Composition

Abstract

The present invention provides a composition comprising (a) 1,1-difluoroethylene (R-1132a), (b) difluoromethane (R-32), (c) trans-1,2-difluoroethylene (R-1132(E)), and (d) one or more of trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), 1,1-difluoroethane (R-152a), and 2,3,3,3-tetrafluoropropene (R-1234yf).

Description

Technical Field

[0001] The present invention relates to a composition, preferably a heat transfer composition that may be suitable as a replacement for existing refrigerants such as R-410A and / or R-454B.

Background Art

[0002] Any listing or discussion of prior published documents or any background in this specification should not necessarily be construed as an admission that the document or background is part of the state of the art or common general knowledge.

[0003] Mechanical cooling systems and related heat transfer devices such as heat pumps and air conditioning systems are well known. In such systems, a refrigerant liquid evaporates at low pressure and takes in heat from the surrounding zone. The resulting vapor is then compressed and sent to a condenser where it condenses and releases heat to a second zone, and the condensate is returned to the evaporator through an expansion valve, thus completing the cycle. The mechanical energy required to compress the vapor and pump the liquid is provided, for example, by an electric motor or an internal combustion engine.

[0004] R-410A is a non-flammable binary mixture of refrigerants R-32 and R-125 and is currently the major refrigerant used for comfortable cooling and heating in residential and light commercial building HVAC systems worldwide. Its high global warming potential (GWP) of 2088 means that it is desirable to replace this refrigerant with one having similar thermodynamic properties and performance characteristics as R-410A but with a lower GWP. Particularly important characteristics are the operating pressure, volumetric cooling capacity, compressor outlet temperature, pressure drop, and energy efficiency, expressed as the coefficient of performance (COP).

[0005] Currently proposed alternative refrigerants with a lower GWP than R-410A include R-32 (675 GWP), R-454B (466 GWP), and R-468C (284 GWP). All of these refrigerants are flammable, and their flammability is classified as "2L" according to the ASHRAE SSPC34 method, meaning a combustion rate of less than 10 cm / sec and a combustion energy of less than 19 MJ / kg. System designs, appliance design standards, and fire safety regulations now recognize and regulate the use of such flammable refrigerants in residential and commercial air conditioning systems. Therefore, it is desirable that any new refrigerants intended as replacement refrigerants also be classified as "2L" flammable.

[0006] While the GWP of R-32, R-454B, and R-468C is lower than that of R-410A, there is still a need for alternatives with even lower GWPs.

[0007] Refrigerants R-454C (31.5% R-32, 78.5% R-1234yf) and R-455A (35% CO2, 21.5% R-32, 75.5% R-1234yf) can all be used as air conditioning refrigerants because they have a GWP of less than 150 and a vapor pressure similar to R-407C and propane (R-290). However, their characteristics differ too much from those of R-410A / R-32 / R-454B to allow for easy adaptation in equipment design.

[0008] Refrigerants such as R-454B, R-454C, and R-455A are formulated using R-1234yf. While R-1234yf possesses desirable performance characteristics, it has been found to rapidly decompose in the environment at 100% molar yield to form trifluoroacetic acid (TFA). TFA is toxic and highly resistant to environmental degradation. Large-scale substitution of R-410A with R-454B would lead to increased levels of TFA in groundwater. Therefore, it would be desirable to develop new refrigerants that produce less TFA than R-454B upon release into the environment.

[0009] Therefore, there is a need to provide alternative refrigerants that have improved properties such as low GWP (Gross Wave Pressure) and also possess acceptable cooling performance, flammability, and toxicology (to reduce the environmental impact of refrigerant leaks). There is also a need to provide alternative refrigerants that can be used in existing devices, such as cooling devices, that require little to no modification.

[0010] More specifically, it would be desirable to develop a refrigerant composition suitable for use as a replacement for R-410A, R-32, or R-454B in integrated air conditioning or heat pump systems, such that the composition has a sufficiently low GWP and physical properties sufficiently close to those of R-410A or R-454B, so that existing equipment designs can be easily adapted to the use of the composition. More preferably, the composition would also be weakly flammable and more environmentally friendly than R-454B, at least in terms of TFA generation. [Disclosure of the Invention]

[0011] The present invention addresses the above and other drawbacks / needs by providing compositions comprising one or more of the following: 1,1-difluoroethylene (R-1132a), difluoromethane (R-32), trans-1,2-difluoroethylene (R-1132(E)), and trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), 2,3,3,3-tetrafluoropropene (R-1234yf), and 1,1-difluoroethane (R-152a). Such compositions are hereinafter referred to as the compositions of the present invention.

[0012] Typically, R-1132a is present in the composition of the present invention in an amount of about 1 to about 20% by weight, for example, about 2 to about 20% by weight, for example, about 3 to about 20% by weight, preferably about 4 to about 18% by weight, for example, about 4 to about 16% by weight.

[0013] The compositions of the present invention typically contain R-32 in an amount of about 1 to about 50% by weight, for example, about 5 to about 45% by weight, for example, about 7 to about 40% by weight, preferably about 10 to about 30% by weight, for example, about 12 to about 25% by weight.

[0014] R-1132(E) is typically present in the compositions of the present invention in amounts of about 1 to about 60% by weight, for example, about 5 to about 55% by weight, for example, about 10 to about 50% by weight, or about 15 to about 45% by weight, preferably about 18 to about 45% by weight. It has been surprisingly found that by including R-1132(E) in these amounts, it is possible to formulate compositions having improved volumetric cooling capacity without impairing GWP.

[0015] One or more of R-1234ze(E), R-152a, and R-1234yf may be present in the composition of the present invention in an amount of about 1 or 2 to about 75% by weight, for example, about 5 to about 70% by weight, for example, about 5 to about 65% by weight, preferably about 10 to about 65% by weight.

[0016] Typically, the compositions of the present invention comprise about 1 to about 20% by weight of R-1132a, about 1 to about 50% by weight of R-32, about 1 to about 60% by weight of R-1132(E), and about 1 or about 2 to about 75% by weight of one or more of R-1234ze(E), R-152a, and R-1234yf.

[0017] More conveniently, the composition of the present invention comprises about 2 to about 20% by weight of R-1132a, about 5 to about 45% by weight of R-32, about 5 to about 55% by weight of R-1132(E), and about 5 to about 70% by weight of one or more of R-1234ze(E), R-152a, and R-1234yf.

[0018] For example, the composition of the present invention comprises about 3 to about 20% by weight of R-1132a, about 7 to about 40% by weight of R-32, about 10 to about 50% by weight of R-1132(E), and one or more of R-1234ze(E), R-152a, and R-1234yf in about 5 to about 65% by weight.

[0019] Advantageously, the compositions of the present invention comprise about 4 to about 18% by weight of R-1132a, about 10 to about 30% by weight of R-32, about 15 to about 45% by weight of R-1132(E), and about 10 to about 65% by weight of one or more of R-1234ze(E), R-152a, and R-1234yf.

[0020] Preferably, the composition of the present invention comprises about 4 to about 16% by weight of R-1132a, about 12 to about 25% by weight of R-32, about 18 to about 45% by weight of R-1132(E), and about 10 to about 65% by weight of one or more of R-1234ze(E), R-152a, and R-1234yf.

[0021] As described above, one or more of R-1234ze(E), R-152a, and R-1234yf are typically present in the compositions of the present invention in amounts of about 1 or about 2 to about 75% by weight, for example, about 5 to about 70% by weight, for example, about 5 to about 65% by weight, preferably about 10 to about 65% by weight. In preferred embodiments, "one or more of R-1234ze(E), R-152a, and R-1234yf" are R-1234ze(E) and R-152a, and are present in the compositions of the present invention in these weight concentrations. It should be understood that R-1234yf may optionally be present in these compositions. In another preferred embodiment, "one or more of R-1234ze(E), R-152a, and R-1234yf" are R-1234ze(E), and are present in these amounts in the compositions of the present invention. It should be understood that R-1234yf and / or R-152a may be present in these compositions at will.

[0022] When present, R-152a is typically included in the composition of the present invention in an amount of about 1 to about 50% by weight, for example, about 2 to about 40% by weight, for example, about 3 to about 35% by weight, preferably about 5 to about 30% by weight.

[0023] When present with R-152a, R-1234ze(E) is typically included in the composition of the present invention in an amount of about 1 to about 70% by weight, for example, about 2 to about 60% by weight, for example, 3 to 50% by weight, or about 3 to about 45% by weight.

[0024] Therefore, the compositions of the present invention may contain R-1132a, R-32, and R-1132(E) in the amounts described above, in particular, as well as about 1 to about 70% by weight of R-1234ze(E) and about 1 to about 50% by weight of R-152a, for example, about 2 to about 60% by weight of R-1234ze(E) and about 2 to about 40% by weight of R-152a, for example, 3 to 50% by weight of R-1234ze(E) and about 3 to about 35% by weight of R-152a, preferably about 3 to 45% by weight of R-1234ze(E) and about 5 to 30% by weight of R-152a.

[0025] When present, R-1234yf is conveniently included in the compositions of the present invention in amounts of about 1 to about 30% by weight, for example, about 1 to about 20% by weight, for example, about 1 to about 10% by weight, or about 1 to about 5% by weight. It has been surprisingly found that including R-1234yf in these amounts ensures that the total potential for TFA production from a unit mass of the compositions of the present invention is significantly lower than the total potential for TFA production from the same amount of R-454B, and at the same time, enables the compositions of the present invention to take advantage of certain advantageous properties such as increased volumetric cooling capacity, reduced temperature glide, and / or reduced compressor outlet temperature.

[0026] Certain preferred compositions of the present invention include R-1132a, R-32, R-1132(E) in particularly the amounts described above, and R-1234ze(E), and also include R-1132a, R-32, R-1132(E) in particularly the amounts described above, and R-1234ze(E) and R-152a. For these compositions, it is also particularly preferred that they contain 0 to about 10% by weight of R-1234yf, for example, 0 to about 5% by weight of R-1234yf, or substantially no R-1234yf.

[0027] For the compositions of the present invention containing R-1132a, R-32, R-1132(E) (in particular in the amounts described above), and R-1234ze(E), R-1234ze(E) is preferably present in an amount of from about 10 to about 50% by weight, for example from about 15 to about 45% by weight, preferably from about 20 to about 40% by weight. For these compositions, it is particularly preferred that they contain from 0 to about 10% by weight of R-1234yf, for example from 0 to about 5% by weight of R-1234yf, or are substantially free of R-1234yf.

[0028] Thus, certain preferred compositions of the present invention contain from about 1 to about 20% by weight of R-1132a, from about 1 to about 50% by weight of R-32, from about 1 to about 60% by weight of R-1132(E), and from about 10 to about 50% by weight of R-1234ze(E).

[0029] Conveniently, such compositions contain from about 2 to about 20% by weight of R-1132a, from about 5 to about 45% by weight of R-32, from about 5 to about 55% by weight of R-1132(E), and from about 10 to about 50% by weight of R-1234ze(E), for example from about 15 to about 45% by weight of R-1234ze(E).

[0030] For example, the compositions of the present invention contain from about 3 to about 20% by weight of R-1132a, from about 7 to about 40% by weight of R-32, from about 10 to about 50% by weight of R-1132(E), and from about 15 to about 45% by weight of R-1234ze(E).

[0031] Advantageously, the compositions of the present invention contain from about 4 to about 18% by weight of R-1132a, from about 10 to about 30% by weight of R-32, from about 15 to about 45% by weight of R-1132(E), and from about 20 to about 40% by weight of R-1234ze(E).

[0032] Preferably, the compositions of the present invention contain from about 4 to about 16% by weight of R-1132a, from about 12 to about 25% by weight of R-32, from about 18 to about 45% by weight of R-1132(E), and from about 20 to about 40% by weight of R-1234ze(E).

[0033] Any of the compositions described above may conveniently further contain carbon dioxide (CO2). While the presence of CO2 generally tends to increase compressor discharge temperature and temperature glide (which can be undesirable), the inventors have surprisingly found that by including CO2 in the compositions of the present invention, both WCF and WCFF can be formulated into low-GWP blends with flammability classified as "2L" under the ASHRAE34 evaluation process.

[0034] What is particularly preferable is, CO2, R-1132a, R-32, R-1132(E), and R-1234ze(E), CO2, R-1132a, R-32, R-1132(E), R-1234ze(E), and R-1234yf, CO2, R-1132a, R-32, R-1132(E), and R-1234yf, as well The present invention comprises CO2, R-1132a, R-32, R-1132(E), and R-1234ze(E) and R-152a.

[0035] When present, CO2 is typically present in the composition of the present invention in an amount of about 1 to about 20% by weight, for example, about 1 or about 2 to about 18% by weight, for example, about 2 to about 16% by weight.

[0036] When CO2 is present in the composition of the present invention, R-1132a may be present in the composition in an amount of about 1 to about 20% by weight, for example, about 1 or about 2 to about 18% by weight, for example, about 2 to about 16% by weight.

[0037] Therefore, R-1132a and CO2 are advantageously present in the composition of the present invention in a combined amount of about 2 to about 25% by weight, for example, about 3 to about 20% by weight, preferably about 4 to about 20% by weight.

[0038] Accordingly, the compositions of the present invention typically include R-1132a and CO2 in a combined amount of about 2 to about 25% by weight, R-32 in about 1 to about 50% by weight, R-1132(E) in about 1 to about 60% by weight, and one or more of R-1234ze(E), R-152a, and R-1234yf in about 1 or about 2 to about 75% by weight.

[0039] The composition of the present invention may contain R-1132a and CO2 in a combined amount of about 2 to about 25% by weight (or, conveniently, about 3 to about 20% by weight), about 5 to about 45% by weight of R-32, about 5 to about 55% by weight of R-1132(E), and one or more of R-1234ze(E), R-152a, and R-1234yf in about 5 to about 70% by weight.

[0040] Conveniently, the composition of the present invention comprises R-1132a and CO2 in a combined amount of about 3 to about 20% by weight, R-32 in about 7 to about 40% by weight, R-1132(E) in about 10 to about 50% by weight, and one or more of R-1234ze(E), R-152a, and R-1234yf in about 5 to about 65% by weight.

[0041] Advantageously, the compositions of the present invention comprise R-1132a and CO2 in a combined amount of about 4 to about 20% by weight, R-32 in about 10 to about 30% by weight, R-1132(E) in about 15 to about 45% by weight, and one or more of R-1234ze(E), R-152a, and R-1234yf in about 10 to about 65% by weight.

[0042] Preferably, the composition of the present invention comprises R-1132a and CO2 in a combined amount of about 4 to about 20% by weight, about 12 to about 25% by weight of R-32, about 18 to about 45% by weight of R-1132(E), and one or more of R-1234ze(E), R-152a, and R-1234yf in an amount of about 10 to about 65% by weight.

[0043] In one embodiment, “one or more of R-1234ze(E), R-152a, and R-1234yf” is (i) R-1234ze(E) and R-152a, or (ii) R-1234ze(E) and R-1234yf, and is present in the composition in the weight concentrations described above with respect to “one or more of R-1234ze(E), R-152a, and R-1234yf”. In a preferred embodiment, “one or more of R-1234ze(E), R-152a, and R-1234yf” is R-1234ze(E), and is present in these amounts. For these compositions, it is particularly preferred that they contain 0 to about 10% by weight of R-1234yf, for example, 0 to about 5% by weight of R-1234yf, or substantially contain no R-1234yf.

[0044] As described above, one or more of R-1234ze(E), R-152a, and R-1234yf are typically present in the composition of the present invention in an amount of about 1 to about 75% by weight, for example, about 5 to about 70% by weight, for example, about 5 to about 65% by weight, preferably about 10 to about 65% by weight.

[0045] When present, R-152a is typically included in the composition of the present invention in an amount of about 1 to about 50% by weight, for example, about 2 to about 40% by weight, for example, about 3 to about 35% by weight, preferably about 5 to about 30% by weight.

[0046] When present with R-152a, R-1234ze(E) is typically included in the composition of the present invention in an amount of about 1 to about 70% by weight, for example, about 2 to about 60% by weight, for example, 3 to 50% by weight, or 3 to 45% by weight.

[0047] Therefore, the composition of the present invention may contain CO2, R-1132a, R-32, R-1132(E) in the amounts described above, in particular, as well as about 1 to about 70% by weight of R-1234ze(E) and about 1 to about 50% by weight of R-152a, for example, about 2 to about 60% by weight of R-1234ze(E) and about 2 to about 40% by weight of R-152a, for example, 3 to 50% by weight of R-1234ze(E) and about 3 to about 35% by weight of R-152a, preferably about 3 to 45% by weight of R-1234ze(E) and about 5 to 30% by weight of R-152a.

[0048] When present, R-1234yf is conveniently included in the compositions of the present invention in amounts of about 1 to about 30% by weight, for example, about 1 to about 20% by weight, for example, about 1 to about 10% by weight, or about 1 to about 5% by weight. It has been surprisingly found that including R-1234yf in these amounts ensures that the total potential for TFA production from a unit mass of the compositions of the present invention is significantly lower than the total potential for TFA production of the same amount of R-454B, and at the same time, enables the compositions of the present invention to take advantage of certain advantageous properties, such as increased volumetric cooling capacity, reduced temperature glide, and / or reduced compressor outlet temperature, particularly the reduced compressor outlet temperature.

[0049] As described above, more preferred compositions of the present invention include CO2, R-1132a, R-32, R-1132(E), and R-1234ze(E). For compositions of the present invention comprising CO2, R-1132a, R-32, R-1132(E) (particularly in the amounts described above), and R-1234ze(E), it is preferable that R-1234ze(E) is present in an amount of about 10 to about 50% by weight, for example, about 15 to about 45% by weight, preferably about 20 to about 40% by weight. For these compositions, it is also particularly preferable that they contain 0 to about 10% by weight of R-1234yf, for example, 0 to about 5% by weight of R-1234yf, or substantially no R-1234yf.

[0050] Such compositions of the present invention typically comprise R-1132a and CO2 in a combined amount of about 2 to about 25% by weight, R-32 in about 1 to about 50% by weight, R-1132(E) in about 1 to about 60% by weight, and R-1234ze(E) in about 10 to about 50% by weight (conveniently, 15 to about 45% by weight of R-1234ze(E)).

[0051] The composition of the present invention may comprise R-1132a and CO2 in a combined amount of about 2 to about 25% by weight (e.g., about 3 to about 20% by weight), about 5 to about 45% by weight of R-32, about 5 to about 55% by weight of R-1132(E), and about 10 to about 50% by weight of R-1234ze(E) (e.g., about 15 to about 45% by weight of R-1234ze(E)).

[0052] Conveniently, the composition of the present invention comprises R-1132a and CO2 in a combined amount of about 3 to about 20% by weight, R-32 in about 7 to about 40% by weight, R-1132(E) in about 10 to about 50% by weight, and R-1234ze(E) in about 15 to about 45% by weight.

[0053] Advantageously, the compositions of the present invention comprise R-1132a and CO2 in a combined amount of about 4 to about 20% by weight, R-32 in about 10 to about 30% by weight, R-1132(E) in about 15 to about 45% by weight, and R-1234ze(E) in about 20 to about 40% by weight.

[0054] Preferably, the composition of the present invention comprises R-1132a and CO2 in a combined amount of about 4 to about 20% by weight, about 12 to about 25% by weight of R-32, about 18 to about 45% by weight of R-1132(E), and about 20 to about 40% by weight of R-1234ze(E).

[0055] Certain preferred compositions of the present invention include CO2 and R-1132a in a combined amount of about 6 to about 18% by weight, R-1132(E) in about 25 to about 45% by weight, R-32 in about 15 to about 28% by weight, and R-1234ze(E) in about 20 to about 40% by weight. Advantageously, the composition includes CO2 and R-1132a in a combined amount of about 8 to about 14% by weight, R-1132(E) in about 30 to about 45% by weight, R-32 in about 18 to about 25% by weight, and R-1234ze(E) in about 25 to about 35% by weight.

[0056] Any of the compositions described above may further contain one or more compounds selected from the group consisting of 1,1,1,2-tetrafluoroethane (R-134a), isobutane (R-600a), propane (R-290), octafluoropropane (R-218), hexafluoropropylene (R-1216), 1,1,1,2,3,3,3-heptafluoropropane (R-227ea), trifluoroethylene (R-1123), fluoromethane (R-41), 3,3,3-trifluoropropene (R-1243zf), and / or fluoroethane (R-161), and mixtures thereof. Typically, the compositions of the present invention contain about 1 to about 15% by weight, for example, about 1 to about 10% by weight, for example, about 1 to about 5% by weight, of one or more compounds. Without being constrained by theory, it is considered that, when present, one or more compounds may increase the vapor pressure of the compositions of the present invention and / or increase their volumetric capacity and / or reduce their thermal glide.

[0057] In one embodiment, the composition may essentially consist of the components described. By the term "essentially consisting of," the inventors include the meaning that the composition of the present invention substantially does not contain other components, in particular further (hydro)(fluoro) compounds (e.g., (hydro)(fluoro)alkanes or (hydro)(fluoro)alkenes) known to be used in heat transfer compositions. The term "consisting of" is included in the meaning of "essentially consisting of."

[0058] In one embodiment, the composition of the present invention substantially contains no components having heat transfer properties other than the specified components. For example, the composition of the present invention may substantially contain no other hydrofluorocarbon compounds.

[0059] By "substantially absent" and "substantially not containing," the inventors include the meaning that the compositions of the present invention contain 0.5% by weight or less, preferably 0.4%, 0.3%, 0.2%, or 0.1% or less of the described components, based on the total weight of the composition.

[0060] In one embodiment, the composition is substantially free of trifluoroiodomethane (CF3I).

[0061] Preferably, the compositions of the present invention are substantially free of trifluoroethylene (R-1123). Surprisingly, such compositions have been found to have improved lifespan and chemical stability when used in heat transfer devices.

[0062] All chemical substances described herein are commercially available. For example, fluorochemicals may be obtained from Apollo Scientific (UK), and carbon dioxide may be obtained from liquefied gas suppliers such as Linde AG.

[0063] When used herein, all percentage amounts referred to in the compositions herein, including in the claims, are by weight based on the total weight of the composition unless otherwise stated.

[0064] By using the term "approximately" in relation to the numerical value of the amount of an ingredient in weight percent, the inventors include the meaning of ±0.5% by weight, for example, ±0.1% by weight.

[0065] To avoid any ambiguity, it should be understood that the stated upper and lower limits for the amounts of components in the compositions of the present invention described herein may be interchangeable in any way, provided that the resulting range falls within the broadest possible range of the present invention.

[0066] The composition of the present invention has an ozone depletion potential of 0.

[0067] Typically, the compositions of the present invention have a global warming potential (GWP) of less than 600. Preferably, the compositions of the present invention have a GWP of less than 500, preferably less than 450, for example less than 350, for example less than 300, for example less than 200, preferably less than 150.

[0068] Typically, the compositions of the present invention have reduced flammability hazards when compared to R-1132a and R-1132(E) alone.

[0069] Flammability may be determined according to ASHRAE Standard 34, which incorporates ASTM Standard E-681 in the test methodology as described on page 34 of the 2004 supplement, the full contents of which are incorporated herein by reference.

[0070] In one embodiment, the composition has one or more of the following characteristics compared to R-1132a and R-1132(E) alone: ​​(a) a higher lower flammability limit, (b) a higher ignition energy (sometimes referred to as auto-ignition energy or pyrolysis), or (c) a lower flame velocity. Preferably, the composition of the present invention is less flammable than R-1132a and R-1132(E) in the following respects, namely, one or more of the following: lower flammability limit at 23°C, lower flammability limit at 60°C, width of the flammability range at 23°C or 60°C, auto-ignition temperature (pyrolysis temperature), minimum ignition energy in dry air, or flame velocity. The flammability limit is determined according to the method specified in ASHRAE-34, and the auto-ignition temperature is determined in a 500 ml glass flask according to the method of ASTM E659-78.

[0071] In some applications, formulations may not need to be classified as non-flammable according to the ASHRAE-34 method. For example, when it is physically impossible to create a flammable mixture by leaking cooling device filler into the surroundings, it is possible to develop fluids whose flammability limits are sufficiently reduced in air to make them safe for use in that application.

[0072] In one embodiment, the composition of the present invention represents a weakly flammable fluid (class 2L) or a flammable fluid (class 2) having flammability that can be classified as 2L or 2 according to the ASHRAE Standard 34 classification system and having a flame velocity lower than 10 cm / sec.

[0073] The flammability of refrigerant compositions is classified by ASHRAE SSPC34 and ISO 817 through a complex evaluation process. Two compositions are considered: "Worst-Case Composition" (WCF) and "Worst-Case Composition for Flammability" (WCFF). WCF is the composition that has the highest permissible level of the most flammable species in the blend, according to the manufacturing tolerances specified by the blend designer during the application process. WCFF is the most flammable composition that may occur during refrigerant vapor leakage from a cylinder or system at any temperature between -40°C and +60°C.

[0074] Typically, at least the WCF of the compositions of the present invention has a flammability classified as "2L" by the ASHRAE-34 evaluation process, and certain compositions of the present invention, as described above, have both WCF and WCFF having a flammability classified as "2L" by the ASHRAE-34 evaluation process.

[0075] The compositions of the present invention are believed to exhibit a completely unexpected combination of low flammability / non-flammability, low GWP, improved lubricant miscibility, and improved cooling performance characteristics. Some of these cooling performance characteristics are described in more detail below.

[0076] The compositions of the present invention typically have a coefficient of performance (COP) that is within about 15% of the COP of R-410A. Advantageously, the COP of the compositions of the present invention is within about 10% of the COP of R-410A, for example, within about 7%, or for example, within about 5%. Preferably, the COP is equivalent to or higher than that of R-410A.

[0077] The compositions of the present invention typically have a volumetric cooling capacity of about 25% or less of the volumetric cooling capacity of R-410A. Advantageously, the compositions of the present invention have a volumetric cooling capacity of about 20% or less of the volumetric cooling capacity of R-410A, for example, about 15% or about 10%, preferably about 5% or less.

[0078] The compositions of the present invention typically have a compressor discharge temperature within approximately 25K of the compressor discharge temperature of R-410A. Preferably, the compositions of the present invention have a compressor discharge temperature within approximately 20K of the compressor discharge temperature of R-410A, for example, within approximately 15K.

[0079] Typically, the compositions of the present invention have a temperature glide in the evaporator or condenser of less than about 20 K. Advantageously, the compositions of the present invention have a temperature glide in the evaporator or condenser of less than about 15 K, preferably less than about 10 K.

[0080] The compositions of the present invention typically have a critical temperature that is within about 15% of the critical temperature of R-410A. Advantageously, the compositions of the present invention have a critical temperature that is equivalent to or higher than the critical temperature of R-410A.

[0081] Conveniently, the composition of the present invention has a combustion rate of less than about 10 cm / second as measured by ASHRAE Standard 34.

[0082] Typically, the compositions of the present invention have a total potential for the production of TFA from a unit mass of the composition that is lower than the total potential for the production of TFA from an equivalent mass of R-454B, for example, 75% or less, for example, 50% or less, preferably 10% or less.

[0083] The compositions of the present invention are typically suitable for use in existing apparatus designs and are compatible with all classes of lubricants currently in use with established HFC refrigerants. They can be optionally stabilized or compatible with mineral oils (e.g., lubricants) by the use of appropriate additives, such as polyol esters (POE), e.g., POE having a viscosity of about 7–32 cSt at about 40°C.

[0084] Therefore, in one embodiment, the composition of the present invention is combined with a lubricant, particularly when used in a heat transfer device.

[0085] Conveniently, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG, also known as polyether), polyalkylene glycol ester (PAG ester), polyvinyl ether (PVE), poly(alpha-olefin), and combinations thereof. PAG and POE are currently preferred lubricants for the compositions of the present invention.

[0086] Advantageously, the lubricant further comprises a stabilizer. In a similar embodiment, the composition of the present invention may be combined with a stabilizer.

[0087] Preferably, the stabilizer is selected from the group consisting of diene compounds, phosphates, phenol compounds (e.g., 2,6-di-tert-butyl-4-methylphenol), epoxides, and mixtures thereof.

[0088] Conveniently, the composition of the present invention can be combined with a flame retardant.

[0089] Advantageously, the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, chloropropyl phosphoric acid, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, fluorinated iodocarbon, fluorinated bromocarbon, trifluoroiodomethane, perfluoroalkylamine, bromo-fluoroalkylamine, and mixtures thereof.

[0090] In another aspect of the present invention, a heat transfer device comprising the composition of the present invention is provided. Preferably, the heat transfer device is a cooling device.

[0091] For convenience, heat transfer devices include residential or commercial air conditioning systems, heat pumps, or commercial or industrial cooling systems.

[0092] The present invention also provides for the use of the compositions of the present invention in heat transfer devices, such as cooling systems, as described herein.

[0093] A further aspect of the present invention provides a method for cooling an article, comprising condensing a composition of the present invention and then evaporating the composition near the article to be cooled.

[0094] According to another aspect of the present invention, a method for heating an article is provided, comprising condensing a composition of the present invention near the article to be heated, and then evaporating the composition.

[0095] The compositions of the present invention may also be prepared simply by mixing one or more of R-1132a, R-32, R-1132(E), and R-1234ze(E), R-152a, and R-1234yf (and R-744, and any optional components such as lubricants, stabilizers, or additional flame retardants) in desired proportions. The compositions can then be added to a heat transfer device (or used in any other way as defined herein).

[0096] In one embodiment, the use of the composition of the present invention as a refrigerant replacement in a heat transfer device is provided. Conveniently, the refrigerant is selected from R-410A, R-454B, R-452B, and R-32, preferably R-410A. Advantageously, the heat transfer device includes residential or commercial air conditioning systems, heat pumps, or commercial or industrial cooling systems.

[0097] According to another aspect of the present invention, a sprayable composition is provided, comprising a material to be sprayed and a propellant comprising the composition of the present invention.

[0098] A further aspect of the present invention provides a method for extracting a substance from biomass, comprising contacting the biomass with a solvent containing the composition of the present invention, and separating the substance from the solvent.

[0099] According to another aspect of the present invention, a method for cleaning an article is provided, comprising contacting the article with a solvent comprising a composition of the present invention.

[0100] A further aspect of the present invention provides a method for extracting a material from an aqueous solution, comprising contacting the aqueous solution with a solvent containing the composition of the present invention, and separating the material from the solvent.

[0101] According to another aspect of the present invention, a method is provided for extracting a material from a particulate solid matrix, comprising contacting the particulate solid matrix with a solvent containing the composition of the present invention, and separating the material from the solvent.

[0102] A further aspect of the present invention provides a mechanical power generation device containing the composition of the present invention.

[0103] Preferably, the mechanical power generation device is adapted to generate action from heat using a Rankine cycle or a modification thereof.

[0104] According to another aspect of the present invention, a method for retrofitting a heat transfer device is provided, comprising the steps of removing an existing heat transfer fluid and introducing a composition of the present invention. Preferably, the heat transfer device is a cooling device, such as an integrated air conditioning and / or heat pump system. Advantageously, the method further comprises the step of obtaining an allocation of greenhouse gas (e.g., carbon dioxide) emission credits.

[0105] According to the retrofit method described above, the existing heat transfer fluid can be completely removed from the heat transfer device before introducing the composition of the present invention. Alternatively, the existing heat transfer fluid can be partially removed from the heat transfer device, and then the composition of the present invention can be introduced.

[0106] A further aspect of the present invention provides a method for reducing the environmental impact resulting from the operation of a product containing an existing compound or composition, the method comprising at least partially substituting the existing compound or composition with the composition of the present invention.

[0107] Environmental impacts include the generation and release of greenhouse gases through the operation of the product.

[0108] As described above, this environmental impact can be considered to include not only the emission of compounds or compositions that have significant environmental impacts from leaks or other losses, but also the emission of carbon dioxide resulting from the energy consumed by the device over its operating life. Such environmental impacts can be quantified by a known measure called Total Equivalent Global Warming Impact (TEWI). This measure has been used, for example, to quantify the environmental impact of certain stationary cooling and air conditioning systems, including supermarket cooling systems.

[0109] Environmental impacts may also be considered to include greenhouse gas emissions resulting from the synthesis and manufacture of compounds or compositions. In this case, manufacturing emissions, in addition to energy consumption and direct loss effects, yield a known measure known as life cycle carbon production (LCCP). The use of LCCP is common when evaluating the environmental impacts of automotive air conditioning systems.

[0110] In preferred embodiments, the use of the compositions of the present invention results in an apparatus having lower total equivalent warming impact and / or lower lifecycle carbon production than that achieved by the use of existing compounds or compositions.

[0111] These methods can be applied to any suitable product in the fields of, for example, air conditioning, cooling, heat transfer, aerosol or sprayable propellants, gaseous dielectrics, flame suppression, solvents (e.g., carriers for flavorings and fragrances), cleaning agents, topical anesthetics, and expanded applications. Preferably, the field is cooling.

[0112] Examples of suitable products include heat transfer devices, sprayable compositions, solvents, and mechanical power generation devices. In a preferred embodiment, the product is a heat transfer device, such as a cooling device.

[0113] Existing compounds or compositions have higher environmental impacts, as measured by GWP and / or TEWI and / or LCCP, than the compositions of the present invention that replace them. Existing compounds or compositions may contain fluorocarbon compounds, such as perfluorocarbon compounds, hydrofluorocarbon compounds, chlorofluorocarbon compounds, or hydrochlorofluorocarbon compounds, or may contain fluorinated olefins.

[0114] Preferably, the existing compound or composition is a heat transfer compound or composition such as a refrigerant. Examples of refrigerants that can be substituted include R-410A, R454B, R-452B, and R-32, preferably R-410A.

[0115] To reduce environmental impact, any amount of existing compounds or compositions may be substituted. This may depend on the environmental impact of the existing compound or composition being substituted and the environmental impact of the substituted composition of the present invention. Preferably, the existing compound or composition in the product is completely replaced by the composition of the present invention.

[0116] Herein, the present invention will be described with reference to the following non-limiting embodiments. [Examples]

[0117] A thermodynamic property model was constructed using the NIST REFPROP 9.1 software package. This was used to model the cooling cycle performance of an idealized vapor compression cycle, using the performance of R-410A as the reference fluid. The assumed cycle conditions for this modeling are listed in Table 1, and the modeling results for R-410A are summarized in Table 2 below. [Table 1] [Table 2]

[0118] Next, the performance of the selected compositions of the present invention was modeled using R-410A as a reference (ref.). The results are summarized in the table below. Surprisingly, it was found that the properties of the compositions of the present invention can be considered sufficiently close to those of R-410A, allowing for their easy adaptation in existing R-410A-based designs of components and piping. In this context, the following properties are considered particularly desirable. (a) Energy efficiency of R-410A within 10% (expressed as COP), (b) A volumetric cooling capacity of no more than approximately 20% of the volumetric cooling capacity of R-410A. (c) Compressor discharge temperature within approximately 15K of the R-410A value, (d) Average temperature glide (temperature change during the evaporation / condensation process) in evaporators and condensers below 15K, (e) The critical temperature of a refrigerant that is equivalent to or higher than the critical temperature of R-410A (71.4℃), (f) Total potential production of trifluoroacetic acid from a unit mass of a refrigerant blend that is lower than the equivalent from the same amount of R-454B.

[0119] Other compositions that provide acceptable operating pressure and flammability but do not meet all of these criteria may also yield acceptable performance in suitably designed new equipment. For example, blends with a volume capacity of less than 80% of R-410A's volume capacity can be used by increasing the compressor volume or compressor speed. Blends with a temperature glide greater than 15K can be used by employing a cross-counterflow heat exchanger design for the condenser and / or evaporator. Blends with good performance characteristics but exhibiting Class 2 flammability can also be used in systems where the fill size and application conditions make them safe for use. [Table 3-1] [Table 3-2]

Claims

1. A composition, (a) 1,1-difluoroethylene (R-1132a), (b) Difluoromethane (R-32) (c) trans-1,2-difluoroethylene (R-1132(E)), and (d) A composition comprising one or more of the following: trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), 1,1-difluoroethane (R-152a), and 2,3,3,3-tetrafluoropropene (R-1234yf).

2. The composition according to any of the prior claims, wherein R-1132a is present in an amount of about 1 to about 20% by weight, for example, about 2 to about 20% by weight, for example, about 3 to about 20% by weight, preferably about 4 to about 18% by weight, for example, about 4 to about 16% by weight.

3. The composition according to claim 1 or 2, wherein R-32 is present in an amount of about 1 to about 50% by weight, for example, about 5 to about 45% by weight, for example, about 7 to about 40% by weight, preferably about 10 to about 30% by weight, for example, about 12 to about 25% by weight.

4. The composition according to any one of the prior claims, wherein R-1132(E) is present in an amount of about 1 to about 60% by weight, for example, about 5 to about 55% by weight, for example, about 10 to about 50% by weight, or about 15 to about 45% by weight, preferably about 18 to about 45% by weight.

5. The composition according to any one of the prior claims, wherein one or more of R-1234ze(E), R-152a, and R-1234yf are present in an amount of about 1 to about 75% by weight, for example, about 5 to about 70% by weight, for example, about 5 to about 65% by weight, for example, about 10 to about 65% by weight, and optionally, the composition comprises about 1 to about 75% by weight of R-1234ze(E), or the composition comprises R-1234ze(E) and R-152a in a combined content of about 1 to about 75% by weight.

6. A composition according to any one of the prior claims, comprising approximately 1 to approximately 20% by weight of R-1132a, approximately 1 to approximately 50% by weight of R-32, approximately 1 to approximately 60% by weight of R-1132(E), and approximately 1 to approximately 75% by weight of one or more of the aforementioned R-1234ze(E), R-152a, and R-1234yf, optionally approximately 1 to approximately 75% by weight of R-1234ze(E), or a combined content of approximately 1 to approximately 75% by weight of R-1234ze(E) and R-152a.

7. Approximately 2 to approximately 20% by weight of R-1132a, approximately 5 to approximately 45% by weight of R-32, approximately 5 to approximately 55% by weight of R-1132(E), and approximately 5 to approximately 70% by weight of one or more of the aforementioned R-1234ze(E), R-152a, and R-1234yf, for example, approximately 3 to approximately 20% by weight of R-1132a, approximately 7 to approximately 40% by weight of R-32, approximately 10 to approximately 50% by weight of R-1132(E), and approximately 5 to approximately 65% ​​by weight A composition according to any one of the prior claims, comprising one or more of the R-1234ze(E), R-152a, and R-1234yf, for example, about 4 to about 18% by weight of R-1132a, about 10 to about 30% by weight of R-32, about 15 to about 45% by weight of R-1132(E), and about 10 to about 65% by weight of one or more of the R-1234ze(E), R-152a, and R-1234yf.

8. A composition according to any one of the prior claims, comprising R-1132a, R-32, R-1132(E), and R-1234ze(E), wherein R-1234ze(E) is present in an amount of about 10 to about 50% by weight, for example, about 15 to about 45% by weight, preferably about 20 to about 40% by weight.

9. The composition according to claim 8, comprising about 1 to about 20% by weight of R-1132a, about 1 to about 50% by weight of R-32, about 1 to about 60% by weight of R-1132(E), and about 10 to about 50% by weight of R-1234ze(E), for example, about 2 to about 20% by weight of R-1132a, about 5 to about 45% by weight of R-32, about 5 to about 55% by weight of R-1132(E), and about 10 to about 50% by weight of R-1234ze(E), for example, about 3 to about 20% by weight of R-1132a, about 7 to about 40% by weight of R-32, about 10 to about 50% by weight of R-1132(E), and about 15 to about 45% by weight of R-1234ze(E).

10. The composition according to any one of claims 1 to 7, wherein R-152a is present in an amount of about 1 to about 50% by weight, for example, about 2 to about 40% by weight, for example, about 3 to about 35% by weight.

11. The composition according to claim 10, wherein the R-1234ze(E) is present in an amount of about 1 to about 60% by weight, for example, 2 to about 50% by weight, for example, about 3 to about 45% by weight.

12. The composition according to any one of the prior claims, wherein R-1234yf is present in an amount of about 1 to about 30% by weight, for example, about 1 to about 20% by weight, for example, about 1 to about 10% by weight, or about 0 to about 10% by weight, for example, 0 to about 5% by weight.

13. The composition contains carbon dioxide (CO2). ２ The composition according to any one of the prior claims, further comprising:

14. The aforementioned CO ２ The composition according to claim 13, which is present in an amount of about 1 to about 20% by weight, for example, about 1 to about 18% by weight, for example, about 2 to about 18% by weight, for example, about 2 to about 16% by weight.

15. The aforementioned R-1132a and the aforementioned CO ２ The composition according to claim 13 or 14, wherein the compound is present in a composite amount of about 3 to about 25% by weight, for example, about 3 to about 20% by weight, for example, about 4 to about 20% by weight.

16. The composition according to any one of claims 13 to 15, wherein one or more of R-1234ze(E), R-152a, and R-1234yf are present in an amount of about 1 to about 75% by weight, for example, about 5 to about 70% by weight, for example, about 5 to about 65% by weight, for example, about 10 to about 65% by weight, and optionally, about 1 to about 75% by weight of R-1234ze(E), or a combined content of about 1 to about 75% by weight of R-1234ze(E) and R-152a, or about 1 to about 75% by weight of R-1234yf.

17. R-1132a and CO in a composite amount of approximately 2 to 25% by weight ２ A composition according to any one of claims 13 to 16, comprising about 1 to about 50% by weight of R-32, about 1 to about 60% by weight of R-1132(E), and about 10 to about 50% by weight of R-1234ze(E), for example, R-1132a and CO in a combined amount of about 2 to about 25% by weight. ２ A composition comprising approximately 5 to approximately 45% by weight of R-32, approximately 5 to approximately 55% by weight of R-1132(E), and approximately 10 to approximately 50% by weight of R-1234ze(E), or a composite amount of approximately 3 to approximately 20% by weight of R-1132a and CO ２ A composition comprising approximately 7 to approximately 40% by weight of R-32, approximately 10 to approximately 50% by weight of R-1132(E), and approximately 15 to approximately 45% by weight of R-1234ze(E).

18. CO2 in a composite amount of approximately 6 to 18% by weight ２ The composition according to any one of claims 13 to 17, comprising R-1132a, about 25 to about 45% by weight of R-1132(E), about 15 to about 28% by weight of R-32, and about 20 to about 40% by weight of R-1234ze(E).

19. A composition according to any one of the prior claims, comprising essentially the components described.

20. The composition according to any one of the prior claims, wherein the composition has a global warming potential (GWP) of less than 450, for example, less than 350, for example, less than 300, for example, less than 200, preferably less than 150.

21. The composition according to any one of the prior claims, wherein the composition is less flammable than R-1132a and / or R-1132(E) alone.

22. The composition is superior to R-1132a and / or R-1132(E) alone. a. A higher lower limit of flammability, b. Higher ignition energy, and / or c. Having a lower flame velocity, The composition according to claim 21.

23. The composition according to any one of the prior claims, wherein the composition has a coefficient of performance (COP) of R-410A that is within about 10%, for example, within about 7%, for example, within about 5%, and preferably, the COP is equal to or higher than that of R-410A.

24. The composition according to any one of the prior claims, wherein the composition has a volumetric cooling capacity of about 20% or less of the volumetric cooling capacity of R-410A, for example, about 10% or less, for example, about 5% or less.

25. The composition according to any one of the prior claims, wherein the composition has a compressor discharge temperature within approximately 20K of the compressor discharge temperature of R-410A, for example, within approximately 15K.

26. The composition according to any one of the prior claims, wherein the composition has a temperature glide in the evaporator or condenser of less than about 15 K, preferably less than about 10 K.

27. The composition according to any one of the prior claims, wherein the composition has a critical temperature equal to or higher than the critical temperature of R-410A.

28. The composition according to any one of the prior claims, wherein the composition has a combustion rate of less than about 10 cm / second as measured by the ASHRAE standard 34.

29. A composition comprising a lubricant, and a composition according to any one of the prior claims, wherein the lubricant is preferably selected from mineral oil, silicone oil, polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG), polyalkylene glycol ester (PAG ester), polyvinyl ether (PVE), poly(alpha-olefin), and combinations thereof, and preferably the lubricant is selected from PAG or POE.

30. A composition comprising a stabilizer, and a composition according to any one of the prior claims, wherein the stabilizer is preferably selected from diene compounds, phosphates, phenol compounds (e.g., 2,6-di-tert-butyl-4-methylphenol), epoxides, and mixtures thereof.

31. A composition comprising a flame retardant, and a composition according to any one of the prior claims, wherein the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, chloropropyl phosphoric acid, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, fluorinated iodocarbon, fluorinated bromocarbon, trifluoroiodomethane, perfluoroalkylamine, bromofluoroalkylamine, and mixtures thereof.

32. A heat transfer device comprising a composition defined in any one of claims 1 to 31, wherein the heat transfer device is a cooling device, for example, the heat transfer device comprising a residential or commercial air conditioning system, a heat pump, or a commercial or industrial cooling system.

33. Use of a composition defined in any one of claims 1 to 31 in a heat transfer device, preferably a cooling device.

34. A method for cooling an article, comprising condensing a composition defined in any one of claims 1 to 31, and then evaporating the composition near the article to be cooled.

35. A method for heating an article, comprising condensing a composition defined in any one of claims 1 to 31 near the article to be heated, and then evaporating the composition.

36. Use of a composition defined in any one of claims 1 to 31 as a substitute for a refrigerant in a heat transfer device, preferably wherein the refrigerant is selected from R-410A, R-454B, R-452B, and R-32, and optionally the heat transfer device includes a residential or commercial air conditioning system, a heat pump, or a commercial or industrial cooling system.

37. A mechanical power generation device comprising a composition defined in any one of claims 1 to 31, wherein the device is adapted to generate action from heat using a Rankine cycle or a modification thereof.

38. A method for retrofitting a heat transfer device, comprising the steps of removing an existing heat transfer composition and introducing a composition defined in any one of claims 1 to 31, wherein the heat transfer device is, for example, a commercial or industrial cooling device, a heat pump, or a residential or commercial air conditioning system.

39. A method for reducing the environmental impact resulting from the operation of a product containing an existing compound or composition, the method comprising at least partially substituting the existing compound or composition with a composition defined in any one of claims 1 to 31, such that the use of the composition of the present invention results in a lower total equivalent warming impact and / or lower life cycle carbon production than would be achieved by the use of the existing compound or composition.

40. The method according to claim 39, which is applied to products from the fields of air conditioning, cooling, heat transfer, aerosol or sprayable propellants, gaseous dielectrics, flame suppressors, solvents, cleaning agents, local anesthetics, and extended applications, wherein, for example, the product is selected from heat transfer devices, sprayable compositions, solvents, or mechanical power generation devices, and preferably the product is a heat transfer device, such as a residential or commercial air conditioning system, a heat pump, or a commercial or industrial cooling system.

41. The method according to any one of claims 38 to 40, wherein the existing compound or composition is a heat transfer composition, preferably the heat transfer composition is a refrigerant selected from R-410A, R-454B, R-452B, and R-32.

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