Low GWP compositions comprising HFO-1132z and uses thereof

Abstract

Disclosed herein are compositions comprising HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2. The compositions are useful in refrigeration, air conditioning, heat pumps and chillers for cooling, heating or replacing other refrigerants.

Description

TITLE OF THE INVENTIONLOW GWP COMPOSITIONS COMPRISING HFO-1132Z AND USES THEREOFFIELD

[0001] The present disclosure relates to compositions useful as refrigerants in refrigeration, air conditioning and heat pump systems. The compositions are useful in methods for producing cooling and heating, methods for replacing existing refrigerants, and refrigeration, air conditioning, heat pump, and chiller systems.BACKGROUND

[0002] The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents and propellants. These new compounds, such as HFC refrigerants, HFC-134a and HFC-125 being the most widely used at this time, have zero ozone depletion potential (ODP) and thus are not affected by the current regulatory phase-out as a result of the Montreal Protocol. In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. HFC refrigerants such as HFC-134a and HFC-125 respectively have global warming potentials (GWP) of 1,430 and 3,500 according to the UN's IPCC Fourth Assessment Report (AR4).

[0003] This regulatory landscape is continuously evolving, taking into consideration properties beyond just ODP and GWP. More particularly, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potentials, but that also provide superior performance in a variety of applications and which meet the standards of evolving regulations.

[0004] The instant invention solves certain problems associated with conventional refrigerants and provides refrigerant blends containing 1 ,1-difluoropropene, which meets the evolving regulatory landscape.SUMMARY

[0005] In one embodiment, compositions are provided comprising HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2.

[0006] According to the foregoing embodiment, the compositions comprise, consist of, or consist essentially of HFO-1132Z and are selected from:HFO-1132Z and HFC-32;HFO-1132Z and HFO-1132E;HFO-1132Z and HFC-134;HFO-1132Z, HFO-1132E, and HFC-32;HFO-1132Z, HFO-1132E, and HFC-134;HFO-1132Z, HFC-32, and CF3I;HFO-1132Z, HFO-1132E, and CF3I;HFO-1132Z, HFC-134, and CF3I;HFO-1132Z, HFC-32, and CO2;HFO-1132Z, HFO-1132E, and CO2;HFO-1132Z, HFC-134, and CO2;HFO-1132Z, HFO-1132E, HFC-32, and CF3I;HFO-1132Z, HFO-1132E, HFC-134, and CF3I;HFO-1132Z, HFO-1132E, HFC-32, and CO2;HFO-1132Z, HFO-1132E, HFC-134, and CO2;HFO-1132Z, HFC-32, CF3I, and CO2;HFO-1132Z, HFO-1132E, CF3I, and CO2;HFO-1132Z, HFC-134, CF3I, and CO2;HFO-1132Z, HFO-1132E, HFC-32, CF3I, and CO2; orHFO-1132Z, HFO-1132E, HFC-134, CF3I, and CO2.

[0007] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 56 to 99 weight percent HFO-1132Z and about 1 to44 weight percent HFC-32, or about 78 to 99 weight percent HFO-1132Z and about 1 to 22 weight percent HFC-32, or about 85 to 92 weight percent HFO-1132Z and about 8 to 15 weight percent HFC-32.

[0008] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 75 to 99 HFO-1132Z and about 1 to 25 weight percent HFO-1132E, or about 78 to 89 weight percent HFO-1132Z and about 11 to 22 weight percent HFO-1132E.

[0009] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 73.5 to 99 weight percent HFO-1132Z and about 1 to 26.5 weight percent HFC-134, or about 86.75 to 99 weight percent HFO-1132Z and about 1 to 13.25 weight percent HFC-134, or about 81 to 99 weight percent HFO- 1132Z and about 1 to 19 weight percent HFC-134, or about 81 to 91 weight percent HFO-1132Z and about 9 to 19 weight percent HFC-134.

[0010] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 31 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 44 weight percent HFC-32, or about 53 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 22 weight percent HFC-32, or about 79 to 92 weight percent HFO-1132Z, about 1 to 21 weight percent 1132E, and about 1 to 14 weight percent HFC-32.

[0011] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 48.5 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 26.5 weight percent HFC-134, or about 61.75 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 13.25 weight percent HFC-134, or about 68 to 88 weight percent HFO-1132Z, about 11 to 22 weight percent HFO-1132E, and about 1 to 13 weight percent HFC-134.

[0012] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 36 to 98 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, and about 1 to 30 weight percent CF3I, or about 58 to 98 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, and about 1 to 30 weight percent CF3I, or about 42 to 93 weight percent HFO-1132Z, about 6 to 15 weight percent HFC-32, and about 1 to 48 weight percent CF3I, or about 24 to 97weight percent HFO-1132Z, about 2 to 15 weight percent HFC-32, and about 1 to 73 weight percent CF3I.

[0013] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 55 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 20 weight percent CF3I, or about 11 to 96 weight percent HFO-1132Z, about 3 to 23 weight percent HFO-1132E, and about 1 to 83 weight percent CF3I, or about 29 to 89 weight percent HFO-1132Z, about 10 to 22 weight percent HFO-1132E, and about 1 to 61 weight percent CF3I, or about 11 to 62 weight percent HFO-1132Z, about 4 to 16 weight percent HFO-1132E, and about 34 to 83 weight percent CF3I, or about 29 to 56 weight percent HFO-1132Z, about 10 to 15 weight percent HFO-1132E, and about 34 to 61 weight percent CF3I.

[0014] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 53.5 to 98 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, and about 1 to 30 weight percent CF3I, or about 66.75 to 98 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, and about 1 to 30 weight percent CF3I.

[0015] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 51 to 98 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, and about 1 to 5 weight percent CO2, or about 73 to 98 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, and about 1 to 5 weight percent CO2.

[0016] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 70 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 5 weight percent CO2.

[0017] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 68.5 to 98 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, and about 1 to 5 weight percent CO2, or about 81.75 to 98 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, and about 1 to 5 weight percent CO2.

[0018] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 11 to 97 weight percent HFO-1132Z, about 1 to 25weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, and about 1 to 30 weight percent CF3I, or about 33 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC-32, and about 1 to 30 weight percent CF3I.

[0019] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 28.5 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, and about 1 to 30 weight percent CF3I, or about 41.75 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, and about 1 to 30 weight percent CF3I.

[0020] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 26 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, and about 1 to 5 CO2, or about 48 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC-32, and about 1 to 5 weight percent CO2.

[0021] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 43.5 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, and about 1 to 5 weight percent CO2, or about 56.75 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, and about 1 to 5 weight percent CO2.

[0022] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 31 to 97 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 53 to 97 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0023] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 50 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 25 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0024] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 48.5 to 97 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 61.75 to 97 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0025] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 6 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 28 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0026] According to any of the foregoing embodiments, disclosed herein are compositions comprising about 23.5 to 96 weight percent HFO-1132Z, 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 36.75 to 96 weight percent HFO-1132Z, 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0027] According to any of the foregoing embodiments, disclosed herein are compositions wherein the CF3I is present at about 1 to 25 weight percent or about 1 to 20 weight percent.

[0028] According to any of the foregoing embodiments, disclosed herein are compositions wherein the CO2 is present at about 1 to 3 weight percent.

[0029] According to any of the foregoing embodiments, disclosed herein are compositions that are classified as class 2L or 1 for flammability according to ASH RAE Standard 34.

[0030] According to any of the foregoing embodiments, disclosed herein are compositions further comprising at least one additional compound selected from the group consisting of methane, ethane, HFC-41, HCC-40, HFCF-22, HFC-23, HFO-1141 , HFO-1132E, HFC-161 , HFC-152, HFC-143, HFC-143a, HFC-134a, PFC-116, HCFO-1122, HCFO-1122aE, HCFO-1122aZ, HCC-150, HCFC-151 , CFO-1112, HCFC-142a, HCFC-132, HCFC-133, HCFC-133b, HCFC-123, HFO-1123, HFO- 1132a, HCFO-1131 E, HCFO-1131Z, ethylene, and acetylene.

[0031] According to any of the foregoing embodiments, disclosed herein are compositions further comprising from 0.1 to 200 ppm by weight of water; from about 10 ppm by volume to about 0.35 volume percent oxygen; and / or from about 100 ppm by volume to about 1.5 volume percent air or NAG.

[0032] According to any of the foregoing embodiments, disclosed herein are compositions further comprising a stabilizer.

[0033] According to any of the foregoing embodiments, disclosed herein are 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.

[0034] According to any of the foregoing embodiments, disclosed herein are compositions, wherein the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-terbutyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, d-limonene, a-terpinene, p-terpinene, a-pinene, p- pinene, or butylated hydroxytoluene.

[0035] According to any of the foregoing embodiments, disclosed herein are compositions, wherein the stabilizer is present in an amount from about 0.001 to 1 .0 weight percent based on the weight of the refrigerant.

[0036] According to any of the foregoing embodiments, disclosed herein are compositions further comprising a lubricant.

[0037] According to any of the foregoing embodiments, the lubricant included in the compositions may be chosen from polyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether.

[0038] According to any of the foregoing embodiments, the lubricant included in the compositions may be chosen from polyol ester, and polyvinyl ether.

[0039] According to any of the foregoing embodiments, the lubricant included in the compositions, wherein said lubricant has at least one property selected from the group consisting of volume resistivity of greater than 1O10Q-m at 20 °C; surface tension of from about 0.02 N / m to 0.04 N / m at 20 °C; kinematic viscosity of from about 20 cSt to about 500 cSt at 40 °C; a breakdown voltage of at least 25 kV; and a hydroxy value of at most 0.1 mg KOH / g.

[0040] According to any of the foregoing embodiments, disclosed herein are compositions further comprising at least one tracer.

[0041] According to any of the foregoing embodiments, disclosed herein are compositions wherein said tracer is present in an amount from about 1.0 ppm by weight to about 1000 ppm by weight.

[0042] According to any of the foregoing embodiments, disclosed herein are compositions wherein said 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.

[0043] According to any of the foregoing embodiments, disclosed herein are compositions wherein said 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-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.

[0044] According to any of the foregoing embodiments, disclosed herein are compositions wherein said composition provides average temperature glide lessthan 8 K, or less than 6 K, or less than 5 K, or less than 4 K, or less than 3 K, or less than 2 K, or less than 1 K.

[0045] According to any of the foregoing embodiments, disclosed herein are compositions wherein the composition is free of or substantially free of Group A Fluorinated Substances, and wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.

[0046] In some embodiments, disclosed herein are methods for cooling comprising evaporating a composition according to any of the foregoing embodiments in the vicinity of a body to be cooled and thereafter condensing said composition.

[0047] In other embodiments, disclosed herein are methods for heating comprising evaporating a composition according to any of the foregoing embodiments, and thereafter condensing said composition in the vicinity of a body to be heated.

[0048] In other embodiments, disclosed herein are systems for cooling or heating comprising a composition according to any of the foregoing embodiments. In other embodiments, the systems comprise an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle. In another embodiment, the system is a residential, light commercial, or industrial airconditioner, heat pump, or chiller. In another embodiment, the system is a medium or low temperature refrigeration system, beverage cooler, supermarket display case, ice machine, or transport refrigeration system. In another embodiment, the system is an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle. In another embodiment, the system is a secondary loop system. In another embodiment, the system does not include a PTC heater.

[0049] In other embodiments, disclosed herein are methods of replacing at least one of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C, in refrigeration, air-conditioning, heat pump, or chiller systems comprising providing the composition of any of the foregoing embodiments to the system in place of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R- 454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C.

[0050] In other embodiments, disclosed herein is the use of a composition of any of the foregoing embodiments as refrigerant in refrigeration, air conditioning, heat pump, or chiller systems. In another embodiment, the use is in a refrigeration, air conditioning, heat pump or chiller system comprising residential, light commercial, or industrial air-conditioner, residential, light commercial, or industrial heat pump, chiller, medium or low temperature refrigeration system, beverage cooler, supermarket display case, ice machine, or transport refrigeration system.

[0051] In another embodiment, the compositions according to any of the foregoing embodiments are used in an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle.

[0052] In another embodiment, the compositions of any of the foregoing embodiments may be used to replace any of R-22, HFC-134a, propane, HFO- 1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R- 449A, R-449B, R-449C, R-452A, or R-452C.DETAILED DESCRIPTION

[0053] The present invention relates to compositions comprising Z-1 ,2- difluoroethylene (HFO-1132Z) and at least one compounds selected from the group consisting of E-1 ,2-difluoroethylene (HFO-1132E), difluoromethane (HFC-32), 1 ,1 ,2,2-tetrafluoroethane (HFC-134), iodotrifluoromethane (CF3I), and carbon dioxide (CO2). These compositions are expected to provide blends with low global warming potential (GWP), improved environmental fate, safety, and performance which meet evolving standards and regulations.

[0054] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during a cycle used to transfer of heat.

[0055] A heat transfer system is the system (or apparatus) used to produce a heating or cooling effect in a particular space. A heat transfer system may be a mobile system or a stationary system.

[0056] Examples of heat transfer systems are any type of refrigeration systems and air conditioning systems including, but not limited to, stationary heat transfer systems, air conditioners, freezers, refrigerators, heat pumps, flooded evaporatorheat pumps, direct expansion chiller heat pumps, chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, mobile refrigerators, mobile heat transfer systems, mobile heat pumps (including heat pumps for cabin comfort cooling and heating in automobiles), mobile air conditioning units (for cooling of passenger compartments in automobiles), dehumidifiers, and combinations thereof.

[0057] Volumetric capacity is the amount of heat absorbed or rejected divided by the theoretical compressor displacement. Heat removed or absorbed is the enthalpy difference across a heat exchanger multiplied by the refrigerant mass flowrate.Theoretical compressor displacement is the refrigerant mass flowrate divided by the density of the gas entering the compressor (i.e., compressor suction density). More simply, volumetric capacity is the suction density multiplied by the heat exchanger enthalpy difference. Higher volumetric capacity allows the use of a smaller compressor for the same heat load. Herein, cooling capacity refers to the volumetric capacity in cooling mode and heating capacity refers to the volumetric capacity in heating mode.

[0058] Coefficient of performance (COP) is the amount of heat absorbed or rejected divided by the required energy input to operate the cycle (approximated by the compressor power). COP is specific to the mode of operation of a heat pump, thus COP for heating or COP for cooling. COP is directly related to the energy efficiency ratio (EER).

[0059] Subcooling refers to the reduction of the temperature of a liquid below that liquid’s saturation point for a given pressure. The liquid saturation point is the temperature at which the vapor is completely condensed to a liquid. By cooling a liquid below the saturation temperature (or bubble point temperature), the net refrigeration effect can be increased. Subcooling thereby improves refrigeration capacity and energy efficiency of a system. The subcool amount is the amount of cooling below the saturation temperature (in degrees).

[0060] Superheating refers to the increase of the temperature of a vapor above that vapor’s saturation point for a given pressure. The vapor saturation point is the temperature at which the liquid is completely evaporated to a vapor. Superheating continues to heat the vapor to a higher temperature vapor at the given pressure. By heating the vapor above the saturation temperature (or dew point temperature), thenet refrigeration effect can be increased. Superheating thereby improves refrigeration capacity and energy efficiency of a system when it occurs in the evaporator. Suction line superheat does not add to the net refrigeration effect and can reduce efficiency and capacity. The superheat amount is the amount of heating above the saturation temperature (in degrees).

[0061] Temperature glide (sometimes referred to simply as "glide") is the absolute value of the difference between the starting and ending temperatures of a phasechange process by a refrigerant within a condenser of a refrigerant system, exclusive of any subcooling or superheating. For an evaporator, the glide is the difference in temperature between the dew point and the evaporator inlet. Glide may be used to describe condensation or evaporation of a near azeotrope or non-azeotropic composition. When referring to the temperature glide of an air conditioning or heat pump system, it is common to provide the average temperature glide being the average of the temperature glide in the evaporator and the temperature glide in the condenser. Glide is applicable to blend refrigerants, i.e., refrigerants that are composed of at least 2 components.

[0062] The net refrigeration effect is the quantity of heat that each kilogram of refrigerant absorbs in the evaporator to produce useful cooling.

[0063] The mass flow rate is the quantity of refrigerant in kilograms circulating through the refrigeration, heat pump or air conditioning system over a given period of time.

[0064] As used herein, the term “lubricant” means any material added to a composition or a compressor (and in contact with any heat transfer composition in use within any heat transfer system) that provides hydrodynamic lubrication to the compressor to aid in preventing parts from seizing.

[0065] Global warming potential (GWP) is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the value referenced. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. Herein, the GWP values are those reported inthe United Nations Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4), for those compounds listed. The GWP of HFO-1132Z has been reported by McLinden (McLinden.et. al., A thermodynamic analysis of refrigerants: Possibilities and tradeoffs for Low-GWP refrigerants, Int J Refrig 38 (2014) 80) as being 1.5, and that value is used herein. The GWP of HFO-1132E is reported by Tokuhashi (Tokuhashi, et. al., Rate Constants for the Reactions of OH Radicals with the (E) / (Z) Isomers of CFCI=CFCI and (E)-CHF=CHF, J. Phys. Chem A (2019), 123, 4834) as being 0.0056, and that value is used herein.

[0066] Ozone depletion potential (ODP) is a number that refers to the amount of ozone depletion caused by a substance. The ODP is the ratio of the impact on ozone of a chemical compared to the impact of a similar mass of CFC-11 (fluorotrichloromethane). Thus, the ODP of CFC-11 is defined to be 1.0. Other CFCs and HCFCs have ODPs that range from 0.01 to 1.0. Hydrofluorocarbons (HFCs) and the hydrofluoro-olefins (HFO’s) described herein have zero ODP because they do not contain chlorine, bromine or iodine, species known to contribute to ozone breakdown and depletion. HFO-1132Z and HFO-1132E have zero ozone depletion potential.

[0067] Z-1 ,2-difluoroethylene (HFO-1132Z or R-1132Z) may be prepared by dehydrochlorination of 1-chloro-1,2-difluoroethane (HCFC-142a) in either the gas phase or liquid phase as described in U.S. Patent Publication 2022-0017438A. The reaction will produce both the E- and Z- isomers of the compound, but they are separable by distillation.

[0068] The other components of the compositions as disclosed herein are available commercially from various fluorochemical manufacturers and / or specialty chemical suppliers.

[0069] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0070] The transitional phrase "consisting of' excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0071] The transitional phrase "consisting essentially of" is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of'. Typically, components of the refrigerant mixtures and the refrigerant mixtures themselves can contain minor amounts (e.g., less than about 0.5 weight percent total) of impurities and / or byproducts (e.g., from the manufacture of the refrigerant components or reclamation of the refrigerant components from other systems) which do not materially affect the novel and basic characteristics of the refrigerant mixture.

[0072] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0073] 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 belongs. Although methods and materials similar or equivalent to those described herein can 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 by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions,will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.REFRIGERANT COMPOSITIONS

[0074] In one embodiment, compositions comprise, consist of, or consist essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2. These compositions provide low Global Warming Potential (GWP), improved environmental fate characteristics, and improved capacity and / or energy efficiency (COP).

[0075] In another embodiment, the compositions comprise, consist of, or consist essentially of HFO-1132Z and are selected from:HFO-1132Z and HFC-32;HFO-1132Z and HFO-1132E;HFO-1132Z and HFC-134;HFO-1132Z, HFO-1132E, and HFC-32;HFO-1132Z, HFO-1132E, and HFC-134;HFO-1132Z, HFC-32, and CF3I;HFO-1132Z, HFO-1132E, and CF3I;HFO-1132Z, HFC-134, and CF3I;HFO-1132Z, HFC-32, and CO2;HFO-1132Z, HFO-1132E, and CO2;HFO-1132Z, HFC-134, and CO2;HFO-1132Z, HFO-1132E, HFC-32, and CF3I;HFO-1132Z, HFO-1132E, HFC-134, and CF3I;HFO-1132Z, HFO-1132E, HFC-32, and CO2;HFO-1132Z, HFO-1132E, HFC-134, and CO2;HFO-1132Z, HFC-32, CF3I, and CO2;HFO-1132Z, HFO-1132E, CF3I, and CO2;HFO-1132Z, HFC-134, CF3I, and CO2;HFO-1132Z, HFO-1132E, HFC-32, CF3I, and C02; orHFO-1132Z, HFO-1132E, HFC-134, CF3I, and CO2.

[0076] In another embodiment, the compositions comprise, consist of, or consist essentially of about 56 to 99 weight percent HFO-1132Z and about 1 to 44 weight percent HFC-32, or about 78 to 99 weight percent HFO-1132Z and about 1 to 22 weight percent HFC-32, or about 85 to 92 weight percent HFO-1132Z and about 8 to 15 weight percent HFC-32.

[0077] In another embodiment, the compositions comprise, consist of, or consist essentially of about 75 to 99 HFO-1132Z and about 1 to 25 weight percent HFO- 1132E, or about 78 to 89 weight percent HFO-1132Z and about 11 to 22 weight percent HFO-1132E.

[0078] In another embodiment, the compositions comprise, consist of, or consist essentially of about 73.5 to 99 weight percent HFO-1132Z and about 1 to 26.5 weight percent HFC-134, or about 86.75 to 99 weight percent HFO-1132Z and about 1 to 13.25 weight percent HFC-134, or about 81 to 95 weight percent HFO-1132Z and about 1 to 19 weight percent HFC-134.

[0079] In another embodiment, the compositions comprise, consist of, or consist essentially of about 31 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 44 weight percent HFC-32, or about 53 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 22 weight percent HFC-32, or about 79 to 92 weight percent HFO-1132Z, about 1 to 21 weight percent HFO-1132E, and about 1 to 14 weight percent HFC-32.

[0080] In another embodiment, the compositions comprise, consist of, or consist essentially of about 48.5 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 26.5 weight percent HFC-134, or about 61.75 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 13.25 weight percent HFC-134, or about 68 to 88 weight percent HFO-1132Z, about 11 to 22 weight percent HFO-1132 E, and about 1 to 13 weight percent HFC- 134.

[0081] In another embodiment, the compositions comprise, consist of, or consist essentially of about 36 to 98 weight percent HFO-1132Z, about 1 to 44 weightpercent HFC-32, and about 1 to 30 weight percent CF3I, or about 58 to 98 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, and about 1 to 30 weight percent CF3I, or about 24 to 97 weight percent HFO-1132Z, about 2 to 15 weight percent HFC-32, and about 1 to 73 weight percent CF3I, or about 42 to 93 weight percent HFO-1132Z, about 6 to 15 weight percent HFC-32, and about 1 to 48 weight percent CF3I.

[0082] In another embodiment, the compositions comprise, consist of, or consist essentially of about 55 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 20 weight percent CF3I, or about 11 to 96 weight percent HFO-1132Z, about 3 to 23 weight percent HFO-1132E, and about 1 to 83 weight percent CF3I, or about 29 to 89 weight percent HFO-1132Z, about 10 to 22 weight percent HFO-1132E, and about 1 to 61 weight percent CF3I, or about 11 to 62 weight percent HFO-1132Z, about 4 to 16 weight percent HFO-1132E, and about 34 to 83 weight percent CF3I, or about 29 to 56 weight percent HFO-1132Z, about 10 to 15 weight percent HFO-1132E, and about 34 to 61 weight percent CF3I.

[0083] In another embodiment, the compositions comprise, consist of, or consist essentially of about 53.5 to 98 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, and about 1 to 30 weight percent CF3I, or about 66.75 to 98 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, and about 1 to 30 weight percent CF3I.

[0084] In another embodiment, the compositions comprise, consist of, or consist essentially of about 51 to 98 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, and about 1 to 5 weight percent CO2, or about 73 to 98 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, and about 1 to 5 weight percent CO2.

[0085] In another embodiment, the compositions comprise, consist of, or consist essentially of about 70 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 5 weight percent CO2.

[0086] In another embodiment, the compositions comprise, consist of, or consist essentially of about 68.5 to 98 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, and about 1 to 5 weight percent CO2, orabout 81.75 to 98 weightpercent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, and about 1 to 5 weight percent CO2.

[0087] In another embodiment, the compositions comprise, consist of, or consist essentially of about 11 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, and about 1 to 30 weight percent CF3I, or about 33 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC-32, and about 1 to 30 weight percent CF3I.

[0088] In another embodiment, the compositions comprise, consist of, or consist essentially of about 28.5 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, and about 1 to 30 weight percent CF3I, or about 41.75 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, and about 1 to 30 weight percent CF3I.

[0089] In another embodiment, the compositions comprise, consist of, or consist essentially of about 26 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, and about 1 to 5 CO2, or about 48 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO- 1132E, about 1 to 22 weight percent HFC-32, and about 1 to 5 weight percent CO2.

[0090] In another embodiment, the compositions comprise, consist of, or consist essentially of about 43.5 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, and about 1 to 5 weight percent CO2, or about 56.75 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, and about 1 to 5 weight percent CO2.

[0091] In another embodiment, the compositions comprise, consist of, or consist essentially of about 31 to 97 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 53 to 97 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0092] In another embodiment, the compositions comprise, consist of, or consist essentially of about 50 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 25 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0093] In another embodiment, the compositions comprise, consist of, or consist essentially of about 48.5 to 97 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, orabout 61.75 to 97 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0094] In another embodiment, the compositions comprise, consist of, or consist essentially of about 6 to 97 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 28 to 97 weight percent HFO- 1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC- 32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0095] In another embodiment, the compositions comprise, consist of, or consist essentially of about 23.5 to 96 weight percent HFO-1132Z, 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, orabout 36.75 to 96 weight percent HFO- 1132Z, 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC- 134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

[0096] In another embodiment, for the compositions according to any of the foregoing embodiments containing CF3I, the content of CF3I is about 1 to 25 weight percent or about 1 to 20 weight percent.

[0097] In another embodiment, for the compositions according to any of the foregoing embodiments containing CO2, the content of CO2 is about 1 to 3 weight percent.

[0098] The compositions of the present invention may be classified by the American Society of Heating Refrigeration and Air Conditioning Engineers (ASHRAE) as class 2, class 2L, or class 1 for flammability.

[0099] Flammability is a term used to mean the ability of a composition to ignite and / or propagate a flame. For refrigerants and other heat transfer compositions or working fluids, the lower flammability limit ("LFL") is the minimum concentration of the heat transfer composition in air that is capable of propagating a flame through a homogeneous mixture of the composition and air under test conditions specified in ASTM (American Society of Testing and Materials) E681. The upper flammability limit ("UFL") is the maximum concentration of the heat transfer composition in air that is capable of propagating a flame through a homogeneous mixture of the composition and air under the same test conditions.

[0100] In order for a refrigerant to be classified by ANSI / ASHRAE (ANSI = American National Standards Institute) as class 1 or non-flammable, it must have no flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa).

[0101] In order for a refrigerant to be classified by ANSI / ASHRAE as low flammability (class 2L), it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa); 2) have an LFL >0.0062 lb / ft3(0.10 kg / m3); 3) have a heat of combustion <8169 Btu / lb (19,000 kJ / kg); and 4) have a maximum burning velocity of <3.9 in. / s (10 cm / s) when tested at 73.4°F (23.0°C) and 14.7 psia (101.3 kPa) in dry air.

[0102] In order for a refrigerant to be classified by ANSI / ASHRAE as flammable (class 2), it must: 1) exhibit flame propagation when tested at 140°F (60°C) and 14.7 psia (101.3 kPa); 2) have an LFL >0.0062 lb / ft3(0.10 kg / m3); and 3) have a heat of combustion <8169 Btu / lb (19,000 kJ / kg).

[0103] ASH RAE Standard 34 provides a methodology to calculate the heat of combustion for refrigerant blends using a balanced stoichiometric equation based on the complete combustion of one mole of refrigerant with enough oxygen for a stoichiometric reaction.

[0104] The compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 may further comprise at least one additional compound. The at least one additional compound may be selected from the group consisting of methane, ethane, HFC-41 (fluoromethane), HCC-40 (chloromethane), HFCF-22 (chlorodifluoromethane), HFC-23 (trifluoromethane),HFO-1141 (fluoroethylene), HFO-1132E (E-1,2-difluoroethylene), HFC-161 (fluoroethane), HFC-152 (1 ,2-difluoroethane), HFC-143 (1 ,1 ,2-trifluoroethane), HFC- 143a (1,1,1-trifluoroethane), HFC-134a (1,1 ,1 ,2-tetrafluoroethane), PFC-116 (hexafluoroethane), HCFO-1122 (1-chloro-2,2-difluoroethylene), HCFO-1122aE (E- 1-chloro-1 ,2-difluoroethylene), HCFO-1122aZ (Z-1-chloro-1 ,2-difluoroethylene), HCC-150 (1,2-dichloroethane), HCFC-151 (1-chloro-2-fluoroethane), CFO-1112E (E- 1 ,2-dichloro-1 ,2-difluoroethylene), CFO-1112Z (Z-1 ,2-dichloro-1 ,2-difluoroethylene), HCFC-142a (1-chloro-1 ,2-difluoroethane), HCFC-132 (1 ,2-dichloro-1 ,2- difluoroethane), HCFC-133 (1-chloro-1 ,1,2-trifluoroethane), HCFC-133b (2-chloro- 1 ,1 ,1 -trifluoroethane), HCFC-123 (1 ,1-dichloro-2,2,2-trifluoroethane), HFO-1123 (trifluoroethylene), HFO-1132a (1,1-difluoroethylene), HCFO-1131 E (E-1-chloro-2- fluoroethylene), HCFO-1131Z (Z-1-chloro-2-fluoroethylene), ethylene, and acetylene.

[0105] The amount of additional compounds present in any of the foregoing refrigerant compositions can be greater than 0 ppm and less than 5,000 ppm and, in particular, can range from greater than zero to about 1,000 ppm, about 5 to about 500 ppm and about 1 to about 100 ppm.

[0106] In one embodiment, the amount of additional compounds present in any of the foregoing refrigerant compositions can be greater than 0 and less than 1 wt% of the refrigerant composition, preferably less than 0.5 weight percent, or more preferably less than 0.1 weight percent.

[0107] The compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 will perform more consistently and be more stable with only minor amounts of water present. Thus, the compositions may further comprise less than 100 ppm (by weight) water, preferably less than 20 ppm (by weight) water, and even more preferably less than 10 ppm (by weight) water.

[0108] Additionally, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 will perform more consistently and be more stable with only minor amounts of oxygen or air present. Therefore, the presently claimed compositions may further comprise less than about 5 volume percent non-adsorbable gases (NAG), preferably less than 3 volumepercent NAG, and more preferably less than 1.5 volume percent NAG. Further, the presently claimed compositions, due to the presence of air or NAG, will contain less than 1 volume percent oxygen, preferably less than 0.5 volume percent oxygen, and more preferably less than 0.3 volume percent oxygen.

[0109] In another embodiment, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 may contain a stabilizer. Such stabilizer compounds are intended to be present in a small amount and prevent various types of chemical reactivity including decomposition due to the presence of water, air, NAG, or oxygen in a system while in use or while the composition is stored. HFO type refrigerants, due to the presence of a double bond, may be subject to thermal instability and decompose under extreme use, handling or storage situations also. Therefore, there may be advantages to adding stabilizers to HFO type refrigerants. Stabilizers may notably include nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2 ,6-d i-tertbutyl-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, butylphenylglycidyl ether, cyclic monoterpenes, terpenes, such as d-limonene, a-terpinene, p-terpinene, y-terpinene, a-pinene, or p-pinene, phosphites, phosphates, phosphonates, thiols and lactones. Examples of suitable stabilizers are disclosed in WO2019213004, WO2020222864, and WO2020222865; the disclosures of which are hereby incorporated by reference.

[0110] If the composition does include a stabilizer, it may include any amount from 0.001 wt% up to 1 wt%, preferably from about 0.001 to about 0.5 weight percent, more preferably, from about 0.001 to about 0.3 weight percent of any of the stabilizers listed above.

[0111] In some embodiments, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 may contain a tracer compound or tracers. The tracer may comprise two or more tracer compounds. In some embodiments, the tracer is present in the compositions at atotal concentration of about 50 parts per million by weight (ppm) to about 1000 ppm, based on the weight of 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.

[0112] The tracer may be present in compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 in predetermined quantities to allow detection of any dilution, contamination, or other alteration of the composition. The presence of certain compounds in the composition may indicate by what method or process one of the components has been produced. The tracer may also be added to the composition in a specified amount in order to identify the source of the composition. In this manner, detection of infringement on patent rights may be accomplished. The tracers may be refrigerant compounds but are present in the composition at levels that are unlikely to impact performance of the refrigerant component of the composition.

[0113] T racer compounds may be hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations 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), HFC-245fa (1, 1,1, 3,3- pentafluoropropane) , HFC-254eb (1 ,1,1, 2-tetrafluoropropane), HFC-263fb (1 ,1 ,1 trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2- fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1, 1,1 , 2, 2, 3, 3,4,4- nonafluorobutane), HFC-329mmz (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 (fluoroethene), HCFO-1130 (1,2-dichloroethene), HCFO-1130a (1 ,1-dichloroethene), HCFO-1131 (1-chloro-2-fluoroethene), HCFO-1122 (2-chloro-1 ,1-difluoroethene), HFO-1123 (1 ,1,2-trifluoroethene), HFO-1234ye (1 ,2,3,3-tetrafluoropropene), 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 -1 Omy (1 ,1,1 , 2,3,3, 3-heptafluoro-2- trifluoromethylpropane), and combinations thereof.

[0114] In another embodiment of the present disclosure, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 further comprise at least one lubricant. Lubricants may be selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), poly-a- olefin (PAO), and polyvinyl ether (PVE). In another embodiment, compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 further comprise POE or PAG lubricants. Lubricants may also comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclic or ring structure saturated hydrocarbons, which may be paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, silicones, and polyalphaolefins. Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), napthenic mineral oilcommercially available under the trademark from Suniso® 3GS and Suniso® 5GS by Crompton Co., naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil commercially available from Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 and branched alkylbenzene, sold by Nippon Oil as HAB 22.

[0115] Lubricants of the present invention further comprise those which have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration and air- conditioning apparatus' operating conditions, 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 ethers (PVEs) such as PVE-FVC68D.

[0116] In one embodiment, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 are combined with a PAG lubricant or a PVE lubricant or a POE lubricant for usage in a refrigeration system, air-conditioning system, heat pump system, or chiller system.

[0117] In the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 including a lubricant, the lubricant may be present in an amount of less than 80 weight percent of the total composition. The lubricant may further be present in an amount of less than 60 weight percent of the total composition. In other embodiments, the amount of lubricant may be between about 0.1 and 50 weight percent of the total composition. The lubricant may also be between about 0.1 and 20 weight percent of the total composition The lubricant may also be between about 0.1 and 5 weight percent of the total composition.

[0118] In another aspect of the invention, the inventive composition comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 is used to introduce lubricant into the air-conditioning or heat pump system as wellas or alternatively other additives, such as a) acid scavengers, b) performance enhancers, and c) flame suppressants. In one preferred embodiment, the present compositions comprise an acid scavenger.

[0119] Examples of the acid scavengers that may be included in the present compositions include, but are not limited, the stabilizers and / or the epoxide component of the stabilizers disclosed in U.S. Patent No. 8,535,555 and the acid scavengers disclosed in International Application Publication No. WO 2020 / 222864, the disclosure of each of which is incorporated herein by reference in its entirety.

[0120] In some embodiments, an 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, epoxybutane.

[0121] The acid scavenger (e.g., the activated aromatic compound, the siloxane, or both) may be present in any concentration that results in a relatively low total acid number, a relatively low total halides concentration, a relatively low total organic acid concentration, or any combination thereof.

[0122] Preferably the acid scavenger is present at a concentration greater than about 0.0050 wt%, more preferably greater than about 0.05 wt% and even more preferably greater than about 0.1 wt% (e.g. greater than about 0.5 wt%) based on the total weight of the refrigerant composition. The acid scavenger preferably is present in a concentration less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, more preferably less than about 2.5 wt% and most preferably greater than about 2 wt% (e. g. less than about 1.8 wt%) based on the total weight of the refrigerant composition.

[0123] Preferred additives include those described in U.S. Pat. Nos. 5,152,926; 4,755,316, which are hereby incorporated by reference. In particular, the preferred extreme pressure additives include mixtures of (A) tolyltriazole or substituted derivatives 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 type), or (ii) a phosphate alcohol (e.g. ZELEC 3337 type), or (iii) a Zinc dialkyldithiophosphate (e.g. Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof.Additional examples of additives which may be used are given in U.S. Pat. No. 5,976,399 (Schnur, 5:12-6:51 , hereby incorporated by reference).

[0124] Acid number is measured according to ASTM D664-01 in units of mg KOH / g. The total halides concentration, the fluorine ion concentration, and the total organic acid concentration is measured by ion chromatography. Chemical stability of the refrigerant system is measured according to ASHRAE 97: 2007 (RA 2017) “Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems”. The viscosity of the lubricant is tested at 40°C according to ASTM D-7042.

[0125] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) teach the use of alkyl silanes as a stabilizer in refrigerant compositions containing fluoroolefins.Phosphates, phosphites, epoxides, and phenolic additives also have been employed in certain refrigerant compositions. These are described for example by Kaneko (U.S. patent application Ser. No. 11 / 575,256, published as U.S. Publication 2007 / 0290164) and Singh et al. (U.S. patent application Ser. No. 11 / 250,219, published as U.S. Publication 2006 / 0116310). All of these aforementioned applications are expressly incorporated herein by reference.

[0126] Preferred flame suppressants include the flame retardants described in patent application “Refrigerant compositions containing fluorine substituted olefins CA 2557873 A1” and incorporated by reference, as well as fluorinated products such as HFC-125, HFC-227ea, HFC-236fa, CF3I, and / or Krytox® lubricants, also incorporated by reference and described in patent application “Refrigerant compositions comprising fluoroolefins and uses thereof W02009018117A1.”

[0127] In another embodiment, the compositions comprise, consist of, or consist essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 provide cooling and or heating performance, such that the average temperature glide is less than 8 K, or less than 6 K, or less than 5 K, or less than 4 K, or less than 3 K, or less than 2 K, or less than 1 K.

[0128] In one embodiment, as used herein, " Group A Fluorinated Substances” includes any substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / CI / Br / l attached to it); and (ii) meetsthe criterion for persistence in soil / sediment and water established in Annex XIII (Section 1.1.1) of the European Union’s REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html as accessed on May 2, 2023) and referenced in the Annex XV Restriction Report dated March 22, 2023, the disclosure of which is hereby incorporated by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea as accessed on May 2, 2023). In one embodiment, Group A Fluorinated Substances include, but are not limited to, trifluoroacetic acid (TFA).

[0129] In another embodiment, as used herein, “Group A Fluorinated Substances” includes any substance that has a Henry’s Law constant < 250 Pa*m3 / mol and contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / CI / Br / l attached to it). In one embodiment, Group A Fluorinated Substances include, but are not limited to, TFA.

[0130] Thus, according to some embodiments, compositions of the present invention which comprise, consist of, or consist essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, H FC- 134, CF3I, and CO2 are free of or substantially free of Group A Fluorinated Substances, such as TFA. In one embodiment, the phrase "free of" as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas sample or liquid sample, and / or ion chromatography by analysis of a water sample after bubbling the thermal fluid through water. Such methodologies are well known to those skilled in the art. In one embodiment, the phrase "substantially free of' as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions 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, when measured by gas chromatographic (GO) techniques, for example gas chromatography (GO) with a flame ionization or electron-capture detector, or GO coupled with a mass detector (gas chromatography / mass spectral (GC / MS) method), by ion chromatograph(IC) orion chromatography mass spectrometry (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography mass spectrometry (HPLC-MS) techniques. The TFA analytical standard may be used in either gas chromatography or ion chromatography and is available from, for example, Sigma Aldrich.

[0131] Further, in some embodiments, degradation products of such compositions of the present invention which comprise, consist of, or consist essentially of HFO- 1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 are free of or substantially free of Group A Fluorinated Substances, such as TFA. In one embodiment, the phrase "free of" as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil / sediment and water produced during tropospheric degradation of the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by GO techniques, for example GO with a flame ionization or electron-capture detector or GC / MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. In one embodiment, the phrase "substantially free of" as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil / sediment and water produced during tropospheric degradation of the compositions 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, when measured by GC techniques, for example GC with a flame ionization or electron-capture detector or GC / MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.METHODS AND SYSTEMS

[0132] The compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 are useful in numerous methods and systems that provide cooling (e.g. air-conditioning or refrigeration) and heating.

[0133] In one embodiment, provided is a method of cooling comprising evaporating a composition comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 in the vicinity of a body to be cooled and thereafter condensing said composition, wherein said cooling is provided by a refrigeration system, air-conditioner, heat pump, or chiller.

[0134] In one embodiment, the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, supermarket and convenience store refrigerated cases for beverages, dairy, and produce and prepared foods. In one embodiment, the refrigeration system is a low or medium temperature refrigeration system, including supermarket and convenience store refrigerator and freezer cabinets and displays, ice machines, self-contained coolers and freezers, such as beverage coolers, walk-in and reach-in coolers and freezers, supermarket rack and distributed systems, and refrigerated or frozen food transport.

[0135] In one embodiment, the air conditioner may be a residential, commercial, or industrial air-conditioning system. These may include, but are not limited to, window, ducted, ductless, packaged terminal, and those exterior to, but connected to the building, such as rooftop systems. These may also include residential heat pumps that provide comfort air-conditioning and heating.

[0136] In another embodiment, the cooling may be performed in a chiller. Chillers, including both flooded evaporator and direct expansion chillers, may be coupled with an air handling and distribution system to provide comfort air conditioning (cooling and dehumidifying the air) to large commercial buildings, including hotels, office buildings, hospitals, universities and the like. In another embodiment, chillers, most likely air-cooled direct expansion chillers, have found additional utility in naval submarines and surface vessels.

[0137] Chillers may be characterized by the compressor used. In one embodiment, the chiller may comprise a centrifugal compressor. In another embodiment, the chiller may comprise a scroll compressor. In another embodiment the chiller may comprise a screw compressor. In yet another embodiment, the chiller may comprise a reciprocating compressor.

[0138] The present method for cooling may be particularly useful in high ambient temperature regions, due to the high critical temperature of blends comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2.

[0139] In another embodiment, the method for producing cooling is particularly useful in regions where the ambient temperature can exceed at least 35°C.

[0140] In geographic 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. As a consequence, these refrigerants do not perform well in extreme hot environments. The energy efficiency of a refrigerant generally decreases as the condensing temperature approaches the refrigerant critical temperature during operation at high ambient temperatures. In hot climates, R-22 has remained the refrigerant of choice for much air conditioning and refrigeration applications as it is not flammable and has a higher critical temperature so that it delivers higher cooling capacity and higher energy efficiency in hot climates as compared to R-410A or R- 32. However, R-22 is an ozone depleting substance in the Montreal Protocol to reduce ozone depletion. As such, R-22 has been mandated and legislated for phase out for manufacture for and use in air conditioning and refrigeration. There is interest in finding a refrigerant with the lowest possible direct GWP and also that performs well in hot climate (or high ambient) temperature regions.

[0141] In the method for producing cooling the body to be cooled may be defined as any space, location, object, or body for which it is desirable to provide cooling. Examples include spaces, open or enclosed, that require cooling such as a residence, such as an apartment or apartment building, university dormitory, townhouse or other attached house, or a single-family home; or the body to be cooled may be any other building, such as an office building, supermarket, college or university classroom or administration buildings.

[0142] In another embodiment, a method for producing air conditioning in high ambient temperatures is provided. The method comprises evaporating a composition comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2and thereafter condensing said composition. The method is particularly useful in regions where ambient temperatures can exceed 35°C or more.

[0143] In another embodiment, a method is provided for replacing HCFC-22 in high ambient air conditioning apparatus comprising providing a composition comprising, consisting essentially of, or consisting of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 to said apparatus. The method of replacing HCFC-22 is particularly useful in regions where ambient temperatures can exceed 35°C or more.

[0144] Similarly, in some industrial air conditioning applications heat must be released in high ambient temperature environments. HCFC-124 has been used as the working fluid in such applications. HCFC-124 is also controlled under the Montreal protocol as an ozone depleting substance and more environmentally sustainable replacements are desirable. Thus, a method is provided for replacing HCFC-124 in industrial air conditioning apparatus, comprising providing a composition comprising, consisting essentially of, or consisting of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 to said apparatus. The method of replacing HCFC-124 is particularly useful in regions where ambient temperatures can exceed 35°C or more.

[0145] In another embodiment, the method for producing cooling and method for replacing HCFC-22 or HCFC-124 are useful for systems operating in ambient temperatures of 40°C or higher. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures of 45°C or higher. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures of 50°C or higher. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures of 55°C or higher. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures of 60°C or higher. In another embodiment, the method for producing cooling is useful for systemsoperating in ambient temperatures from 35-50°C. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures from 35-60°C. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures from 40- 60°C. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures from 45-60°C. In another embodiment, the method for producing cooling is useful for systems operating in ambient temperatures from 50-60°C.

[0146] In another embodiment, provided is a method of heating comprising evaporating a composition comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132EHFC-32, HFC-134, CF3I, and CO2 and thereafter condensing said composition in the vicinity of a body to be heated.

[0147] In one embodiment, the heating is accomplished by a heat pump, which may be a residential, light commercial, commercial, or industrial heat pump system. These may include, but are not limited to, residential heat pumps that provide comfort air-conditioning and heating, hot water heat pumps for heating air (by secondary loop) or for heating water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high temperature heat pumps (with condensing temperature of 50 deg C or higher).

[0148] Due to the high critical temperature of blends comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 it is possible to heat water to higher temperatures than propane or R-454C.

[0149] In another embodiment, is provided a system for cooling or heating comprising a composition comprising, consisting of, or consisting essentially of HFO- 1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2. The system comprises an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle. In another embodiment, the system may further comprise a lubricant. The lubricant may be selected from the group consisting ofpolyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether. In another embodiment, the lubricant is selected from POE or PVE.

[0150] The system for cooling or heating may be a refrigeration system, airconditioner, heat pump, or chiller.

[0151] In one embodiment, the refrigeration system may be a residential, commercial, or industrial refrigeration system. These may include, but are not limited to, supermarket and convenience store refrigerated cases for beverages, dairy, and produce and prepared foods. In one embodiment, the refrigeration system is a low or medium temperature refrigeration system, including supermarket and convenience store refrigerator and freezer cabinets and displays, ice machines, self-contained coolers and freezers, such as beverage coolers, walk-in and reach-in coolers and freezers, supermarket rack and distributed systems, and refrigerated or frozen food transport.

[0152] In one embodiment, the air conditioner may be a residential, commercial, or industrial air-conditioning system. These may include, but are not limited to, window, ducted, ductless, packaged terminal, and those exterior to, but connected to the building, such as rooftop systems. These may also include residential heat pumps that provide comfort air-conditioning and heating.

[0153] In one embodiment, the system is a heat pump, which may be a residential, light commercial, commercial, or industrial heat pump system. These may include, but are not limited to, residential heat pumps that provide comfort air-conditioning and heating, hot water heat pumps for heating air (by secondary loop) or for heating water for residential or commercial use, heat pumps for heating manufacturing process equipment, and high temperature heat pumps (with condensing temperature of 50 deg C or higher).

[0154] In another embodiment, the system is a chiller. Chillers, including both flooded evaporator and direct expansion chillers, may be coupled with an air handling and distribution system to provide comfort air conditioning (cooling and dehumidifying the air) to large commercial buildings, including hotels, office buildings, hospitals, universities and the like. In another embodiment, chillers, most likely air-cooled direct expansion chillers, have found additional utility in naval submarines and surface vessels.

[0155] Chillers may be characterized by the compressor used. In one embodiment, the chiller may comprise a centrifugal compressor. In another embodiment, the chiller may comprise a scroll compressor. In another embodiment the chiller may comprise a screw compressor. In yet another embodiment, the chiller may comprise a reciprocating compressor. When replacing a refrigerant in a chiller, the compressor, often designed for the refrigerant to be used, may need modification. Therefore, for centrifugal chillers, the impeller diameter or impeller tip speed for the new refrigerant must be similar or match that for the original refrigerant to be used as a drop-in replacement.

[0156] In another embodiment, the system containing the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 may be an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle. Electric or hybrid vehicles include automobiles with no internal combustion engine (ICE) or those that maintain an ICE but also use electric power and are therefore hybrid electric vehicles (HEV) or plug-in hybrid electric vehicles (PHEV) or mild hybrid electric vehicles (MHEV). Additionally, electric or hybrid vehicles include full electric vehicles (EV), such as battery electric vehicles (BEV). All of these electric or hybrid vehicles use at least one electric motor, wherein the electric motor provides some form of propulsion for the vehicles normally provided by the ICE found in gasoline / diesel powered vehicles.

[0157] In one embodiment, the automobile heat pump is a secondary loop system. The secondary loop allows the separation of a flammable refrigerant from the passenger compartment, using a heat transfer fluid to produce cooling or heating in the passenger compartment.

[0158] In another embodiment, the automobile heat pump does not include a positive temperature coefficient (PTC) heater. The PTC heater often used in electric vehicles is needed in the absence of an ICE to provide adequate heating to the passenger compartment.

[0159] In another embodiment, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 may be used in amethod of replacing at least one of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R- 449C, R-452A, or R-452C, in refrigeration, air-conditioning, heat pump, or chiller systems comprising providing any of the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 to the system in place of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C.

[0160] In one embodiment, the method for replacement may be a retrofit for existing equipment. Therefore, the method is specific to replacing a refrigerant in equipment that was designed for, or originally contained R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C. In another embodiment, the replacement is simply providing a new refrigerant for an application or use, wherein the new refrigerant can provide improved performance, or meet regulatory requirements that are not met by the incumbent refrigerant.

[0161] The compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO- 1132E, HFC-32, HFC-134, CF3I, and CO2 provide performance that would allow replacement of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C..

[0162] In another embodiment, the compositions comprising, consisting of, or consisting essentially of HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2 provide performance that enables the use as refrigerant in refrigeration, air-conditioning, heat pump, or chiller systems. In particular, the refrigeration, air-conditioning, heat pump, or chiller systems comprise mobile or stationary air conditioning, mobile or stationary heat pumps, residential, light commercial, commercial, or industrial air-conditioner, residential, light commercial, commercial, or industrial heat pump, centrifugal chiller, screw chiller, scroll chiller, flooded evaporator chiller, direct expansion chiller, medium or low temperature refrigeration system, beverage cooler, supermarketdisplay case, ice machine, or transport refrigeration or freezer system. Additionally, the compositions are useful wherein the system is an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle. Further, the compositions may be useful in replacing refrigerants such as R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R- 454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, or R-452C.

[0163] The following Examples are provided to illustrate certain aspects of the invention and shall not limit the scope of the appended claims.EXAMPLESExamples for Residential and EV heat pumps

[0164] In the examples to follow, the conditions for electronic vehicle heat pumps in cooling and heating mode are 0 °C and 40 °C as the average evaporator and condenser temperatures, 10 K of superheat and 0 K of subcooling and -30 °C and 50 °C as the average evaporator and condenser temperatures, 10 K of superheat and 0 K of subcooling respectively.Example 1 : HFO-1132Z and HFC-32

[0165] Broadly, a composition range of 56 to 99 wt-% of R-1132Z and 1 to 44 wt- % R-32 will have a GWP < 300 and a composition range of 78 to 99 wt-% of R- 1132Z and 1 to 22 wt-% R-32 will have a GWP < 150. Table X1 lists example compositions within the GWP < 300 range.

[0166] Blend composition ranges within a composition range of 85 to 92 wt-% of R-1132Z and 8 to 15 wt-% R-32 will have a GWP < 103, a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 2 or 2L, and a minimum cooling capacity (CAP) relative to R-457C of -10 %. The optimal composition for cooling capacity, which is only 1.5% less than that of incumbent fluid R-457C, is 85 wt-% R-1132Z and 15 wt-% R-32, where the COP for cooling is 6% greater than that for the COP of R-457C, the average glide is 4.2 K, and the GWP is 103. The composition with the maximum COP is 92 wt-% R-1132Z and 8 wt-% R-32, where the COP is 6.4% greater than that of R-457C. It is also determined that the mixture will remain as a 2L flammability classification from 1 to 60 wt-% R-1132Z.

[0167] Table X1 : EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / R-32 in Example 1.Example 2: HFO-1132Z and HFO-1132E

[0168] Broadly, blend composition ranges within a composition range of 75 to 99 wt-% of R-1132Z and 1 to 25 wt-% R-1132E will have a GWP close to 1. Table X2 lists example compositions.

[0169] Blend composition ranges within a composition range of 78 to 89 wt-% of R-1132Z and 11 to 22 wt-% R-1132E will have a GWP of about 1 , a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 2, and a minimum cooling capacity relative to R-457C of -10 %. The optimal composition for cooling capacity, which matches that of incumbent fluid R-457C, is 78 wt-% R-1132Z and 22 wt-% R-1132E, where the COP for cooling is 5.5% greater than that for the COP of R-457C, the average glide is 4.3 K, and the GWP is 1.2.The composition with the maximum COP is 89 wt-% R-1132Z and 11 wt-% R-1132E, where the COP is 6.4% greater than that of R-457C. All mixture compositions are class 2 in ASHRAE flammability.

[0170] Table X2: EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / R-1132E in Example 2.Example 3: HFO-1132Z and HFC-134

[0171] Broadly, a composition range of 74 to 99 wt-% of R-1132Z and 1 to 26 wt- % R-32 will have a GWP < 300, and a composition range of 87 to 99 wt-% of R- 1132Z and 1 to 13 wt-% R-32 will have a GWP < 150. Table X3 lists example compositions within the GWP < 300 range. The composition ranges all have class 2 flammability.

[0172] Blend composition ranges within a composition range of 81 to 99 wt-% of R-1132Z and 1 to 19 wt-% R-134 will have a GWP of less than 215, a maximum heat exchanger glide of 0.1 K (in the evaporator), and an ASHRAE flammability classification of 2. The cooling capacity and COP are 7.4% greater and 20% less than that of R-457C. These preferred compositions also all have class 2 flammability.

[0173] Table X3: EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / R-134 in Example 3.Example 4: HFO-1132Z, HFO-1132E, and HFC-32

[0174] Broadly, a composition range of 31 to 99 wt-% of R-1132Z, 1 to 25 wt-% R- 1132E and 1 to 44 wt-% R-32 will have a GWP < 300; and a composition range of 53 to 99 wt-% of R-1132Z, 1 to 25 wt-% R-1132E and 1 to 22 wt-% R-32 will have a GWP < 150. Table X4 lists example compositions within the GWP < 300 range, all of which are of flammability category 2. In order for the mixture to be of 2L flammability at least 40 wt-% of R-32 is required in the blend composition.

[0175] Blend composition ranges within a composition range of 79 to 92 wt-% of R-1132Z, 1 to 21 of R-1132E, and 1 to 14 wt-% R-32 will have a GWP < 96, a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 2, and a minimum cooling capacity of 10% less than that of R-457C. The optimal composition for cooling efficiency, which is 6% greater in COP than that of incumbent fluid R-457C, is 91 wt-% R-1132Z, 6 wt-% R-1132E, and 3 wt-% R-32, where the CAP for cooling is 10% less than that for the CAP of R-457C, the average glide is 2.3 K, and the GWP is 22. The composition with the maximum CAP is 78.6 wt-% R-1132Z, 20.9 wt-% R-1132E, and 0.5 wt-% R-32, where the CAP is matches that of R-457C, and the flammability category is 2.

[0176] Table X4: EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / R-1132E / R-32 in Example 4.Table X4: continuedExample 5: HFO-1132Z, HFO-1132E, and HFC-134

[0177] Broadly, a composition range of 49 to 98 wt-% of R-1132Z, 1 to 25 wt-% R- 1132E and 1 to 27 wt-% R-134 will have a GWP < 300; and a composition range of 62 to 99 wt-% of R-1132Z, 1 to 25 wt-% R-1132E and 1 to 13 wt-% R-134 will have a GWP < 150. Table X5 lists example compositions within the GWP < 300 range. In order to become a 2L or 1 at least 34 wt-% of R-134 is required in the blend.

[0178] Preferred blend composition ranges within a composition range of 68 to 88 wt-% of R-1132Z, 11 to 22 of R-1132E, and 1 to 13 wt-% R-134 will have a GWP < 150, a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 2, and a minimum cooling capacity of 10% less than that of R-457C. The optimal composition for cooling capacity, which is matches the CAP of incumbent fluid R-457C, is 76 wt-% R-1132Z, 23 wt-% R-1132E, and 1 wt-% R- 134, where the COP for cooling is 5.5% greater than that for the COP of R-457C, the average glide is 3.7 K, and the GWP is 12. This same composition also results in the maximum heat capacity in heating mode conditions. The composition with the maximum COP in cooling mode, which is 6.4% greater than that for the COP of R- 457C, is 88.6 wt-% R-1132Z, 10.9 wt-% R-1132E, and 0.5 wt-% R-134, where the CAP is 10% less than that of R-457C, and the flammability category is 2. Similarly, the composition with the maximum COP in heating mode, which is 9.7% greater thanthat for the COP for heating of R-457C, is 94 wt-% R-1132Z, 4 wt-% R-1132E, and 2 wt-% R-134, where the CAP for heating is 10% less than that of R-457C, and the flammability category is 2.

[0179] Table X5: EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / R-1132E / R-134 in Example 5.Example 6: HFO-1132Z, CF3I, and HFC-32

[0180] Broadly, a composition range of 36 to 98 wt-% of R-1132Z, 1 to 20 wt-%CF3I and 1 to 44 wt-% R-32 will have a GWP < 300; and a composition range of 58to 100 wt-% of R-1132Z, 1 to 20 wt-% CF3I and 1 to 22 wt-% R-32 will have a GWP< 150. Table X6 lists example compositions within the GWP < 300 range. In order for the blend to have a GWP < 300 and have an ASHRAE flammability class of 1, 2 or 2L, the composition ranges are 1 to 66 wt-% R-1132Z, 1 to 98 wt-% CF3I and 1 to 44 wt-% R-32.

[0181] Preferred blend composition ranges for cooling within a composition range of 46 to 93 wt-% of R-1132Z, 1 to 48 of CF3I, and 6 to 15 wt-% R-32 will have a GWP< 102, a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 2L or 2, and a minimum cooling capacity of 10% less than that of R-457C.

[0182] Preferred blend composition ranges for heating within a composition range of 24 to 97 wt-% of R-1132Z, 1 to 73 of CF3I, and 2 to 15 wt-% R-32 will have a GWP< 102, a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 1 , 2L or 2, and a minimum heating capacity of 10% less than that of R-457C.

[0183] The optimal composition for cooling efficiency, which is 6.4% greater than the COP of incumbent fluid R-457C in the same conditions, is 81 wt-% R-1132Z, 12 wt-% CF3I, and 7 wt-% R-32, where the CAP for cooling is 10% less than that for the CAP of R-457C, the average glide is 2.6 K, the GWP is 49, and the flammability class is 2.

[0184] The optimal composition for heating efficiency, which is 10% greater than the COP of incumbent fluid R-457C in the same conditions, is 72 wt-% R-1132Z, 26 wt-% CF3I, and 2 wt-% R-32, where the CAP for heating is 10% less than that for the CAP of R-457C for heating, the average glide is 0.8 K, the GWP is 15, and the flammability class is 2. The optimal composition for heating capacity, which is 6% greater than the CAP of incumbent fluid R-457C in the same conditions, is 83 wt-% R-1132Z, 2 wt-% CF3I, and 15 wt-% R-32, where the COP for heating is 9% more than that for the COP of R-457C for heating, the average glide is 3.5 K, the GWP is 103, and the flammability class is 2.

[0185] Table X6: EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / CF3I / R-32 in Example 6.Example 7: HFO-1132Z, HFO-1132E, and CF-J

[0186] According to the foregoing embodiment, disclosed herein are compositions comprising HFO-1132Z, HFO-1132E and CF3I. Broadly, a composition range of 55 to 98 wt-% of R-1132Z, 1 to 25 wt-% R-1132E, and 1 to 20 wt-% CF3I will have a GWP close to 1. Table X7 lists example compositions within this range that have ASHRAE flammability classifications of 1 or 2L.

[0187] Preferred blend composition ranges for cooling within a composition range of 29 to 89 wt-% of R-1132Z, 10 to 22 wt-% of R-1132E, and 1 to 61 of CF3I will have a GWP ~ 1, a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 1, 2L or 2, and a minimum cooling capacity of 10% less than that of R-457C.

[0188] Preferred blend composition ranges for heating within a composition range of 11 to 96 wt-% of R-1132Z, 3 to 23 of R-1132E, and 1 to 83 wt-% CF3I will have a GWP about 1 , a maximum heat exchanger glide of 5 K (in the condenser), an ASHRAE flammability classification of 1 , 2L or 2, and a minimum heating capacity of 10% less than that of R-457C.

[0189] Even more preferred composition ranges for cooling mode that result in ASHRAE flammability classifications of 1 and 2L are 29 to 56 wt-% R-1132Z, 10 to15 wt-% R-1132E, and 34 to 61 wt-% CF3I, where the minimum and maximum heating capacities are 10% and 4% less than those of R-457C respectively. The composition for this maximum heating capacity (only 4% less than for incumbent R- 457C at the same conditions) for a 2L blend is 49 wt-% R-1132Z, 15 wt-% R-1132E and 36 wt-% CF3I.

[0190] Even more preferred composition ranges for heating mode that result in ASHRAE flammability classifications of 1 and 2L are 11 to 62 wt-% R-1132Z, 4 to 16 wt-% R-1132E, and 34 to 83 wt-% CF3I, where the minimum and maximum heating capacities are 10% less and 4.4% greater than those of R-457C respectively. The composition for this maximum heating capacity for a 2L blend is 50 wt-% R-1132Z,16 wt-% R-1132E and 34 wt-% CF3L

[0191] The optimal composition for cooling efficiency, which is 6.4% greater than the COP of incumbent fluid R-457C evaluated at the same conditions, is 84 wt-% R- 1132Z, 10 wt-% R-1132E and 6 wt-% CF3I, where the CAP for cooling is 10% less than that for the CAP of R-457C, the average glide is 2.3 K, the GWP is about 1 , and the flammability class is 2. The optimal composition for cooling capacity, which is the same as that for incumbent fluid R-457C in the same conditions, is 77 wt-% R- 1132Z, 22 wt-% R-1132E, and 1 wt-% CF3I, where the COP for heating is 5.5% more than that for the COP of R-457C for heating, the average glide is 4.3 K, the GWP is about 1 , and the flammability class is 2.

[0192] The optimal composition for heating efficiency within the preferred composition range of

[0025] , which is 10% greater than the COP of incumbent fluid R-457C in the same conditions, is 71 wt-% R-1132Z, 3 wt-% R-1132E and 26 wt-% CF3I, where the heating capacity is 10% less than that for R-457C, the average glide is 0.8 K, the GWP is about 1, and the flammability class is 2. The optimal composition for heating capacity, which is 8% greater than the heating capacity of incumbent fluid R-457C in the same conditions, is 75 wt-% R-1132Z, 23 wt-% R- 1132E, and 2 wt-% CF3I, where the COP for heating is 8% more than that for the COP of R-457C for heating, the average glide is 3.7 K, the GWP is about 1, and the flammability class is 2.

[0193] Table X7: EVHP conditions in cooling mode, cycle metric performance and fluid property ranges for R-1132Z / R-1132E / CF3I in Example 7.Table X7: (continued)

Claims

CLAIMSWhat is claimed is:

1. A composition comprising HFO-1132Z and at least one compound selected from the group consisting of HFO-1132E, HFC-32, HFC-134, CF3I, and CO2.

2. The composition of claim 1 , comprising HFO-1132Z and selected from the group consisting of: about 56 to 99 weight percent HFO-1132Z and about 1 to 44 weight percent HFC-32, or about 78 to 99 weight percent HFO-1132Z and about 1 to 22 weight percent HFC-32, or about 85 to 92 weight percent HFO-1132Z and about 8 to 15 weight percent HFC-32; about 75 to 99 HFO-1132Z and about 1 to 25 weight percent HFO-1132E, or about 78 to 89 weight percent HFO-1132Z and about 11 to 22 weight percent HFO-1132E; about 73.5 to 99 weight percent HFO-1132Z and about 1 to 26.5 weight percent HFC-134, or about 86.75 to 99 weight percent HFO-1132Z and about 1 to 13.25 weight percent HFC-134, or about 81 to 99 weight percent HFO- 1132Z and about 1 to 19 weight percent HFC-134; about 31 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 44 weight percent HFC-32, or about 53 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 22 weight percent HFC-32, or about 79 to 92 weight percent HFO- 1132Z, about 1 to 21 weight percent HFO-1132E, and about 1 to 14 weight percent HFC-32; about 48.5 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 26.5 weight percent HFC-134, or about 61.75 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 13.25 weight percent HFC-134, or about 68 to 88 weight percent HFO-1132Z, about 11 to 22 weight percent 1132E, and about 1 to 13 weight percent HFC-134; about 36 to 98 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, and about 1 to 30 weight percent CF3I, or about 58 to 98 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, and about 1 to 30weight percent CF3I, or about 24 to 97 weight percent HFO-1132Z, about 1 to 73 weight percent HFC-32, and about 2 to 15 weight percent CF3I, or about 42 to 93 weight percent HFO-1132Z, about 1 to 48 weight percent HFC-32, and about 6 to 15 weight percent CF3I ; about 55 to 98 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 20 weight percent CF3I, or about 11 to 96 weight percent HFO-1132Z, about 3 to 23 weight percent HFO-1132E, and about 1 to 83 weight percent CF3I, or about 29 to 89 weight percent HFO-1132Z, about 10 to 22 weight percent HFO-1132E, and about 1 to 61 weight percent CF3I, or about 11 to 62 weight percent HFO-1132Z, about 4 to 16 weight percent HFO-1132E, and about 34 to 83 weight percent CF3I, or about 29 to 56 weight percent HFO-1132Z, about 10 to 15 weight percent HFO-1132E, and about 34 to 61 weight percent CF3I; about 53.5 to 98 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, and about 1 to 30 weight percent CF3I, or about 66.75 to 98 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, and about 1 to 30 weight percent CF3I, or about 24 to 97 weight percent HFO-1132Z, about 2 to 15 weight percent HFC-32, and about 1 to 73 weight percent CF3I, or about 42 to 92 weight percent HFO-1132Z, about 6 to 15 weight HFC-32, and about 1 to 48 weight percent CF3I; about 51 to 99 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, and about 1 to 5 weight percent CO2, or about 73 to 99 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, and about 1 to 5 weight percent CO2; about 70 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, and about 1 to 5 weight percent CO2; about 68.5 to 99 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, and about 1 to 5 weight percent CO2, or about 81.75 to 99 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, and about 1 to 5 weight percent CO2; about 11 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, and about 1 to 30 weightpercent CF3I, or about 33 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC-32, and about 1 to 30 weight percent CF3I; about 28.5 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, and about 1 to 30 weight percent CF3I; about 26 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, and about 1 to 5 CO2, or about 48 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent HFC-32, and about 1 to 5 weight percent CO2; about 43.5 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 26.5 weight percent HFC-134, and about 1 to 5 weight percent CO2, or about 56.75 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, and about 1 to 5 weight percent CO2; about 31 to 99 weight percent HFO-1132Z, about 1 to 44 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 53 to 99 weight percent HFO-1132Z, about 1 to 22 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2; about 50 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 25 weight percent CF3I, and about 1 to 5 weight percent CO2; about 48.5 to 99 weight percent HFO-1132Z, about 1 to 26.5 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 61 .75 to 99 weight percent HFO-1132Z, about 1 to 13.25 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2; about 6 to 99 weight percent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 44 weight percent HFC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, or about 28 to 99 weightpercent HFO-1132Z, about 1 to 25 weight percent HFO-1132E, about 1 to 22 weight percent H FC-32, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2; and about 23.5 to 99 weight percent HFO-1132Z, 1 to 25 weight percent HFO- 1132E, about 1 to 26.5 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2, orabout 36.75 to 99 weight percent HFO-1132Z, 1 to 25 weight percent HFO-1132E, about 1 to 13.25 weight percent HFC-134, about 1 to 30 weight percent CF3I, and about 1 to 5 weight percent CO2.

3. The composition of claim 1 or 2, wherein the CF3I is present at about 1 to 25 weight percent or about 1 to 20 weight percent.

4. The composition of claim 1 or 2, wherein the CO2 is present at about 1 to 3 weight percent.

5. The composition of any of claims 1 to 4, wherein said composition is classified as class 2L or 1 for flammability according to ASHRAE Standard 34.

6. The composition of any of claim 1 to 5, further comprising at least one additional compound selected from the group consisting of methane, ethane, HFC-41 , HCC-40, HFCF-22, HFC-23, HFO-1141 , HFO-1132E, HFC-161 , HFC- 152, HFC-143, HFC-143a, HFC-134a, PFC-116, HCFO-1122, HCFO-1122aE, HCFO-1122aZ, HCC-150, HCFC-151 , CFO-1112, HCFC-142a, HCFC-132, HCFC-133, HCFC-133b, HCFC-123, HFO-1123, HFO-1132a, HCFO-1131 E, HCFO-1131Z, ethylene, and acetylene.

7. The composition of any of claims 1 to 6, wherein said composition further comprises from 0.1 to 200 ppm by weight of water; from about 10 ppm by volume to about 0.35 volume percent oxygen; and / or from about 100 ppm by volume to about 1.5 volume percent air or NAG.

8. The composition of any of claims 1 to 7, wherein said composition comprises a stabilizer.

9. The composition of claim 8, wherein the stablilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, and lactones.

10. The composition of any of claims 8 or 9, wherein the stabilizer is selected from tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butyl hydroquinone, 2,6- di-terbutyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, d- limonene, a-terpinene, p-terpinene, a-pinene, p-pinene, or butylated hydroxytoluene.

11. The composition of any of claims 8 to 10, wherein the stabilizer is present in an amount from about 0.001 to 1.0 weight percent based on the weight of the refrigerant.

12. The composition of any of claims 1 to 11 , wherein the composition further comprises a lubricant.

13. The composition of claim 12, wherein said lubricant is at least one selected from the group consisting of polyalkylene glycol, polyol ester, poly-a-olefin, and polyvinyl ether.

14. The composition of claim 12 or 13, wherein said lubricant is a polyol ester or a polyvinyl ether.

15. The composition of any of claims 12 to 14, wherein said lubricant has at least one property selected from the group consisting of volume resistivity of greater than 1010Q-m at 20 °C; surface tension of from about 0.02 N / m to 0.04 N / m at 20 °C; kinematic viscosity of from about 20 cSt to about 500 cSt at 40 °C; a breakdown voltage of at least 25 kV; and a hydroxy value of at most 0.1 mg KOH / g.

16. The composition of any of claims 1 to 15, wherein the composition comprises at least one tracer.

17. The composition of claim 16, wherein said tracer is present in an amount from about 1.0 ppm by weight to about 1000 ppm by weight.

18. The composition of any of claims 16 or 17, wherein said 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.

19. The composition of any of claims 16 to 18, wherein said 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-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.

20. The composition of any of claims 1 or 19, wherein the composition is free of or substantially free of Group A Fluorinated Substances, and wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.

21. A method for cooling comprising evaporating a composition of any of claims 1 to 20 in the vicinity of a body to be cooled and thereafter condensing said composition.

22. A method for heating comprising evaporating a composition of any of claims 1 to 20 and thereafter condensing said composition in the vicinity of a body to be heated.

23. A system for cooling or heating comprising a composition of any of claims 1 to 20.

24. The system of claim 23, comprising an evaporator, compressor, condenser, and expansion device, each operably connected to perform a vapor compression cycle.

25. The system of claim 23 or 24, wherein said system is a residential, light commercial, or industrial air-conditioner, heat pump, or chiller.

26. The system of claim 23 to 25, wherein said system is a medium or low temperature refrigeration system, beverage cooler, supermarket display case, ice machine, or transport refrigeration or freezer system.

27. The system of any of claims 23 to 25, wherein the system is an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle.

28. The system of any of claims 23 to 27, wherein the system is a secondary loop system.

29. The system of any of claims 23 to 25, 27, or 28, wherein the system does not include a PTC heater.

30. A method of replacing at least one of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R- 449A, R-449B, R-449C, R-452A, R-452C, or in refrigeration, air-conditioning, heat pump, or chiller systems comprising providing the composition of any of claims 1 to 20 to the system in place of R-22, HFC-134a, propane, HFO- 1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R-449C, R-452A, R-452C.

31. Use of the composition of any of claims 1 to 20 as refrigerant in refrigeration, air-conditioning, heat pump, or chiller systems.

32. The use of claim 31, wherein the refrigeration, air-conditioning, heat pump, or chiller systems comprise mobile or stationary air conditioning, mobile or stationary heat pumps, residential, light commercial, or industrial airconditioner, residential, light commercial, or industrial heat pump, centrifugal chiller, screw chiller, scroll chiller, flooded evaporator chiller, direct expansion chiller, medium or low temperature refrigeration system, beverage cooler,supermarket display case, ice machine, or transport refrigeration or freezer system.

33. The use of claim 31 or 32, wherein the system is an automobile heat pump for cooling and heating the passenger compartment of an electric or hybrid vehicle.

34. The use of any of claims 31 to 33, wherein the system is a secondary loop system.

35. The use of any of claims 31 to 34, wherein the system does not include a PTC heater.

36. The use of any of claims 31 to 35, wherein the composition of claims 1 to 20 is replacing any one of R-22, HFC-134a, propane, HFO-1234yf, R-407C, R-404A, R-410A, R-513A, R-454A, R-454B, R-454C, R-448A, R-449A, R-449B, R- 449C, R-452A, or R-452C.

37. The composition of any of claims 1 to 20, wherein said composition provides average temperature glide less than 8 K, or less than 6 K, or less than 5 K, or less than 4 K, or less than 3 K, or less than 2 K, or less than 1 K.

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