Refrigerant with low GWP and system and method for providing refrigeration

Abstract

The refrigerant comprises from about 15% to about 22% by weight of R-32; from about 61% by weight to about 71.5% by weight of HFO-1234yf; from about 4% by weight to about 14.5% by weight of HFO-1132 (E); and 1% to 4% by weight of CO2.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] The present invention relates to and claims the benefit of priority of each of U.S. Provisional Application Nos. 63 / 436,574 and 63 / 436,575, each of which was filed on December 31, 2022 (Attorney Docket No. H230108-US-PROV), and each of which is incorporated herein by reference. Technical Field

[0003] The present invention relates to low global warming potential ("low GWP") refrigerants and heat transfer compositions, heat transfer methods, and heat transfer systems that have particular benefits in medium and low temperature refrigeration systems, cascade refrigeration systems, transport refrigeration systems, and heat pumps. In particular aspects, the present invention relates to walk-in refrigeration and / or freezer units that are 3,000 square feet or less in size, and to beverage and food coolers that are located in corridors and aisles and provide cooling at medium and low temperature 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 using relatively high GWP refrigerants (including R448A), particularly in walk-in refrigeration and / or freezer units that are 3,000 square feet or less in size and in beverage and food coolers that are located in corridors and aisles. Background Art

[0004] Certain single-component fluorocarbons, including chlorofluorocarbons ("CFCs"), hydrochlorofluorocarbons ("HCFCs"), and hydrofluoroolefins ("HFOs"), have been used in many heat transfer applications. One advantage of single-component fluids as refrigerants is that, for a given pressure, the boiling point is constant. This is highly desirable because it allows a refrigeration system or process to be designed with a refrigerant temperature along the evaporator that varies very little during the evaporation process, assuming there is little or no pressure drop as the refrigerant flows through the evaporator.

[0005] Those skilled in the art have primarily used single-component refrigerants, such as HFC-134a, in many refrigeration applications and have avoided refrigerant blends because blends generally experience significant changes in boiling point temperature upon evaporation, which has heretofore been considered a major obstacle in determining a blend with the correct balance of properties for use in such systems. This change in boiling point temperature is typically reflected in a blend characteristic known as the "glide" of the blend. Typically, the greater the glide, the greater the difference in boiling temperature that occurs in various refrigeration equipment. For many important applications, this parameter is considered to be critical for the success of the refrigerant and / or the refrigeration system in which it is used, and a relatively low glide may provide significant advantages in many important applications.

[0006] Another refrigerant property that has become increasingly important in recent years is the refrigerant's environmental friendliness, which is now crucial for many applications. This environmental friendliness can be measured, at least in part, by the projected impact of the refrigerant on global warming if released into the atmosphere. This projected impact is often measured in terms of the refrigerant's global warming potential (GWP), with refrigerants with a high GWP being highly preferred and / or required by law for use in many applications.

[0007] Flammability is another important consideration for refrigerants used in an application. Currently, the most preferred refrigerants are non-flammable materials classified as Class 1 by ASHRAE. The second most preferred non-flammability category is Class 2L by ASHRAE. Applicants and others in the art have recognized that it is very difficult to develop new refrigerants that are simultaneously environmentally friendly, preferably have a GWP of less than 150, have a low glide, preferably less than 3°C, and are non-flammable, preferably having a classification of 2L or 1. Applicants have particularly recognized that in many applications, it is extremely difficult to identify a single component fluid, let alone a refrigerant that is a blend of multiple components, that possesses a full set of properties that give it particular advantages in applications of the type described herein. For example, in many important applications, it is desirable to identify a refrigerant that simultaneously: (1) has an operable glide; (2) has a low global warming potential (GWP) (i.e., less than about 150); (3) is non-flammable (i.e., Class 1 or Class 2L according to ASHRE); (4) has low or essentially no toxicity; and (5) has heat transfer and other properties (e.g., chemical stability) that match the needs of a particular application, particularly in medium-temperature heat transfer systems. While in many cases one or two of these requirements can be met using a single-component refrigerant, those skilled in the art have found that it has been difficult (if not impossible) to date to find a refrigerant (whether single-component or otherwise) that can meet all five requirements, i.e., achieve each of (1)-(5). Here, low-toxicity materials are classified as Class "A" by ASHRAE Standard 34-2016. According to ASHRAE Standard 34-2016, materials that are both non-flammable and low-toxic are classified as "A1" or A2L.

[0008] It is also highly desirable to provide refrigerants and heat transfer compositions that can be used in a variety of cooling applications. Applicants have recognized that in order to meet this need and many other important needs mentioned above, refrigerants and heat transfer compositions must be able to operate within industrial 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) have implemented new energy efficiency rules, commonly referred to as "AWEF," which apply to walk-in coolers and freezers (hereinafter sometimes referred to as "WICF") that are 3,000 square feet or less. These rules include the specification of the Annual Walk-In Energy Factor (AWEF) created by the Air Conditioning, Heating and Refrigeration Institute (AHRI). The glide of the refrigerant is particularly important in such applications because refrigerants with glide tend to operate at lower evaporating temperatures to meet the dew point standards of the AWEF, which affects the capacity under the AWEF. To date, the refrigerant used to meet these stringent requirements is R448A. However, R448A has a serious drawback of having a GWP greater than 150.

[0009] Therefore, the search for low-GWP alternative refrigerants, especially for WICFs 3,000 square feet and smaller and / or for refrigeration systems used in confined spaces, represents a significant and difficult-to-solve technical challenge. This challenge is particularly difficult when using A2L refrigerants, given the need to meet safety requirements, as there are sometimes restrictions on the refrigerant charge that can be used in such systems. For example, ANSI / ASHRAE 15, the standard for refrigeration systems, is commonly used by code agencies for on-site installation of refrigeration equipment (including vending machines). However, prior to code revisions, the requirements in ANSI / ASHRAE 15 did not allow refrigeration systems (which may include refrigerated vending machines) to be installed in public hallways or lobbies if they used refrigerants that were not Class A1. The rationale for this requirement relates to the need to allow building occupants 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 hallways, lobbies, or similar areas could emit flammable refrigerants during a fire, potentially restricting occupants from escaping the building and hindering access by firefighters. However, research in 2020 led to a change in the ANSI / ASHRAE 15 requirement to allow the use of A2L refrigerants in such systems, provided the flammable refrigerant charge in the system does not exceed three times the lower flammable limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) (or 106 times the LFL expressed in pounds per cubic foot in English units). This change was based on the conclusion that if such a refrigerant could be determined to be used in such a system, it would not materially increase the risk to occupants who would need to escape the building during a fire.

[0010] Applicants have recognized that by using the refrigerants of the present invention, an unexpected mosaic of difficult-to-achieve properties can be met, as explained in detail below. Summary of the Invention

[0011] As described in detail below, applicants have unexpectedly and advantageously discovered that certain refrigerants based on a combination of carefully selected amounts of R-32, HFO-1234yf, HFO-1132(E), and CO can result in a refrigerant that meets many of the requirements discussed above, and preferably all of the requirements, as well as additional requirements and / or advantages as described below.

[0012] Applicants have discovered refrigerants, heat transfer compositions, refrigeration methods and systems that utilize one or more compositions of the present invention as a refrigerant, particularly including in WICFs of 3,000 square feet or less and in vending machines and the like located in public hallways, lobbies, or similar areas.

[0013] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0014] a. greater than 15 wt% to less than 22 wt% R-32;

[0015] b. greater than 60.5 wt % to about 71.5 wt % HFO-1234yf;

[0016] c. 4 wt% to less than 14.5 wt% HFO-1132(E); and

[0017] d. Greater than 1.5 wt% to 3.5 wt% CO2.

[0018] The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 1A for convenience.

[0019] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0020] a. about 15% to about 22% by weight of R-32;

[0021] b. about 61 wt % to about 71.5 wt % HFO-1234yf;

[0022] c. about 4 wt % to about 14.5 wt % HFO-1132(E); and

[0023] d. 1 to 4 wt% CO2,

[0024] A prerequisite is that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 1B for convenience.

[0025] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0026] a. 15.5 to 21.5 wt% R-32;

[0027] b. 61 wt % to about 71.5 wt % HFO-1234yf;

[0028] c. 4 to 14 wt% HFO-1132(E); and

[0029] d. 2% to 3.5% by weight of CO2.

[0030] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 1C for convenience.

[0031] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0032] a. 19 wt% to less than 22 wt% R-32;

[0033] b. 61 wt% to less than 65 wt% HFO-1234yf;

[0034] c. from about 11 wt% to less than 14.5 wt% HFO-1132(E); and

[0035] d. 2% to 3.5% by weight of CO2.

[0036] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 2A for convenience.

[0037] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0038] a. 19 wt% to less than 22 wt% R-32;

[0039] b. 61 wt% to less than 65 wt% HFO-1234yf;

[0040] c. from about 11 wt% to less than 14.5 wt% HFO-1132(E); and

[0041] d. 2 wt% to 3.5 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.

[0042] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 2B for convenience.

[0043] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0044] a. 19 to 21.5 wt% R-32;

[0045] b. 61 to 64.5 wt% HFO-1234yf;

[0046] c. about 11 wt% to 14 wt% HFO-1132(E); and

[0047] e. 2.5 to 3 wt% CO2.

[0048] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 3A for convenience.

[0049] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0050] a. 19 to 21.5 wt% R-32;

[0051] b. 61 to 64.5 wt% HFO-1234yf;

[0052] c. about 11 wt% to 14 wt% HFO-1132(E); and

[0053] d. 2.5 wt% to 3 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.

[0054] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 3B for convenience.

[0055] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0056] a. about 21.5% by weight of R-32,

[0057] b. 63% to 64.5% by weight of HFO-1234yf;

[0058] c. about 11 wt% HFO-1132(E); and

[0059] d. 2 to 4 wt% CO2.

[0060] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 4A for convenience.

[0061] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0062] a. about 21.5% by weight of R-32,

[0063] b. 63% to 64.5% by weight of HFO-1234yf;

[0064] c. about 11 wt% HFO-1132(E); and

[0065] d. 2 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.

[0066] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 4B for convenience.

[0067] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0068] a. about 21.5% by weight of R-32,

[0069] b. 61 to 63 wt% HFO-1234yf;

[0070] c. about 14 wt% HFO-1132(E); and

[0071] d. 2 to 4 wt% CO2.

[0072] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 5A for convenience.

[0073] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0074] a. about 21.5% by weight of R-32,

[0075] b. 61 to 63 wt% HFO-1234yf;

[0076] c. about 14 wt% HFO-1132(E); and

[0077] d. 2 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.

[0078] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 5B for convenience.

[0079] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0080] a. about 21.5% by weight of R-32,

[0081] b. about 65.5 wt% HFO-1234yf;

[0082] c. about 11 wt% HFO-1132(E); and

[0083] d. 1.5 wt% to 4 wt% CO2.

[0084] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 6A for convenience.

[0085] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0086] a. about 21.5% by weight of R-32,

[0087] b. about 65.5 wt% HFO-1234yf;

[0088] c. about 11 wt% HFO-1132(E); and

[0089] d. 1.5 wt% to 4 wt% CO2.

[0090] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 6B for convenience.

[0091] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0092] a. about 21.5% by weight of R-32,

[0093] b. about 65.5 wt% HFO-1234yf;

[0094] c. about 11 wt% HFO-1132(E); and

[0095] d. 1.5 wt% to 4 wt% CO2.

[0096] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 6C for convenience.

[0097] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0098] a. 21.5 wt% + / - 0.5 wt% R-32;

[0099] b. 65.5 wt% + / - 1 wt% HFO-1234yf;

[0100] c. 11 wt% + / - 1 wt% HFO-1132(E); and

[0101] d. 2 wt% + / - 0.5 wt% CO2.

[0102] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 7A for convenience.

[0103] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0104] a. 21.5 wt% + / - 0.5 wt% R-32;

[0105] b. 65.5 wt% + / - 1 wt% HFO-1234yf;

[0106] c. 11 wt% + / - 1 wt% HFO-1132(E); and

[0107] d. 2 wt% + / - 0.5 wt% CO2.

[0108] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 7B for convenience.

[0109] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0110] a. 21.5 wt% + / - 0.5 wt% R-32;

[0111] b. 65.5 wt% + / - 1 wt% HFO-1234yf;

[0112] c. 11 wt% + / - 1 wt% HFO-1132(E); and

[0113] d. 2 wt% + / - 0.5 wt% CO2.

[0114] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 7C for convenience.

[0115] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0116] a. 21.5 wt% + / - 0.5 wt% R-32;

[0117] b. 65 wt% + / - 1 wt% HFO-1234yf;

[0118] c. 11 wt% + / - 1 wt% HFO-1132(E); and

[0119] d. 2.5 wt% + / - 0.5 wt% CO2.

[0120] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 8A for convenience.

[0121] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0122] a. 21.5 wt% + / - 0.5 wt% R-32;

[0123] b. 65 wt% + / - 1 wt% HFO-1234yf;

[0124] c. 11 wt% + / - 1 wt% HFO-1132(E); and

[0125] d. 2.5 wt% + / - 0.5 wt% CO2.

[0126] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 8B for convenience.

[0127] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0128] a. 21.5 wt% + / - 0.5 wt% R-32;

[0129] b. 65 wt% + / - 1 wt% HFO-1234yf;

[0130] c. 11 wt% + / - 1 wt% HFO-1132(E); and

[0131] d. 2.5 wt% + / - 0.5 wt% CO2.

[0132] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 8C for convenience.

[0133] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0134] a. 21.5 wt% + / - 0.5 wt% R-32;

[0135] b. 64 wt% + / - 1 wt% HFO-1234yf;

[0136] c. 11 wt% HFO-1132(E); and

[0137] d. 3.5 wt% + / - 0.5 wt% CO2.

[0138] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 9A for convenience.

[0139] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0140] a. 21.5 wt% + / - 0.5 wt% R-32;

[0141] b. 64 wt% + / - 1 wt% HFO-1234yf;

[0142] c. 11 wt% HFO-1132(E); and

[0143] d. 3.5 wt% + / - 0.5 wt% CO2.

[0144] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 9B for convenience.

[0145] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0146] a. 21.5 wt% + / - 0.5 wt% R-32;

[0147] b. 64 wt% + / - 1 wt% HFO-1234yf;

[0148] c. 11 wt% HFO-1132(E); and

[0149] d. 3.5 wt% + / - 0.5 wt% CO2.

[0150] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 9C for convenience.

[0151] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0152] a. about 21.5% by weight of R-32,

[0153] b. about 62 wt% HFO-1234yf;

[0154] c. about 14 wt% HFO-1132(E); and

[0155] d. 1.5 wt% to 4 wt% CO2.

[0156] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 10A for convenience.

[0157] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0158] a. about 21.5% by weight of R-32,

[0159] b. about 62 wt% HFO-1234yf;

[0160] c. about 14 wt% HFO-1132(E); and

[0161] d. 1.5 wt% to 4 wt% CO2.

[0162] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 10B for convenience.

[0163] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0164] a. about 21.5% by weight of R-32,

[0165] b. about 62 wt% HFO-1234yf;

[0166] c. about 14 wt% HFO-1132(E); and

[0167] d. 1.5 wt% to 4 wt% CO2.

[0168] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 10C for convenience.

[0169] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0170] a. 21.5 wt% + / - 0.5 wt% R-32;

[0171] b. 62.5 wt% + / - 1 wt% HFO-1234yf;

[0172] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0173] d. 2.0 wt% + / - 0.5 wt% CO2.

[0174] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 11A for convenience.

[0175] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0176] a. 21.5 wt% + / - 0.5 wt% R-32;

[0177] b. 62.5 wt% + / - 1 wt% HFO-1234yf;

[0178] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0179] d. 2.0 wt% + / - 0.5 wt% CO2.

[0180] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 11B for convenience.

[0181] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0182] a. 21.5 wt% + / - 0.5 wt% R-32;

[0183] b. 62.5 wt% + / - 1 wt% HFO-1234yf;

[0184] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0185] d. 2.0 wt% + / - 0.5 wt% CO2.

[0186] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 11C for convenience.

[0187] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0188] a. 21.5 wt% + / - 0.5 wt% R-32;

[0189] b. 62 wt% + / - 1 wt% HFO-1234yf;

[0190] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0191] d. 2.5 wt% + / - 0.5 wt% CO2.

[0192] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 12A for convenience.

[0193] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0194] a. 21.5 wt% + / - 0.5 wt% R-32;

[0195] b. 62 wt% + / - 1 wt% HFO-1234yf;

[0196] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0197] d. 2.5 wt% + / - 0.5 wt% CO2.

[0198] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 12B for convenience.

[0199] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0200] a. 21.5 wt% + / - 0.5 wt% R-32;

[0201] b. 62 wt% + / - 1 wt% HFO-1234yf;

[0202] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0203] d. 2.5 wt% + / - 0.5 wt% CO2.

[0204] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 12C for convenience.

[0205] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0206] a. 21.5 wt% + / - 0.5 wt% R-32;

[0207] b. 61 wt% + / - 1 wt% HFO-1234yf;

[0208] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0209] d. 3.5 wt% + / - 0.5 wt% CO2.

[0210] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 13A for convenience.

[0211] The present invention comprises a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0212] a. 21.5 wt% + / - 0.5 wt% R-32;

[0213] b. 61 wt% + / - 1 wt% HFO-1234yf;

[0214] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0215] d. 3.5 wt% + / - 0.5 wt% CO2.

[0216] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 13B for convenience.

[0217] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0218] a. 21.5 wt% + / - 0.5 wt% R-32;

[0219] b. 61 wt% + / - 1 wt% HFO-1234yf;

[0220] c. 14 wt% + / - 1 wt% HFO-1132(E); and

[0221] d. 3.5 wt% + / - 0.5 wt% CO2.

[0222] Refrigerant according to this paragraph is sometimes referred to herein as refrigerant 13C for convenience.

[0223] The present invention includes a refrigerant comprising the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0224] a. 21.5 wt% + / - 0.5 wt% R-32;

[0225] b. 63.5 wt% + / - 2 wt% HFO-1234yf;

[0226] c. 13 wt% + / - 2 wt% HFO-1132(E); and

[0227] d. 2 to 4 wt% CO2.

[0228] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 14A for convenience. The present invention includes a refrigerant consisting essentially of the following four components in the following relative concentrations:

[0229] a. 21.5 wt% + / - 0.5 wt% R-32;

[0230] b. 63.5 wt% + / - 2 wt% HFO-1234yf;

[0231] c. 13 wt% + / - 2 wt% HFO-1132€; and

[0232] d. 2 to 4 wt% CO2.

[0233] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 14B for convenience.

[0234] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0235] a. 21.5 wt% + / - 0.5 wt% R-32;

[0236] b. 63.5 wt% + / - 2 wt% HFO-1234yf;

[0237] c. 13 wt% + / - 2 wt% HFO-1132(E); and

[0238] d. 2 to 4 wt% CO2.

[0239] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 14C for convenience.

[0240] The present invention comprises a refrigerant consisting of the following four components in the following relative concentrations:

[0241] a. 21.5 wt% + / - 0.5 wt% R-32;

[0242] b. 63.5 wt% + / - 2 wt% HFO-1234yf;

[0243] c. 13 wt% + / - 2 wt% HFO-1132(E); and

[0244] d. 2 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater.

[0245] The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 15 for convenience.

[0246] The present invention also includes a method for providing heat transfer, the method comprising:

[0247] a. providing a refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0248] i. greater than 15 wt% to less than 22 wt% R-32;

[0249] ii. greater than 61 wt % to about 71.5 wt % HFO-1234yf;

[0250] iii. 4 wt% to less than 14.5 wt% HFO-1132(E); and

[0251] iv. greater than 1.5 wt% to 3.5 wt% CO2; and

[0252] b. Transferring heat to or from the refrigerant in a heat transfer system. The method according to this paragraph is sometimes referred to herein as Heat Transfer Method 1 for convenience.

[0253] The present invention also includes a method for providing heat transfer, the method comprising:

[0254] a. providing a refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0255] i. about 15% to about 22% by weight of R-32;

[0256] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0257] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0258] iv. 1 wt% to 4 wt% CO2; and

[0259] b. transferring heat to or from the refrigerant in a heat transfer system comprising at least one compressor, at least one condenser, at least

[0260] an expansion device and at least one evaporator, wherein:

[0261] 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; and

[0262] ii. The power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0263] The method according to this paragraph is sometimes referred to herein as Heat Transfer Method 2A for convenience. The present invention also includes a method for providing heat transfer, the method comprising:

[0264] a. providing a refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0265] i. about 15% to about 22% by weight of R-32;

[0266] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0267] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0268] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or greater; and

[0269] b. transferring heat to or from the refrigerant in a heat transfer system comprising at least one compressor, at least one condenser, at least

[0270] an expansion device and at least one evaporator, wherein:

[0271] 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; and

[0272] ii. The power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0273] The method according to this paragraph is sometimes referred to herein as Heat Transfer Method 2B for convenience. The present invention also includes a method for providing heat transfer, the method comprising:

[0274] a. providing a refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0275] i. about 15% to about 22% by weight of R-32;

[0276] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0277] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0278] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0279] b. providing the refrigerant in a heat transfer system comprising 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 does not exceed the value specified in ANSI / ASHRAE 15 (2020) in kg / min.

[0280] Three times the lower flammable limit (LFL) of the refrigerant expressed in cubic meters (kg / m3).

[0281] The method according to this paragraph is sometimes referred to herein as Heat Transfer Method 3A for convenience.

[0282] The present invention also includes a method for providing heat transfer in a low and / or medium temperature refrigeration system, the method comprising:

[0283] a. providing a refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0284] i. about 15% to about 22% by weight of R-32;

[0285] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0286] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0287] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0288] b. providing the refrigerant in a heat transfer system comprising at least one compressor, at least one condenser, at least one expansion device, and at least one evaporator, wherein:

[0289] i. The amount of refrigerant in the system does not exceed the amount specified in ANSI / ASHRAE 15

[0290] (2020) Lower flammable limit of refrigerants expressed in kilograms per cubic meter (kg / m3)

[0291] Three times (LFL);

[0292] 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; and iii. the power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0293] The method according to this paragraph is sometimes referred to herein as Heat Transfer Method 3B for convenience.

[0294] The present invention also includes a method for providing heat transfer in a medium temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight of the total amount of all refrigerants;

[0295] The following four components are present in the following relative concentrations in %:

[0296] i. about 15% to about 22% by weight of R-32;

[0297] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0298] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0299] iv. 1 wt% to 4 wt% CO2; and

[0300] b. Providing the refrigerant in the medium temperature refrigeration system.

[0301] The method according to this paragraph is sometimes referred to herein as heat transfer method 4A for convenience. The present invention also includes a method for providing heat transfer in a medium temperature refrigeration system, the method comprising:

[0302] a. providing a refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerants:

[0303] i. about 15% to about 22% by weight of R-32;

[0304] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0305] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0306] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0307] b. Providing the refrigerant in a medium-temperature refrigeration system.

[0308] The method according to this paragraph is sometimes referred to herein as heat transfer method 4B for convenience. The present invention also includes a method for providing heat transfer in a medium temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0309] The following four components are present in the following relative concentrations in %:

[0310] i. about 15% to about 22% by weight of R-32;

[0311] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0312] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0313] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0314] b. Providing the refrigerant in a medium temperature refrigeration system comprising 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 does not exceed three times the lower flammable limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) according to ANSI / ASHRAE 15 (2020).

[0315] The method according to this paragraph is sometimes referred to herein as heat transfer method 4C for convenience. The present invention also includes a method for providing heat transfer in a medium temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0316] The following four components are present in the following relative concentrations in %:

[0317] i. about 15% to about 22% by weight of R-32;

[0318] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0319] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0320] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0321] b. providing the refrigerant in the medium temperature refrigeration system, the heat transfer system comprising at least one compressor, at least one condenser, at least one expansion device and at least one evaporator

[0322] transmitter, of which:

[0323] 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; and

[0324] ii. The power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0325] The method according to this paragraph is sometimes referred to herein as heat transfer method 4D for convenience. The present invention also includes a method for providing heat transfer in a medium temperature refrigeration system, the method comprising: c. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0326] The following four components are present in the following relative concentrations in %:

[0327] i. about 15% to about 22% by weight of R-32;

[0328] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0329] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0330] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and d. providing said refrigerant in said medium temperature refrigeration system, the heat transfer system comprising at least

[0331] A compressor, at least one condenser, at least one expansion device and at least one steam generator

[0332] transmitter, of which:

[0333] i. The amount of the refrigerant in the system does not exceed three times the lower flammable limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) in accordance with ANSI / ASHRAE 15(2020);

[0334] 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; and

[0335] iii. The power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0336] The method according to this paragraph is sometimes referred to herein as heat transfer method 4E for convenience. The present invention also includes a method for providing heat transfer in a low temperature refrigeration system, the method comprising: c. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0337] The following four components are present in the following relative concentrations in %:

[0338] i. about 15% to about 22% by weight of R-32;

[0339] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0340] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0341] iv. 1 wt% to 4 wt% CO2; and d. providing the refrigerant in the low temperature refrigeration system.

[0342] The method according to this paragraph is sometimes referred to herein as heat transfer method 5A for convenience. The present invention also includes a method for providing heat transfer in a low temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0343] The following four components are present in the following relative concentrations in %:

[0344] i. about 15% to about 22% by weight of R-32;

[0345] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0346] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0347] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0348] b. Providing the refrigerant in a low-temperature refrigeration system.

[0349] The method according to this paragraph is sometimes referred to herein as heat transfer method 5B for convenience. The present invention also includes a method for providing heat transfer in a low temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0350] The following four components are present in the following relative concentrations in %:

[0351] i. about 15% to about 22% by weight of R-32;

[0352] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0353] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0354] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0355] b. Providing the refrigerant in a low temperature refrigeration system comprising 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 does not exceed three times the lower flammable limit (LFL) of the refrigerant expressed in kilograms per cubic meter (kg / m3) according to ANSI / ASHRAE 15(2020).

[0356] The method according to this paragraph is sometimes referred to herein as heat transfer method 5C for convenience. The present invention also includes a method for providing heat transfer in a low temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight based on the total amount of all refrigerants;

[0357] The following four components are present in the following relative concentrations in %:

[0358] i. about 15% to about 22% by weight of R-32;

[0359] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0360] iii. from about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0361] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0362] b. providing the refrigerant in the low temperature refrigeration system, the heat transfer system comprising at least one compressor, at least one condenser, at least one expansion device and at least one evaporator

[0363] transmitter, of which:

[0364] 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; and

[0365] ii. The power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0366] The method according to this paragraph is sometimes referred to herein as heat transfer method 5D for convenience. The present invention also includes a method for providing heat transfer in a low temperature refrigeration system, the method comprising: a. providing a refrigerant comprising at least about 95% by weight of the total amount of all refrigerants;

[0367] The following four components are present in the following relative concentrations in %:

[0368] i. about 15% to about 22% by weight of R-32;

[0369] ii. from about 61 wt% to about 71.5 wt% HFO-1234yf;

[0370] iii. about 4 wt% to about 14.5 wt% HFO-1132(E); and

[0371] iv. 1 wt% to 4 wt% CO2, provided that the refrigerant has a GWP of 150 or less and a CO2 content of 0.25 kg / m 3 or greater lower flammability limit; and

[0372] b. providing the refrigerant in the low temperature refrigeration system, the heat transfer system comprising at least one compressor, at least one condenser, at least one expansion device and at least one evaporator, wherein:

[0373] i. The amount of refrigerant in the system does not exceed the amount specified in ANSI / ASHRAE 15

[0374] (2020) Lower flammable limit of refrigerants expressed in kilograms per cubic meter (kg / m3)

[0375] Three times (LFL);

[0376] 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; and

[0377] iii. The power consumption in the compressor is less than or equal to 115% of the power consumption of R448A operating in the heat transfer system.

[0378] The method according to this paragraph is sometimes referred to herein as Heat Transfer Method 5E for convenience. BRIEF DESCRIPTION OF THE DRAWINGS

[0379] Figure 1 Schematic diagram of an exemplary heat transfer system that can be used for low-temperature and medium-temperature refrigeration.

[0380] Figure 2 Schematic diagram of an exemplary heat transfer system that may be used for low and medium temperature refrigeration and includes an optional steam ejector.

[0381] Figure 3 Schematic diagram of an exemplary heat transfer system that may be used for low and medium temperature refrigeration and includes an optional liquid ejector.

[0382] Figure 4 Schematic diagram of an exemplary heat transfer system that can be used for low and medium temperature refrigeration and includes an optional suction line / liquid line heat exchanger.

[0383] Figure 5 Schematic diagram of an exemplary heat transfer system that may be used for low and medium temperature refrigeration and includes an optional steam ejector and oil separator.

[0384] Description of preferred compositions

[0385] definition :

[0386] The term "about" in connection with an amount expressed as a weight percent means that the amount of that component may vary by + / - 2 weight percent.

[0387] The term "about" in reference to temperatures in degrees Celsius (°C) means that the temperature may vary by an amount of + / - 5°C.

[0388] The term "capacity" refers to the amount of cooling provided by the refrigerant in a refrigeration system (measured in BTU / hour). This is determined experimentally by multiplying the enthalpy change (measured in BTU / lb) of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. The enthalpy can be determined by measuring the pressure and temperature of the refrigerant. The capacity of a refrigeration system relates to its ability to keep an area cooled at a specific temperature. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the compressor's ability to pump heat for a given volume flow of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power.

[0389] The phrase "coefficient of performance" (hereinafter referred to as "COP") is a measure of refrigerant performance that is generally accepted, and is particularly useful for representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, the term represents the ratio of available refrigeration or cooling capacity to the energy applied by the compressor when compressing vapor, and therefore represents the ability of a given compressor to pump heat for a given volumetric flow of heat transfer fluid such as a refrigerant. In other words, given a specific compressor, a refrigerant with a higher COP will deliver more cooling or heating power. A method for estimating the COP of a refrigerant under specific operating conditions is to estimate it from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, RC Downing, " Fluorocarbon Refrigerants Handbook ", Chapter 3, Prentice-Hall, 1988, which is incorporated herein by reference in its entirety).

[0390] 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 thermal protection aspects of the system, which are preferably designed to protect the compressor components, and avoids the use of expensive control measures (such as liquid injection) to reduce the discharge temperature.

[0391] The phrase "global warming potential" (hereinafter "GWP") was coined to allow comparison of the global warming impact of different gases. It compares the amount of heat trapped by a certain mass of gas over a specific time period to the amount of heat trapped by a similar mass of carbon dioxide. Carbon dioxide was chosen by the Intergovernmental Panel on Climate Change (IPCC) as the reference gas, and its GWP was taken to be 1. The greater the GWP, the more a given gas warms the Earth compared to CO2 over that time period. The time period commonly used for GWP is 100 years. GWP provides a universal metric—allowing analysts to add up emission estimates for different gases. See http: / / www.protocolodemontreal.org.br / site / images / publicacoes / setor_manufatur a_equipamentos_refrigeracao_arcondicionado / Como_calcular_el_Potencial_de_Calentamiento_Atmosferico_en_las_mezclas_de_refrigerantes.pdf

[0392] The term "occupational exposure limit (OEL)" is determined in accordance with ASHRAE Standard 34-2016, "Designation and Safety Classification of Refrigerants."

[0393] As used herein, the phrase "acceptable toxicity" means that the composition is classified as Class "A" by ASHRAE Standard 34-2016 Nomenclature and Safety Classification of Refrigerants and is described in Appendix Bl of ASHRAE Standard 34-2016 (as various standards existed prior to the filing date of this application).

[0394] The term "A1" means a material that is non-flammable and low toxic and is classified as "A1" by ASHRAE Standard 34-2016 Nomenclature and Safety Classification of Refrigerants and described in Annex B1 of ASHRAE Standard 34-2016, as each standard existed prior to the filing date of this application.

[0395] The term "A2" means a material that is mildly flammable and of low toxicity and is classified as "A2L" by ASHRAE Standard 34-2019 Nomenclature and Safety Classification of Refrigerants and described in Annex B1 of ASHRAE Standard 34-2019 (as each standard existed prior to the filing date of this application).

[0396] The term "mass flow rate" is the mass of refrigerant passing through a conduit per unit time.

[0397] The term "non-flammable" refers to a compound or composition of A1 or A2L as defined herein.

[0398] As used herein, the term "evaporator glide" refers to 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 evaporator inlet. As used herein, the phrase "saturation temperature" refers to the temperature at which liquid refrigerant boils into vapor at a given pressure.

[0399] As used herein, the phrase "acceptable toxicity" means that the composition is classified as Class "A" by ASHRAE Standard 34-2016, Nomenclature and Safety Classification of Refrigerants, and is described in Appendix B1 of ASHRAE Standard 34-2016 (as various standards existed before the filing date of this application). Non-flammable and low toxicity materials are classified as Class "A1" by ASHRAE Standard 34-2016, Nomenclature and Safety Classification of Refrigerants, and are described in Appendix B1 of ASHRAE Standard 34-2016 (as various standards existed before the filing date of this application).

[0400] As used herein, the term "replacement" means the use of a composition of the present invention in a heat transfer system that has been designed for use with, or is adapted for use with, another refrigerant. By way of example, when a refrigerant or heat transfer composition of the present invention is used in a heat transfer system that has been designed for use with R-22, then the refrigerant or heat transfer composition of the present invention is a replacement for R-22 in the system. It should therefore be understood that the term "replacement" encompasses the use of the refrigerants and heat transfer compositions of the present invention in both new and existing systems that have been designed for use with, or are adapted for use with, a given refrigerant, such as R-22.

[0401] The term "commercial refrigeration" refers to cold storage equipment used in commercial settings 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 items frozen; and commercial coolers / 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, etc.; plug-in enclosed vending machines, especially those located in areas that may attract egress restrictions (such as corridors, aisles, etc.); built-in coolers; draft beer systems; undercounter refrigerators; and refrigerated display cases.

[0402] The term "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.

[0403] 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 -12°C to about 0°C.

[0404] The term "superheat" or simply "superheat" refers to the temperature of the refrigerant at the evaporator outlet rising above the saturated vapor temperature (or dew point temperature) of the refrigerant.

[0405] The terms "HFO-1132(E)" and "trans-HFO-1132(E)" each mean the trans isomer of 1,2-difluoroethylene.

[0406] The terms "HFO-1234ze(E)" and trans-HFO-1234ze mean the trans isomer of 1,3,3,3-tetrafluoropropene.

[0407] The term "HFO-1234yf" means 2,3,3,3-tetrafluoropropene.

[0408] The terms "HFO-1336mzz(E)" and "trans-HFO-1336mzz" each mean the trans isomer of 1,1,1,4,4,4-hexafluoro-2-butene.

[0409] The terms "HFC-32" and "R-32" each mean difluoromethane.

[0410] The terms "HFC-134a" and "R-134a" each mean 1,1,1,2-tetrafluoroethane.

[0411] The term "R-22" means chlorodifluoromethane.

[0412] The term "R-404A" means a blend of refrigerants consisting of 44 wt% + / - 2 wt% R-125, 52 wt% + / - 2 wt% R-143a and 4 wt% + / - 2 wt% R134a).

[0413] The term "R407F" means a refrigerant blend consisting of 30 wt% + / - 2 wt% R-32, 30 wt% + / - 2 wt% R-125, and 40 wt% + / - 2 wt% R134a.

[0414] The term "R-410A" means a refrigerant blend consisting of 50 wt% + 0.5 / - 1 wt% R-32 and 50 wt% + 1.5 / - 0.5 wt% R125).

[0415] The term "R-448A" means a refrigerant blend consisting of 26 wt% R-32, 26 wt% R-125, 26 wt% R-125, 21 wt% R134a, 7 wt% trans-HFO-1234ze and 20 wt% HFO-1234yf).

[0416] The term "R-449A" means a refrigerant blend consisting of 24.3 wt% R-32, 24.7 wt% R-125, 25.7 wt% R-134a, and 25.3 wt% HFO-1234yf). DETAILED DESCRIPTION

[0417] Refrigerants and heat transfer compositions :

[0418] Applicants have discovered that the refrigerants of the present invention (including each of Refrigerants 1-15 as described herein) and the methods of the present invention (including Heat Transfer Methods 1-5) can provide exceptionally advantageous properties, including: heat transfer properties and heat transfer performance, acceptable toxicity and non-flammability (i.e., A2L class), unexpectedly high lower flammability limit ("LFL"), zero or near zero ozone depletion potential ("ODP"), and lubricant compatibility, including miscibility with POE and / or PVE lubricants over the operating temperature and concentration ranges used in medium and low temperature refrigeration systems, cascade refrigeration systems, transport refrigeration systems, stationary refrigeration, and heat pumps.

[0419] As used herein, reference to a group of compounds, processes, etc. defined by a number, such as reference to "any of refrigerants 1-15" in the preceding paragraph specifically includes all such numbered combinations, including all numbered combinations with suffixes. For example, reference to "any of refrigerants 13-14" includes each of refrigerant 13A, refrigerant 13B, refrigerant 13C, refrigerant 14A, refrigerant 14B, and refrigerant 14C.

[0420] A particular advantage of the refrigerants of the present invention (including specifically each of refrigerants 1-15) is that they are mildly flammable, have an advantageously high LFL, and have acceptable toxicity, i.e., each is a Class A1 refrigerant. Those skilled in the art will appreciate that the flammability of a refrigerant may be a characteristic that is considered in certain important heat transfer applications, and that refrigerants classified as Class A2L may generally be superior to non-Class A2L refrigerants. Therefore, the art would like to provide a refrigerant composition that can be used as a replacement for existing refrigerants (such as R-22, R404A, R407F, R448A, R449A, R-134a, R404A, and R410A) that do not have the combination of properties provided by the refrigerants of the present invention (or as a replacement or modification for R-32 and R454B). This desired advantage can be achieved by the refrigerants of the present invention.

[0421] Applicants have discovered that the refrigerant compositions of the present invention (including each of Refrigerants 1-15) are capable of achieving a difficult to achieve combination of properties, including an exceptionally low GWP. Thus, the compositions of the present invention have a GWP of 150 or less.

[0422] Furthermore, the refrigerant compositions of the present invention (including each of Refrigerants 1-15) have an ODP of zero or close to zero. Thus, the compositions of the present invention have an ODP of no greater than 0.02, and more preferably zero.

[0423] Furthermore, 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 will be appreciated by those skilled in the art, mildly flammable refrigerants having an OEL greater than about 400 are advantageous because they result in the refrigerant being classified as the desired ASHRAE Standard 34 A2L category.

[0424] Preferred refrigerant compositions of the present invention exhibit acceptable toxicity and mild flammability and are therefore Class A2L refrigerants according to ASHRAE Standard 34. Applicants have discovered that the heat transfer compositions of the present invention (including heat transfer compositions comprising each of Refrigerants 1-15 as described herein) can provide an exceptionally advantageous and unexpected combination of properties, including: good heat transfer performance, chemical stability under use conditions, acceptable toxicity, non-flammability, a relatively high LFL, zero or near-zero ozone depletion potential ("ODP"), and lubricant compatibility, including miscibility with POE and / or PVE lubricants over the 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 aisles 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 conditioners, commercial air conditioners, and mobile air conditioners.

[0425] The heat transfer composition can consist essentially of any refrigerant of the present invention, including each of Refrigerants 1-15.

[0426] The refrigerants of the present invention can be provided in the form of heat transfer compositions. Thus, the heat transfer compositions of the present invention include the refrigerants of the present invention, including any of the preferred refrigerant compositions disclosed herein, and in particular each of Refrigerants 1-15. Preferably, the present invention relates to a heat transfer composition comprising the refrigerant (including 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 may consist essentially of or consist of the refrigerant.

[0427] The heat transfer compositions of the present invention may be composed of any of the refrigerants of the present invention, including each of Refrigerants 1-15.

[0428] The heat transfer compositions of the present invention may include other components for the purpose of enhancing or providing specific functionality to the composition. In addition to the refrigerants of the present invention (including each of Refrigerants 1-15), such other components may include one or more of lubricants, passivators, flame retardants, dyes, solubilizers, compatibilizers, stabilizers, antioxidants, corrosion inhibitors, extreme pressure additives, and anti-wear 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.

[0429] lubricant

[0430] The heat transfer composition of the present invention may comprise a refrigerant as described herein (including each of Refrigerants 1-15) and a lubricant.The heat transfer composition as described in this paragraph is sometimes referred to as Heat Transfer Composition 1 for convenience.

[0431] The heat transfer compositions of the present invention may also comprise a refrigerant as described herein (including each of Refrigerants 1-15) and a polyol ester (POE) lubricant.The heat transfer composition as described in this paragraph is sometimes referred to as Heat Transfer Composition 2 for convenience.

[0432] The heat transfer compositions of the present invention may also comprise a refrigerant as described herein (including each of Refrigerants 1 to 15) and a polyol vinyl ether (PVE) lubricant. The heat transfer composition as described in this paragraph is sometimes referred to as Heat Transfer Composition 3 for convenience.

[0433] The applicants have discovered that the heat transfer compositions of the present invention, including each of Heat Transfer Compositions 1-3, can provide exceptionally advantageous properties, in addition to the advantageous properties identified herein with respect to refrigerants, including excellent refrigerant / lubricant compatibility, including miscibility with POE and / or PVE lubricants within the operating temperature and concentration ranges used in stationary air conditioning systems (including residential air conditioning, commercial air conditioning, VRF air conditioning), chillers (including air-cooled chillers), heat pump systems (including residential air-to-water heat pump systems), and commercial refrigeration (including medium temperature refrigeration and low temperature refrigeration).

[0434] A lubricant consisting essentially of a POE having a viscosity of about 30 to about 70 as measured at 40°C according to ASTM D445 is referred to herein as Lubricant 1.

[0435] Commercially available POEs preferred for use in the heat transfer compositions of the present invention include neopentyl glycol dipelargonate, available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark), and pentaerythritol derivatives, including those sold by CPI Fluid Engineering under the trade names Emkarate RL32-3MAF and Emkarate RL68H. Emkarate RL32-3MAF and Emkarate RL68H are preferred POE lubricants having the properties identified below:

[0436]

[0437]

[0438] A preferred heat transfer composition comprises a refrigerant of the present invention (including each of Refrigerants 1-15) and Lubricant 1. The heat transfer composition as described in this paragraph is sometimes referred to as Heat Transfer Composition 4 for convenience.

[0439] A lubricant consisting essentially of a POE having a viscosity of about 30 to about 70, based on the weight of the heat transfer composition, as measured at 40°C according to ASTM D445, is referred to herein as Lubricant 2.

[0440] Commercially available polyethylene ethers having a viscosity at 40°C of about 30 to about 70 as measured according to ASTM D445 that are preferred for use in the heat transfer compositions of the present invention include those lubricants sold under the tradenames FVC32D and FVC68D available from Idemitsu.

[0441] A preferred heat transfer composition comprises a refrigerant of the present invention (including each of Refrigerants 1-15) and Lubricant 2. The heat transfer composition as described in this paragraph is sometimes referred to as Heat Transfer Composition 5 for convenience.

[0442] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-5, wherein the lubricant is present in the heat transfer composition in an amount from about 0.1% to about 5% by weight of the heat transfer composition. The heat transfer composition as described in this paragraph is sometimes referred to as heat transfer composition 6 for convenience.

[0443] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-6, wherein the lubricant is present in the heat transfer composition in an amount from about 0.1% to about 2% by weight of the heat transfer composition. The heat transfer composition as described in this paragraph is sometimes referred to as heat transfer composition 7 for convenience.

[0444] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-7, wherein the lubricant is present in the heat transfer composition in an amount from about 0.1% to about 1% by weight of the heat transfer composition. The heat transfer composition as described in this paragraph is sometimes referred to as heat transfer composition 8 for convenience.

[0445] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-8, wherein the lubricant is present in the heat transfer composition in an amount from about 0.1% to about 0.5% by weight of the heat transfer composition. The heat transfer composition as described in this paragraph is sometimes referred to as heat transfer composition 9 for convenience.

[0446] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-9, wherein the lubricant is present in the heat transfer composition in an amount from about 0.2% to about 0.5% by weight of the heat transfer composition. The heat transfer composition as described in this paragraph is sometimes referred to as heat transfer composition 10 for convenience.

[0447] Stabilizers and protective agents

[0448] While it is contemplated that in many embodiments, the refrigerants and heat transfer compositions of the present invention may be used without stabilizers and / or protectants, the present invention also includes heat transfer compositions comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protectant and / or stabilizer. Preferred protectants and stabilizers are described below:

[0449] stabilizer

[0450] Preferably, the heat transfer composition of the present invention (including each of heat transfer compositions 1-10) comprises a stabilizer. Preferably, one or more of the following stabilizers are included.

[0451] Alkylated naphthalene

[0452] 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 compounds having the following structure:

[0453]

[0454] wherein R1 to R8 are each independently selected from a linear alkyl group, a branched alkyl group, and hydrogen. The specific lengths of the alkyl chains and mixtures of branched and linear chains with hydrogen may vary within the scope of the present invention, and those skilled in the art will recognize and understand that such variations reflect the physical properties of the alkylated naphthalenes, particularly including the viscosity of the alkylated compounds, and that producers of such materials often define materials by reference to one or more of such properties as alternative specifications for a particular R group.

[0455] Applicants have discovered that the use of alkylated naphthalenes according to the present invention having the following properties as stabilizers is associated with unexpected, surprising, and advantageous results (including each of heat transfer compositions 1-10), and for convenience, the alkylated naphthalene compounds having the described properties are referred to herein as Alkylated Naphthalene 1 or (AN1) through Alkylated Naphthalene 5 (or AN5), as shown in rows 1 through 5 of Table AN-A below, respectively:

[0456] Table AN-A

[0457]

[0458] As used herein, in conjunction with the viscosity at 40°C measured according to ASTM D445, the term "about" means + / - 4 cSt.

[0459] As used herein, in conjunction with the viscosity at 100°C measured according to ASTM D445, the term "about" means + / - 0.4 cSt.

[0460] As used herein, in connection with pour point measured according to ASTM D97, the term "about" means + / - 5°C.

[0461] Applicants have also discovered that the use of alkylated naphthalenes according to the present invention having the following properties as stabilizers is associated with unexpected, surprising, and advantageous results (including each of heat transfer compositions 1-27), and for convenience, the alkylated naphthalene compounds having the described properties are referred to herein as Alkylated Naphthalene 6 or (AN6) through Alkylated Naphthalene 10 (or AN10), as shown in rows 6 through 10 of Table AN-B below, respectively:

[0462] Table AN-B

[0463]

[0464]

[0465] Examples of alkylated naphthalenes within the meaning of Alkylated Naphthalene 1 and Alkylated Naphthalene 6 include those sold by Kinshiki 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.

[0466] Examples of alkylated naphthalenes within the meaning of Alkylated Naphthalene 2 and Alkylated Naphthalene 7 include those sold by Kinshi Industries under the following trade names: NA-LUBE KR-007A; KR-008; KR-009; and KR-005FG.

[0467] Examples of alkylated naphthalenes within the meaning of Alkylated Naphthalene 5 and Alkylated Naphthalene 10 include the product sold under the trade name NA-LUBE KR-008 by Kinshi Industries.

[0468] The present invention includes heat transfer compositions (including each of heat transfer compositions 1-5) wherein the alkylated naphthalene is AN1, AN2, or AN3, or AN4, or AN5, or AN6, or AN7, or AN8, or AN9, or AN10.

[0469] Acid Depletion Section (ADM)

[0470] Without undue experimentation, one skilled in the art will be able to identify a variety of ADMs that may be used in accordance with the present invention, and all such ADMs are within the scope of the present invention.

[0471] Epoxide

[0472] Applicants have discovered that epoxides, and particularly alkylated epoxides, are effective in producing the enhanced stability described herein, particularly and preferably when used in combination with alkylated naphthalene stabilizers, and while Applicants are not necessarily bound by theory, it is believed that this synergistic enhancement is at least in part due to their effective use as ADMs in the heat transfer compositions of the present invention.

[0473] In a preferred aspect of the present invention, the heat transfer composition of the present invention (including each of heat transfer compositions 1-10) comprises an epoxide selected from the group consisting of epoxides that undergo a ring-opening reaction with an acid, thereby depleting the acid system while not otherwise adversely affecting the system.

[0474] Useful epoxides include aromatic epoxides, alkyl epoxides (including alkyl ether epoxides), and alkenyl epoxides.

[0475] Preferred epoxides include those of Formula I:

[0476]

[0477] wherein at least one of R1-R4 is selected from a two- to fifteen-carbon (C2-C15) acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. Epoxide groups according to Formula I with R groups as defined in this paragraph are sometimes referred to herein as ADM1A for convenience.

[0478] Preferred epoxides also include epoxides of the following formula I:

[0479]

[0480] wherein said R1-R4 are each independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, with the proviso that at least one of said R1-R4 is H and at least one of said R1-R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. Epoxide groups according to Formula I having R groups as defined in this paragraph are sometimes referred to herein as ADM1B for convenience.

[0481] Preferred epoxides also include epoxides of the following formula I:

[0482]

[0483] wherein said R1-R4 are each independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, with the proviso that at least two of said R1-R4 are H and at least one of said R1-R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. Epoxide groups according to Formula I having R groups as defined in this paragraph are sometimes referred to herein as ADM1C for convenience.

[0484] Preferred epoxides also include epoxides of the following formula I:

[0485]

[0486] wherein said R1-R4 are each independently selected from H, a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group, provided that at least three of said R1-R4 are H and one of said R1-R4 is selected from a C2-C15 acyclic group, a C2-C15 aliphatic group, and a C2-C15 ether group. Epoxide groups according to Formula I having R groups as defined in this paragraph are sometimes referred to herein as ADM1D for convenience.

[0487] In a preferred embodiment, at least one of R1-R4 of Formula II is an ether having the following structure:

[0488] R5-O-R6 Formula II

[0489] wherein each of R5 and R6 is independently a C1-C14 linear or branched (preferably unsubstituted) alkyl group.Epoxide groups as defined in this paragraph are sometimes referred to herein as ADM2A for convenience.

[0490] In a preferred embodiment, at least one of R1-R4 of Formula II is an ether having the following structure:

[0491] R5-O-R6 Formula II

[0492] wherein R5 is a C1-C3 alkyl group, preferably unsubstituted; and

[0493] R6 is a C3-C10 linear or branched (preferably unsubstituted) alkyl group.The epoxide groups defined in this paragraph are sometimes referred to herein as ADM2B for convenience.

[0494] In a preferred embodiment, one of R1 to R4 of Formula I is an ether having the following structure:

[0495] R5-O-R6 Formula II

[0496] wherein each of R5 and R6 is independently a C1-C14 linear or branched (preferably unsubstituted) alkyl group, and the remaining three of R1 to R4 are H. The epoxide groups defined in this paragraph are sometimes referred to herein as ADM3A for convenience.

[0497] In a preferred embodiment, one of R1 to R4 of Formula I is an ether having the following structure:

[0498] R5-O-R6 Formula II

[0499] wherein R5 is connected to the epoxide group and is a C1-C3 linear or branched unsubstituted alkyl group; and R6 is a C3-C10 linear or branched unsubstituted alkyl group, and the remaining three of R1-R4 are H. The epoxide group as defined in this paragraph is sometimes referred to herein as ADM3B for convenience.

[0500] In a preferred embodiment, one of R1 to R4 of Formula I is an ether having the following structure:

[0501] R5-O-R6 Formula II

[0502] wherein R5 is connected to the epoxide group and is a C1 unsubstituted alkyl group; and

[0503] R6 is a C8 branched, unsubstituted alkyl group, and the remaining three of R1-R4 are H. The epoxide groups defined in this paragraph are sometimes referred to herein as ADM3C for convenience.

[0504] In a preferred embodiment, the epoxide comprises, consists essentially of, or consists of 2-ethylhexyl glycidyl ether, which is an ADM3C compound having the structure:

[0505]

[0506] Epoxides according to this paragraph are sometimes referred to herein as ADM4 for convenience.

[0507] In a preferred embodiment, one of R1 to R4 of Formula I is an ether having the following structure:

[0508] R5-O-R6 Formula II

[0509] wherein each of R5 and R6 is independently a C1-C14 linear or branched (substituted or unsubstituted) alkyl group, and the remaining three of R1 to R4 are H. The epoxide groups defined in this paragraph are sometimes referred to herein as ADM5A for convenience.

[0510] In a preferred embodiment, one of R1-R4 of Formula II is an ether having the following structure:

[0511] R5-O-R6 Formula II

[0512] R5 is connected to the epoxide group and is a C1-C3 straight or branched, unsubstituted alkyl group; and R6 is a C3-C10 straight or branched, substituted alkyl group, and the remaining three of R1 to R4 are H. The epoxide group as defined in this paragraph is sometimes referred to herein as ADM5B for convenience.

[0513] In a preferred embodiment, one of R1-R4 of Formula II is an ether having the following structure:

[0514] R5-O-R6 Formula II

[0515] wherein R5 is attached to the epoxide group and is a C1 unsubstituted alkyl group; and R6 is a C8 branched, substituted alkyl group, and the remaining three of R1-R4 are H. Epoxide groups according to Formula I having R groups as defined in this paragraph are sometimes referred to herein as ADM5C for convenience.

[0516] In a preferred embodiment, one of R1 to R4 of Formula I is an ether having the following structure:

[0517]

[0518] wherein R5 is attached to the epoxide group and is a C1 unsubstituted alkyl group; and R6 is a C8 branched oxygen-substituted alkyl group, and the remaining three of R1-R4 are H. Epoxide groups according to Formula I having R groups as defined in this paragraph are sometimes referred to herein as ADM5D for convenience.

[0519] In a preferred embodiment, the epoxide comprises, consists essentially of, or consists of glycidyl neodecanoate, which is an ADM5C compound wherein the substituent on R6 is O and has the structure:

[0520]

[0521] Epoxides according to this paragraph are sometimes referred to herein as ADM6 for convenience.

[0522] In another aspect, the heat transfer composition of the present invention comprises a stable epoxy compound according to Formula II below:

[0523]

[0524] wherein each R1 is independently an epoxy-terminated ethoxy, propoxy or butoxy group. Epoxides according to this paragraph are sometimes referred to herein as naphthylepoxides 1 for convenience.

[0525] In another aspect, the heat transfer composition of the present invention comprises a stable epoxy compound according to Formula II below:

[0526]

[0527] wherein each R1 is independently an epoxy-terminated ethoxy or propoxy group.Epoxides according to this paragraph are sometimes referred to herein as naphthylepoxides 2 for convenience.

[0528] In another aspect, the heat transfer composition of the present invention comprises a stable epoxy compound according to Formula II below:

[0529]

[0530] wherein each R1 is independently an epoxy-terminated ethoxy, propoxy, or butoxy group, provided that at least one R1 is an epoxy-terminated ethoxy group.Epoxides according to this paragraph are sometimes referred to herein as naphthylepoxides 3 for convenience.

[0531] In another aspect, the heat transfer composition of the present invention comprises a stable epoxy compound according to Formula II below:

[0532]

[0533] wherein each R1 is independently an epoxy-terminated ethoxy or propoxy group, provided that at least one R1 is an epoxy-terminated ethoxy group.Epoxides according to this paragraph are sometimes referred to herein as naphthylepoxides 3 for convenience.

[0534] In another aspect, the heat transfer composition of the present invention comprises a stable epoxy compound according to Formula II below:

[0535]

[0536] wherein each R1 is independently an epoxy-terminated ethoxy group. Epoxides according to this paragraph are sometimes referred to herein as naphthylepoxides 4 for convenience.

[0537] In another aspect, the heat transfer composition of the present invention comprises a stable epoxy compound according to Formula II below, wherein each R 1 is an epoxy-terminated ethoxy group, as depicted below:

[0538]

[0539] 1,6-Diglycidylnaphthyl ether. The epoxide according to this paragraph is sometimes referred to herein as naphthyl epoxide 5 for convenience.

[0540] The present invention includes heat transfer compositions (including 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 these heat transfer compositions further comprise any one or more of ADM1-ADM6.

[0541] In the heat transfer compositions of the present invention (including each of heat transfer compositions 1-10), the ADM is preferably present in an amount from about 0.05 wt% to about 2.5 wt%, preferably from 0.05 wt% to about 1.5 wt%, or preferably from 0.05 wt% to 0.5 wt%, based on the weight of the lubricant plus ADM.

[0542] In the heat transfer compositions of the present invention (including each of heat transfer compositions 1-10), the alkylated naphthalene is preferably present in an amount of 0.01% to about 10%, or from about 1.5% to about 4.5%, or from about 2.5% to about 3.5%, wherein these amounts are expressed as weight percentages based on the amount of alkylated naphthalene plus refrigerant in the system. The amounts specified in this paragraph are particularly preferred when ADM is also present.

[0543] In the heat transfer compositions of the present invention (including 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%, where these amounts are expressed as weight percentages based on the amount of alkylated naphthalene plus 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 (including each of heat transfer compositions 1-27) that contain one or more of naphthyl epoxides 1-5.

[0544] The present invention includes heat transfer compositions (including each of heat transfer compositions 1-27) comprising one or more of naphthyl epoxides 1-5 and further comprising an alkylated naphthalene.

[0545] The present invention includes heat transfer compositions (including each of heat transfer compositions 1-27 herein) comprising one or more of naphthyl epoxides 1-5 and further comprising AN1 or AN2 or AN3 or AN4 or AN5 or AN6 or AN7 or AN8 or AN9 and AN10.

[0546] The present invention includes heat transfer compositions (including each of the heat transfer compositions 1-27 herein) that contain one or more of the naphthyl epoxides 1-5 and further contain any one or more of AN1 or AN2 or AN3 or AN4 or AN5 or AN6 or AN7 or AN8 or AN9 or AN10 and ADM1-ADM6.

[0547] Carbodiimide

[0548] The ADM may include a carbodiimide. In a preferred embodiment, the carbodiimide includes a compound having the following structure:

[0549] R 1 -N=C=NR 2

[0550] Other stabilizers

[0551] It is contemplated that stabilizers other than alkylated naphthalenes and ADM may be included in the heat transfer compositions of the present invention, including each of heat transfer compositions 1 to 27. Examples of such other stabilizers are described below.

[0552] Phenol-based compounds

[0553] In a preferred embodiment, the stabilizer further comprises a phenol-based compound.

[0554] The phenol-based compound may be one or more compounds selected from the group consisting of: 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-butylenebis(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-methylphenol (BHT); 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-α-dimethylamino-p-cresol; 2,6-di-tert-butyl-4 (N,N'-dimethylaminomethylphenol); 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(2-methyl-6-tert-butylphenol); Bis(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 tert-butylhydroquinone, and preferably BHT.

[0555] Phenolic compounds, and in particular BHT, may be provided in the heat transfer composition in an amount greater than 0 wt % and preferably from 0.0001 wt % to about 5 wt %, preferably from 0.001 wt % to about 2.5 wt %, and more preferably from 0.01 wt % to about 1 wt %. In each case, the weight percentages refer to the weight of the heat transfer composition.

[0556] Phenol-based compounds, and in particular BHT, may be provided in the heat transfer composition in an amount greater than 0 wt % and preferably from 0.0001 wt % to about 5 wt %, preferably from 0.001 wt % to about 2.5 wt %, and more preferably from 0.01 wt % to about 1 wt %. In each case, the weight percentages refer to the weight based on the weight of the lubricant in the heat transfer composition.

[0557] The present invention also includes a stabilizer comprising from about 40 wt % to about 95 wt % of an alkylated naphthalene (including each of AN1 to AN10) and from 0.1 to about 10 wt % of BHT, based on the weight of all stabilizer components in the composition.

[0558] The present invention also includes a stabilizer comprising from about 40 wt % to about 95 wt % of alkylated naphthalene (including each of AN1 to AN10), from about 5 wt % to about 30 wt % of ADM (including each of ADM1 to ADM6), and from 0.1 to about 10 wt % of BHT, based on the weight of all stabilizer components in the composition.

[0559] Diene-based compounds

[0560] Diene-based compounds include C3 to C15 dienes and compounds formed by the reaction of any two or more C3 to C4 dienes. Preferably, the diene-based compound is selected from allyl ethers, propadiene, butadiene, isoprene, and terpenes. The diene-based compound is preferably a terpene, including but not limited to rutenene, retinal, geraniol, terpinene, δ3-carene, terpinolene, phellandrene, fenchene, myrcene, farnesene, pinene, nerol, citral, camphor, menthol, limonene, nerolidol, phytol, carnosic acid, and vitamin A1. Preferably, the stabilizer is farnesene. Preferred terpene stabilizers are described in U.S. Provisional Patent Application No. 60 / 638,003, filed December 12, 2004, published as US 2006 / 0167044A1, which is incorporated herein by reference.

[0561] In addition, the diene-based compound may be present in the heat transfer composition in an amount greater than 0 wt % and preferably from 0.0001 wt % to about 5 wt %, preferably from 0.001 wt % to about 2.5 wt %, and more preferably from 0.01 wt % to about 1 wt %. In each case, the weight percentages refer to the weight of the heat transfer composition.

[0562] Phosphorus-based compounds

[0563] The phosphorus compound may be a phosphite or a phosphate compound. For the purposes of the present invention, the phosphite compound may be a diaryl, dialkyl, triaryl and / or trialkyl phosphite, and / or a mixed aryl / alkyl di- or tri-substituted phosphite, in particular one or more compounds selected from the group consisting of hindered phosphites, tris-(di-tert-butylphenyl) phosphite, di-n-octyl phosphite, isooctyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphate, triphenyl phosphite and diphenyl phosphite, in particular diphenyl phosphite.

[0564] The phosphate compound may be triaryl phosphate, trialkyl phosphate, alkyl monoacid phosphate, aryl diacid phosphate, amine phosphate, preferably triaryl phosphate and / or trialkyl phosphate, in particular tri-n-butyl phosphate.

[0565] The present invention includes heat transfer compositions (including each of Heat Transfer Compositions 1-10) wherein the composition further comprises a phosphate.

[0566] The present invention includes heat transfer compositions (including each of Heat Transfer Compositions 1-10) wherein the composition further comprises a triaryl phosphate.

[0567] The present invention includes heat transfer compositions (including each of Heat Transfer Compositions 1-10) wherein the composition further comprises a trialkyl phosphate.

[0568] Phosphorus compounds may be provided in the heat transfer compositions of the present invention (including each of heat transfer compositions 1-10) in an amount greater than 0 wt %, and preferably from 0.0001 wt % to about 5 wt %, preferably from 0.001 wt % to about 2.5 wt %, and more preferably from 0.01 wt % to about 1 wt %. In each case, by weight refers to the weight of the heat transfer composition.

[0569] Phosphorus compounds may be present in the heat transfer compositions of the present invention (including each of heat transfer compositions 1-10) in an amount greater than 0 wt %, and preferably from 0.0002 wt % to about 10 wt %, preferably from 0.002 wt % to about 5 wt %, and more preferably from 0.02 wt % to about 2 wt %. In each case, the weight in this paragraph refers to the weight of the lubricant and the phosphate stabilizer.

[0570] nitrogen compounds

[0571] When the stabilizer is a nitrogen compound, the stabilizer may include an amine-based compound, such as one or more secondary or tertiary amines selected from the group consisting of diphenylamine, p-phenylenediamine, triethylamine, tributylamine, diisopropylamine, triisopropylamine, and triisobutylamine. The amine-based compound may be an amine antioxidant, such as a substituted piperidine compound, i.e., an alkyl-substituted piperidyl, piperidinyl, piperazinone, or alkoxypiperidinyl derivative, in particular one or more amine antioxidants selected from the group consisting of 2,2,6,6-tetramethyl-4-piperidone, 2,2,6,6-tetramethyl-4-piperidinol, bis(1,2,2,6,6-pentamethylpiperidinol), ... bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidinylsuccinate); alkylated p-phenylenediamines such as N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine or N,N'-di-sec-butyl-p-phenylenediamine; and hydroxylamines such as tallowamine, methyl bis-tallowamine and bis-tallowamine; or phenol-α-naphthylamine or (Ciba), 1944 (Mayzo Inc) and 1770 (Mayzo Inc). For the purposes of the present invention, the amine-based compound may also be an alkyldiphenylamine such as bis(nonylaniline), a dialkylamine such as (N-(1-methylethyl)-2-propylamine, or one or more of phenyl-α-naphthylamine (PANA), alkyl-phenyl-α-naphthyl-amine (APANA) and bis(nonylphenyl)amine. Preferably, the amine-based compound is one or more of phenyl-α-naphthylamine (PANA), alkyl-phenyl-α-naphthyl-amine (APANA) and bis(nonylphenyl)amine, and more preferably phenyl-α-naphthylamine (PANA).

[0572] Alternatively, or in addition to the nitrogen compounds specified above, one or more compounds selected from dinitrobenzene, nitrobenzene, nitromethane, nitrosobenzene, and TEMPO[(2,2,6,6-tetramethylpiperidin-1-yl)oxy] may be used as stabilizers.

[0573] The nitrogen compound can be provided in the heat transfer composition in an amount greater than 0 wt % and from 0.0001 wt % to about 5 wt %, preferably from 0.001 wt % to about 2.5 wt %, and more preferably from 0.01 wt % to about 1 wt %. In each case, the weight percentages refer to the weight of the heat transfer composition.

[0574] Isobutylene

[0575] Isobutene can also be used as stabilizer according to the invention.

[0576] Protective agent

[0577] The present invention includes heat transfer compositions comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protectant comprising a compound according to Formula I:

[0578]

[0579] wherein at least one of R and R1 is a C1-C20 alkylthio group, which is hereinafter referred to as protective agent 1 for convenience.

[0580] The present invention also includes heat transfer compositions comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protective agent comprising a compound according to Formula I above, but wherein each R and R1 is independently a C1-C20 alkylthio group, hereinafter referred to as Protective Agent 2 for convenience.

[0581] The present invention also includes heat transfer compositions comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protective agent comprising a compound according to Formula I above, but wherein each R and R1 is independently a C5-C20 alkylthio group, which for convenience will be referred to as Protective Agent 3 below.

[0582] The present invention also includes heat transfer compositions comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protective agent comprising a compound according to Formula I above, but wherein each R and R1 is independently a C5-C10 alkylthio group, hereinafter referred to as Protective Agent 4 for convenience.

[0583] The present invention includes heat transfer compositions comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protectant comprising a compound according to Formula II:

[0584]

[0585] For convenience, it will be referred to as protective agent 5A hereinafter.

[0586] The present invention includes a heat transfer composition comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and a protectant comprising a compound according to Formula II above and further comprising dioctyl disulfide, hereinafter referred to for convenience as Protectant 5A.

[0587] Specific heat transfer compositions of the present invention include those identified in the following Table HTC, wherein the first column of the table includes "HTC" as an abbreviation for the defined heat transfer composition. In Table 1 below: Refrigerant Number means the refrigerant number as defined above (i.e., the number 1 in the third column below means that the heat transfer composition (HTC) contains a refrigerant according to Refrigerant 1, the number 2 in the third column below means that the heat transfer composition (HTC) contains a refrigerant according to Refrigerant 2 as defined above, and so on); "Terp" in the "Other Components" column means a terpene-type stabilizer; "Lim" in the "Other Components" column means a limonene stabilizer; "NR" means that the component or specific amount is "not required" according to the definition of the specified HTC, and therefore its presence in any amount or in no amount is permitted; "Yes" means that the component is required, but any type or amount is permitted; "Comp" means that the specified composition contains the item identified in the table; "CEO" means that the specified composition consists essentially of the item identified in the table; and "CO" means that the composition consists of the item identified in the table.

[0588] Table HTC

[0589]

[0590]

[0591]

[0592]

[0593]

[0594]

[0595]

[0596] The present invention also includes heat transfer compositions, including each of heat transfer compositions 1-26, and these heat transfer compositions further comprise naphthyl epoxy 1. Heat transfer compositions according to this paragraph are sometimes referred to herein as heat transfer composition 27A for convenience.

[0597] The present invention also includes heat transfer compositions, including each of heat transfer compositions 1-26, and these heat transfer compositions further comprise naphthyl epoxy 2. Heat transfer compositions according to this paragraph are sometimes referred to herein as heat transfer composition 27B for convenience.

[0598] The present invention also includes heat transfer compositions, including each of heat transfer compositions 1-26, and these heat transfer compositions further comprise naphthyl epoxy 3. Heat transfer compositions according to this paragraph are sometimes referred to herein for convenience as heat transfer composition 27C.

[0599] The present invention also includes heat transfer compositions, including each of heat transfer compositions 1-26, and these heat transfer compositions further comprise naphthyl epoxy 4. Heat transfer compositions according to this paragraph are sometimes referred to herein for convenience as heat transfer composition 27D.

[0600] The present invention also includes heat transfer compositions, including each of heat transfer compositions 1-26, and these heat transfer compositions further comprise naphthyl epoxy 5. Heat transfer compositions according to this paragraph are sometimes referred to herein for convenience as heat transfer composition 27E.

[0601] The present invention also includes heat transfer compositions, including each of heat transfer compositions 1-26, and these heat transfer compositions further comprise naphthyl epoxy 6. Heat transfer compositions according to this paragraph are sometimes referred to herein for convenience as heat transfer composition 27F.

[0602] Those skilled in the art may also, in view of the teachings contained herein, include other additives not mentioned herein without departing from the novel and essential characteristics of the present invention.

[0603] Combinations of surfactants and solubilizers may also be added to the compositions of the present invention to aid oil solubility, as disclosed in US Patent No. 6,516,837, the disclosure of which is incorporated by reference in its entirety.

[0604] Methods, uses and systems

[0605] system

[0606] The present invention includes all types of heat transfer systems that include the refrigerant of the present invention (including each of refrigerants 1-15) and / or include the heat transfer composition of the present invention (including each of heat transfer compositions 1-27). The heat transfer system described in this paragraph is sometimes referred to as heat transfer system 1 for convenience.

[0607] The present invention also includes, and provides certain advantages associated with, a low-temperature refrigeration system comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and / or comprising a heat transfer composition of the present invention (including each of Heat Transfer Compositions 1-27). The heat transfer system as described in this paragraph is sometimes referred to as Heat Transfer System 2 for convenience.

[0608] The present invention also includes, and provides certain advantages associated with, medium temperature refrigeration systems that include a refrigerant of the present invention (including each of Refrigerants 1-15) and / or a heat transfer composition of the present invention (including each of Heat Transfer Compositions 1-27). The heat transfer system described in this paragraph is sometimes referred to as Heat Transfer System 3 for convenience.

[0609] The present invention also includes, and provides certain advantages associated with, a cascade refrigeration system comprising a refrigerant of the present invention (including each of Refrigerants 1-15) and / or comprising a heat transfer composition of the present invention (including each of Heat Transfer Compositions 1-27). The heat transfer system as described in this paragraph is sometimes referred to as Heat Transfer System 4 for convenience.

[0610] The present invention also includes, and provides certain advantages associated with, coolers (including air-cooled coolers) that include a refrigerant of the present invention (including each of refrigerants 1-15) and / or a heat transfer composition of the present invention (including each of heat transfer compositions 1-27). The heat transfer system described in this paragraph is sometimes referred to as heat transfer system 5 for convenience.

[0611] The present invention also includes, and provides certain advantages associated with, heat pump systems that include a refrigerant of the present invention (including each of refrigerants 1-15) and / or a heat transfer composition of the present invention (including each of heat transfer compositions 1-27). The heat transfer system described in this paragraph is sometimes referred to as heat transfer system 6 for convenience.

[0612] The present invention also includes and provides certain advantages associated with commercial refrigeration (including low-temperature commercial refrigeration and medium-temperature commercial refrigeration) that includes the refrigerant of the present invention (including each of Refrigerants 1-15) and / or includes the heat transfer composition of the present invention (including each of Heat Transfer Compositions 1-27). The heat transfer system as described in this paragraph is sometimes referred to as heat transfer system 7 for convenience.

[0613] For heat transfer systems of the present invention including a compressor and a lubricant for the compressor in the system, the system may include a load of a refrigerant (including each of Refrigerants 1-15) and a lubricant (including POE and PVE lubricants) of the present invention such that the lubricant load in the system is from about 5% to 60% by weight, or from about 10% to about 60% by weight, or from about 20% to about 50% by weight, or from about 20% to about 40% by weight, or from about 20% to about 30% by weight, or from about 30% to about 50% by weight, or from about 30% to about 40% by weight. As used herein, the term "lubricant load" refers to the total weight of the lubricant contained in the system as a percentage of the total amount of lubricant and refrigerant contained in the system. Such systems may also include a lubricant load of from about 5% to about 10% by weight, or about 8% by weight of the heat transfer composition.

[0614] In particular aspects, the heat transfer composition of the present invention comprises any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricant in a low temperature refrigeration system, as follows:

[0615]

[0616]

[0617] In particular aspects, the heat transfer composition of the present invention comprises any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricant in a low temperature refrigeration system, as follows:

[0618] refrigerant lubricant Refrigeration system Refrigerant 1 POE or PVE Medium temperature refrigeration Refrigerant 2 POE or PVE Medium temperature refrigeration Refrigerant 3 POE or PVE Medium temperature refrigeration Refrigerant 4 POE or PVE Medium temperature refrigeration Refrigerant 5 POE or PVE Medium temperature refrigeration Refrigerant 6 POE or PVE Medium temperature refrigeration Refrigerant 7 POE or PVE Medium temperature refrigeration Refrigerant 8 POE or PVE Medium temperature refrigeration Refrigerant 9 POE or PVE Medium temperature refrigeration Refrigerant 10 POE or PVE Medium temperature refrigeration Refrigerant 11 POE or PVE Medium temperature refrigeration Refrigerant 12 POE or PVE Medium temperature refrigeration Refrigerant 13 POE or PVE Medium temperature refrigeration Refrigerant 14 POE or PVE Medium temperature refrigeration Refrigerant 15 POE or PVE Medium temperature refrigeration

[0619] A heat transfer composition comprising any of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricant in a retail food refrigeration system, as follows:

[0620]

[0621]

[0622] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a walk-in freezer system, as follows:

[0623] refrigerant lubricant Refrigeration system Refrigerant 1 POE or PVE Walk-in Freezer Refrigerant 2 POE or PVE Walk-in Freezer Refrigerant 3 POE or PVE Walk-in Freezer Refrigerant 4 POE or PVE Walk-in Freezer Refrigerant 5 POE or PVE Walk-in Freezer Refrigerant 6 POE or PVE Walk-in Freezer Refrigerant 7 POE or PVE Walk-in Freezer Refrigerant 8 POE or PVE Walk-in Freezer Refrigerant 9 POE or PVE Walk-in Freezer Refrigerant 10 POE or PVE Walk-in Freezer Refrigerant 11 POE or PVE Walk-in Freezer Refrigerant 12 POE or PVE Walk-in Freezer Refrigerant 13 POE or PVE Walk-in Freezer Refrigerant 14 POE or PVE Walk-in Freezer Refrigerant 15 POE or PVE Walk-in Freezer

[0624] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a transport refrigeration system, as follows:

[0625]

[0626]

[0627] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a transport refrigeration system, as follows:

[0628] refrigerant lubricant Refrigeration system Refrigerant 1 POE or PVE vending machines Refrigerant 2 POE or PVE vending machines Refrigerant 3 POE or PVE vending machines Refrigerant 4 POE or PVE vending machines Refrigerant 5 POE or PVE vending machines Refrigerant 6 POE or PVE vending machines Refrigerant 7 POE or PVE vending machines Refrigerant 8 POE or PVE vending machines Refrigerant 9 POE or PVE vending machines Refrigerant 10 POE or PVE vending machines Refrigerant 11 POE or PVE vending machines Refrigerant 12 POE or PVE vending machines Refrigerant 13 POE or PVE vending machines Refrigerant 14 POE or PVE vending machines Refrigerant 15 POE or PVE vending machines

[0629] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a transport refrigeration system, as follows:

[0630] refrigerant lubricant Refrigeration system Refrigerant 1 POE or PVE heat pump Refrigerant 2 POE or PVE heat pump Refrigerant 3 POE or PVE heat pump Refrigerant 4 POE or PVE heat pump Refrigerant 5 POE or PVE heat pump Refrigerant 6 POE or PVE heat pump Refrigerant 7 POE or PVE heat pump Refrigerant 8 POE or PVE heat pump Refrigerant 9 POE or PVE heat pump Refrigerant 10 POE or PVE heat pump Refrigerant 11 POE or PVE heat pump Refrigerant 12 POE or PVE heat pump Refrigerant 13 POE or PVE heat pump Refrigerant 14 POE or PVE heat pump Refrigerant 15 POE or PVE heat pump

[0631] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a transport refrigeration system, as follows:

[0632] refrigerant lubricant Refrigeration system Refrigerant 1 POE or PVE Fixed air conditioner Refrigerant 2 POE or PVE Fixed air conditioner Refrigerant 3 POE or PVE Fixed air conditioner Refrigerant 4 POE or PVE Fixed air conditioner Refrigerant 5 POE or PVE Fixed air conditioner Refrigerant 6 POE or PVE Fixed air conditioner Refrigerant 7 POE or PVE Fixed air conditioner Refrigerant 8 POE or PVE Fixed air conditioner Refrigerant 9 POE or PVE Fixed air conditioner Refrigerant 10 POE or PVE Fixed air conditioner Refrigerant 11 POE or PVE Fixed air conditioner Refrigerant 12 POE or PVE Fixed air conditioner Refrigerant 13 POE or PVE Fixed air conditioner Refrigerant 14 POE or PVE Fixed air conditioner Refrigerant 15 POE or PVE Fixed air conditioner

[0633] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a transport refrigeration system, as follows:

[0634]

[0635]

[0636] A heat transfer composition comprising any one of refrigerants 1 to 15, and / or a heat transfer composition comprising refrigerants 1 to 15, including each of heat transfer compositions 1-27, and a lubricating oil in a transport refrigeration system, as follows:

[0637] refrigerant lubricant Refrigeration system Refrigerant 1 POE or PVE Transport Refrigeration Refrigerant 2 POE or PVE Transport Refrigeration Refrigerant 3 POE or PVE Transport Refrigeration Refrigerant 4 POE or PVE Transport Refrigeration Refrigerant 5 POE or PVE Transport Refrigeration Refrigerant 6 POE or PVE Transport Refrigeration Refrigerant 7 POE or PVE Transport Refrigeration Refrigerant 8 POE or PVE Transport Refrigeration Refrigerant 9 POE or PVE Transport Refrigeration Refrigerant 10 POE or PVE Transport Refrigeration Refrigerant 11 POE or PVE Transport Refrigeration Refrigerant 12 POE or PVE Transport Refrigeration Refrigerant 13 POE or PVE Transport Refrigeration Refrigerant 14 POE or PVE Transport Refrigeration Refrigerant 15 POE or PVE Transport Refrigeration

[0638] Exemplary Heat Transfer Systems

[0639] As described in detail below, a preferred system of the present invention includes a compressor, a condenser, an expansion device, and an evaporator, all of which are connected in fluid communication using piping, valves, and a control system so that the refrigerant and the relevant components of the heat transfer composition can flow through the system in a known manner to complete the refrigeration cycle. An exemplary schematic diagram of such a basic system is shown in FIG. Figure 1 Specifically, Figure 1 The system schematically illustrated in FIG. 1 shows a compressor 10 that provides compressed refrigerant vapor to a condenser 20. The compressed refrigerant vapor is condensed to produce liquid refrigerant, which is then directed to an expansion device 40 that produces refrigerant at a reduced temperature and pressure, which is then, in turn, provided to an evaporator 50. In the evaporator 50, the liquid refrigerant absorbs heat from the body or fluid being cooled, thereby producing refrigerant vapor, which is then provided to the suction line of the compressor.

[0640] Figure 2 The refrigeration system shown in the above is combined with Figure 1 The same as described above, except that it includes a vapor injection system that includes a heat exchanger 30 and a bypass expansion valve 25. The bypass expansion device 25 diverts a portion of the refrigerant flow at the condenser outlet through the device, providing liquid refrigerant to the heat exchanger 30 at a reduced pressure and, therefore, at a lower temperature. This relatively cooler liquid refrigerant then exchanges heat with the remaining relatively hot liquid from the condenser. This operation produces subcooled liquid to the main expansion device 40 and evaporator 50, and returns relatively cooler refrigerant vapor to the compressor 10. In this way, injecting cooled refrigerant vapor into the suction side of the compressor serves to maintain the compressor discharge temperature within acceptable limits, which can be particularly advantageous in low-temperature systems utilizing high compression ratios.

[0641] Figure 3 The refrigeration system shown in the above is combined with Figure 1 The same as described above, except that it includes a liquid injection system that includes a bypass valve 26. The bypass valve 26 diverts a portion of the liquid refrigerant leaving the condenser to the compressor, preferably to a liquid injection port in the compressor 10. In this way, injecting liquid refrigerant into the suction side of the compressor serves to maintain the compressor discharge temperature within acceptable limits, which can be particularly advantageous in low temperature systems utilizing high compression ratios.

[0642] Figure 4 The refrigeration system shown in the above is combined with Figure 1The same as described above, 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 leaving the evaporator 50 and then introduced into the compressor 10.

[0643] Figure 5 The refrigeration system shown in the above is combined with Figure 2 The same as described above, except that it includes an oil separator 60 connected to the outlet of the compressor 10. As is known to those skilled in the art, a certain amount of compressor lubricant is typically carried over into the compressor discharge refrigerant vapor, and an oil separator is included to provide a means for separating the lubricant liquid from the refrigerant vapor, with the resulting refrigerant vapor having a reduced lubricating oil content being passed to the condenser inlet, and then returning the liquid lubricant to a lubricant reservoir used in lubricated compressors, such as a lubricant receiver. In a preferred embodiment, the oil separator comprises a chelating material as described herein, preferably in the form of a filter or solid core.

[0644] It should be understood by those skilled in the art that Figure 2-5 The different equipment / configuration options shown in each of the examples may be combined and used together as deemed advantageous for any application.

[0645] use :

[0646] General Purpose

[0647] The methods and systems of the present invention may include any heat transfer system and / or any heat transfer method that utilizes a refrigerant (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions 1-27) to absorb heat, or block heat, or both. Thus, the present invention provides uses and methods for heating or cooling a fluid or body using a refrigerant (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions 1-27).

[0648] The present invention also encompasses the use of the refrigerants of the present invention (including each of Refrigerants 1-15) in medium temperature refrigeration systems and provides specific advantages associated therewith.

[0649] The present invention also includes the use of the refrigerants of the present invention (including each of refrigerants 1-15), and / or heat transfer compositions comprising refrigerants 1 to 15 (including each of heat transfer compositions 1-27) in low-temperature refrigeration systems, and provides specific advantages associated therewith.

[0650] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) in walk-in freezers, and provides specific advantages associated therewith.

[0651] The present invention also encompasses the use of the refrigerants of the present invention, including each of Refrigerants 1-15, in walk-in freezers and provides certain advantages associated therewith.

[0652] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) in vending machines, and provides specific advantages associated therewith.

[0653] The present invention also includes the use of the refrigerants of the present invention (including each of refrigerants 1-15), and / or heat transfer compositions comprising refrigerants 1 to 15 (including each of heat transfer compositions 1-27) in vending machines located in corridors or aisles, and provides specific advantages associated therewith.

[0654] The present invention also includes the use of the refrigerants of the present invention (including each of refrigerants 1-15), and / or heat transfer compositions comprising refrigerants 1 to 15 (including each of heat transfer compositions 1-27) in stationary air conditioners, and provides specific advantages associated therewith.

[0655] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) in commercial air conditioning, and provides specific advantages associated therewith.

[0656] The present invention also includes the use of the refrigerants of the present invention (including each of refrigerants 1-15), and / or heat transfer compositions comprising refrigerants 1 to 15 (including each of heat transfer compositions 1-27) in cascade refrigeration systems, and provides specific advantages associated therewith.

[0657] The present invention also includes the use of the refrigerants of the present invention (including each of refrigerants 1-15), and / or heat transfer compositions comprising refrigerants 1 to 15 (including each of heat transfer compositions 1-27) in heat pumps, and provides specific advantages associated therewith.

[0658] The present invention also includes the use of the refrigerants of the present invention (including each of refrigerants 1-15), and / or heat transfer compositions comprising refrigerants 1 to 15 (including each of heat transfer compositions 1-27) in transport refrigeration refrigeration systems, and provides specific advantages associated therewith.

[0659] Alternative uses

[0660] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-22 and provides specific advantages associated therewith.

[0661] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-404A, and provides specific advantages associated therewith.

[0662] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-407F, and provides specific advantages associated therewith.

[0663] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-448A, and provides specific advantages associated therewith.

[0664] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-449A, and provides specific advantages associated therewith.

[0665] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-134A, and provides specific advantages associated therewith.

[0666] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-410A, and provides specific advantages associated therewith.

[0667] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-22 in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0668] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-22 in low temperature refrigeration, and provides specific advantages associated therewith.

[0669] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-22 in heat pumps, and provides specific advantages associated therewith.

[0670] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-22 in transport refrigeration systems, and provides specific advantages associated therewith.

[0671] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-22 in cascade refrigeration systems, and provides specific advantages associated therewith.

[0672] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-404A in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0673] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-404A in low temperature refrigeration, and provides specific advantages associated therewith.

[0674] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-404A in heat pumps, and provides specific advantages associated therewith.

[0675] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-404A in transport refrigeration systems, and provides specific advantages associated therewith.

[0676] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-404A in cascade refrigeration systems, and provides specific advantages associated therewith.

[0677] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-407F in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0678] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-407F in low temperature refrigeration, and provides specific advantages associated therewith.

[0679] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-407F in heat pumps, and provides specific advantages associated therewith.

[0680] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-407F in transport refrigeration systems, and provides specific advantages associated therewith.

[0681] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-407F in cascade refrigeration systems, and provides specific advantages associated therewith.

[0682] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-448A in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0683] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-448A in low temperature refrigeration, and provides specific advantages associated therewith.

[0684] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-448A in heat pumps, and provides specific advantages associated therewith.

[0685] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-448A in transport refrigeration systems, and provides specific advantages associated therewith.

[0686] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-448A in cascade refrigeration systems, and provides specific advantages associated therewith.

[0687] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-134A in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0688] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-134A in low temperature refrigeration, and provides specific advantages associated therewith.

[0689] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-134A in heat pumps, and provides specific advantages associated therewith.

[0690] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-134A in transport refrigeration systems, and provides specific advantages associated therewith.

[0691] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-134A in cascade refrigeration systems, and provides specific advantages associated therewith.

[0692] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-449A in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0693] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-449A in low temperature refrigeration, and provides specific advantages associated therewith.

[0694] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-449A in heat pumps, and provides specific advantages associated therewith.

[0695] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-449A in transport refrigeration systems, and provides specific advantages associated therewith.

[0696] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-449A in cascade refrigeration systems, and provides specific advantages associated therewith.

[0697] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-410A in medium temperature refrigeration systems, and provides specific advantages associated therewith.

[0698] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-410A in low temperature refrigeration, and provides specific advantages associated therewith.

[0699] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-410A in heat pumps, and provides specific advantages associated therewith.

[0700] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as replacements for R-410A in transport refrigeration systems, and provides specific advantages associated therewith.

[0701] The present invention also includes the use of the refrigerants of the present invention (including each of Refrigerants 1-15), and / or heat transfer compositions comprising Refrigerants 1 to 15 (including each of Heat Transfer Compositions 1-27) as a replacement for R-410A in cascade refrigeration systems, and provides specific advantages associated therewith.

[0702] Cooling method

[0703] The present invention includes a method for providing cooling, the method comprising:

[0704] (a) evaporating the refrigerant according to the present invention near the body or product or fluid to be cooled

[0705] (including any refrigerant selected from each of refrigerants 1-15);

[0706] (b) compressing the refrigerant vapor to produce a refrigerant having a discharge temperature of less than about 150° C.; and

[0707] (c) condensing the refrigerant from the compressor. The cooling method according to this paragraph is referred to herein as Cooling Method 1.

[0708] The present invention includes a method for providing cooling, the method comprising:

[0709] (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 at a temperature of about -40°C to about +10°C to produce a refrigerant vapor;

[0710] (b) compressing the refrigerant vapor to produce a refrigerant having a discharge temperature of less than about 150° C.; and

[0711] (c) condensing the refrigerant from the compressor at a temperature of about 20° C. to about 70° C. to produce a refrigerant vapor. The cooling method according to this paragraph is referred to herein as Cooling Method 2.

[0712] The present invention includes cooling according to any one of cooling methods 1-3 in a medium-temperature refrigeration system.

[0713] The present invention includes performing cooling according to any one of cooling methods 1-3 in a low-temperature refrigeration system.

[0714] The present invention comprises performing cooling according to any one of cooling methods 1-3 in a transport refrigeration system.

[0715] The present invention includes cooling according to any one of cooling methods 1-3 in a cascade refrigeration system.

[0716] The present invention includes performing cooling according to any one of cooling methods 1-3 in an electronic device cooling system.

[0717] The present invention includes performing cooling according to any one of cooling methods 1-3 in a heat pump system.

[0718] The present invention comprises performing cooling according to any one of cooling methods 1-3 in a commercial refrigeration system.

[0719] The present invention comprises cooling according to any one of cooling methods 1-3 in a commercial low temperature refrigeration system.

[0720] The present invention comprises cooling according to any one of cooling methods 1-3 in a commercial medium temperature refrigeration system.

[0721] The present invention comprises cooling according to any of Cooling Methods 1-3 in a walk-in freezer.

[0722] The present invention comprises cooling according to any one of cooling methods 1-3 in a walk-in refrigerator.

[0723] The present invention comprises performing cooling according to any one of cooling methods 1-3 in a stationary air conditioner.

[0724] The present invention includes performing cooling according to any one of cooling methods 1-3 in a commercial air conditioner.

[0725] The present invention includes performing cooling according to any one of cooling methods 1-3 in a vending machine.

[0726] The specific cooling method is described in more detail below.

[0727] Applicants have discovered that numerous advantages can be achieved in conjunction with heat transfer methods in which a refrigerant (including each of Refrigerants 1-15) or a heat transfer composition of the present invention including a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27) is used to absorb heat from a fluid surrounding an article, or is otherwise in thermal communication with the article itself, such as may occur with cooling produce and / or other refrigerated foods, or such as may occur with respect to certain electronic equipment. In such cases, the fluid may be air or a secondary coolant (e.g., water, glycol, a water / glycol mixture, brine, etc.), such as would occur if the refrigerant were used in an evaporator in a system and method that requires that the temperature of the article or fluid being cooled not be exposed to temperatures below a certain limit.

[0728] Thus, generally speaking, the methods of the present invention utilize apparatus and / or processes that allow the refrigerants or heat transfer compositions of the present invention to absorb heat, and also utilize apparatus and / or processes that then remove the absorbed heat from the refrigerant.

[0729] It should be understood that the evaporator for absorbing heat from the product or fluid being cooled can include conduits, such as, for example, cooling coils, through which refrigerant (including each of refrigerants 1-15), and / or heat transfer compositions including refrigerants 1 to 15 (including each of heat transfer compositions 1-27), flows, while such conduits are exposed (directly or indirectly) to the product or fluid to be cooled. In this way, heat flows from the cooled fluid (e.g., air) and / or nearby products (such as fresh produce, such as fruits, vegetables, and flowers) through the metal or other thermally conductive material of the conduits and into the refrigerant (including each of refrigerants 1-15), and / or heat transfer compositions including refrigerants 1 to 15 (including each of heat transfer compositions 1-27) of the present invention.

[0730] Refrigeration method

[0731] The present invention also provides a method for cooling a fluid or a body using a refrigeration system, wherein the method comprises the steps of: (a) evaporating a refrigerant composition (including each of Refrigerants 1-15) and / or a heat transfer composition (including each of Refrigerants 1 to 15) of the present invention near the fluid or body to be cooled, and (b) condensing the refrigerant. Specific and preferred operations of the preferred heat transfer method are described below.

[0732] Medium temperature refrigeration method

[0733] The refrigerants and heat transfer compositions of the present invention can be used in any refrigeration system. However, the applicant has found that the present refrigerants (including each of Refrigerants 1-15) and the present heat transfer compositions comprising the refrigerants of the present invention (including each of Heat Transfer Compositions 1-27) provide particular advantages in medium-temperature refrigeration systems. Therefore, the present invention provides a method for cooling a fluid or body in a medium-temperature refrigeration system, the method comprising the steps of: (a) evaporating a refrigerant composition of the present invention (including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27) in the vicinity of the fluid or body to be cooled, and (b) condensing the refrigerant, wherein the evaporation temperature is from about -15°C to about 5°C, more preferably from about -10°C to about 5°C.

[0734] As used herein, a medium temperature refrigeration system refers to a refrigeration system that utilizes one or more compressors and operates 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) a superheat at the evaporator outlet of about 0° C. to about 10° C., preferably a superheat at the evaporator outlet of about 1° C. to about 6° C.; and optionally (d) a superheat in the suction line of about 5° C. to about 40° C., preferably a superheat in the suction line of about 15° C. to about 30° C. Superheat along the suction line can also be generated by a heat exchanger.

[0735] Examples of medium temperature refrigeration systems and medium temperature refrigeration methods include small refrigeration systems (including vending machines, ice machines, and appliances), commercial refrigeration systems (such as supermarket refrigeration systems and walk-in coolers), residential refrigeration systems, industrial refrigeration systems, and ice rinks.

[0736] In the case of storing perishable products (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 (for example, such as cooling fresh-cut fruits, vegetables, and flowers) about 2°C to about 3°C. In addition, in many applications, it is preferred that the refrigerant temperature along the evaporator does not reach below about 0°C (the freezing point of water) to avoid frost formation. Preferably, at the same time, the superheat at the evaporator outlet should be maintained at a typical value of about 3°C to about 5°C, and preferably about 4°C.

[0737] Thus, the present invention includes a medium temperature refrigeration method comprising a refrigerant (including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27), wherein the evaporator temperature of the refrigerant is from about 0°C to about 5°C.

[0738] Cascade refrigeration method

[0739] The present invention also includes a cascade refrigeration method comprising a refrigerant or heat transfer composition of the present invention. Generally speaking, a cascade system has two or more stages. When a cascade system has two stages, these stages are generally referred to as an upper stage and a lower stage. The refrigerant of the present invention (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions 1-27) can be used for the upper or lower stage of a cascade refrigeration system. However, preferably, the refrigerant of the present invention (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions) is used for the upper stage of a cascade system. According to the teachings contained herein, those skilled in the art will be able to determine the appropriate refrigerant for the lower stage of a cascade system, and 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.

[0740] Low temperature refrigeration method

[0741] The present invention also provides a low-temperature refrigeration method, which comprises a refrigerant (including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27). The present invention also provides a method for cooling a fluid or a body in a low-temperature refrigeration system, the method comprising the steps of: (a) evaporating a refrigerant composition of the present invention (including each of Refrigerants 1-15) near the fluid or body 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.

[0742] As used herein, a low temperature refrigeration system refers to a refrigeration system that utilizes one or more compressors and operates 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) a superheat at the evaporator outlet of about 0°C to about 10°C, preferably about 1°C to about 6°C; and optionally (d) a superheat in the suction line of about 15°C to about 40°C, preferably about 20°C to about 30°C.

[0743] 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.

[0744] Transport Refrigeration Methods

[0745] Transport refrigeration creates a link in the cold chain, allowing frozen or refrigerated products to reach the end user at the correct temperature. The present invention relates to transport refrigeration systems comprising a refrigerant of the present invention (including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27). Examples of transport refrigeration include refrigerated road vehicles (such as trucks and vans), train railcars, and containers that can be transported by road vehicles, trains, and ships / boats.

[0746] Heat pump method

[0747] The present invention relates to a heat pump method comprising a refrigerant of the present invention (including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0748] The present invention also provides a method for heating a fluid or a body using a heat pump, the method comprising the steps of: (a) condensing a refrigerant composition of the present invention (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions 1-27) near the fluid or body to be heated; and (b) evaporating the refrigerant. Examples of heat pumps include heat pump tumble dryers, reversible heat pumps, high-temperature heat pumps, and air / air heat pumps.

[0749] Secondary loop method

[0750] The refrigerants of the present invention (including each of refrigerants 1-15) or heat transfer compositions comprising the refrigerants of the present invention (including each of heat transfer compositions 1-27) can be used as secondary fluids in secondary loop systems. The secondary loop system includes a primary vapor compression system loop that uses a primary refrigerant and has an evaporator that cools the secondary loop fluid. The secondary fluid then provides the necessary cooling for the application. The secondary fluid must be non-flammable and have low toxicity because the refrigerant in such a loop is potentially exposed to humans near the cooled space. In other words, the refrigerants of the present invention (including each of refrigerants 1-15) or heat transfer compositions comprising the refrigerants of the present invention (including each of heat transfer compositions 1-27) can be used as "secondary fluids." The primary fluid used in the primary circuit (vapor compression cycle, external / outdoor part of the circuit) may include, but is not limited to, the following refrigerants: R404A, R507, R410A, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, R1234ze(E), R1234yf and R449A.

[0751] Air conditioning methods

[0752] The present invention relates to an air conditioning system comprising a refrigerant of the present invention (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions 1-27). The present invention also provides a method of air conditioning using an air conditioning system, the method comprising the steps of: (a) evaporating a refrigerant composition of the present invention (including each of refrigerants 1-15) near a fluid or body to be cooled; and (b) condensing the refrigerant. Air can be conditioned directly or indirectly by a refrigerant of the present invention (including each of refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of heat transfer compositions 1-27). Examples of air conditioning systems include chillers, residential air conditioners, industrial air conditioners, commercial air conditioners, and mobile air conditioners, including air conditioners for road vehicles (such as cars, trucks, and buses), and air conditioners for boats and trains.

[0753] Preferred refrigeration systems of the present invention include chillers comprising a refrigerant of the present invention (especially including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0754] Preferred refrigeration systems of the present invention include stationary air conditioning systems comprising a refrigerant of the present invention (especially including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0755] Preferred refrigeration systems of the present invention include commercial air conditioning systems that include a refrigerant of the present invention (especially including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0756] Preferred refrigeration systems of the present invention include vending machines comprising a refrigerant of the present invention (especially including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0757] Preferred refrigeration systems of the present invention include walk-in freezers comprising a refrigerant of the present invention (especially including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0758] Preferred refrigeration systems of the present invention include walk-in freezers comprising a refrigerant of the present invention (especially including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27).

[0759] It should be understood that any of the above-described refrigeration, air conditioning, or heat pump systems using the refrigerant of the present invention (including each of Refrigerants 1-14) or the heat transfer composition comprising the refrigerant of the present invention (including each of Heat Transfer Compositions 1-27) may include a suction line / liquid line heat exchanger (SL-LL HX).

[0760] Organic Rankine cycle system

[0761] The refrigerant compositions of the present invention (including each of Refrigerants 1-15) or heat transfer compositions comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27) can be used in an organic Rankine cycle (ORC). In the context of the ORC, the refrigerant used in these systems can also be classified as a "working fluid." The Rankine cycle system is known to be a simple and robust device for converting thermal energy into mechanical shaft energy.

[0762] In industrial environments, flammable working fluids (such as toluene and pentane) may be used, especially when the industrial environment already has a large amount of combustibles on site during processing or storage. However, in situations where the risks associated with using flammable and / or toxic working fluids are unacceptable, such as power generation in populated areas or near buildings, non-flammable and / or non-toxic refrigerants must be used as working fluids. There is also a drive in industry to make these materials environmentally acceptable in terms of GWP.

[0763] A process for recovering waste heat in an organic Rankine cycle system involves pumping a liquid working fluid through a heat exchanger (boiler), where an external (waste) heat source (such as a process stream) heats the working fluid, causing it to evaporate into a saturated or superheated vapor. This vapor is expanded through a turbine, where the waste heat energy is converted into mechanical energy. The gaseous working fluid is then condensed into a liquid and pumped back into the boiler to repeat the regenerative cycle. Thus, the present invention relates to the use of a refrigerant of the present invention (including each of Refrigerants 1-15) or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27) in an organic Rankine cycle.

[0764] Thus, the present invention provides a method for converting thermal energy into mechanical energy in a Rankine cycle, the method comprising the steps of: i) evaporating a working fluid with a heat source and expanding the resulting vapor, or evaporating a working fluid with a heat source and expanding the resulting vapor, and then ii) cooling the working fluid with a heat sink to condense the vapor, wherein the working fluid is a refrigerant or a refrigerant of the present invention (including each of Refrigerants 1-15), or a heat transfer composition comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27). The mechanical work can be transferred to an electrical device such as a generator to generate electricity.

[0765] The heat source can be provided by a thermal energy source selected from industrial waste heat, solar energy, geothermal hot water, low-pressure steam, distributed power generation equipment using fuel cells, internal combustion engines or prime movers. Preferably, the low-pressure steam is low-pressure geothermal steam or provided by a power plant powered by fossil fuels.

[0766] It should be understood that the heat source temperature can vary widely, for example, from about 90° C. to >800° C., and can depend on many factors for certain combustion gases and some fuel cells, including geographic location, time of year, etc. The source temperature for systems based on sources such as wastewater or low-pressure steam (from, for example, plastics manufacturing plants and / or from chemical or other industrial plants, refineries, etc.), as well as geothermal sources, can be at or below about 100° C., and in some cases as low as about 90° C. or even as low as about 80° C. The source temperature for gaseous heat sources (such as exhaust from combustion processes or from any heat source where subsequent processing to remove particulates and / or corrosive materials results in low temperatures) can also be at or below about 130° C., at or below about 120° C., at or below about 100° C., at or below about 100° C., and in some cases as low as about 90° C. or even as low as about 80° C.

[0767] Electronic device cooling

[0768] The refrigerant compositions of the present invention (including any of Refrigerants 1 to 15), or heat transfer compositions comprising a refrigerant of the present invention (including each of Heat Transfer Compositions 1-27), can be used in conjunction with systems and methods for electronic device cooling, such as chip cooling, electronic board cooling, battery cooling (including batteries used in cars, trucks, buses and other electronic transportation vehicles), computer cooling, and the like.

[0769] Example

[0770] In the following examples, the embodiments of the 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. For the characteristics of each binary and ternary component pair used in the refrigerant, the experimental data collected were used for analysis. In the experimental evaluation, each pair of compositions was varied over a series of relative percentages, and each pair of mixture parameters was regressed into experimentally obtained data. The known vapor / liquid equilibrium behavior data derived from the U.S. National Institute of Science and Technology (NIST) reference fluid thermodynamics and transport properties database software (Refprop 9.1NIST standard database 23, from April 2016) were used for the embodiments. The parameters selected for implementation analysis were: the same compressor displacement for all refrigerants, the same operating conditions for all refrigerants, the same compressor isentropic and volumetric efficiency for all refrigerants. In each embodiment, the simulation was implemented using the vapor-liquid equilibrium data measured. The simulation results of each embodiment have been reported.

[0771] The refrigerant compositions identified below as Refrigerants Al, A2, A3, A4, A5 and A6 in Table 1 are A2L refrigerants within the broad scope of the present invention as described herein.

[0772] Table 1: GWP and LFL characteristics of A1-A6

[0773]

[0774]

[0775] Comparative Examples C1-C6

[0776] The following compositions were prepared and tested and found to have the GWP values shown in Tables C1-6A and C1-6B below.

[0777] Table C1-6A

[0778]

[0779] Table C1-6B

[0780]

[0781] As can be seen from the table above, many compositions containing R32, R1132E and R1234yf and CO2 cannot achieve a GWP value of 150 or greater and / or a GWP value of 0.25 kg / m 3 or larger LFL.

[0782] Examples 1-14: Refrigerant Performance / Capacity / Compressor Power and LFL in Medium and Low Temperature Refrigeration

[0783] Under the operating conditions defined below, performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf, and CO2 in a medium-temperature refrigeration system and a low-temperature refrigeration system, which are typically as follows: Figure 1 Disclosed.

[0784] Operating conditions

[0785] 1. Condensation temperature = 45°C

[0786] 2. Condenser subcooling = 5°C

[0787] 3. Evaporation temperature, MT = -3.8 ° C, evaporation temperature, LT = -28.8 ° C

[0788] 4. Evaporator superheat = 3.8℃

[0789] 5. Isentropic efficiency = 70%

[0790] 6. Volumetric efficiency = 100%

[0791] The results of this testing are reported in Table E1-14 below.

[0792] Table E1-14

[0793]

[0794] As can be seen from the results identified in Tables E1-E14 above, while the applicant has found several compositions comprising R32, R1132(E), R1234yf and CO2, as shown in Examples Ex1-Ex4, which are capable of achieving the preferred levels of LFL for the refrigerants according to the present invention (as well as achieving a GWP of 150 or less), they are unable to achieve the most preferred capacity levels of greater than 95% relative to R448A in either MT or LT refrigeration.

[0795] Compared to Ex1-Ex4, the compositions of Examples Ex5-Ex14 each achieve an LFL corresponding to 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 a most preferred capacity level in MT or LT refrigeration of at least 95% relative to R448A. This is a highly desirable but unexpected result.

[0796] Examples 15-29: Refrigerant Performance / Capacity / Compressor Power and LFL in Medium and Low Temperature Refrigeration

[0797] Under the operating conditions defined below, performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf, and CO2 in a medium-temperature refrigeration system and a low-temperature refrigeration system, which are typically as follows: Figure 1 Disclosed.

[0798] Table E15-29

[0799]

[0800] As can be seen from the results identified in Tables E15-E29 above, Applicants have discovered that each of Examples 15-29 is capable of achieving the preferred LFL levels for refrigerants according to the present invention (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less and a most preferred capacity level of at least 95% of MT or LT cooling relative to R448A, and a power rating of 115% or less for both MT and LT cooling relative to R448A. This is a highly desirable, yet unexpected, result.

[0801] Examples 30-34: Performance (compressor power) and LFL of the refrigerants of the present invention in medium and low temperature refrigeration

[0802] Under the operating conditions defined below, several refrigerants including R32, R1132(E), R1234yf, and CO2 were subjected to performance testing of power consumption in the compressor relative to R448A in a medium-temperature refrigeration system and a low-temperature refrigeration system, which are generally as follows: Figure 1 Disclosed.

[0803] Operating conditions

[0804] 1. Condensation temperature = 45°C

[0805] 2. Condenser subcooling = 5°C

[0806] 3. Evaporation temperature, MT = -3.8 ° C, evaporation temperature, LT = -28.8 ° C

[0807] 4. Evaporator superheat = 3.8℃

[0808] 5. Isentropic efficiency = 70%

[0809] 6. Volumetric efficiency = 100%

[0810] The results of this testing are reported in Tables E30-34 below.

[0811] Table E30-34

[0812]

[0813] As can be seen from the results identified in Tables E30-E34 above, Applicants have discovered that each of Examples 30-34 is capable of achieving an LFL corresponding to the preferred LFL levels for the refrigerants of the present invention (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and that Examples 30-33 is also capable of achieving a highly preferred power rating of 115% or less relative to both MT and LT refrigeration of R448A, which is a highly desirable and unexpected result.

[0814] Examples 35-40: Capacity and Discharge Temperature of Refrigerants A1-A6 in Medium-Temperature Refrigeration

[0815] Under the operating conditions defined below, several refrigerants including R32, R1132(E), R1234yf and CO2 were tested for performance in a medium temperature refrigeration system, typically such as Figure 1 Disclosed.

[0816] Operating conditions:

[0817] Condensation temperature = 45°C

[0818] Condensation temperature - ambient temperature = 10°C

[0819] Condenser recooling = 0.0°C (system with receiver)

[0820] Evaporation temperature = -8°C,

[0821] Evaporator superheat = 5.5℃

[0822] Compressor isentropic efficiency = 65%

[0823] Volumetric efficiency = 100%

[0824] Temperature rise in the suction line = 10°C

[0825] The results of this testing are reported in Tables E35-40 below.

[0826] Table E35-40

[0827]

[0828] As can be seen from the results identified in Tables E35-E40 above, Applicants have discovered that each of Examples 35-40 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a surprising and significant ability to achieve 99% or greater of the highly preferred capacity and an acceptable match to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0829] Examples 41-46: Capacity and Discharge Temperature of Refrigerants A1-A6 in Low-Temperature Refrigeration

[0830] Under the operating conditions defined below, several refrigerants including R32, R1132(E), R1234yf and CO2 were tested for performance in a low temperature refrigeration system, typically such as Figure 1 Disclosed.

[0831] Operating conditions:

[0832] Condensation temperature = 45°C

[0833] Condensation temperature - ambient temperature = 10°C

[0834] Condenser subcooling = 0.0°C (system with receiver)

[0835] ●Evaporation temperature = -35℃, corresponding box temperature = -25℃

[0836] ●Evaporator superheat=5.5℃

[0837] ●Compressor isentropic efficiency = 65%

[0838] Volumetric efficiency = 100%

[0839] ●Temperature rise in the suction line = 10°C

[0840] The results of this testing are reported in Tables E41-46 below, which include results for various existing refrigerants for comparison purposes.

[0841] Table E41-46

[0842]

[0843] As can be seen from the results identified in Tables E35-E40 above, Applicants have discovered that each of Examples 35-40 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and that each of these Examples exhibits a surprising and significant ability to achieve approximately 100% or greater of the highly preferred capacity and an acceptable match to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0844] Examples 47-52: Capacity and Discharge Temperature of Refrigerants A1-A6 in Vending Machines

[0845] Under the operating conditions defined below, several refrigerants including R32, R1132(E), R1234yf and CO2 were tested for performance in a vending machine refrigeration system. The low temperature refrigeration system is typically Figure 1 Disclosed.

[0846] Operating conditions:

[0847] Condensation temperature = 45°C

[0848] Condensation temperature - ambient temperature = 10°C

[0849] Condenser subcooling = 5.5°C (system with receiver)

[0850] ●Evaporation temperature=-8℃

[0851] ●Evaporator superheat=3.5℃

[0852] ●Compressor isentropic efficiency = 60%

[0853] Volumetric efficiency = 100%

[0854] ●Temperature rise in the suction line = 5°C

[0855] The results of this testing are reported in Tables E47-52 below, which include results for various existing refrigerants for comparison purposes.

[0856] Table E47-52

[0857]

[0858] As can be seen from the results identified in Tables E35-E40 above, Applicants have discovered that each of Examples 35-40 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a surprising and significant ability to achieve approximately 95% or greater of the highly preferred capacity and an acceptable match to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0859] Examples 53-58: Capacity and Discharge Temperature of Refrigerants A1-A6 in Air Source Heat Pump Water Heaters

[0860] Performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf and CO2 in an air source heat pump water heater system under the following defined operating conditions.

[0861] Operating conditions:

[0862] Condensation temperature = 55°C

[0863] ●Water inlet temperature = 45℃, water outlet temperature = 50℃

[0864] Condenser subcooling = 5.0°C

[0865] ●Evaporation temperature = -5℃, corresponding ambient temperature = 10℃

[0866] ●Evaporator superheat=3.5℃

[0867] ●Compressor isentropic efficiency = 65%

[0868] Volumetric efficiency = 100%

[0869] ●Temperature rise in the suction line = 5°C

[0870] The results of this testing are reported in Tables E53-58 below, which include results for various existing refrigerants for comparison purposes.

[0871] Table E53-58

[0872]

[0873] As can be seen from the results identified in Tables E53-58 above, Applicants have discovered that each of Examples 53-58 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a surprising and significant ability to achieve approximately 100% or greater of the highly preferred capacity and an acceptable match to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0874] Examples 59-64: Capacity Matching of Several Condenser Temperatures in Mobile Air Conditioning Systems (Buses, Trains, Cars)

[0875] Performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf, and CO2 in a mobile air conditioning system under the operating conditions identified below.

[0876] Operating conditions:

[0877] Condensation temperature = 45°C to 75°C

[0878] Condenser subcooling = 5.0°C

[0879] ●Evaporation temperature = 4℃, corresponding indoor room temperature = 35℃

[0880] ●Evaporator superheat=5.0℃

[0881] ●Compressor isentropic efficiency = 65%

[0882] Volumetric efficiency = 100%

[0883] ●Temperature rise in the suction line = 0℃

[0884] The results of this testing are reported in Tables E59-64 below, which include results for various existing refrigerants for comparison purposes.

[0885] Table E59-64

[0886]

[0887] As can be seen from the results identified in Tables E59-64 above, Applicants have discovered that each of Examples 59-64 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to 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 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.

[0888] Examples 65-70: Capacity Matching of Several Condenser Temperatures in a Stationary Air Conditioning System

[0889] Performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf, and CO2 in a stationary air conditioning system under the operating conditions identified below.

[0890] Operating conditions:

[0891] Condensation temperature = 45°C to 65°C

[0892] Condenser subcooling = 5.0°C

[0893] ●Evaporation temperature = 10℃, corresponding indoor room temperature = 35℃

[0894] ●Evaporator superheat=5.0℃

[0895] ●Compressor isentropic efficiency = 72%

[0896] Volumetric efficiency = 100%

[0897] The results of this testing are reported in Tables E65-71 below, which include results for various existing refrigerants for comparison purposes.

[0898] Table E65-70

[0899]

[0900] As can be seen from the results identified in Tables E65-70 above, Applicants have discovered that each of Examples 65-70 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to 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 surprising and significant ability to achieve a highly preferred capacity of about 97% or greater relative to R448A, which is a highly desirable and unexpected result.

[0901] Examples 71-76: Capacity Matching of Several Condenser Temperatures in a Commercial Air Conditioning System

[0902] Several refrigerants including R32, R1132(E), R1234yf, and CO2 were performance tested in a commercial air conditioning system under the operating conditions identified below.

[0903] Operating conditions:

[0904] Condensation temperature = 45°C to 65°C

[0905] Condenser subcooling = 5.0°C

[0906] ●Evaporation temperature = 10℃, corresponding indoor room temperature = 35℃

[0907] ●Evaporator superheat=5.0℃

[0908] ●Compressor isentropic efficiency = 72%

[0909] Volumetric efficiency = 100%

[0910] The results of this testing are reported in Tables E71-76 below, which include results for various existing refrigerants for comparison purposes.

[0911] Table E71-76

[0912]

[0913] As can be seen from the results identified in Tables E71-76 above, Applicants have discovered that each of Examples 71-76 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a surprising and significant ability to achieve a highly preferred capacity of about 97% or greater relative to R448A, which is a highly desirable and unexpected result.

[0914] Examples 77-79: Capacity and Discharge of Refrigerants A1-A6 in Medium-Temperature Refrigeration Systems for Transport (Refrigerated Trucks, Containers) Temperature

[0915] Performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf and CO2 in an air source heat pump water heater system under the following defined operating conditions.

[0916] Operating conditions:

[0917] Condensation temperature = 45°C

[0918] Condensation temperature - ambient temperature = 10°C

[0919] Condenser subcooling = 0.0°C (system with receiver)

[0920] ●Evaporation temperature=-8℃

[0921] ●Evaporator superheat=5.5℃

[0922] ●Compressor isentropic efficiency = 65%

[0923] Volumetric efficiency = 100%

[0924] ●Temperature rise in the suction line = 15°C

[0925] The results of this testing are reported in Tables E77-79 below, which include results for various existing refrigerants for comparison purposes.

[0926] Table E77-79

[0927]

[0928] As can be seen from the results identified in Tables E77-82 above, Applicants have discovered that each of Examples 77-82 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a surprising and significant ability to achieve approximately 99% or greater of the highly preferred capacity and an acceptable match to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

[0929] Examples 83-89: Capacity and Discharge of Refrigerants A1-A6 in Low-Temperature Refrigeration Applications for Transport (Refrigerated Trucks, Containers) Temperature

[0930] Performance tests were conducted on several refrigerants including R32, R1132(E), R1234yf and CO2 in an air source heat pump water heater system under the following defined operating conditions.

[0931] Operating conditions:

[0932] Condensation temperature = 45°C

[0933] Condensation temperature - ambient temperature = 10°C

[0934] Condenser subcooling = 0.0°C (system with receiver)

[0935] ●Evaporation temperature = -35℃, corresponding box temperature = -25℃

[0936] ●Evaporator superheat=5.5℃

[0937] ●Compressor isentropic efficiency = 65%

[0938] Volumetric efficiency = 100%

[0939] ●Temperature rise in the suction line = 15°C

[0940] The results of this testing are reported in Tables E83-89 below, which include results for various existing refrigerants for comparison purposes.

[0941] Table E83-89

[0942]

[0943] As can be seen from the results identified in Tables E77-82 above, Applicants have discovered that each of Examples 77-82 (refrigerants A1-A6 of the present invention) is capable of achieving an LFL corresponding to the preferred LFL level (LFL of 0.25 or greater), as well as achieving a GWP of 150 or less, and each of these Examples exhibits a surprising and significant ability to achieve a highly preferred capacity of approximately 101% or greater and an acceptable match to the compressor discharge temperature of R448A, which is a highly desirable and unexpected result.

Claims

1. A refrigerant comprising the following four components in relative concentrations of at least about 95% by weight based on the total amount of all refrigerant components: a. greater than 15 wt% to 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); and d. Greater than 1.5 wt% to 3.5 wt% CO2.

2. A heat transfer composition comprising the refrigerant according to claim 1 and 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 depleting moiety, and a protectant.

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

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

6. The heat transfer composition according to 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 the following four components in the following relative concentrations of at least about 95% by weight based on the total amount of all refrigerant components: a. about 15% to about 22% by weight of R-32; b. about 61 wt % to about 71.5 wt % HFO-1234yf; c. about 4 wt % to about 14.5 wt % HFO-1132(E); and d. 1 to 4 wt% CO2, A prerequisite is that the refrigerant has a GWP of 150 or less and a lower flammability limit of 0.25 or more.

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

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

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 depleting moiety, and a protective agent.

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