can be seen from the results identified in Tables E1-E14 above, applicants have found several compositions shown in Examples Ex1-Ex4, including R32, R1132(E), R1234yf, and CO2, that are capable of achieving LFL (as well as achieving a GWP of 150 or less) in accordance with the preferred levels of refrigerants of the present invention, yet are unable to achieve the most preferred capacity levels in either MT or LT refrigeration of greater than 95% relative to R448A.

[0442] In contrast to Examples (Ex) 1-4, the compositions of Examples 5-14 are each able to achieve LFL in accordance with the preferred LFL levels of the refrigerants of the present invention (LFL of 0.25 or greater), and are also able to achieve both a GWP of 150 or less and the most preferred capacity levels for either MT or LT refrigeration of at least 95% relative to R448A, a highly desirable and unexpected result.

[0443] Examples 15-29: Refrigerant performance / capacity / compressor power and LFL in medium and low temperature refrigeration Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested in medium and low temperature refrigeration systems, such as those generally disclosed in FIG. 1, under the operating conditions specified below.

[0444] [Table 19]

[0445] As can be seen from the results identified in Tables E15-E29 above, Applicants have found that each of Examples 15-29 can achieve an LFL in accordance with the preferred LFL levels of the refrigerants of the present invention (LFL of 0.25 or greater), and can also achieve both a GWP of 150 or less and the most preferred capacity levels for either MT or LT refrigeration of at least 95% relative to R448A, and a power rating of 115% or less for both MT and LT refrigeration relative to R448A, a highly desirable and unexpected result.

[0446] Examples 30-34: Performance (compressor output) and LFL of the refrigerant of the present invention in medium- and low-temperature refrigeration Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested for compressor power consumption compared to R448A in medium and low temperature refrigeration systems as generally disclosed in FIG. 1 under the operating conditions specified below.

[0447] Operating conditions 1. Condensation temperature = 45℃ 2. Condenser subcooling = 5°C 3. Evaporation temperature MT=-3.8℃, Evaporation temperature LT=-28.8℃ 4. Evaporator superheat = 3.8°C 5. Insulation efficiency = 70% 6. Volumetric efficiency = 100%

[0448] The results of this test are reported in Table E30-34 below.

[0449] [Table 20]

[0450] As can be seen from the results identified in Tables E30-E34 above, Applicants have found that each of Examples 30-34 is capable of achieving both an LFL in accordance with the preferred LFL levels of the refrigerants of the present invention (LFL of 0.25 or greater), as well as a GWP of 150 or less, and Examples 30-33 are also capable of achieving highly desirable power ratings of 115% or less for both MT and LT refrigeration relative to R448A, which are highly desirable and unexpected results.

[0451] Examples 35 to 40: Capacity and discharge temperature of refrigerants A1 to A6 in medium-temperature refrigeration Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested in a medium temperature refrigeration system as generally disclosed in Figure 1 under the operating conditions specified below.

[0452] Operating conditions: Condensation temperature: 45℃ Condensation temperature - ambient temperature = 10°C Condenser subcooling = 0.0°C (system with a receiver) Evaporation temperature: -8℃ Evaporator superheat: 5.5℃ Compressor adiabatic efficiency = 65% Volumetric efficiency = 100% Temperature rise in intake line = 10°C

[0453] The results of this test are reported in Tables E35-40 below.

[0454] [Table 21]

[0455] As can be seen from the results identified in Tables E35-E40 above, Applicants have found that each of Examples 35-40 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a highly preferred ability of 99% or greater, and a surprisingly significant ability to achieve acceptable matching to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0456] Examples 41 to 46: Capacity and discharge temperature of refrigerants A1 to A6 in low-temperature refrigeration Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested in a low temperature refrigeration system such as generally disclosed in FIG. 1 under the operating conditions specified below.

[0457] Operating conditions: Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C Condenser subcooling = 0.0°C (system with a receiver) Evaporation temperature = -35°C, corresponding internal temperature = -25°C Evaporator superheat = 5.5℃ Compressor adiabatic efficiency = 65% Volumetric efficiency = 100% -Temperature rise in intake line = 10℃

[0458] The results of this testing are reported below in Tables E41-46, which include results for various conventional refrigerants for comparison purposes.

[0459] [Table 22]

[0460] As can be seen from the results identified in Tables E35-E40 above, Applicants have found that each of Examples 35-40 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a highly preferred ability of about 100% or greater, and a surprisingly significant ability to achieve acceptable matching to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0461] Examples 47 to 52: Capacity and discharge temperature of refrigerants A1 to A6 in vending machines Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested in a vending machine refrigeration system as generally disclosed in Figure 1 under the operating conditions specified below.

[0462] Operating conditions: Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C Condenser subcooling = 5.5°C (system with a receiver) Evaporation temperature = -8°C Evaporator superheat = 3.5℃ Compressor adiabatic efficiency = 60% Volumetric efficiency = 100% -Temperature rise in intake line = 5°C

[0463] The results of this testing are reported below in Tables E47-52, which include results for various conventional refrigerants for comparison purposes.

[0464] [Table 23]

[0465] As can be seen from the results identified in Tables E35-E40 above, Applicants have found that each of Examples 35-40 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a highly preferred ability of about 95% or greater, and a surprisingly significant ability to achieve acceptable matching to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0466] Examples 53 to 58: Capacity and discharge temperature of refrigerants A1 to A6 in air source heat pump water heaters Several refrigerants, including R32, R1132(E), R1234yf and CO2, are performance tested in an air source heat pump water heater system under the operating conditions specified below.

[0467] Operating conditions: Condensation temperature = 55℃ ·Inlet temperature = 45℃, water outlet temperature = 50℃ Condenser subcooling = 5.0℃ Evaporation temperature = -5℃, corresponding ambient temperature = 10℃ Evaporator superheat = 3.5℃ Compressor adiabatic efficiency = 65% Volumetric efficiency = 100% -Temperature rise in intake line = 5°C

[0468] The results of this testing are reported below in Tables E53-58, which include results for various conventional refrigerants for comparison purposes.

[0469] [Table 24]

[0470] As can be seen from the results identified in Tables E53-58 above, Applicants have found that each of Examples 53-58 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a highly preferred ability of about 100% or greater, and a surprisingly significant ability to achieve acceptable matching to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0471] Examples 59-64: Capacity Adaptation at Several Condenser Temperatures in Mobile Air Conditioning Systems (Bus, Train, Car) Several refrigerants, including R32, R1132(E), R1234yf and CO2, are performance tested in a mobile air conditioning system under the operating conditions specified below.

[0472] Operating conditions: Condensation temperature: 45℃~75℃ Condenser subcooling = 5.0℃ Temperature = 4℃, corresponding room temperature = 35℃ Evaporator superheat = 5.0℃ Compressor adiabatic efficiency = 65% Volumetric efficiency = 100% -Temperature rise in intake line = 0℃

[0473] The results of this testing are reported below in Tables E59-64, which include results for various conventional refrigerants for comparison purposes.

[0474] [Table 25]

[0475] As can be seen from the results identified in Tables E59-64 above, Applicants have found that each of Examples 59-64 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), and similarly, is capable of achieving a GWP of 150 or less, and each of these Examples demonstrates a surprising and significant ability to achieve a highly preferred capacity of about 100% or greater relative to R448A, which is a highly desirable and unexpected result.

[0476] Examples 65-70: Capacity compatibility at several condenser temperatures in stationary air conditioning systems Several refrigerants, including R32, R1132(E), R1234yf and CO2, are performance tested in a stationary air conditioning system under the operating conditions specified below.

[0477] Operating conditions: Condensation temperature: 45℃~65℃ Condenser subcooling = 5.0℃ Temperature = 10℃, corresponding room temperature = 35℃ Evaporator superheat = 5.0℃ Compressor adiabatic efficiency = 72% Volumetric efficiency = 100%

[0478] The results of this testing are reported below in Tables E65-71, which include results for various conventional refrigerants for comparison purposes.

[0479] [Table 26]

[0480] As can be seen from the results identified in Tables E65-70 above, Applicants have found that each of Examples 65-64 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), and similarly, is capable of achieving a GWP of 150 or less, and each of these Examples demonstrates a surprising and significant ability to achieve a highly preferred performance of about 97% or greater relative to R448A, which is a highly desirable and unexpected result.

[0481] Examples 71-76: Capacity compatibility of several condenser temperatures in commercial air conditioning systems Several refrigerants, including R32, R1132(E), R1234yf, and CO2, are performance tested in a commercial air conditioning system under the operating conditions specified below.

[0482] Operating conditions: Condensation temperature: 45℃~65℃ Condenser subcooling = 5.0℃ Temperature = 10℃, corresponding room temperature = 35℃ Evaporator superheat = 5.0℃ Compressor adiabatic efficiency = 72% Volumetric efficiency = 100%

[0483] The results of this testing are reported below in Tables E71-76, which include results for various conventional refrigerants for comparison purposes.

[0484] [Table 27]

[0485] As can be seen from the results identified in Tables E71-76 above, Applicants have found that each of Examples 71-64 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), and similarly, is capable of achieving a GWP of 150 or less, and each of these Examples demonstrates a surprising and significant ability to achieve a highly preferred performance of about 97% or greater relative to R448A, which is a highly desirable and unexpected result.

[0486] Examples 77 to 79: Capacity and discharge temperature of refrigerants A1 to A6 in a medium-temperature refrigeration system for transportation (refrigerated trucks, containers) Several refrigerants, including R32, R1132(E), R1234yf and CO2, are performance tested in an air source heat pump water heater system under the operating conditions specified below.

[0487] Operating conditions: Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C Condenser subcooling = 0.0°C (system with a receiver) Evaporation temperature = -8°C Evaporator superheat = 5.5℃ Compressor adiabatic efficiency = 65% Volumetric efficiency = 100% -Temperature rise in intake line = 15°C

[0488] The results of this testing are reported below in Tables E77-79, which include results for various conventional refrigerants for comparison purposes.

[0489] [Table 28]

[0490] As can be seen from the results identified in Tables E77-82 above, Applicants have found that each of Examples 77-58 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a highly preferred ability of about 99% or greater, and a surprisingly significant ability to achieve acceptable matching to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0491] Examples 83 to 89: Capacity and discharge temperature of refrigerants A1 to A6 in low-temperature refrigeration applications for transportation (refrigerated trucks, containers) Several refrigerants, including R32, R1132(E), R1234yf and CO2, are performance tested in an air source heat pump water heater system under the operating conditions specified below.

[0492] Operating conditions: Condensation temperature = 45℃ Condensation temperature - ambient temperature = 10°C Condenser subcooling = 0.0°C (system with a receiver) Evaporation temperature = -35°C, corresponding internal temperature = -25°C Evaporator superheat = 5.5℃ Compressor adiabatic efficiency = 65% Volumetric efficiency = 100% -Temperature rise in intake line = 15°C

[0493] The results of this testing are reported below in Tables E83-89, which include results for various conventional refrigerants for comparison purposes.

[0494] [Table 29]

[0495] As can be seen from the results identified in Tables E77-82 above, Applicants have found that each of Examples 77-58 (Refrigerants A1-A6 of the present invention) is capable of achieving an LFL in accordance with the preferred LFL levels (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a highly favorable ability of about 101% or greater, and a surprisingly significant ability to achieve acceptable matching to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

Claims

1. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the sum of all refrigerant components: a. greater than 15 wt% and less than 22 wt% R-32; b. greater than 60.5 wt. % to about 71.5 wt. % HFO-1234yf; c. 4 wt.% to less than 14.5 wt.% HFO-1132(E); d. More than 1.5 wt % to 3.5 wt % CO ２ and, a refrigerant.

2. A heat transfer composition comprising the refrigerant of claim 1, a stabilizer, and a lubricant.

3. The heat transfer composition of claim 2 , wherein the stabilizer comprises one or more of an alkylated naphthalene, an acid-depleted moiety, and a protectant.

4. 3. The heat transfer composition of claim 2, wherein the stabilizer comprises an alkylated naphthalene, the alkylated naphthalene comprising at least one of AN4, AN5, AN9, and AN10.

5. 3. The heat transfer composition of claim 2, wherein the stabilizer comprises an acid-depleted portion, the acid-depleted portion comprising at least one of ADM1A, ADM1D, ADM2A, ADM4, and ADM5.

6. 6. The heat transfer composition of any one of claims 1 to 5, further comprising at least one of naphthyl epoxy 1, naphthyl epoxy 2, naphthyl epoxy 3, naphthyl epoxy 4, naphthyl epoxy 5, and naphthyl epoxy 6.

7. A refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the sum of all refrigerant components: a. about 15% to about 22% by weight of R-32; b. about 61% to about 71.5% by weight of HFO-1234yf; c. about 4% to about 14.5% by weight of HFO-1132(E); d. 1% to 4% by weight of CO ２ and, However, the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more.

8. 1. A method for providing heat transfer, comprising: a. a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of the refrigerant: i. greater than 15 wt% and less than 22 wt% R-32; ii. greater than 61 wt. % to about 71.5 wt. % HFO-1234yf; and iii. 4% to less than 14.5% by weight of HFO-1132(E); iv. greater than 1.5 wt% to 3.5 wt% CO ２ providing a refrigerant, b) transferring heat to or from said refrigerant in a heat transfer system.

9. 1. A method for providing heat transfer, comprising: a. a refrigerant comprising at least about 95% by weight of the following four components in the following relative concentrations, based on the total amount of the refrigerant: i. about 15% to about 22% by weight of R-32; ii. about 61% to about 71.5% by weight of HFO-1234yf; iii. about 4% to about 14.5% by weight of HFO-1132(E); iv. 1% to 4% by weight of CO ２ providing a refrigerant, b. transferring heat to or from the refrigerant in a heat transfer system including at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator; i. the capacity of the refrigerant in the heat transfer system is at least 95% of the capacity of R448A in the heat transfer system; ii. The power consumption of the compressor is 115% or less of the power consumption of R448A operating in the heat transfer system.

10. 10. The method of claim 9, further comprising adding a stabilizer to the refrigerant, the stabilizer comprising one or more of an alkylated naphthalene, an acid-depleted moiety, and a protectant.

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