Blended compositions containing difluoropropene

Abstract

The present disclosure relates to a composition comprising at least one of HFC-32 or HFO-1234ze-E, and HFO-1252zc. The present disclosure relates to a composition comprising at least one of HFC-32 or HFO-1234ze-E and These compositions are useful in methods of heating and cooling, air conditioning systems and heat pump systems, and methods of replacing existing refrigerants.

Description

Technical Field

[0001] This disclosure relates to compositions that can be used as refrigerants, and particularly for use in air conditioning systems and heat pump systems. The compositions disclosed herein can be used in methods of refrigeration and heating, methods of replacing refrigerants, and in air conditioning systems and heat pump systems. Background Technology

[0002] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) as they are phased out under the Montreal Protocol. Solutions for many applications involve the commercialization of HFC compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a, and HFC-125, have zero ozone depletion potential (ODP) and are therefore unaffected by the current Montreal Protocol phase-out provisions. In addition to ozone depletion, global warming is another environmental concern for many of these applications. According to the UN IPCC Fourth Assessment Report (AR4), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,430 and 3,500, respectively.

[0003] This regulatory environment is constantly evolving, and the nature of consideration is no longer limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also provide excellent performance in a wide range of applications and meet evolving regulatory standards.

[0004] This invention addresses certain problems associated with conventional refrigerants and provides refrigerant blends containing 1,1-difluoropropylene that meet the evolving regulatory environment. Summary of the Invention

[0005] To meet the rapidly changing regulatory environment, the inventors have identified a fluoroolefin compound that provides properties associated with existing refrigerants that would allow its use even with the standards of an evolving regulatory environment.

[0006] Some embodiments disclosed herein relate to fluoropropylene compositions comprising 1,1-difluoropropylene (also known as HFO-1252zc or R-1252zc). This document shows that the compound has advantageous properties for refrigerant applications.

[0007] In one embodiment, this document discloses a composition comprising at least one of HFO-1234ze-E (i.e., the E-isomer) or HFC-32 and HFO-1252zc.

[0008] According to any of the foregoing embodiments, this document also discloses a composition comprising at least one of about 17% to 80% by weight of HFO-1234ze-E or HFC-32 and about 20% to 83% by weight of HFO-1252zc.

[0009] According to any of the foregoing embodiments, this document also discloses a composition comprising at least one of about 19 wt% to 80 wt% of HFO-1234ze-E or HFC-32 and about 20 wt% to 81 wt% of HFO-1252zc.

[0010] According to any of the foregoing embodiments, this document also discloses compositions comprising about 20% to 83% by weight of HFO-1252zc and about 17% to 80% by weight of HFC-32.

[0011] According to any of the foregoing embodiments, this document also discloses compositions comprising about 20% to 81% by weight of HFO-1252zc and about 19% to 80% by weight of HFO-1234ze-E.

[0012] According to any of the foregoing embodiments, this document also discloses compositions comprising about 50% to 81% by weight of HFO-1252zc and about 19% to 50% by weight of HFO-1234ze-E.

[0013] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc and HFC-32, wherein: the concentration of HFO-1252zc in the composition is in the range of about X1 wt% to about Y1 wt% based on the weight of HFO-1252zc and HFC-32; the concentration of HFC-32 in the composition is in the range of about X2 wt% to about Y2 wt% based on the weight of HFO-1252zc and HFC-32; X1 is selected from 20, 50, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 and 70. Any number; Y1 is any number selected from 50, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, and 83; X2 is any number selected from 17, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, and 50; Y2 is any number selected from 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 50, and 80; and the sum of the weight percentages of HFO-1252zc and HFC-32 is 100.

[0014] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc and HFO-1234ze-E, wherein: the concentration of HFO-1252zc in the composition is in the range of about X1 wt% to about Y1 wt% based on the weight of HFO-1252zc and HFO-1234ze-E; the concentration of HFO-1234ze-E in the composition is in the range of about X3 wt% to about Y3 wt% based on the weight of HFO-1252zc and HFO-1234ze-E; X1 is selected from 1, 4, 7, 10, 13, 16, 19, 20, 22, 25, 28, 31, 34, 37, 40, 43, 46, 49 and Any number from 50; Y1 is any number selected from 4, 7, 10, 13, 16, 19, 20, 22, 25, 28, 31, 34, 37, 40, 43, 46, 49, 50, and 81; X3 is any number selected from 19, 50, 51, 54, 57, 60, 63, 66, 69, 72, 75, 78, 80, 81, 84, 87, 90, 93, and 96; Y3 is any number selected from 50, 51, 54, 57, 60, 63, 66, 69, 72, 75, 78, 80, 81, 84, 87, 90, 93, 96, and 99; and the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100.

[0015] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: the concentration of HFO-1252zc in the composition is in the range of about X1 wt% to about Y1 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; the concentration of HFC-32 in the composition is in the range of about X2 wt% to about Y2 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO- The concentration of 1234ze-E is in the range of approximately X3 wt% to approximately Y3 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; X1 is any number selected from 0.5, 5, 10, 14, 17, 21, 22, 24, 27, 28, 30, 32, 33, 35, 37, 39, 40, 42, 44, 45, 46, 47, 48, 49, 51, 52, 54, 55, 56, 57, 58, 59, 60, 62, and 63; Y1 is selected from 5, 10, 14, 17, 21, 22, 24, 27 X1 is any number selected from 28, 30, 32, 33, 35, 37, 39, 40, 42, 44, 45, 46, 47, 48, 49, 51, 52, 54, 55, 56, 57, 58, 59, 60, 62, 63, and 64; X2 is any number selected from 17, 18, 19, 20, 21, 23, 24, 28, 29, 32, 33, 34, 35, 36, 38, 41, 42, 43, 78, and 44; Y2 is any number selected from 17, 18, 19, 20, 21, 23, 24, 28, 29, 32, 33, 34, 35, 36, 38, 41, 42, 43, 78, and 44; X3 is any number selected from 4, 5, 14, 17, 19, 21, 22, 23, 24, 26, 27, 28, 3 0, 32, 34, 35, 36, 37, 38, 39, 42, 43, 44, 45, 47, 51, 54, 55, 55.72, and 56; Y3 is any number selected from 5, 14, 17, 19, 21, 22, 23, 24, 26, 27, 28, 30, 32, 34, 35, 36, 37, 38, 39, 42, 43, 44, 45, 47, 51, 54, 55, 55.72, 56, and 62; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0016] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc and HFC-32, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 70 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 30 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

[0017] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc and HFC-32, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 68 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 32 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

[0018] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc and HFC-32, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 65 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 35 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

[0019] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 33 wt% to about 45 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 18 wt% to about 20 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 19 wt% to about 47 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0020] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 0.05 wt% to about 24 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 34 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 37 wt% to about 62 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0021] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 51 wt% to about 63 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 23 wt% to about 38 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4 wt% to about 21 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0022] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 31 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 31 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0023] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 0.05 wt% to about 25 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 36 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 39 wt% to about 57 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0024] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 36 wt% to about 60 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 18 wt% to about 42 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0025] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc and HFO-1234ze-E, wherein: HFO-1252zc is present at a concentration of about 1 wt% to about 16 wt% based on the weight of HFO-1252zc and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 84 wt% to about 99 wt% based on the weight of HFO-1252zc and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100.

[0026] According to any of the foregoing embodiments, this document discloses a composition comprising HFO-1252zc, HFC-32, and HFO-1234ze-E, wherein: HFO-125zc is present at a concentration of about 19 wt% to about 23 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 18 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and HFO-1234ze-E is present at a concentration of about 57 wt% to about 61 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E.

[0027] According to any of the foregoing embodiments, this document discloses compositions further comprising at least one additional compound selected from the group consisting of: HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, and HFO-37. 4. n-Butane, propadiene, 2-Butene, cyclobutene, 2-Methylpropene, HCFO-1122, HFO-1132, HFO-1132a, HFO-1141, ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO-1243zf, HCFO-1251, HCO-1260zf, HFO-1261zf, propylene, HFO-1345, HFO-1252zc, HFO-1252yf, HFO-1252zf, HFO-1252ye and E / Zt-BuO-CF=CH-CH3.

[0028] According to any of the foregoing embodiments, this document discloses compositions further comprising at least one additional compound selected from the group consisting of HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252zc, HFO-1252yf, HFO-1252zf, and HFO-1252ye.

[0029] According to any of the foregoing embodiments, compositions are disclosed herein, wherein the compositions further comprise 0.1 ppm to 200 ppm of water by weight; about 10 ppm to about 0.35% by volume of oxygen by volume; and / or about 100 ppm to about 1.5% by volume of air or NAG.

[0030] According to any of the foregoing embodiments, compositions are disclosed herein, wherein the compositions comprise a stabilizer.

[0031] According to any of the foregoing embodiments, this document discloses compositions wherein the stabilizer is selected from the group consisting of: nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

[0032] According to any of the foregoing embodiments, this document discloses compositions wherein the stabilizer is selected from toluenetriazole, benzotriazole, tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

[0033] According to any of the foregoing embodiments, a composition is disclosed herein in which the stabilizer is present in an amount of about 0.001% by weight to 1.0% by weight based on the weight of the refrigerant.

[0034] According to any of the foregoing embodiments, this document discloses a composition, wherein the composition further comprises a lubricant, said lubricant being at least one selected from the group consisting of: polyalkylene glycols, polyol esters, poly-α-olefins, and polyethylene ethers.

[0035] According to any of the foregoing embodiments, this document discloses compositions wherein the lubricant is a polyol ester or a polyethylene ether.

[0036] According to any of the foregoing embodiments, a composition is disclosed herein, wherein the lubricant has at least one property selected from the group consisting of: greater than 10 at 20°C. 10 Volume resistivity in Ω-m; surface tension of about 0.02 N / m to 0.04 N / m at 20 °C; kinematic viscosity of about 20 cSt to about 500 cSt at 40 °C; breakdown voltage of at least 25 kV; and hydroxyl value of up to 0.1 mg KOH / g.

[0037] According to any of the foregoing embodiments, this document discloses compositions comprising at least one tracer.

[0038] According to any of the foregoing embodiments, this document discloses a composition wherein the tracer is present in an amount from about 1.0 ppm by weight to about 1000 ppm by weight.

[0039] According to any of the foregoing embodiments, this document discloses compositions wherein the at least one tracer is selected from the group consisting of: hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

[0040] According to any of the foregoing embodiments, compositions are disclosed herein, wherein the at least one tracer is selected from the group consisting of: HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-23 ... FC-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243zf, HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

[0041] According to any of the foregoing embodiments, this document discloses compositions that are free of or substantially free of Group A fluorinated substances, and wherein the degradation products of the compositions are free of or substantially free of Group A fluorinated substances.

[0042] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 70 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 30 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

[0043] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 68 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 32 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

[0044] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 65 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 35 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

[0045] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 33 wt% to about 45 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 18 wt% to about 20 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 19 wt% to about 47 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the GWP of the composition is <160.

[0046] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 0.05 wt% to about 24 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 34 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 37 wt% to about 62 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the composition has a flammability rating of 2L (when measured according to ANSI / ASHRAE Standard 34).

[0047] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 51 wt% to about 63 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 23 wt% to about 38 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4 wt% to about 21 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

[0048] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 31 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 31 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

[0049] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 0.05 wt% to about 25 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 36 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 39 wt% to about 57 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the composition has a flammability rating of 2L (when measured according to ANSI / ASHRAE Standard 34).

[0050] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 36 wt% to about 60 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 18 wt% to about 42 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the GWP of the composition is <160.

[0051] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 1 wt% to about 16 wt% based on the weight of HFO-1252zc and HFO-1234ze-E, and HFO-1234ze-E is present at a concentration of about 84 wt% to about 99 wt% based on the weight of HFO-1252zc and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100; and the composition has a flammability rating of 2L (when measured according to ANSI / ASHRAE Standard 34).

[0052] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-125zc is present at a concentration of about 19% by weight to about 23% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234zc; HFC-32 is present at a concentration of about 18% by weight to about 22% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 57% by weight to about 61% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

[0053] According to any of the foregoing embodiments, this document discloses a composition wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 70 wt% based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 30 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32; and the sum of the weight percentages of HFO-1252zc and HFC-32 is 100; and it also shows a heat pump operating in a cooling mode.

[0054] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 0.5 wt% to about 63 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 18 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4 wt% to about 62 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

[0055] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 0.5 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 57 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

[0056] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 18 wt% to about 20 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 6 wt% to about 21 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59 wt% to about 76 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252ze, HFC-32 and HFO-1234ze-E is 100; and the composition exhibits a GWP < 160 and a flammability rating of 2L.

[0057] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 20% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 21% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32 and HFO-1234ze-E is 100.

[0058] According to any of the foregoing embodiments, a composition is disclosed herein, wherein: HFO-1252zc is present at a concentration of about 18 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 19 wt% to about 23 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 57 wt% to about 61 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32 and HFO-1234ze-E is 100.

[0059] According to any of the foregoing embodiments, this document discloses a method for cooling comprising evaporating a composition near a subject to be cooled and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

[0060] According to any of the foregoing embodiments, this document discloses a composition and a method for heating, which includes evaporating the composition and then condensing the composition near a body to be heated, wherein the heating is provided by a heat pump.

[0061] According to any of the foregoing embodiments, this document discloses a system for cooling or heating, comprising the composition of any of the foregoing embodiments. In another embodiment, these systems include an evaporator, a compressor, a condenser, and an expander, each operatively connected to perform a vapor compression cycle. In yet another embodiment, the system may be a two-stage loop system.

[0062] According to any of the foregoing embodiments, this document discloses a method for replacing R-454C or propane in an air conditioning system or heat pump system, comprising providing the system with a composition of any of the foregoing embodiments to replace R-454C or propane.

[0063] According to any of the foregoing embodiments, this document discloses the use of the composition of any of the foregoing embodiments as a refrigerant in an air conditioning system or a heat pump system. Detailed Implementation

[0064] This invention relates to compositions containing at least one of difluoromethane (HFC-32) or E-1,3,3,3-tetrafluoropropylene (HFO-1234ze-E) and 1,1-difluoropropylene (HFO-1252zc). These compositions may be candidates for alternative refrigerants (such as R-454C, R-410A, or propane) that have low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP).

[0065] The composition comprises at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc. These compositions provide refrigerant blends with low global warming potential, improved slip compared to other proposed refrigerant blends, improved coefficient of performance compared to existing refrigerants and other proposed alternatives, and compliance with evolving regulatory environments.

[0066] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and returns during the cycle used to transfer heat.

[0067] A heat transfer system is a system (or device) used to produce a heating or cooling effect in a specific space. Heat transfer systems can be mobile or stationary.

[0068] Examples of heat transfer systems include any type of refrigeration and air conditioning system, including but not limited to stationary heat transfer systems, air conditioners, refrigerators, chillers, heat pumps, flooded evaporator heat pumps, direct expansion heat pumps, coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, portable refrigeration units, portable heat transfer systems, portable heat pumps (including heat pumps for comfort cooling and heating of automotive cabins), portable air conditioning units (for cooling passenger compartments in automobiles), dehumidifiers, and combinations thereof. The focus of this application is air conditioning systems and heat pump systems.

[0069] Volumetric capacity is the heat absorbed or discharged divided by the theoretical compressor displacement. The heat removed or absorbed is the refrigerant mass flow rate multiplied by the enthalpy difference of the heat exchanger. The theoretical compressor displacement is the refrigerant mass flow rate divided by the density of the gas entering the compressor (i.e., the compressor suction density). More simply, volumetric capacity is the density at the compressor suction inlet (e.g., kg / m³). 3 Multiply by the enthalpy difference of the heat exchanger. A higher volumetric capacity allows for the use of a smaller compressor under the same heat load. Here, cooling capacity refers to the volumetric capacity in cooling mode, while heating capacity refers to the volumetric capacity in heating mode.

[0070] The coefficient of performance (COP) is the heat absorbed or released divided by the energy input required to operate the cycle (approximately the compressor power). COP is specific to the operating mode of a heat pump, so COP is used for heating or COP is used for cooling. COP is directly related to the energy efficiency ratio (EER).

[0071] Subcooling refers to the temperature of a liquid dropping below its saturation point at a given pressure. The saturation point of a liquid is the temperature at which vapor completely condenses into a liquid. By cooling the liquid below its saturation temperature (or bubble point), the net cooling effect can be increased. Subcooling thus improves the cooling capacity and energy efficiency of a system. Subcooling is the amount of cooling to below the saturation temperature (in degrees Celsius).

[0072] Superheating refers to the temperature of vapor rising above its saturation point at a given pressure. The vapor saturation point is the temperature at which a liquid completely evaporates into vapor. At a given pressure, superheating continues to heat the vapor to a higher temperature. By heating the vapor above its saturation temperature (or dew point), the net refrigeration effect can be increased. Therefore, when superheating occurs in the evaporator, the system's refrigeration capacity and energy efficiency can be improved. Superheating in the suction line does not increase the net refrigeration effect and reduces efficiency and capacity. Superheat is the amount of heat generated above the saturation temperature (in degrees Celsius).

[0073] Temperature glide (sometimes simply called "glide") is the absolute value of the difference between the onset and termination temperatures of a refrigerant phase change process within the condenser of a refrigerant system, excluding any subcooling or superheating. For the evaporator, glide is the temperature difference between the dew point and the evaporator inlet. Glide can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to temperature glide in air conditioning or heat pump systems, it is common to provide an average temperature glide, which is the average of the temperature glide in the evaporator and the temperature glide in the condenser. Glide applies to blended refrigerants, i.e., refrigerants composed of at least two components.

[0074] Net cooling efficiency is the amount of heat absorbed by each kilogram of refrigerant in the evaporator to produce usable cooling.

[0075] Mass flow rate is the amount (in kilograms) of refrigerant that circulates through a refrigeration system, heat pump system, or air conditioning system within a given time period.

[0076] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition used in any heat transfer system) that provides hydrodynamic lubrication to the compressor to help prevent parts from seizing.

[0077] Global warming potential (GWP) is an indicator used to estimate the relative contribution of atmospheric emissions of a specific greenhouse gas to global warming compared to the emission of one kilogram of carbon dioxide. GWP can be calculated over different time periods, showing the impact on the atmospheric lifetime of a given gas. GWP over a 100-year time period is typically a reference value. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. In this paper, the GWP values ​​are those reported in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4). The GWP estimate for 1252 zc is 1.

[0078] Ozone depletion potential (ODP) refers to the amount of ozone loss caused by a substance. ODP is the ratio of the effect of a chemical on ozone to the effect of a similar mass of CFC-11 (trichlorofluoromethane). Therefore, the ODP of CFC-11 is defined as 1.0. Other CFCs and HCFCs have ODPs ranging from 0.01 to 1.0. The hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFOs) described herein have zero ODP because they do not contain chlorine, bromine, or iodine compounds known to cause ozone decomposition and depletion. HFO-1252zc has zero ozone depletion potential.

[0079] 1,1-Difluoropropylene (HFO-1252zc or R-1252zc) can be prepared by hydrogenating 3,3,3-trifluoropropylene (HFO-1243zf) on a carbon-supported palladium catalyst to form 1,1,1-trifluoropropane (HFC-263fb), followed by dehydrofluorination of HFC-263fb on a chromium catalyst or by pyrolysis at high temperature (see Agent's File No. FL2084 filed with this document and incorporated herein by reference).

[0080] E-1,3,3,3-Tetrafluoropropylene (HFO-1234ze-E or R-1234ze-E) is commercially available from Honeywell (Charlotte, North Carolina, USA). Difluoromethane (HFC-32 or R-32) is commercially available from various sources worldwide.

[0081] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus.

[0082] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those stated, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements set forth in that clause; other elements as a whole are not excluded from the claims.

[0083] The transitional phrase "consistently composed of..." is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that the additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel characteristics of the invention protected by the claims. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...". Typically, the components of a refrigerant mixture and the refrigerant mixture itself may contain trace amounts (e.g., less than about 0.5% by weight in total) of impurities and / or byproducts (e.g., refrigerant components from the preparation of the refrigerant components or refrigerant components reused from other systems) that do not substantially affect the novel and essential characteristics of the refrigerant mixture.

[0084] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0085] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. While methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety unless specific paragraphs are cited. In case of any conflict, this specification and its included definitions shall prevail. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

[0086] Refrigerant Composition

[0087] In one embodiment, the composition comprises at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or is composed of or substantially composed of them. These compositions provide low global warming potential (GWP), improved environmental fate characteristics, and improved energy efficiency (COP). The compositions claimed in this invention, comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or are composed of or substantially composed of them, also provide flammability classified as ASHRAE Category 2.

[0088] In another embodiment, the composition comprises, consists of, or is substantially composed of at least one of HFO-1234ze-E or HFC-32, at about 17% to 80% by weight, and about 20% to 83% by weight, HFO-1252zc.

[0089] In another embodiment, the composition comprises, consists of, or is substantially composed of at least one of HFO-1234ze-E or HFC-32, at about 19% to 80% by weight, and about 20% to 81% by weight, HFO-1252zc.

[0090] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 20% to 83% by weight of HFO-1252zc and about 17% to 80% by weight of HFC-32.

[0091] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 20% to 50% by weight of HFO-1252zc and about 50% to 80% by weight of HFC-32. These compositions provide lower average slip and higher capacity. Compared to R-410A and R-454C, these compositions also provide improved COP.

[0092] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 50% to 83% by weight of HFO-1252zc and about 17% to 50% by weight of HFC-32. These compositions provide lower compressor discharge temperatures, have a capacity more similar to R-454C than both R-410A and R-454C, and still improve COP.

[0093] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 20% to 81% by weight of HFO-1252zc and about 19% to 80% by weight of HFO-1234ze-E.

[0094] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 50% to 81% by weight of HFO-1252zc and about 19% to 50% by weight of HFO-1234ze-E. These compositions provide higher capacity. Additionally, these compositions provide improved COP compared to R-410A and R-454C.

[0095] In another embodiment, the composition comprises, consists of, or substantially comprises: about 56 wt% to about 70 wt% of HFO-1252zc based on HFO-1252zc and HFC-32; and about 30 wt% to about 44 wt% of HFC-32 based on HFO-1252zc and HFC-32. When these compositions are used in a heat pump in cooling (or heating) mode, the heat pump exhibits a cooling (or heating) capacity of at least 90% of the volumetric cooling capacity of R-454C.

[0096] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 56 wt% to about 68 wt% of HFO-1252zc based on HFO-1252zc and HFC-32; and about 32 wt% to about 44 wt% of HFC-32 based on HFO-1252zc and HFC-32. When these compositions are used in a heat pump in cooling (or heating) mode, the heat pump exhibits a slip of <8K.

[0097] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 56 wt% to about 65 wt% of HFO-1252zc based on HFO-1252zc and HFC-32; and about 35 wt% to about 44 wt% of HFC-32 based on HFO-1252zc and HFC-32. When these compositions are used in a heat pump in cooling mode, the heat pump exhibits a slip of <8K.

[0098] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 33% to about 45% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 18% to about 20% by weight of HFC-32, based on HFO-1252zc, HFC-32, and HFO-1234ze-E; about 19% to about 47% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. This composition exhibits a GWP < 160.

[0099] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 0.05 wt% to about 24 wt% of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 34 wt% to about 43.78 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 37 wt% to about 62 wt% of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. This composition exhibits a flammability rating of 2L (when measured according to ANSI / ASHRAE Standard 34).

[0100] In another embodiment, the composition comprises, consists of, or substantially comprises: about 51 wt% to about 63 wt% of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 23 wt% to about 38 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 4 wt% to about 21 wt% of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. When this composition is used in a heat pump in cooling mode, the heat pump exhibits a slip of <8K.

[0101] In another embodiment, the composition comprises, consists of, or substantially comprises: about 31 wt% to about 64 wt% of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 17 wt% to about 43 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 1 wt% to about 31 wt% of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. When this composition is used in a heat pump in heating mode, the heat pump exhibits a slip of <8K.

[0102] In another embodiment, the composition comprises, consists of, or substantially consists of: about 0.05 wt% to about 25 wt% of HFO-1252zc present at a concentration based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 36 wt% to about 43.78 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 39 wt% to about 57 wt% of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. This composition exhibits a flammability rating of 2L (when measured according to ANSI / ASHRAE Standard 34).

[0103] In another embodiment, the composition comprises, consists of, or substantially consists of: about 36 wt% to about 60 wt% of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 17 wt% to about 22 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 18 wt% to about 42 wt% of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. This composition exhibits a GWP < 160.

[0104] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 1% to about 16% by weight of HFO-1252zc based on the weight of HFO-1252zc and HFO-1234ze-E; about 84% to about 99% by weight of HFO-1234ze-E based on the weight of HFO-1252zc and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100. The flammability rating of this composition is 2L (when measured according to ANSI / ASHRAE Standard 34).

[0105] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 19% to about 23% by weight of HFO-125zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234zc; about 18% to about 22% by weight of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 57% to about 61% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100.

[0106] In another embodiment, the composition comprises, consists of, or substantially consists of: about 0.5 wt% to about 63 wt% of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 18 wt% to about 43.78 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 4 wt% to about 62 wt% of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. When this composition is used in a heat pump in cooling mode, the heat pump exhibits a cooling capacity that differs from that of R-454C by less than 20%.

[0107] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 0.5 wt% to about 64 wt% of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 17 wt% to about 43.78 wt% of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 1 wt% to about 57 wt% of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100. When this composition is used in a heat pump in heating mode, the heat pump exhibits a heating capacity that differs from that of R-454C by less than 20%.

[0108] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 18% to about 20% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 6% to about 21% by weight of HFC-32 based on HFO-1252zc, HFC-32, and HFO-1234ze-E; about 59% to about 76% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100. This composition exhibits a GWP < 160 and a flammability rating of 2L.

[0109] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 20% by weight of HFO-1252zc based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 21% by weight of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 59% by weight of HFO-1234ze-E based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100.

[0110] In another embodiment, the composition comprises, consists of, or is substantially composed of: about 18% to about 22% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 19% to about 23% by weight of HFC-32 based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; about 57% to about 61% by weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100.

[0111] Flammability is a term used to describe the ability of a composition to ignite and / or spread a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit (“LFL”) is the minimum concentration of a heat transfer composition in air that, under the test conditions specified in ASTM E681, is capable of spreading a flame through a homogeneous mixture of the composition and air. The upper flammability limit (“UFL”) is the maximum concentration of a heat transfer composition in air that, under the same test conditions, is capable of spreading a flame through a homogeneous mixture of the composition and air.

[0112] In order for a refrigerant to be classified as low flammability (2L class) by ANSI / ASHRAE, it must: 1) exhibit flame spread when tested at 140℉ (60℃) and 14.7psia (101.3kPa); 2) have a flame density of >0.0062 lb / ft. 3 (0.10kg / m 3 1) LFL; 2) Heat of combustion <8169 Btu / lb (19,000 kJ / kg); 3) Maximum combustion rate ≤3.9 in. / s (10 cm / s) when tested in dry air at 73.4℉ (23.0℃) and 14.7 psia (101.3 kPa).

[0113] For a refrigerant to be classified as flammable (Class 2) by ANSI / ASHRAE, it must: 1) exhibit flame spread when tested at 140℉ (60℃) and 14.7psia (101.3kPa); 2) have a flame density of >0.0062 lb / ft. 3 (0.10kg / m 3 ) LFL; 3) has a heat of combustion of <8169 Btu / lb (19,000 kJ / kg).

[0114] ASHRAE Standard 34 provides a method for calculating the heat of combustion of refrigerant blends using an equilibrium stoichiometric equation based on the complete combustion of one mole of refrigerant with enough oxygen for a stoichiometric reaction.

[0115] HFO-1252zc can be combined with HFC-32 or HFO-1234ze-E to provide estimated flammability ratings of Class 2 or 2L as defined by ANSI / ASHRAE Standard 34 and ISO 817. Class 2 and 2L flammability ratings may be controllable in air conditioning and heat pump applications. Specific applications may have different flammability requirements.

[0116] Compositions containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially of them, may also contain at least one additional compound from the list in Table 1.

[0117]

[0118] In another embodiment, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting of or substantially consisting of them, may further comprise at least one additional compound selected from HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFO-263fb, HFO-1252zc, HFO-1252yf, HFO-1252zf, and HFO-1252ye. In another embodiment, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting of or substantially consisting of them, may further comprise at least one additional compound comprising HFO-1234yf. In another embodiment, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting thereof or substantially thereof, may further comprise at least one additional compound comprising HFO-1243zf. In another embodiment, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting thereof or substantially thereof, may further comprise at least one additional compound comprising HFO-263fb.

[0119] Some of the compounds identified in Table 1 that are present in the compositions of the present invention can exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers, or any combination or mixture thereof. For example, 1,2-difluoroethylene (HFO-1132) is intended to represent any combination or mixture of cis-isomers (Z), trans-isomers (E), or any ratio of two isomers. Single or multiple isomers of the same compound can be used in any proportion.

[0120] The amount of additional compounds present in any of the aforementioned refrigerant compositions may be greater than 0 ppm and less than 5,000 ppm, and in particular may be in the range of zero to about 1,000 ppm, about 5 ppm to about 500 ppm and about 1 ppm to about 100 ppm.

[0121] In one embodiment, the amount of the additional compound present in any of the aforementioned refrigerant compositions may be greater than 0% by weight and less than 1% by weight, preferably less than 0.5% by weight, or more preferably less than 0.1% by weight of the refrigerant composition.

[0122] Compositions containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or composed of or substantially composed of them, will behave more consistently and stably in the presence of only a small amount of water. Therefore, the composition may also contain less than 100 ppm (by weight) of water, preferably less than 20 ppm (by weight), and even more preferably less than 10 ppm (by weight).

[0123] Furthermore, compositions containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or composed of or substantially composed of them, will behave more consistently and stably in the presence of only trace amounts of oxygen or air. Therefore, the compositions claimed in this invention may also contain less than about 5% by volume of non-adsorbable gas (NAG), preferably less than 3% by volume, and more preferably less than 1.5% by volume. In addition, due to the presence of air or NAG, the compositions claimed in this invention will contain less than 1% by volume of oxygen, preferably less than 0.5% by volume, and more preferably less than 0.3% by volume.

[0124] In another embodiment, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially comprising them, may contain a stabilizer. This stabilizer compound is intended to be present in small amounts and to prevent decomposition due to the presence of water, air, NAG, or oxygen in the system during use or storage. Due to the presence of double bonds, HFO-type refrigerants may experience thermal instability and decomposition under extreme use, handling, or storage conditions. Therefore, the addition of a stabilizer to HFO-type refrigerants can be advantageous. Stabilizers may particularly include nitromethane, ascorbic acid, terephthalic acid, azoles such as toluenetriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (possibly fluorinated or perfluorinated alkyl epoxides or alkenyl or aromatic epoxides) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, cyclic monoterpenes, terpenes such as d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene or β-pinene, phosphites, phosphates, phosphonates, thiols and lactones. Examples of suitable stabilizers are disclosed in WO2019213004, WO2020222864 and WO2020222865; the disclosure of which is incorporated herein by reference.

[0125] If the composition does contain a stabilizer, it may contain any amount of any of the stabilizers listed above, from 0.001 wt% to 1 wt%, preferably from about 0.001 wt% to about 0.5 wt%, more preferably from about 0.001 wt% to about 0.3 wt%.

[0126] In some embodiments, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially comprising them, may contain a tracer compound or tracer. The tracer may include two or more tracer compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million parts (ppm) to about 1000 ppm by weight based on the total composition. In other embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0127] The tracer may be present in a predetermined amount in a composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially comprising them, to allow detection of any dilution, contamination, or other alteration of the composition. The presence of certain compounds in the composition can indicate the method or process by which one of the components was produced. The tracer may also be added to the composition in a specific amount to identify the source of the composition. In this way, the detection of patent infringement can be achieved. The tracer may be a refrigerant compound, but present in the composition at a level unlikely to affect the performance of the refrigerant component of the composition.

[0128] The tracer compound can be a hydrofluorocarbon, a hydrofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochlorofluoroolefin, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochloroolefin, a chlorofluorocarbon, a chlorofluoroolefin, a hydrocarbon, a perfluorocarbon, a perfluoroolefin, or a combination thereof. Examples of tracer compounds include, but are not limited to, HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-125 (pentafluoroethane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), and HFC-245fa (1,1,1,3,3-pentafluoropropane). Propane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2-fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (1,1,1-trifluoro-2-methylpropane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane) CFC-12 (dichlorodifluoromethane), CFC-11 (trichlorofluoromethane), CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-114a (1,1,-dichloro-1,2,2,2-tetrafluoroethane), HCFC-22 (chlorodifluoromethane), HCFC-123 (1,1-dichloro-2,2,2-trifluoroethane), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), HCFC-124a (1-chloro-1,1,2,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142b (1-chloro-1,1... -difluoroethane), HCFC-151a (1-chloro-1-fluoroethane), HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane), HCC-40 (chloromethane), HFO-1141 (ethylene fluoride), HCFO-1130 (1,2-dichloroethylene), HCFO-1130a (1,1-dichloroethylene), HCFO-1131 (1-chloro-2-fluoroethane), HCFO-1122 (2-chloro-1,1-difluoroethylene), HFO-1123 (1,1,2-trifluoroethylene), HFO-1234ye (1,2,3,3-tetrafluoropropylene), HFO-1243zf (3,3,3-Trifluoropropene), HFO-1225ye (1,2,3,3,3-pentafluoropropene), HFO-1225zc (1,1,3,3,3-pentafluoropropene), PFC-116 (hexafluoroethane), PFC-C216 (hexafluorocyclopropane), PFC-218 (octafluoropropane), PFC-C318 (octafluorocyclobutane), PFC-1216 (hexafluoroethane), PFC-31-10mc (1,1,1,2,2,3,3,4,4,4-decafluorobutane), PFC-31-10my (1,1,1,2,3,3,3-heptafluoro-2-trifluoromethylpropane), and combinations thereof.

[0129] In another embodiment of this disclosure, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially comprising them, further comprises at least one lubricant. The lubricant may be selected from polyol esters, polyvinyl ethers, and polyalkylene glycols. The lubricant may also include those commonly referred to as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include alkanes (i.e., saturated hydrocarbons with straight and branched carbon chains), cycloalkanes (i.e., saturated hydrocarbons with cyclic or cyclic structures, which may be alkanes), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention also include those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryl compounds (i.e., straight and branched alkylalkylbenzenes), synthetic alkanes and cycloalkanes, organosilicones, and polyalphaolefins. A representative conventional lubricant of this invention is commercially available BVM 100 N (an alkane mineral oil sold by BVAOils), which is available from Crompton Co. under the trademark Suniso. ® 3GS and Suniso ® 5GS commercially available cycloalkane mineral oil, can be branded as Sontex ® 372LT is a cycloalkanes mineral oil purchased from Pennzoil, and can be marketed under the trademark Calumet. ® RO-30 is a cycloalkanes mineral oil obtained from Calumet Lubricants, and can be marketed under the brand name Zerol. ® 75. Zerol ® 150 and Zerol ® 500 linear alkylbenzenes obtained commercially from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0130] The lubricants of this invention also include those designed for hydrofluorocarbon refrigerants and miscible with the refrigerants of this invention under the operating conditions of compression refrigeration and air conditioning equipment. Lubricants include, but are not limited to, polyol esters (POEs) (such as Castrol). ® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) (such as RL-488A from Dow (Dow Chemical, Midland, Mich.)) and polyvinyl ether (PVE) (such as PVE-FVC68D).

[0131] In one particular embodiment, a composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially comprising thereto, is combined with a PAG lubricant or a PVE lubricant or a POE lubricant for use in an air conditioning system or a heat pump system.

[0132] In a composition containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially thereof, the lubricant may be present in an amount of less than 80% by weight of the total composition. The lubricant may also be present in an amount of less than 60% by weight of the total composition. In other embodiments, the amount of lubricant may be between about 0.1% by weight and 50% by weight of the total composition. The lubricant may also be between about 0.1% by weight and 20% by weight of the total composition. The lubricant may also be between about 0.1% by weight and 5% by weight of the total composition.

[0133] In another aspect of the invention, the composition of the invention comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting of or substantially consisting of them, is used to introduce a lubricant and, alternatively, other additives (such as a) an acid remover, b) a performance enhancer, and c) a flame retardant) into an air conditioning system or a heat pump system. In a preferred embodiment, the composition of the invention comprises an acid remover.

[0134] Examples of acid scavengers that may be included in the compositions of the present invention include, but are not limited to, the stabilizers and / or epoxide components of stabilizers disclosed in U.S. Patent No. 8,535,555 and the acid scavengers disclosed in International Application Publication No. WO 2020 / 222864, the disclosures of which are incorporated herein by reference in their entirety.

[0135] In some embodiments, the acid scavenger may comprise one or more epoxides, one or more amines, and / or one or more hindered amines, such as, for example, but not limited to, epoxide.

[0136] Acid scavengers (e.g., activated aromatic compounds, siloxanes, or both) may be present at any concentration that results in a relatively low total acid value, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof.

[0137] Preferably, the acid scavenger is present at a concentration greater than about 0.0050% by weight, more preferably greater than about 0.05% by weight, and even more preferably greater than about 0.1% by weight (e.g., greater than about 0.5% by weight) based on the total weight of the refrigerant composition. Based on the total weight of the refrigerant composition, the acid scavenger is preferably present at a concentration less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably greater than about 2% by weight (e.g., less than about 1.8% by weight).

[0138] Preferred additives include those described in U.S. Patents 5,152,926 and 4,755,316, which are incorporated herein by reference in the form of =. In particular, preferred extreme pressure additives comprise mixtures of: (A) toluenetriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., Antara LP-700), or (ii) a phosphorohydrin (e.g., ZELEC 3337), or (iii) zinc dialkyl dithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-thiadiazole derivative (e.g., Curvan 826) or mixtures thereof. Additional examples of additives that may be used are given in U.S. Patent No. 5,976,399 (Schnur, 5:12-6:51, which is hereby incorporated by reference).

[0139] Acid value was measured in mg KOH / g according to ASTM D664-01. Total halide ion concentration, fluoride ion concentration, and total organic acid concentration were measured by ion chromatography. The chemical stability of the refrigerant system was measured according to ASHRAE 97:2007 (RA2017), "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems." The viscosity of the lubricant was tested at 40°C according to ASTM D-7042.

[0140] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) proposed the use of alkylsilanes as stabilizers in refrigerant compositions containing fluoroolefins. Phosphates, phosphites, epoxides, and phenolic additives have also been used in certain refrigerant compositions. These are described, for example, by Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Publication 2007 / 0290164) and Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as U.S. Publication 2006 / 0116310). All of the foregoing applications are expressly incorporated herein by reference.

[0141] Preferred flame retardants include those described and incorporated herein by reference in patent application CA 2557873 A1, entitled "Refrigerant compositions containing fluorine-substituted olefins", and fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and / or Krytox. ® Lubricant.

[0142] In one embodiment, as used herein, “Group A fluorinated substance” includes any substance that meets the following criteria: (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto); as well as (ii) Complies with the persistence standards in soil / sediments and water as specified in Annex XIII (Section 1.1.1) of the EU REACH Regulation. https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html Visited on May 2, 2023 This standard is referenced in Annex XV Restriction Report dated March 22, 2023, and its disclosure is incorporated herein by reference. https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414- 8823-b49b9fd43aea, accessed May 2, 2023 In one implementation, Group A fluorinated substances include, but are not limited to, trifluoroacetic acid (TFA).

[0143] In another implementation, as used herein, “Group A fluorinated substances” include those with a Henry’s Law constant ≤250 Pa*m 3 / mol andAny substance containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I bonded to it). In one embodiment, Group A fluorinated substances include, but are not limited to, TFA.

[0144] Therefore, according to some embodiments, the compositions of the present invention comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting of or substantially consisting of them, are free from or substantially free from Group A fluorinated substances, such as TFA. In one embodiment, as used herein, the phrase “free from” regarding the presence of Group A fluorinated substances in the compositions of the present invention means that the amount of such substances in the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing a gaseous or liquid sample), and / or ion chromatography (by analyzing a water sample after bubbling a hot fluid through water). Such methods are well known to those skilled in the art. In some embodiments, as used herein, the phrase "substantially free" regarding the presence of Group A fluorinated substances in the compositions of the invention means, when measured by gas chromatography (GC), such as gas chromatography (GC) with a flame ionization or electron capture detector, or GC coupled with a mass detector (GC / MS method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high performance liquid chromatography (HPLC) or high performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0 wt% and ≤5 wt%, or >0 wt% and ≤4 wt%, or >0 wt% and ≤3 wt%, or >0 wt% and ≤2 wt%, or >0 wt% and ≤1 wt%, and all values ​​and ranges therebetween. TFA analytical standards are available for gas chromatography or ion chromatography and are available from, for example, Sigma Aldrich. In some embodiments, the stabilized composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting of or substantially consisting of them, is free of Group A fluorinated substances, meaning that these substances are not detectable by the methods and techniques described herein.

[0145] Furthermore, in some embodiments, the degradation products of such compositions of the present invention, comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or consisting of or substantially consisting of them, are free from or substantially free from Group A fluorinated substances, such as TFA. In one embodiment, as used herein, the phrase “free from” in relation to the formation of Group A fluorinated substances from the compositions of the present invention means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. In one embodiment, as used herein, the phrase “substantially free” regarding the formation of Group A fluorides by the compositions of the present invention means, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is >0% and ≤5%, or >0% and ≤4%, or >0% and ≤3%, or >0% and ≤2%, or >0% and ≤1%, and all values ​​and ranges therebetween. In some embodiments, the degradation products of such compositions of the present invention, comprising, consisting of, or substantially consisting of stabilizing compositions, are free of Group A fluorides (such as TFA), these stabilizing compositions comprising, consisting of, or substantially consisting of HFO-1252zc, meaning that these substances are undetectable by the methods and techniques described herein.

[0146] Methods and Systems

[0147] Compositions containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially composed of them, can be used in many methods and systems for providing air conditioning and heating.

[0148] In one embodiment, a cooling method is provided, comprising evaporating a composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, or substantially comprising thereto, near a body to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

[0149] In one embodiment, the air conditioning system can be a residential, commercial, or industrial air conditioning system. These can include, but are not limited to, window-type, ducted, ductless, enclosed terminals, and those located outside the building but connected to it, such as rooftop systems. The method of the present invention may be particularly useful in regions with high ambient temperatures due to the high critical temperature of blends containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc.

[0150] In another embodiment, a heating method is provided, comprising evaporating a composition containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, and then condensing the composition near the body to be heated, wherein the heating is provided by a heat pump.

[0151] In one embodiment, the heat pump is a residential, light commercial, or industrial heat pump system. These heat pumps may include, but are not limited to, residential heat pumps providing comfortable air conditioning and heating, hot water heat pumps for heating air (via a secondary loop) or for heating water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high-temperature heat pumps. Due to the high critical temperature of blends containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, it is possible to heat water to temperatures higher than propane or R-454C.

[0152] In another embodiment, the method for refrigeration is particularly useful in areas where the ambient temperature may exceed 35°C.

[0153] In geographical areas with high ambient temperatures, where air conditioning becomes essential, refrigerant compositions with high critical temperatures and high thermal stability are desirable. Currently available hydrofluorocarbon (HFC) refrigerants (such as R-410A, R-407C, or R-32) have relatively low critical temperatures. Therefore, these refrigerants perform poorly in extremely hot environments. During operation at high ambient temperatures, the energy efficiency of the refrigerant typically decreases as the condensing temperature approaches the refrigerant's critical temperature. In hot climates, R-22 remains the refrigerant of choice for many air conditioning and refrigeration applications because it is non-flammable and has a higher critical temperature, thus providing higher cooling capacity and higher energy efficiency in hot climates compared to R-410A or R-32. However, R-22 is an ozone-depleting substance (ODS) in the Montreal Protocol on ozone depletion. Therefore, R-22 has been mandated and legislated for phase-out in the manufacture and use of air conditioning and refrigeration. There is interest in finding refrigerants with the lowest possible direct GWP and that perform well in hot (or high ambient) temperature regions.

[0154] In methods of refrigeration, the subject to be cooled can be defined as any space, location, object, or subject for which cooling is desired. Examples include open or enclosed spaces requiring cooling, such as residences, such as apartments or apartment buildings, university dormitories, townhouses or other attached houses, or single-family homes; or the subject to be cooled can be any other building, such as office buildings, supermarkets, college or university classrooms, or administrative buildings.

[0155] In another embodiment, a method for generating air conditioning at high ambient temperatures is provided. The method comprises evaporating a composition containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, substantially composed of or composed of these, and then condensing said composition. This method is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0156] In another embodiment, a method is provided for replacing HCFC-22 in a high-ambient-temperature air conditioning device, comprising supplying the device with a composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, substantially comprising or comprising thereof. This method of replacing HCFC-22 is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0157] Similarly, in some industrial air conditioning applications, heat must be released in high ambient temperatures. HCFC-124 has been used as a working fluid in such applications. HCFC-124 is also controlled as an ozone-depleting substance under the Montreal Protocol, and a more environmentally friendly and sustainable alternative is needed. Therefore, a method for replacing HCFC-124 in industrial air conditioning equipment is provided, comprising supplying said equipment with a composition containing at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, substantially composed of or composed of these. This method of replacing HCFC-124 is particularly useful in areas where ambient temperatures may exceed 35°C or higher.

[0158] In another embodiment, the cooling method and the method for replacing HCFC-22 or HCFC-124 can be used in systems operating at ambient temperatures of 40°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 45°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 50°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 55°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures of 60°C or higher. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 35°C and 50°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 35°C and 60°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 40°C and 60°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 45°C and 60°C. In another embodiment, the cooling method can be used in systems operating at ambient temperatures between 50°C and 60°C.

[0159] In another embodiment, a system for cooling or heating is provided, comprising a composition including at least one of HFC-32 or HFO-1234ze-E and HFO-1252zc, and optionally a lubricant, or consisting of or substantially consisting of these components. The system includes an evaporator, a compressor, a condenser, and an expander, each operatively connected to perform a vapor compression cycle.

[0160] The air conditioning or heat pump system can be a residential, light commercial, or industrial air conditioning or heat pump. Various such systems have been previously described herein. In another embodiment, the air conditioning or heat pump system containing the composition can be a two-loop system, the composition comprising at least one of HFC-32 or HFO-1234ze-E and HFO-1234ze-E, consisting of, or substantially consisting of them.

[0161] The following examples are provided to illustrate certain aspects of the invention and should not limit the scope of the appended claims.

[0162] Example

[0163] Example 1

[0164] For an evaporator temperature of -10°C, the cooling and heating performance of compositions containing HFO-1252zc and HFO-1234ze-E, as well as compositions containing HFO-1252zc and HFC-32, were compared with those of R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The results are shown in Tables 2A and 2B.

[0165]

[0166]

[0167]

[0168] Data shows that the COP of all compositions of the present invention is improved compared to R-410A and R-454C. Furthermore, some compositions of the present invention have cooling and heating capacities similar to R-410A or R-454C, and the average temperature glide is reasonable. Additionally, the critical temperature (particularly for compositions containing HFO-1252zc and HFO-1234ze-E) is high enough to enable these blends to function well as coolants in high-environment regions (such as the Middle East) and can also be used to supply high-temperature water in water-heated heat pumps.

[0169] Example 2

[0170] For an evaporator temperature of -15°C, the cooling and heating performance of compositions containing HFO-1252zc and HFO-1234ze-E, as well as compositions containing HFO-1252zc and HFC-32, were compared with those of R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The results are shown in Tables 3A and 3B.

[0171]

[0172]

[0173]

[0174] Data show that the COP of all compositions of the present invention is improved compared to R-410A and R-454C. Furthermore, some compositions of the present invention have cooling and heating capacities similar to R-410A or R-454C, and the average temperature glide is reasonable. Results show that heat pumps operating in heating (or cooling) mode using compositions of 20 wt% to 83 wt% HFO-1252z and 17 wt% to 80 wt% HFC-32 exhibit heating (or cooling) capacities at least 80% of the heating (or cooling) capacity of R-454C.

[0175] Example 3

[0176] For an evaporator temperature of -20°C, the cooling and heating performance of compositions containing HFO-1252zc and HFO-1234ze-E, as well as compositions containing HFO-1252zc and HFC-32, were compared with those of R-454C (ASHRAE designation for a refrigerant containing 78.5 wt% HFO-1234yf and 21.5 wt% HFC-32) and R-410A (ASHRAE designation for a refrigerant containing 50 wt% HFC-125 and 50 wt% HFC-32). The results are shown in Tables 4A and 4B.

[0177]

[0178]

[0179]

[0180] Data show that the COP of all compositions of the present invention is improved compared to R-410A and R-454C. Furthermore, some compositions of the present invention have cooling and heating capacities similar to R-410A or R-454C, and the average temperature glide is reasonable.

[0181] Example 4

[0182] Table 5 provides flammability estimates for compositions containing HFO-1252zc and HFO-1234ze-E, as well as compositions containing HFO-1252zc and HFC-32. HOC stands for heat of combustion.

[0183]

[0184] The compositions claimed herein all fall within ASHRAE Flammability Class 2, with an HOC of less than 19,000 kJ / kg.

[0185] Residential heat pump system

[0186] In Tables 6 through 17B below, “T_condenser” is the condenser temperature, “T_evaporator” is the evaporator temperature, “COP” is the coefficient of performance (similar to energy efficiency), and “CAP” is the volumetric cooling capacity. In Examples 5 through 8, the refrigerant performance of the exemplary compositions of the present invention in a residential heat pump system was determined compared to R-410A and R-454C in both cooling and heating modes. Cooling mode data are based on the conditions set forth in Table 6. Heating mode data are based on the conditions set forth in Table 7.

[0187]

[0188]

[0189] Example 5: HFO-1252zc / HFC-32 (Cooling Mode)

[0190] In cooling mode, the refrigerant performance of exemplary compositions of the present invention containing HFO-1252zc and HFC-32 was determined in residential heat pump systems compared to R-410A and R-454C. Performance metrics and composition property ranges are summarized in Table 8, wherein the ASHRAE flammability rating remains at 2, the average temperature glide is <10 K, the cooling capacity is not less than 90% of the cooling capacity of R-454C, and the GWP is <300. Tables 9A and 9B list several compositions with optimal cooling efficiency and capacity.

[0191]

[0192]

[0193]

[0194] The results showed that, for cooling in residential heat pump systems, the HFO-1252zc and HFC-32 compositions of the present invention provide an improved COP relative to R-410A and an improved capacity relative to R-454C. The results also showed that heat pumps operating in cooling mode using compositions of 56 wt% to 68 wt% HFO-1252zc and 32 wt% to 44 wt% HFC-32 exhibited a slip of <8°K. They further showed that heat pumps operating in cooling mode using compositions of 56 wt% to 70 wt% HFO-1252zc and 30 wt% to 44 wt% HFC-32 exhibited at least 80% of the cooling capacity of R-454C.

[0195] Example 6: HFO-1252zc / HFC-32 (Heating Mode)

[0196] In heating mode, the refrigerant performance of exemplary compositions of the present invention comprising HFO-1252zc and HFC-32 was determined in residential heat pump systems compared to R-410A and R-454C. Performance metrics and composition property ranges are summarized in Table 10, wherein the ASHRAE flammability rating remains 2, the average temperature glide is <10 K, the heating capacity is at least 10% less than that of R-454C, and the GWP is <300. Table 11 lists several compositions with optimal cooling efficiency and capacity.

[0197]

[0198]

[0199]

[0200] The results show that, for heating using residential heat pump systems, the HFO-1252zc and HFC-32 compositions of the present invention provide an improved COP relative to R-410A and an improved capacity relative to R-454C (in some cases, more than 25% higher). The results also show that heat pumps operating in heating mode using compositions of 56 wt% to 65 wt% HFO-1252zc and 36 wt% to 44 wt% HFC-32 exhibit a slip of <8°K. They further show that heat pumps operating in heating mode using compositions of 56 wt% to 70 wt% HFO-1252zc and 30 wt% to 44 wt% HFC-32 exhibit at least 80% of the heating capacity of R-454C.

[0201] Example 7: HFO-1252zc / HFO-1234ze(E) / HFC-32 (Cooling Mode)

[0202] In cooling mode, the refrigerant performance of exemplary compositions of the present invention comprising HFO-1252zc, HFO-1234ze(E), and HFC-32 was determined in residential heat pump systems compared to R-410A and R-454C. Performance metrics and composition property ranges are summarized in Table 12, wherein the ASHRAE flammability rating remains 2L or 2, the average temperature glide is <10K, the cooling capacity is at least 10% less than that of R-454C, and the GWP is <300. Performance metrics and composition property ranges are summarized in Table 13, wherein the ASHRAE flammability rating remains 2L or 2, the average temperature glide is <10K, the cooling capacity is at least 10% less than that of R-454C, and the GWP is <150. Table 14 lists several compositions with optimal cooling efficiency and capacity.

[0203]

[0204]

[0205]

[0206]

[0207] The results showed that, for cooling in residential heat pump systems, the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide improved COP or similar energy efficiency relative to R-454C. Furthermore, in many cases, the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide improved cooling capacity relative to R-454C. The results also showed that compositions of 0.5 wt% to 24 wt% HFO-1252zc, 29 wt% to 43.78 wt% HFC-32, and 37 wt% to 62 wt% HFO-1234ze-E have a flammability rating of 2L. They also showed that heat pumps using compositions of 14 wt% to 63 wt% HFO-1252zc, 23 wt% to 44 wt% HFC-32, and 4 wt% to 37 wt% HFO-1234ze-E exhibited a slip of <8°K when operating in cooling mode. Finally, they also showed that compositions of 30 wt% to 63 wt% HFO-1252zc, 18 wt% to 23 wt% HFC-32, and 14 wt% to 47 wt% HFO-1234ze-E had a GWP <160. They further showed that heat pumps using compositions of 0.5 wt% to 63 wt% HFO-1252zc, 18 wt% to 43.78 wt% HFC-32, and 4 wt% to 62 wt% HFO-1234ze-E, when operating in cooling mode, exhibited at least 80% of the cooling capacity of R-454C.

[0208] Example 8: HFO-1252zc / HFO-1234ze(E) / HFC-32 (Heating Mode)

[0209] In heating mode, the refrigerant performance of exemplary compositions of the present invention comprising HFO-1252zc, HFO-1234ze(E), and HFC-32 was determined in residential heat pump systems compared to R-410A and R-454C. Performance metrics and composition property ranges are summarized in Table 15, wherein the ASHRAE flammability rating remains 2L or 2, the average temperature glide is <10K, the heating capacity is at least 10% less than that of R-454C, and the GWP is <300. Performance metrics and composition property ranges are summarized in Table 16, wherein the ASHRAE flammability rating remains 2L or 2, the average temperature glide is <10K, the heating capacity is at least 10% less than that of R-454C, and the GWP is <150. Table 17 lists several compositions with optimal cooling efficiency and capacity.

[0210]

[0211]

[0212]

[0213]

[0214] The results show that, for heating using residential heat pump systems, the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide improved COP or similar energy efficiency relative to R-454C. Furthermore, in many cases, the HFO-1252zc, HFO-1234ze(E), and HFC-32 compositions of the present invention provide improved heating capacity relative to R-454C. The results also show that compositions of 0.5 wt% to 25 wt% HFO-1252zc, 35 wt% to 43.78 wt% HFC-32, and 39 wt% to 57 wt% HFO-1234ze-E have a flammability rating of 2L. They also showed that heat pumps using compositions of 31 to 64 wt% HFO-1252zc, 17 to 43 wt% HFC-32, and 1 to 31 wt% HFO-1234ze-E exhibited a slip of <8°K when operating in heating mode. Finally, they also showed that compositions of 36 to 60 wt% HFO-1252zc, 17 to 22 wt% HFC-32, and 18 to 42 wt% HFO-1234ze-E had a GWP <160. They further showed that heat pumps using compositions of 0.5 to 64 wt% HFO-1252zc, 17 to 43.78 wt% HFC-32, and 1 to 57 wt% HFO-1234ze-E, operating in heating mode, exhibited at least 80% of the heating capacity of R-454C.

[0215] Example 9: HFO-1252zc / HFO-1234ze-E (Cooling Mode)

[0216] In cooling mode, the refrigerant performance of exemplary compositions of the present invention comprising HFO-1252zc and HFO-1234ze-E was determined in residential heat pump systems compared to R-410A and R-454C. Performance metrics and composition property ranges are summarized in Table 18, wherein the ASHRAE flammability rating remains 2L or 2, the average temperature glide is <2K, the cooling capacity is at least 10% less than that of R-454C, and the GWP is <300. There is no composition range that maintains an ASHRAE flammability rating of 2L or 2, an average temperature glide of <10K, a cooling capacity at least 50% of that of R-454C, and a GWP of ~1. Table 19 lists several compositions with optimal cooling efficiency and capacity.

[0217]

[0218]

[0219]

[0220] The results showed that, for cooling in residential heat pump systems, the HFO-1252zc and HFO-1234ze-E compositions of the present invention provide an improved COP compared to R-410A and R-454C. The results also showed that compositions of 1 wt% to 16 wt% HFO-1252zc and 84 wt% to 99 wt% HFO-1234ze-E have a flammability rating of 2L. They further showed that heat pumps operating in cooling mode using compositions of 1 wt% to 49 wt% HFO-1252zc and 51 wt% to 99 wt% HFO-1234ze-E exhibit a slip of <1.1°K.

[0221] Example 10: HFO-1252zc / HFO-1234ze(E) / HFC-32 (Heating Mode)

[0222] In Example 10, the refrigerant performance of the exemplary composition of the present invention in a residential heat pump system was determined compared to R-454C under both cooling and heating modes. The data are based on the conditions listed in Table 20.

[0223]

[0224] Tables 21A and 21B list the components for optimal cooling efficiency and capacity.

[0225]

[0226]

[0227] The results showed that compositions containing 18 to 20 wt% HFO-1252zc, 6 to 21 wt% HFC-32, and 59 to 76 wt% HFO-1234ze(E) exhibited a GWP <160 and a flammability rating of 2L. They also showed that heat pumps operated with these compositions exhibited a slip of <10K. Furthermore, they showed that heat pumps operated with compositions containing approximately 20 wt% HFO-1252zc, approximately 21 wt% R-32, and approximately 59 wt% HFO-1234ze-E exhibited at least 90% of the cooling (or heating) capacity of R-454C.

Claims

1. A composition comprising at least one of HFO-1234ze-E or HFC-32 and HFO-1252zc.

2. The composition according to claim 1, wherein the composition comprises at least one of about 17% to 80% by weight of HFO-1234ze-E or HFC-32 and about 20% to 83% by weight of HFO-1252zc.

3. The composition according to claim 1 or 2, wherein the composition comprises at least one of about 19% to 80% by weight of HFO-1234ze-E or HFC-32 and about 20% to 81% by weight of HFO-1252zc.

4. The composition according to claim 1 or 2, wherein the composition comprises about 20% to 83% by weight of HFO-1252zc and about 17% to 80% by weight of HFC-32.

5. The composition according to claim 1 or 2, wherein the composition comprises about 20% to 81% by weight of HFO-1252zc and about 19% to 80% by weight of HFO-1234ze-E.

6. The composition according to any one of claims 1 to 5, wherein the composition further comprises at least one additional compound selected from the group consisting of: HCFC-22, HFC-23, HCC-30, HCFC-31, HCC-40, HFC-41, methane, HFC-125, HFC-143, HFC-143a, HFC-152a, HFC-245cb, HCFC-253dc, HFC-254fb, HCC-260fb, HCFC-261fc, HCFC-262fc, HFC-263fb, HFC-272fb, propane, HFO-37 4. n-Butane, propadiene, 2-Butene, cyclobutene, 2-Methylpropene, HCFO-1122, HFO-1132, HFO-1132a, HFO-1141, ethylene, HCFO-1233xf, HFO-1234yf, HCFO-1242zf, HFO-1243zf, HCFO-1251, HCO-1260zf, HFO-1261zf, propylene, HFO-1345, HFO-1252zc, HFO-1252yf, HFO-1252zf, HFO-1252ye and E / Zt-BuO-CF=CH-CH3.

7. The composition according to any one of claims 1 to 6, wherein the composition further comprises at least one additional compound selected from the group consisting of HCFC-22, HCC-40, HFO-1234yf, HFO-1243zf, HFC-263fb, HFO-1252zc, HFO-1252yf, HFO-1252zf and HFO-1252ye.

8. The composition according to any one of claims 1 to 7, wherein the composition further comprises 0.1 ppm to 200 ppm of water by weight; about 10 ppm to about 0.35% by volume of oxygen; and / or about 100 ppm to about 1.5% by volume of air or NAG.

9. The composition according to any one of claims 1 to 8, wherein the composition comprises a stabilizer.

10. The composition according to claim 9, wherein the stabilizer is selected from the group consisting of: nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

11. The composition according to any one of claims 9 or 10, wherein the stabilizer is selected from toluenetriazole, benzotriazole, tocopherol, hydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, fluorinated epoxide, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, α-pinene, β-pinene, or butylated hydroxytoluene.

12. The composition according to any one of claims 7 to 9, wherein the stabilizer is present in an amount of about 0.001% by weight to 1.0% by weight based on the weight of the refrigerant.

13. The composition according to any one of claims 1 to 12, wherein the composition further comprises a lubricant.

14. The composition of claim 13, wherein the lubricant is at least one selected from the group consisting of: polyalkylene glycols, polyol esters, poly-α-olefins, and polyethylene ethers.

15. The composition according to claim 13 or 14, wherein the lubricant is a polyol ester or a polyethylene ether.

16. The composition according to any one of claims 13 to 15, wherein the lubricant has at least one property selected from the group consisting of: greater than 10 at 20°C 10 Volume resistivity in Ω-m; surface tension of about 0.02 N / m to 0.04 N / m at 20 °C; kinematic viscosity of about 20 cSt to about 500 cSt at 40 °C; breakdown voltage of at least 25 kV; and hydroxyl value of up to 0.1 mg KOH / g.

17. The composition according to any one of claims 1 to 16, wherein the composition comprises at least one tracer.

18. The composition of claim 17, wherein the tracer is present in an amount from about 1.0 ppm to about 1000 ppm by weight.

19. The composition according to any one of claims 17 or 18, wherein the at least one tracer is selected from the group consisting of: hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

20. The composition according to any one of claims 17 to 19, wherein the at least one tracer is selected from the group consisting of: HFC-23, HCFC-31, HFC-41, HFC-161, HFC-143a, HFC-134a, HFC-125, HFC-236fa, HFC-236ea, HFC-245cb, HFC-245fa, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCF C-22, HCFC-123, HCFC-124, HCFC-124a, HCFC-141b, HCFC-142b, HCFC-151a, HCFC-244bb, HCC-40, HFO-1141, HCFO-1130, HCFO-1130a, HCFO-1131, HCFO-1122, HFO-1123, HFO-1234yf, HFO-1234ye, HFO-1243zf, HFO-1225ye, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

21. The composition according to any one of claims 1 to 20, wherein the composition is free from or substantially free from Group A fluorinated substances, and wherein the degradation products of the composition are free from or substantially free from Group A fluorinated substances.

22. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 56% to about 70% by weight based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 30% to about 44% by weight based on the weight of HFO-1252zc and HFC-32.

23. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 68 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 32 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

24. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 65 wt% based on the weight of HFO-1252zc and HFC-32; and HFC-32 is present at a concentration of about 35 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32.

25. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 33% to about 45% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 18% to about 20% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 19% to about 47% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100; and the GWP of the composition is <160.

26. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 0.05 wt% to about 24 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 34 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 37 wt% to about 62 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the flammability rating of the composition is 2L (when measured according to ANSI / ASHRAE standard 34).

27. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 51 wt% to about 63 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 23 wt% to about 38 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4 wt% to about 21 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

28. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 31 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 31 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

29. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 0.05 wt% to about 25 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 36 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 39 wt% to about 57 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the flammability rating of the composition is 2L (when measured according to ANSI / ASHRAE Standard 34).

30. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 36 wt% to about 60 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 18 wt% to about 42 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100; and the GWP of the composition is <160.

31. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 1% to about 16% by weight based on the weight of HFO-1252zc and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 84% to about 99% by weight based on the weight of HFO-1252zc and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc and HFO-1234ze-E is 100; and the flammability rating of the composition is 2L (when measured according to ANSI / ASHRAE Standard 34).

32. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-125zc is present at a concentration of about 19 wt% to about 23 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234zc; HFC-32 is present at a concentration of about 18 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 57 wt% to about 61 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

33. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 70 wt% based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 30 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32; and the sum of the weight percentages of HFO-1252zc and HFC-32 is 100.

34. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 0.5 wt% to about 63 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 18 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4 wt% to about 62 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

35. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 0.5 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 57 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100.

36. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 18% by weight to about 20% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 6% by weight to about 21% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59% by weight to about 76% by weight based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252ze, HFC-32 and HFO-1234ze-E is 100; and the composition exhibits a GWP < 160 and a flammability rating of 2L.

37. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of approximately 20% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of approximately 21% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of approximately 59% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100.

38. The composition according to any one of claims 1 or 6 to 21, wherein: HFO-1252zc is present at a concentration of about 18 wt% to about 22 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 19 wt% to about 23 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 57 wt% to about 61 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32 and HFO-1234ze-E is 100.

39. A method for cooling, the method comprising evaporating a composition according to any one of claims 1 to 38 near a body to be cooled, and then condensing the composition, wherein the cooling is provided by an air conditioner or a heat pump.

40. The method of claim 39, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 68 wt% based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 32 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32; the cooling is provided by a heat pump; and the heat pump exhibits a slip of <8°K.

41. The method according to claim 39, wherein: HFO-1252zc is present at a concentration of approximately 51 wt% to approximately 63 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of approximately 23 wt% to approximately 38 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of approximately 4 wt% to approximately 21 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100; the cooling is provided by a heat pump; and the heat pump exhibits a slip of <8°K.

42. The method according to claim 39, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 70 wt% based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 30 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32; the sum of the weight percentages of HFO-1252zc and HFC-32 is 100; the cooling is provided by a heat pump; and the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

43. The method according to claim 39, wherein: HFO-1252zc is present at a concentration of about 0.5 wt% to about 63 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 18 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 4 wt% to about 62 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32, and HFO-1234ze-E is 100; the cooling is provided by a heat pump; and the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

44. The method of claim 39, wherein: HFO-1252zc is present at a concentration of about 20% to about 83% by weight based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 17% to about 80% by weight based on the weight of HFO-1252zc and HFC-32; the sum of the weight percentages of HFO-1252zc and HFC-32 is 100; the cooling is provided by a heat pump; and the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

45. The method according to claim 39, wherein: HFO-1252zc is present at a concentration of about 0.5 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43.78 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 57 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the heat pump exhibits a cooling capacity of at least 80% of the cooling capacity of R-454C.

46. ​​The method according to claim 39, wherein: HFO-1252zc is present at a concentration of about 18 wt% to about 20 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 6 wt% to about 21 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59 wt% to about 76 wt% based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100; the cooling is provided by a heat pump; and the heat pump exhibits a slip of <10°K.

47. The method of claim 39, wherein HFO-1252zc is present at a concentration of about 20% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 21% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100; the cooling is provided by a heat pump; and the heat pump exhibits a cooling capacity of at least 90% of the cooling capacity of R-454C.

48. A method for heating, the method comprising evaporating a composition according to any one of claims 1 to 38 and then condensing the composition near a body to be heated, wherein the heating is provided by a heat pump.

49. The method according to claim 48, wherein: HFO-1252zc is present at a concentration of about 56 wt% to about 65 wt% based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 35 wt% to about 44 wt% based on the weight of HFO-1252zc and HFC-32; and the heat pump exhibits a slip of <8°K.

50. The method of claim 48, wherein: HFO-1252zc is present at a concentration of about 31 wt% to about 64 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFC-32 is present at a concentration of about 17 wt% to about 43 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 1 wt% to about 31 wt% based on the weight of HFO-1252zc, HFC-32 and HFO-1234ze-E; the sum of the weight percentages of HFO-1252zc, HFC-32 and HFO-1234ze-E is 100; and the heat pump exhibits a slip of <8°K.

51. The method according to claim 48, wherein: HFO-1252zc is present at a concentration of about 56% to about 70% by weight based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 30% to about 40% by weight based on the weight of HFO-1252zc and HFC-32; the sum of the weight percentages of HFO-1252zc and HFC-32 is 100; and the heat pump exhibits a heating capacity of at least 80% of the heating capacity of R-454C.

52. The method according to claim 48, wherein: HFO-1252zc is present at a concentration of about 20% to about 83% by weight based on the weight of HFO-1252zc and HFC-32; HFC-32 is present at a concentration of about 17% to about 80% by weight based on the weight of HFO-1252zc and HFC-32; the sum of the weight percentages of HFO-1252zc and HFC-32 is 100; and the heat pump exhibits a heating capacity of at least 80% of the heating capacity of R-454C.

53. The method of claim 48, wherein HFO-1252zc is present at a concentration of about 20% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFC-32 is present at a concentration of about 21% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; HFO-1234ze-E is present at a concentration of about 59% by weight based on the weight of HFO-1252zc, HFC-32, and HFO-1234ze-E; and the sum of the weight percentages of HFO-1252ze, HFC-32, and HFO-1234ze-E is 100; and the heat pump exhibits a heating capacity of at least 90% of the heating capacity of R-454C.

54. A system for cooling or heating, said system comprising the composition according to any one of claims 1 to 38.

55. The system of claim 54, the system comprising an evaporator, a compressor, a condenser, and an expander, each operatively connected to perform a vapor compression cycle.

56. The system of claim 54 or 55, wherein the air conditioner or heat pump is a residential, light commercial, or industrial air conditioner or heat pump.

57. A method of replacing R-454C or propane in an air conditioning system or heat pump system, the method comprising providing the system with a composition according to any one of claims 1 to 38 to replace R-454C or propane.

58. Use of the composition according to any one of claims 1 to 38 as a refrigerant in an air conditioning system or a heat pump system.

59. The system according to any one of claims 54 to 56, wherein the system is a two-stage loop system.

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