Compositions containing hexafluorobutene, tetrafluoropropene, and tetrafluoroethane, and uses thereof

Abstract

Disclosed herein are cooling and heating compositions comprising a refrigerant consisting essentially of HFO-1336mzzE, HFO-1234ze, and HFC-134. These compositions are useful in methods for replacing HFO-1234zeE, R-515A, or R-515B. The compositions of the present invention provide a non-flammable, low-GWP refrigerant that can match the performance of HFO-1234zeE.

Description

[Technical Field]

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

[0002] The refrigeration industry has been working to find replacements for the ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which are being phased out as a result of the Montreal Protocol. Hydrofluorocarbons (HFCs) have served this purpose for the past few decades. Now, due to new regulations regarding global warming potential (GWP), HFCs also need to be replaced.

[0003] The hydrofluoroolefin 1,3,3,3-tetrafluoropropene (HFO-1234zeE) has a low GWP and is currently used in chillers and other medium-pressure applications. However, HFO-1234zeE is classified as a 2L flammable refrigerant by the American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE). Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need for non-flammable (Class 1) refrigerants for these same applications. [Means for solving the problem]

[0005] The present disclosure provides compositions comprising a refrigerant consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134. These compositions have surprisingly been found to provide non-flammable, low GWP refrigerants that are comparable in cooling capacity and COP to HFO-1234zeE alone.

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

[0007] In one embodiment of the invention, a composition comprises a refrigerant comprising about 18 to 62 weight percent HFO-1336mzzE, about 26 to 69 weight percent HFO-1234zeE, and about 1 to 13 weight percent HFC-134.

[0008] In another embodiment of the invention, a composition comprises a refrigerant comprising about 18 to 31 weight percent HFO-1336mzzE, about 56 to 69 weight percent HFO-1234zeE, and about 5 to 13 weight percent HFC-134.

[0009] In another embodiment of the invention, a composition comprises a refrigerant comprising about 18 to 22 weight percent HFO-1336mzzE, about 65 to 69 weight percent HFO-1234zeE, and about 10 to 13 weight percent HFC-134.

[0010] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant that is non-flammable per ASTM E681.

[0011] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant having a GWP of less than 300, preferably less than 150.

[0012] Also disclosed herein, in accordance with any of the foregoing embodiments, are compositions comprising a refrigerant that provides a volumetric cooling capacity within 20%, preferably within 10%, of HFO-1234zeE at the same operating conditions.

[0013] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant having an average temperature gradient of 6.0 K or less, preferably 5.0 K or less, and more preferably 4.0 K or less.

[0014] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition further comprising at least one lubricant.

[0015] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant, wherein the lubricant is selected from the group consisting of polyalkylene glycols, polyol esters, and polyvinyl ethers, and combinations thereof.

[0016] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant, further comprising at least one stabilizer.

[0017] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, an azole, a phenolic compound, a cyclic monoterpene, a terpene, a phosphite, a phosphate, a phosphonate, a thiol, a lactone, and combinations thereof.

[0018]

[0013] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant, wherein the stabilizer is selected from the group consisting of tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, butylated hydroxytoluene, and combinations thereof.

[0019] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant, further comprising at least one tracer.

[0020] Also disclosed herein, in accordance with any of the foregoing embodiments, is a composition comprising a refrigerant, wherein the tracer is selected from a hydrofluorocarbon, a hydrofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a hydrochlorofluorocarbon, a hydrochlorofluoroolefin, a hydrochlorocarbon, a hydrochloroolefin, a chlorofluorocarbon, a chlorofluoroolefin, a hydrocarbon, a perfluorocarbon, a perfluoroolefin, and combinations thereof.

[0021] According to any of the foregoing embodiments, there is provided a composition comprising a refrigerant, wherein the tracer is selected from the group consisting of HFC-23, HCFC-31, HFC-41, HFC-161, HFC-152a, HFC-143a, HFC-125, HFC-227ca, HFC-227ea, HFC-236fa, HFC-236cb, HFC-236ea, HFC-245cb, HFC-245fa, HFC-245eb, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281fa, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-115, CFC-116, CFC-117, CFC-118, CFC-119 ...

[0013] Also disclosed herein are compositions selected from HCFC-4a, 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-1234ye, HFO-1243zf, HFO-1225yeZ, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PFC-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, and combinations thereof.

[0022] In another embodiment, disclosed herein is a refrigerant storage vessel containing a composition according to any of the preceding embodiments, wherein the refrigerant comprises a gas phase and a liquid phase.

[0023] In another embodiment, disclosed herein is a process for producing cooling, comprising evaporating a composition according to any of the preceding embodiments in the vicinity of a body to be cooled, and then condensing the composition.

[0024] In some embodiments, disclosed herein is a process for producing heating, the process comprising condensing a composition according to any of the preceding embodiments in the vicinity of a body to be heated, and then evaporating the composition.

[0025] In another embodiment, disclosed herein is a system for refrigeration comprising an evaporator, a compressor, a condenser, and an expansion device, the system comprising the composition of any of the previous embodiments.

[0026] In another embodiment, the cooling and / or heating system is a chiller. In another embodiment, the cooling and / or heating system is a direct expansion or flooded evaporative chiller. In another embodiment, the cooling and / or heating system includes a compressor selected from a centrifugal, screw, scroll, or reciprocating compressor. In another embodiment, the cooling and / or heating system includes a centrifugal compressor. In another embodiment, the cooling and / or heating system includes a screw compressor. In another embodiment, the cooling and / or heating system includes a scroll compressor. In another embodiment, the cooling and / or heating system includes a reciprocating compressor.

[0027] In another embodiment, a system for heating includes an evaporator, a compressor, a condenser, and an expansion device, the system containing a composition according to any of the previous embodiments. In another embodiment, the system for cooling and heating is a heat pump. In another embodiment, the system is a high temperature heat pump. In another embodiment, the system is a water heating heat pump. In another embodiment, the system is an air heating heat pump.

[0028] In another embodiment, disclosed herein is a method for replacing HFO-1234zeE in a system for cooling or heating, comprising providing the system with a composition of any of the preceding embodiments. In another embodiment, the method replaces HFO-1234zeE in a chiller. In another embodiment, the method replaces HFO-1234zeE in a heat pump. In another embodiment, the method replaces HFO-1234zeE in a water-heating heat pump. In another embodiment, the method replaces HFO-1234zeE in an air-heating heat pump. In another embodiment, the method replaces HFO-1234zeE in a high-temperature heat pump.

[0029] In another embodiment, also disclosed herein is a process for generating mechanical energy, comprising: evaporating a working fluid; expanding the working fluid in an expander, thereby producing mechanical energy; condensing the working fluid; and pumping the working fluid back to an evaporator, wherein the working fluid comprises a composition according to any of the preceding embodiments.

[0030] In another embodiment, also disclosed herein is the use of a composition according to any of the preceding embodiments as a working fluid in a power cycle, in which the power cycle may be an Organic Rankine cycle (ORC).

[0031] Also disclosed is a power cycle device comprising an evaporator, an expander, a condenser, and a pump, the device containing a working fluid comprising a composition according to any of the preceding embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0032] definition As used herein, the term heat transfer fluid (also called heat transfer medium) refers to a composition used to transport heat from a heat source to a heat sink.

[0033] A heat source is defined as any space, location, object, or body to which it is desirable to add, transfer, move, or remove heat. Examples of heat sources are spaces (open or enclosed) requiring refrigeration or cooling, such as supermarket refrigerators or freezer cases, refrigerated shipping containers, building spaces requiring air conditioning, industrial water coolers, or the passenger compartment of an automobile requiring air conditioning. In some embodiments, the heat transfer composition may remain constant (i.e., not evaporate or condense) throughout the transfer process. In other embodiments, the heat transfer composition may also be utilized in steam cooling processes.

[0034] A heat sink is defined as any space, place, thing, or object that can absorb heat. A vapor compression refrigeration system is one example of such a heat sink.

[0035] A refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again in a cycle used to transfer heat.

[0036] A heat transfer system is a system (or device) used to produce a heating or cooling effect in a specific space. Heat transfer systems can be portable or stationary.

[0037] Examples of heat transfer systems are any type of refrigeration and air conditioning system, including, but not limited to, stationary heat transfer systems, air conditioners, freezers, refrigerators, heat pumps, high temperature heat pumps, water-heated heat pumps, chillers, water coolers, flooded evaporative chillers, direct expansion chillers, walk-in coolers, portable refrigerators, portable heat transfer systems, portable air conditioning units, dehumidifiers, and combinations thereof.

[0038] Refrigeration capacity (also called cooling capacity) is a term that defines the change in enthalpy of the refrigerant in the evaporator per pound of circulating refrigerant, or the heat removed by the refrigerant in the evaporator per unit volume (volume) of refrigerant vapor leaving the evaporator. Refrigeration capacity is a measure of the ability of a refrigerant or heat transfer composition to produce cooling. Thus, the higher this capacity, the greater the degree of cooling produced. Cooling rate refers to the heat removed per unit time by the refrigerant in the evaporator.

[0039] The Coefficient of Performance (COP) is the amount of heat removed divided by the energy input required to run the cycle. The higher the COP, the more energy efficient it is. COP is directly related to the energy efficiency ratio (EER), which is a rating of the efficiency of a refrigeration or air conditioning unit at a specific combination of internal and external temperatures.

[0040] The term "subcooling" refers to lowering the temperature of a liquid below its saturation point at a given pressure. While the saturation point is the temperature at which vapor is completely condensed into a liquid, subcooling continues to cool the liquid to a lower temperature at a given pressure. Cooling a liquid below its saturation temperature (or boiling point temperature) can increase the net refrigeration capacity. Subcooling thereby improves the refrigeration capacity and energy efficiency of the system. The amount of subcooling is the amount of cooling below the saturation temperature (degrees).

[0041] Superheat is a term that defines how much a vapor composition is heated above its saturated vapor temperature (the temperature at which the first drop of liquid forms when the composition is cooled, also called the "dew point").

[0042] Temperature gradient (sometimes simply referred to as "gradient") is the absolute value of the difference between the start and end temperatures of a phase change process by a refrigerant within a refrigerant system component, excluding any subcooling or superheating. The term can be used to describe the condensation or evaporation of near-azeotropic or non-azeotropic compositions. When referring to the temperature gradient of a refrigeration, air conditioning, or heat pump system, it is common to provide the average temperature gradient, which is the average of the evaporator temperature gradient and the condenser temperature gradient.

[0043] Mass flow rate is the amount of refrigerant (in kilograms) circulating through a refrigeration, heat pump, or air conditioning system at a given time.

[0044] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition in use in any heat transfer system) that provides lubrication to the compressor to help prevent parts from seizing.

[0045] Flammability is a term used to refer to the ability of a composition to ignite and / or propagate a flame. For refrigerants and other heat transfer compositions, the lower flammability limit (LFL) is the lowest concentration of the heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the test conditions specified in ASTM E-681. The upper flammability limit (UFL) is the highest concentration of the heat transfer composition in air that can propagate a flame through a homogeneous mixture of the composition and air under the same test conditions. Testing under ASTM E-681 conditions also determines whether a refrigerant compound or mixture is flammable or nonflammable.

[0046] When a refrigerant leaks, the lower boiling point components of the mixture may leak preferentially. This can change the composition of the system and the vapor leak over time. This can cause a non-flammable mixture to become flammable under potential leak conditions. To be classified as non-flammable by ASHRAE (American Society of Heating, Refrigeration and Air-Conditioning Engineers), a refrigerant or heat transfer composition must be non-flammable not only when blended but also under leak conditions.

[0047] Global warming potential (GWP) is an index used to estimate the relative global warming contribution resulting from the atmospheric emission of one kilogram of a particular greenhouse gas compared to the emission of one kilogram of carbon dioxide. GWP can be calculated for various time horizons and indicates the impact of a given gas's atmospheric lifetime. The GWP for a 100-year time horizon is the commonly referenced value. For mixtures, a weighted average can be calculated based on the individual GWPs of each component.

[0048] Ozone depletion potential (ODP) is a number that indicates the amount of ozone destruction caused by a substance. ODP is the ratio of a chemical's effect on the ozone compared to the effect of a similar mass of CFC-11 (fluorotrichloromethane). For this reason, CFC-11 is defined as having an ODP of 1.0. Other CFCs and HCFCs have ODPs ranging from 0.01 to 1.0. HFCs and HFOs contain no chlorine or other ozone-depleting halogens and therefore have an ODP of zero.

[0049] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or device that comprises listed elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent in such composition, process, method, article, device, etc.

[0050] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. In the context of a claim, such a phrase closes the claim to including materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase limits only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0051] The transitional phrase "consisting essentially of" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of." Typically, the components of a refrigerant mixture, and the refrigerant mixture itself, may contain small amounts (e.g., less than about 0.5 weight percent in total) of impurities and / or by-products (e.g., from the production of the refrigerant component or recycling of the refrigerant component from other systems) that do not materially affect the novel and basic characteristics of the refrigerant mixture.

[0052] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should (unless otherwise expressly stated) be construed as also describing inventions that use the terms "consisting essentially of" or "consisting of."

[0053] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0054] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which 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 specific passage is cited. In the event of a conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be limiting.

[0055] composition The present inventors have discovered a refrigerant composition that provides a non-flammable, low-GWP refrigerant with cooling and heating performance comparable or similar to that of HFO-1234zeE. The composition includes a refrigerant composed of HFO-1336mzzE (E-1,1,1,4,4,4-hexafluorobutene), HFO-1234zeE (E-1,3,3,3-tetrafluoropropene), and HFC-134 (1,1,2,2-tetrafluoroethane). Alternatively, the composition may consist essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134.

[0056] HFO-1336mzzE can be made by methods known in the art, such as reacting 1,1,1,4,4,4-hexafluoro-2-iodobutane with KOH using a phase transfer catalyst.

[0057] HFO-1234zeE can be made by methods known in the art, such as by contacting 1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a chromium-based catalyst at elevated temperatures, as described in EP 974,571 (also incorporated herein by reference), or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH) or Mg(OH). HFO-1234zeE is also commercially available.

[0058] HFC-134 can be made by methods known in the art such as the hydrogenation of 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114).

[0059] In one embodiment, a composition comprises a refrigerant consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134. The addition of HFO-1336mzzE to HFO-1234zeE provides a refrigerant with reduced flammability compared to HFO-1234zeE alone. The addition of HFC-134 to the refrigerant of the composition of the present invention provides both increased capacity and further flammability suppression. In one embodiment, a composition comprising a refrigerant consisting essentially of HFO-1336mzzE, HFC-1234zeE, and HFC-134 may be non-flammable according to ASTM E681. In another embodiment, the refrigerants disclosed herein are non-flammable at 60°C. In another embodiment, these refrigerants are non-flammable at 100°C. Many applications in industry prefer or even require non-flammable refrigerants.

[0060] In one embodiment, a composition comprising, consisting of, or consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134 with up to 69 wt% HFO-1234zeE is non-flammable at 60°C per ASTM E681.

[0061] In a preferred embodiment, the refrigerants consisting essentially of HFO-1336mzzE, HFC-1234zeE, and HFC-134 are classified by the American Society of Heating, Refrigeration and Air-Conditioning Engineers (ASHRAE) as non-flammable, Class 1, in accordance with ASHRAE Standard 34. This means that not only are the nominal formulations non-flammable, but the compositions produced during a leak situation also remain non-flammable.

[0062] In another embodiment, the refrigerant containing HFO-1336mzzE, HFC-1234zeE, and HFC-134 has a low GWP. In one embodiment, the refrigerant has a GWP of less than 150, or preferably less than 100, or more preferably less than 50.

[0063] In another embodiment, a composition containing HFO-1336mzzE, HFC-1234zeE, and HFC-134 provides a volume similar to that of HFO-1234zeE alone under the same operating conditions. In one embodiment, the composition disclosed herein provides a volume within 20% of that of HFO-1234zeE alone under the same conditions. In another embodiment, the composition disclosed herein provides a volume within 15% of that of HFO-1234zeE alone under the same conditions. In a preferred embodiment, the composition disclosed herein provides a volume within 10% of that of HFO-1234zeE alone under the same conditions.

[0064] In another embodiment, the compositions containing HFO-1336mzzE, HFO-1234zeE, and HFC-134 disclosed herein provide an average temperature gradient of 5° C. or less over the operating range of interest, or alternatively, 4° C. or less over the operating range of interest, or preferably 3° C. or less over the operating range of interest.

[0065] In addition to the refrigerant, the composition of the present invention may contain other additional compounds, which may be chosen from lubricants, stabilizers, tracers, UV dyes, among others.

[0066] In one embodiment, the compositions disclosed herein containing refrigerants including HFO-1336mzzE, HFO-1234zeE, and HFC-134 may further include at least one refrigeration lubricant. In one embodiment, the at least one lubricant is selected from the group consisting of polyalkylene glycols (PAGs), polyol esters (POEs), and polyvinyl ethers (PVEs), and combinations thereof. Additionally, the compositions of the present invention may include other lubricants, such as mineral oil, alkyl benzenes, and polyalphaolefins, among others. The amount of lubricant included in the compositions of the present invention may vary over a wide range. When the refrigerant is charged into a cooling or heating system, the amount of lubricant mixed with the refrigerant will vary depending on the location within the system.

[0067] The lubricants disclosed herein for combination with the compositions of the present invention have a viscosity of 10°C at 20°C. 10 It has a volume resistivity of greater than Ω-m, a surface tension of about 0.02 N / m to 0.04 N / m at 20°C, a kinematic viscosity of about 20 cSt to about 500 cSt at 40°C, a breakdown voltage of at least 25 kV, and a hydroxyl number of at most 0.1 mg KOH / g.

[0068] In another embodiment, stabilizers can be added to refrigerants containing HFO-1336mzzE, HFO-1234zeE, and optionally HFC-134. The stabilizers function to inhibit decomposition of refrigerant molecules due to the presence of water or oxygen in the system. Additionally, the stabilizers can prevent polymerization of the HFO components of the refrigerant mixture. Thus, provided herein are compositions comprising a refrigerant comprising or consisting essentially of HFO-1336mzzE, HFO-1234zeE, and optionally HFC-134, and further comprising at least one stabilizer. In one embodiment, the at least one stabilizer can be selected from nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, lactones, and combinations thereof. In another embodiment, the stabilizer is selected from the group consisting of tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, butylated hydroxytoluene, and combinations thereof.

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

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

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

[0072] The tracer compound may be selected from hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof. In particular, tracers include HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-161 (fluoroethane), HFC-152a (1,1-difluoromethane), HFC-143a (1,1,1-trifluoroethane), HFC-125 (pentafluoroethane), HFC-227ca (1,1,1,2,2,3,3-heptafluoropropane), HFC-227ea (1,1 ,1,2,3,3,3-heptafluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236cb (1,1,1,2,2,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-245cb (1,1,1,2,2-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane) HFC-245eb (1,1,1,2,3-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281ea (2-fluoropropane), HFC-281fa (1-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (2 -trifluoromethyl-1,1,1,3,3,3-hexafluoropropane), HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane), CFC-12 (dichlorodifluoromethane), CFC-11 (trichlorofluoromethane), CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane), CFC-114a (2,2-dichloro-1,1,1,2-tetrafluoroethane), HCFC-22 (chlorodifluoromethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane), HCFC-124a (1-chloro-1,1,2,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142b (1-chloro-1,1-difluoroethane), HCFC-151a (1-chloro-1-fluoroethane), HCFC- 244bb (2-chloro-1,1,1,2-tetrafluoropropane), HCC-40 (chloromethane), HFO-1141 (fluoroethylene), HCFO-1130 (1,2-dichloroethylene, E- and / or Z-isomer), HCFO-1130a (1,1-dichloroethylene), HCFO-1131 (1-chloro-2-fluoroethylene, E- and / or Z-isomer), HCFO-1131a (1-chloro-1-fluoroethylene), HCFO-1122 (2-chloro-1,1-difluoroethylene), HFO-1123 (trifluoroethylene) ethylene), HFO-1234ye (1,2,3,3-tetrafluoropropene), HFO-1243zf (3,3,3-trifluoropropene), HFO-1225yeZ (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 (hexafluoropropene) ), PFC-31-10mc (decafluorobutane), PFC-31-10my (2-trifluoromethyl-1,1,1,2,3,3,3-heptafluoropropane), 2-chloro-1,1,2-trifluoroethylene (CFC-1113), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-10mee), 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, hexafluorobutadiene, 3,3,3-Trifluoropropyne, HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene), HCFO-1333azd (1,1,3-trichloro-4,4,4-trifluoro-1-butene), HCFO-1333mxz (1,1,2-trichloro-4,4,4-trifluoro-2-butene), HCFO-1334kzz (1,1-dichloro-1,4,4,4-tetrafluoro-2-butene), E- or Z-HCFO-1334bzd (1,3-dichloro-1,4,4,4-tetrafluoro-1-butene), HCFO-1335czd (3-chloro-1,1,4,4,4-pentafluoro-1-butene), HCFO-1335lzz (1-chloro-1,1,4,4,4-pentafluoro-2-butene), HCFC-133a (1-chloro-2,2,2-trifluoroethane), HCFC-345lfd (1,3-dichloro-2,2,2-trifluoroethane), HCFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane), HFC-347mef (1,1,1,2,4,4,4-heptafluorobutane), HFC-356mff (1,1,1,4,4,4-hexafluorobutane), hexafluoroisobutylene (HFIB), HCO-1140 (chloroethene), Z- or E-HCFO-1326mxz (2-chloro-1,1,1,4,4,4-hexafluoro-2-butene), Z-HFO-1336mzz (Z-1,1,1,4,4,4-hexafluoro-2-butene), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons, or one hydrofluorocarbon combined with one or more perfluorocarbons. In other embodiments, the tracer is a blend of at least one CFC and at least one HCFC, HFC, or PFC.

[0073] In another embodiment, provided herein is a storage vessel for a refrigerant containing a composition comprising HFO-1336mzzE, HFO-1234zeE, and HFC-134, as described herein, wherein the refrigerant comprises a vapor phase and a liquid phase.

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

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

[0076] The compositions of the present invention can be prepared by any convenient method for combining the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and then combine the components in a suitable vessel. Agitation may be used if desired. In another embodiment, any of the aforementioned refrigerant compositions can be prepared by blending HFO-1336mzzE, HFO-1234zeE, and HFC-134.

[0077] Methods, processes, and apparatus A vapor compression refrigeration, air conditioning, or heat pump system includes an evaporator, a compressor, a condenser, and an expansion device. The vapor compression cycle reuses refrigerant in multiple steps, producing a cooling effect in some steps and a heating effect in others. The cycle can be simply described as follows: Liquid refrigerant passes through an expansion device and enters an evaporator, where it boils and removes heat from the environment, forming a low-temperature gas and producing cooling. The low-pressure gas enters a compressor, where it is compressed, increasing its pressure and temperature. The high-pressure (compressed) gaseous refrigerant then enters a condenser, where it condenses and releases its heat to the environment. The refrigerant returns to the expansion device, through which the liquid expands from the higher-pressure level in the condenser to the lower-pressure level in the evaporator, thus repeating the cycle.

[0078] In one embodiment, provided herein is a process for producing cooling, the process comprising evaporating any of the compositions described herein in the vicinity of a body to be cooled, and then condensing the composition.

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

[0080] An object to be cooled or heated may be defined as any space, location, object, or object to which it is desirable to provide cooling or heating. Examples include, but are not limited to, spaces (open or enclosed) requiring air conditioning, cooling, or heating, such as rooms, apartments, or buildings, such as apartment buildings, college dormitories, townhouses, or other tenement or single-family homes, hospitals, office buildings, supermarkets, classrooms or administrative buildings at a college or university, and passenger compartments in automobiles or trucks. Additionally, objects to be cooled may include electronic equipment, such as computer equipment, central processing units (CPUs), data centers, server banks, and personal computing devices, among others.

[0081] In some cases, such as with chillers, the object to be cooled is a secondary fluid that is transferred to the space, location, object, or body to which it is desired to provide cooling. The secondary fluid can be, by way of non-limiting example, water, an aqueous brine solution (such as CaCl, MgCl, or the like for cooling equipment in manufacturing processes), or an aqueous glycol or alcohol solution. The same is true for water-heating heat pumps, where the object to be heated is, for example, water that is transferred to a home for heating or to heat water for use in appliances.

[0082] In a cooling process, "proximate" means that the evaporator of a system containing the refrigerant blend of the present invention is located either within or in close proximity to the object to be cooled, such that air moving through the evaporator moves through or around the object to be cooled. In a process for producing heating, "proximate" means that the condenser of a system containing the refrigerant is located either within or in close proximity to the object to be heated, such that air moving through the condenser moves through or around the object to be heated. In some embodiments, with respect to heat transfer, "proximate" can mean, for example, that the object to be cooled is directly immersed in the refrigerant, or that tubing containing the refrigerant flows into, through, and out of electronic equipment.

[0083] In another embodiment, a system for refrigeration is provided, the system including an evaporator, a compressor, a condenser, and an expansion device, the system containing any of the compositions disclosed herein.

[0084] In one embodiment, the system for cooling may be a chiller. In some embodiments, the chiller is a direct expansion evaporative chiller or a flooded evaporative chiller. In some embodiments, the heat exchanger for the chiller operates in a counter-current mode, which increases the efficiency of the system. In some embodiments, the chiller includes a compressor selected from a centrifugal, screw, scroll, or reciprocating compressor.

[0085] A chiller is a heat transfer device that cools (or chills) a liquid and then uses that liquid to cool or heat a secondary location. For example, they are often used to air condition buildings such as office buildings, apartment buildings, and hospitals. Chillers can be used in manufacturing processes to cool equipment such as distillation columns. Additionally, chillers can be used to refrigerate display cases in supermarkets.

[0086] In another embodiment, a system for heating is provided, the system including an evaporator, a compressor, a condenser, and an expansion device, the system containing any of the compositions disclosed herein. In one embodiment, the system for heating can be a heat pump. In one embodiment, the heat pump can be a residential heat pump for heating air. In another embodiment, the heat pump can be a high temperature heat pump. In another embodiment, the heat pump can be a high temperature heat pump for heating water.

[0087] Heat pumps, similar to chillers, can include flooded or direct expansion evaporators. Heat pumps can utilize positive displacement compressors or dynamic compressors (e.g., centrifugal compressors). Positive displacement compressors include reciprocating, screw, or scroll compressors. Of note are heat pumps that use screw compressors. Also of note are heat pumps that use centrifugal compressors.

[0088] Residential heat pumps are used to produce heated air to heat a residence or dwelling (including a single-family home or an attached apartment building) and to produce a maximum condenser operating temperature of about 30°C to about 50°C.

[0089] Of note are high temperature heat pumps that can be used to heat air, water, another heat transfer medium, or some portion of an industrial process, such as a piece of equipment, a storage area, or a process stream. In one embodiment, these high temperature heat pumps use a condenser operating temperature above about 55° C. In one embodiment, the condenser operating temperature for a high temperature heat pump is from about 55° C. to about 150° C. In one embodiment, the system for heating can be a water-heating heat pump.

[0090] Chillers and heat pumps can be characterized by the compressors used therein. Compressors can generally be classified as reciprocating, rotary, jet, centrifugal, scroll, screw, or axial, depending on the mechanical means of compressing the fluid, or as positive displacement (e.g., reciprocating, scroll, or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid being compressed. In one embodiment, the apparatus of the present invention utilizes a centrifugal compressor.

[0091] Centrifugal compressors use rotating elements to accelerate the refrigerant radially and typically include an impeller and diffuser housed in a casing. Centrifugal compressors usually take fluid in at the impeller eye, or central inlet of a circularly moving impeller, and accelerate the fluid radially outward. Some static pressure rise occurs within the impeller, but the majority of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser pair is a compressor stage. Centrifugal compressors are constructed with one to twelve or more stages, depending on the desired final pressure and the volume of refrigerant being handled.

[0092] The pressure ratio or compression ratio of a compressor is the ratio of the absolute discharge pressure to the absolute suction pressure. The pressure delivered by a centrifugal compressor is virtually constant over a relatively wide range of volumes.

[0093] Positive displacement compressors draw vapor into a chamber, which reduces its volume, compressing the vapor. Once compressed, the vapor is forced out of the chamber by further reducing the chamber's volume to zero or near zero. Positive displacement compressors can increase pressure, but this pressure is limited only by volumetric efficiency and the strength of the components that can withstand the pressure.

[0094] Unlike positive displacement compressors, centrifugal compressors rely entirely on the centrifugal force of a high-speed impeller to compress the vapor passing through it. There is no positive displacement, rather there is what is called dynamic compression.

[0095] Multi-stage impeller systems may be used in centrifugal compressors to improve compressor efficiency, thus requiring less power during use. In a two-stage system, the discharge of one stage impeller passes to the inlet of a second impeller during operation. Both impellers may operate using a single shaft. Each stage can create a compression ratio of approximately 4 to 1: that is, the absolute discharge pressure can be four times the absolute suction pressure. Some examples of two-stage centrifugal compressor systems, particularly for automotive applications, are described in U.S. Patent Nos. 5,065,990 and 5,363,674.

[0096] The pressure that a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the impeller diameter and its revolutions per minute. Tip speed and impeller diameter can be estimated by developing a basic relationship for refrigeration equipment that uses centrifugal compressors. The torque that the impeller ideally imparts to the gas is defined as follows: T=m * (v2 * r2-v1 * r1) Equation 1 During the ceremony, T = torque, Newton-meters m=mass flow rate, kg / s v2 = tangential velocity (tip speed) of the refrigerant leaving the impeller, meters / second r2 = radius of outlet impeller, meters v1 = tangential velocity of the refrigerant entering the impeller, meters / second r1 = radius of impeller inlet, meters

[0097] Assuming the refrigerant enters the impeller essentially axially, the tangential component of the velocity is v1=0, and therefore: T=m * v2 * r2 formula 2

[0098] The power required by the shaft is the product of the torque and the rotational speed, P=T * w formula 3 During the ceremony, P=power, W w = rotational speed, revolutions per second Therefore, the following is true: P=T * w=m * v2 * r2 * w formula 4

[0099] At low refrigerant flow rates, the impeller tip speed and the tangential velocity of the refrigerant are approximately the same, and therefore: r2 * w=v2 Equation 5 and P=m * v2 * v2 formula 6

[0100] Another expression for ideal power is the product of mass flow rate and isentropic compression work, P=m * H i * (1000J / kJ) Equation 7 During the ceremony, H i = difference in enthalpy of the refrigerant from saturated vapor at evaporating condition to saturated condensing condition, kJ / kg.

[0101] Combining the two equations, Equation 6 and Equation 7, we obtain the following equation: v2 * v2=1000 * H i formula 8

[0102] Equation 8 is based on some basic assumptions but provides a good estimate of the impeller tip speed.

[0103] The volume of a centrifugal compressor is determined by the size of the flow path through the impeller. This makes the size of the compressor more dependent on the required pressure than on the volume. Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small-scale centrifugal compressors (mini-centrifuges) are designed for high speeds, from about 20,000 RPM to about 75,000 RPM, and typically have small impeller diameters of less than about 0.15 meters (about 6 inches). In another embodiment, mini-centrifugal compressors operate at impeller speeds of 30,000 to 50,000 RPM and have impeller diameters of less than 0.10 meters (about 4 inches).

[0104] In another embodiment, disclosed herein is a method for replacing HFO-1234zeE in a system for cooling or heating, comprising providing the system with a composition of any of the preceding embodiments. In another embodiment, the method replaces HFO-1234zeE in a chiller. In another embodiment, the method replaces HFO-1234zeE in a heat pump. In another embodiment, the method replaces HFO-1234zeE in a water-heating heat pump. In another embodiment, the method replaces HFO-1234zeE in an air-heating heat pump. In another embodiment, the method replaces HFO-1234zeE in a high-temperature heat pump.

[0105] In one embodiment where a system for cooling or heating includes a centrifugal compressor, it is useful for the tip speed (or impeller diameter) of the refrigerant being replaced to be closely comparable to the tip speed (or impeller diameter) used in the replacement, in order to retrofit the system without major modifications. In other words, a good substitute for HFO-1234zeE in a centrifugal system would provide a tip speed that closely approximates the tip speed of HFO-1234zeE. The compositions disclosed herein provide such nearly comparable tip speeds to that of HFO-1234zeE, and therefore make good refrigerants for in-situ retrofit of HFO-1234zeE in centrifugal systems. Additionally, R-515B (ASHRAE designation for a mixture of 8.9 wt% HFC-227ea and 91.1 wt% HFO-1234zeE) and R-515A (ASHRAE designation for a mixture of 12 wt% HFC-227ea and 88 wt% HFO-1234zeE) are non-flammable alternatives to the use of HFO-1234zeE in centrifuge systems. R-515A and R-515B have similar performance to HFO-1234zeE in centrifuge systems and have GWPs of 389 and 289 (AR4), respectively. Thus, the presently claimed compositions containing HFO-1225yeE, HFO-1234zeE, and optionally HFC-134 also serve as good competitors for field retrofits of R-515A or R-515B with similar performance, including lower GWP and similar tip speeds for centrifugal systems.

[0106] Rankine cycle systems are known to be a simple and reliable means of converting thermal energy into mechanical shaft power. Organic working fluids are useful alternatives to water / steam when low-grade thermal energy is encountered. Water / steam systems operating at low-grade thermal energy (typically below 400°F) have associated high volumes and low pressures. To keep system size small and efficiency high, organic working fluids with boiling points near room temperature are used. Such fluids will have higher gas densities, resulting in higher capacity and favorable transport, and heat transfer properties, resulting in higher efficiency compared to water at low operating temperatures. In industrial environments, flammable working fluids such as toluene and pentane are more common, especially when the industrial environment already has large amounts of flammable materials in-situ in the process or at storage locations. When the risks associated with using flammable working fluids were unacceptable, such as for power generation in densely populated areas or near buildings, other fluids such as CFC-113 and CFC-11 were used. While these materials were non-flammable, they posed environmental risks due to their potential ozone depletion. Ideally, organic working fluids should be environmentally acceptable, non-flammable, have low toxicity, and operate at positive pressure.

[0107] Organic Rankine cycle (ORC) systems are often used to recover waste heat from industrial processes. In cogeneration applications, waste heat from the combustion of fuel used to drive a prime mover in a power generation facility is recovered and used, for example, to generate heat or to produce hot water to operate an absorption chiller that supplies heat and provides cooling. In some cases, the demand for hot water is small or nonexistent. The most challenging case occurs when thermal requirements are variable, making load matching difficult and compromising the efficient operation of the cogeneration system. In such cases, it is more useful to use an organic Rankine cycle system to convert the waste heat into shaft power. The shaft power can be used, for example, to operate a pump or to generate electricity. This approach results in higher overall system efficiency and a higher fuel utilization rate. More electricity can be generated for the same amount of fuel input, thereby reducing air emissions from fuel combustion.

[0108] The process that produces the waste heat is at least one selected from the group consisting of fuel cells, internal combustion engines, internal compression engines, external combustion engines, and turbines. Other sources of waste heat can be found in association with refineries, petrochemical plants, oil and gas pipelines, chemical industries, commercial buildings, hotels, shopping malls, supermarkets, bakeries, food processing industries, restaurants, paint curing ovens, furniture manufacturing, plastic molders, cement kilns, lumber kilns (drying), baking operations, steel industries, glass industries, foundries, smelting, air conditioning, refrigeration, and central heating operations. See U.S. Patent No. 7,428,816, the disclosure of which is incorporated herein by reference.

[0109] A preferred composition for use in ORC power cycles includes a refrigerant consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134. The composition includes a refrigerant comprising or consisting essentially of 18 to 62 weight percent HFO-1336mzzE, about 26 to 69 weight percent HFO-1234zeE, and about 1 to 13 weight percent HFC-134. Alternatively, the composition includes a refrigerant comprising about 18 to 31 weight percent HFO-1336mzzE, about 56 to 69 weight percent HFO-1234zeE, and about 5 to 13 weight percent HFC-134. In another embodiment, the composition includes a refrigerant comprising about 18 to 22 weight percent HFO-1336mzzE, about 65 to 69 weight percent HFO-1234zeE, and about 10 to 13 weight percent HFC-134.

[0110] An ORC system will include a heat source that supplies heat to a heat supply heat exchanger. When the working fluid flows through the heat supply heat exchanger (e.g., an evaporator), the working fluid may be vaporized. In other words, the heat supply heat exchanger receives thermal energy from a heat source by any known means of heat transfer. The working fluid of an ORC system circulates through the heat supply heat exchanger where it obtains heat. At least a portion of the liquid working fluid is transformed into a vapor in the heat supply heat exchanger (and possibly the evaporator).

[0111] The working fluid, now in vapor form, is sent to an expander where the expansion process converts at least a portion of the thermal energy provided by the heat source into mechanical energy, typically shaft energy. The shaft power can be used to perform any mechanical work by employing conventional configurations of belts, pulleys, gears, transmissions, or similar devices, depending on the desired speed and torque required. In one embodiment, the shaft can be connected to a power generation device, such as an induction generator. The electricity generated can be used locally or delivered to the grid.

[0112] The working fluid leaving the expander 32, still in vapor form, proceeds to a condenser where heat is suitably removed and the fluid condenses to a liquid.

[0113] The working fluid in liquid form may be returned to the heat supply heat exchanger by flowing to the pump where the fluid pressure is increased, thus completing the Rankine cycle loop. It may also be desirable to locate a liquid surge tank between the condenser and the pump to ensure that there is always an adequate supply of working fluid in liquid form for pump suction.

[0114] Thus, provided herein is a process for generating mechanical energy comprising: evaporating a working fluid; expanding the working fluid in an expander, thereby producing mechanical energy; condensing the working fluid; and pumping the working fluid back to an evaporator, wherein the working fluid comprises a composition described herein as comprising or consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134.

[0115] Additionally provided herein is the use of a composition described herein as comprising or consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134 as a working fluid in a power cycle. In one embodiment, the power cycle is an organic Rankine cycle.

[0116] Finally, provided herein is a power cycle apparatus (e.g., an organic Rankine cycle apparatus) comprising an evaporator, an expander, a condenser, and a pump, the apparatus containing a working fluid comprising a composition described herein as comprising or consisting essentially of HFO-1336mzzE, HFO-1234zeE, and HFC-134.

[0117] The present invention will be described in more detail below by way of specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize a variety of non-critical parameters that can be changed or modified to achieve essentially the same results. [Example]

[0118] Example 1 Cooling performance The cooling performance of compositions containing HFO-1234zeE, HFO-1336mzzE, and HFC-134 was determined under typical conditions for air conditioning and heat pump systems and is shown in Table 1 in comparison to HFO-1234zeE. GWP values ​​are taken from the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report, Working Group I, 2007 (AR4). Average Temp Glide (average of the temperature gradient in the evaporator and the temperature gradient in the condenser), cooling capacity (capacity) compared to 1234zeE, and COP compared to 1234zeE are calculated from physical property measurements of the compositions of the present invention under the following specific conditions:

[0119] [Table 1]

[0120] [Table 2]

[0121] The data clearly demonstrate that all compositions of the present invention have capacities within 20% of that of R-1234zeE alone, slightly improved COPs over R-1234ze alone, reasonable average temperature gradients, and GWPs of less than 150. Thus, compositions containing 18 to 39 weight percent HFO-1336mzzE, 49 to 69 weight percent HFO-1234zeE, and 1 to 13 weight percent HFC-134 provide a non-flammable, low-GWP alternative to R-1234zeE.

[0122] Additionally, the data show that compositions containing 18 to 31 weight percent HFO-1336mzzE, 56 to 69 weight percent HFO-1234zeE, and 5 to 13 weight percent HFC-134 provide capacities within 15% of that of R-1234zeE alone, slightly improved COP, average temperature gradients of less than 4.0°C, and GWPs of 150 or less.

[0123] Finally, the data show that compositions containing 18-22 weight percent HFO-1336mzzE, about 65-69 weight percent HFO-1234zeE, and about 10-13 weight percent HFC-134 provide capacity within 10% of that of R-1234zeE alone, a slightly improved COP, an average temperature gradient of less than 4.0°C, and a GWP of 150 or less.

[0124] Example 2 Power cycle performance R-1234ze and R-515B are currently proposed as working fluids for organic Rankine cycles (OCRs) for power generation. R-515B (a blend of 91.1 wt.% R-1234zeE and 8.9 wt.% R-227ea) offers a non-flammable alternative to R-1234ze, with a GWP of 292, similar capacity to R-1234ze, and azeotrope-like behavior with a slope near 0 K. Operating in a subcritical OCR, the blend of the present invention may be a desirable alternative that exceeds both the power generation capacity and efficiency of R-515B under the same conditions, while maintaining a GWP of less than 150 below 0 K, where flame propagation is zero and the slope is very low. The performance of a composition containing 81 wt.% R-1234zeE, 6 wt.% R-1336mzzE, and 13 wt.% R-134 was estimated using the conditions described below.

[0125] ORC conditions

[0126] [Table 3]

[0127] In summary, the results show that the composition tested here, 81 / 6 / 13 wt% R-1234ze / R-1336mzzE / R-134, offers increased efficiency and power generation capacity compared to R-515B. The new composition has a GWP of 147, 0.3 kg / m 3 A 2.2% increase in efficiency (1.5% more than R-1234zeE) and a 1% increase in power generation (0.34% higher than R-1234zeE) are achieved while maintaining an LFL of 2.00, a heat of combustion of 2.12 kcal / g, a condenser gradient of 0.95 K, and a boiler gradient of 0.5 K. Thus, the new composition demonstrates improved performance when compared to either R-1234zeE or R-515B.

[0128] Example 3 flammable Several compositions related to the present invention were tested using ASTM E681 conditions at 60° C. The results are shown in Table 2 below.

[0129] [Table 4]

[0130] The results show that many of the compositions of the present invention are non-flammable according to ASTM E681. In particular, compositions of the present invention containing 69 wt. % or less HFO-1234zeE are non-flammable.

Claims

1. A composition comprising a refrigerant comprising HFO-1336mzzE, HFO-1234zeE, and HFC-134.

2. 10. The composition of claim 1 comprising about 18 to 39 weight percent HFO-1336mzzE, about 49 to 69 weight percent HFO-1234zeE, and about 1 to 13 weight percent HFC-134.

3. 3. The composition of claim 1 or 2 comprising about 18 to 31 weight percent HFO-1336mzzE, about 56 to 69 weight percent HFO-1234zeE, and about 5 to 13 weight percent HFC-134.

4. 4. The composition of any one of claims 1, 2, or 3 comprising about 18 to 22 weight percent HFO-1336mzzE, about 65 to 69 weight percent HFO-1234zeE, and about 10 to 13 weight percent HFC-134.

5. 5. The composition of any one of claims 1, 2, 3, or 4 comprising about 18 weight percent HFO-1336mzzE, about 69 weight percent HFO-1234zeE, and about 13 weight percent HFC-134.

6. 6. The composition of any one of claims 1 to 5, wherein the refrigerant is non-flammable at 60°C according to ASTM E681.

7. A composition according to any one of claims 1 to 6, wherein the refrigerant has a GWP of less than 300, preferably less than 150.

8. The composition of any one of claims 1 to 7, providing an average temperature gradient of 6.0K or less, preferably 5.0K or less, more preferably 4.0K or less.

9. A composition according to any one of claims 1 to 8, which provides a volumetric cooling capacity within 20%, preferably within 10%, of HFO-1234zeE at the same operating conditions.

10. The composition of any one of claims 1 to 9, further comprising at least one lubricant.

11. 11. The composition of claim 10, wherein the lubricant is selected from the group consisting of polyalkylene glycols, polyol esters, and polyvinyl ethers, and combinations thereof.

12. The composition of any one of claims 1 to 11, further comprising at least one stabilizer.

13. 13. The composition of claim 12, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, cyclic monoterpenes, terpenes, phosphites, phosphates, phosphonates, thiols, lactones, and combinations thereof.

14. 14. The composition of claim 12 or 13, wherein the stabilizer is selected from the group consisting of tolutriazole, benzotriazole, tocopherol, hydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, fluorinated epoxides, n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenyl glycidyl ether, d-limonene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, butylated hydroxytoluene, and combinations thereof.

15. The composition of any one of claims 1 to 14, further comprising at least one tracer.

16. 16. The composition of claim 15, wherein the tracer is selected from hydrofluorocarbons, hydrofluoroolefins, hydrochlorocarbons, hydrochloroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorocarbons, hydrochloroolefins, chlorofluorocarbons, chlorofluoroolefins, hydrocarbons, perfluorocarbons, perfluoroolefins, and combinations thereof.

17. The tracer is HFC-23, HCFC-31, HFC-41, HFC-161, HFC-152a, HFC-143a, HFC-125, HFC-227ca, HFC-227ea, HFC-236fa, HF C-236cb, HFC-236ea, HFC-245cb, HFC-245fa, HFC-245eb, HFC-254eb, HFC-263fb, HFC-272ca, HFC-281ea, HFC-281f a, HFC-329p, HFC-329mmz, HFC338mf, HFC-338pcc, CFC-12, CFC-11, CFC-114, CFC-114a, HCFC-22, HCFC-123, HCFC-1 24, 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-1234ye, HFO-1243zf, HFO-1225yeZ, HFO-1225zc, PFC-116, PFC-C216, PFC-218, PF C-C318, PFC-1216, PFC-31-10mc, PFC-31-10my, HFO-1327mz, HCFO-1333azd, HCFO-1333mxz, HCFO-1334kzz, E- or Z- 17. The composition of claim 15 or 16, wherein the fluorocarbon fluoride is selected from HCFO-1334bzd, HCFO-1335czd, HCFO-1335lzz, HCFC-133a, HCFC-345lfd, HCFC-346mdf, HFC-347mef, HFC-356mff, hexafluoroisobutylene (HFIB), HCO-1140, Z- or E-HCFO-1326mxz, Z-HFO-1336mzz, and combinations thereof.

18. A storage vessel for a refrigerant containing the composition of any one of claims 1 to 17, wherein the refrigerant comprises a gas phase and a liquid phase.

19. 18. A process for producing cooling, comprising evaporating a composition according to any one of claims 1 to 17 in the vicinity of a body to be cooled and then condensing said composition.

20. 18. A process for producing heating, comprising condensing a composition according to any one of claims 1 to 17 in the vicinity of a body to be heated and then evaporating said composition.

21. 18. A system for refrigeration comprising an evaporator, a compressor, a condenser, and an expansion device, said system containing the composition of any one of claims 1 to 17.

22. 22. The system of claim 21, which is a chiller.

23. 23. The system of claim 21 or 22, which is a direct expansion or flooded evaporative chiller.

24. 24. The system of claim 21, 22, or 23, wherein the compressor is selected from a centrifugal, screw, scroll, or reciprocating compressor.

25. 24. The system of claim 21, 22, or 23, wherein the system includes a centrifugal compressor.

26. 24. The system of claim 21, 22, or 23, wherein the system includes a screw compressor.

27. 24. The system of claim 21, 22, or 23, wherein the system includes a scroll compressor.

28. 18. A system for heating, comprising an evaporator, a compressor, a condenser, and an expansion device, said system containing the composition of any one of claims 1 to 17.

29. 30. The system of claim 28, which is a heat pump.

30. 30. The system of claim 28 or 29, which is a high temperature heat pump.

31. 31. The system of claim 28, 29, or 30, which is a water heating heat pump.

32. 31. The system of claim 28, 29, or 30, wherein the system includes a centrifugal compressor.

33. 31. The system of claim 28, 29, or 30, wherein the system includes a screw compressor.

34. 31. The system of claim 28, 29, or 30, wherein the system includes a scroll compressor.

35. 26. A method for replacing HFO-1234zeE in a system for cooling or heating, comprising providing to said system a composition according to any one of claims 1 to 25.

36. 36. The method of claim 35, wherein the system for cooling or heating is a chiller.

37. 37. The method of claim 36, wherein the system for cooling or heating is a heat pump.

38. 38. The method of claim 35, 36, or 37, wherein the system for cooling or heating is a water-heating heat pump.

39. 38. The method of claim 35, 36, or 37, wherein the system for cooling or heating is a high temperature heat pump.

40. 18. A method for replacing HFO-1234zeE or R-515A or R-515B in a system for cooling or heating, the method comprising providing the composition of any one of claims 1 to 17 to the system, the system comprising a centrifugal compressor.

41. 41. The method of claim 40, wherein the composition provides a tip velocity within 20%, or preferably within 10%, of the tip velocity of HFO-1234zeE or R-515A or R-515B.

42. 1. A process for generating mechanical energy, comprising:

18. A process comprising the steps of evaporating a working fluid, expanding the working fluid in an expander thereby producing mechanical energy, condensing the working fluid, and pumping the working fluid back to an evaporator, wherein the working fluid comprises the composition of any one of claims 1 to 17.

43. Use of a composition according to any one of claims 1 to 17 as a working fluid in a power cycle.

44. 44. The use of claim 43, wherein the power cycle is an organic Rankine cycle.

45. 18. A power cycle device comprising an evaporator, an expander, a condenser, and a pump, said device containing a working fluid comprising the composition of any one of claims 1 to 17.

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