Refrigerant compositions and uses thereof

Abstract

A refrigerant composition and uses thereof are described. Uses of a composition as a refrigerant in a heat pump system in an electric vehicle are described. The composition includes 1,1-difluoroethene (R-1132a) and at least one fluorocarbon refrigerant compound selected from the group consisting of 2,3,3,3-tetrafluoropropene (R-1234yf), difluoromethane (R-32), 1,3,3,3-tetrafluoropropene (R-1234ze(E)), and 1,1-difluoroethane (R-152a).

Description

[0001] This application is a divisional application of Chinese patent application No. 201980054110.7 entitled "Refrigerant Composition and Use Thereof". Patent application No. 201980054110.7 is a national application that entered the Chinese national phase under the Patent Cooperation Treaty (PCT / GB2019 / 052290) filed on August 14, 2019, with a priority date of August 14, 2018. Technical Field

[0002] This invention relates to a refrigerant composition, and more particularly to a refrigerant composition comprising 1,1-difluoroethylene (R-1132a; vinylidene fluoride), said refrigerant composition for use in mobile or automotive heat pump systems, particularly for systems in electric vehicles. Background Technology

[0003] The enumeration or discussion of previously disclosed documents or any background in this specification should not necessarily be regarded as an admission that the documents or background are part of the prior art or common general knowledge.

[0004] In the absence of an internal combustion engine to provide heat for the passenger cabin, the introduction of electric vehicles means an increasing emphasis on using the vehicle's air conditioning unit as a heat pump in cold weather. This is achieved by reversing the direction of refrigerant flow around the air conditioning circuitry, causing the refrigerant to evaporate at low temperatures using heat from the ambient air and condense at high temperatures to prevent air from circulating into the passenger cabin. Compared to using an air conditioning system to provide heat by resistively heating the incoming cabin air, this method allows the system to deliver more heat to the cabin per unit of energy drawn from the battery.

[0005] When the outside air is coldest, the demand for heating the passenger air is highest, which presents specific challenges to operating the air conditioning unit as a heat pump. Specifically:

[0006] ● Ambient air temperature may be as low as -25 to -30°C, which means that in order to achieve heat pump operation under these conditions, the refrigerant should evaporate at a temperature below -30°C.

[0007] ● Passenger air entering the cabin through the ventilation openings is ideally heated to 40-50°C, which means that the refrigerant must condense at a temperature above 40°C.

[0008] ● The refrigerant evaporation pressure should not be lower than 1 atmosphere to prevent air from entering the system.

[0009] ● In both air conditioning and heat pump operating modes, the same refrigerant fluid should have acceptable performance.

[0010] ● To ensure that new liquids comply with EU F-Gas regulations, the Global Warming Potential (GWP) should be below 150.

[0011] For many years, 1,1,1,2-tetrafluoroethane (R-134a) became the preferred refrigerant in automotive air conditioning systems after the phase-out of dichlorodifluoromethane (R-12) (whose CFCs have a high ozone depletion potential). Then the EU F-Gas directive was implemented, limiting the global warming potential (GWP) of new vehicle mobile air conditioning (MAC) systems to 150. As a result, in Europe, the use of R-134a has been largely replaced by newer systems using the flammable 2,3,3,3-tetrafluoropropylene (R-1234yf). R-1234yf is slightly less efficient than R-134a, and newer system designs now include additional equipment (internal heat exchangers) to compensate for the efficiency loss.

[0012] If the ambient temperature is below approximately -15 to -20°C, portable air conditioning systems using R-134a or R-1234yf as refrigerants cannot operate efficiently in heat pump mode because the evaporation pressure of the portable air conditioning system will drop below atmospheric pressure at the required evaporation temperature. Carbon dioxide (R-744) is a high-pressure refrigerant that works well as a low-temperature heat pump fluid. However, it is known that at medium to high ambient air temperatures, carbon dioxide performs worse (and less energy efficient) than R-134a or R-1234yf in the air conditioning mode of automotive systems.

[0013] A refrigerant composition is needed that can operate effectively in mobile (e.g., automotive) heat pump systems used for heating vehicles, particularly electric vehicles. A working refrigerant fluid for combined mobile heat pump / air conditioning systems in electric vehicles needs to be found, capable of operating as a heat pump cycle working fluid at a positive value (greater than atmospheric suction pressure) at evaporation temperatures as low as approximately -30°C, while also providing acceptable performance (energy efficiency) when used in air conditioning mode. Furthermore, any new refrigerant developed for automotive systems must have a Global Warming Potential (GWP) of less than 150 to comply with European environmental regulations. Summary of the Invention

[0014] It has been found that compositions of 1,1-difluoroethylene (R-1132a; vinylidene fluoride) with other hydrofluorocarbon refrigerants offer the potential for improved performance compared to R-1234yf when used in automotive heat pump systems, particularly in electric vehicles. These compositions also provide acceptable performance when used in air conditioning mode. The compositions are capable of absorbing heat from the environment at potentially lower ambient temperatures than R-1234yf or R-134a, and additionally offer improved energy efficiency. This is a particularly desirable combination of characteristics for electric vehicles, which would otherwise have to rely on battery energy to provide heating for passenger comfort.

[0015] Therefore, in a first aspect, the present invention provides a use of a composition as a refrigerant in a heat pump system in an electric vehicle, said composition comprising 1,1-difluoroethylene (R-1132a) and at least one fluorocarbon refrigerant compound selected from the group consisting of: 2,3,3,3-tetrafluoropropylene (R-1234yf), difluoromethane (R-32), 1,3,3,3-tetrafluoropropylene (R-1234ze(E)) and 1,1-difluoroethane (R-152a).

[0016] Conveniently, the refrigerant composition further comprises at least one of the following: trifluoroethylene (R-1123), trifluoroiodomethane (CF3I), carbon dioxide (R-744, CO2), and 1,1,1,2-tetrafluoroethane (R-134a).

[0017] In another aspect, the present invention provides a use of a composition as a refrigerant in a heat pump system in an electric vehicle, said composition comprising 1,1-difluoroethylene (R-1132a) and trifluoroiodomethane (CF3I). Preferably, the refrigerant composition comprises about 1% to about 30% by weight of R-1132a and about 70% to about 99% by weight of CF3I.

[0018] The preferred composition of the present invention contains 1% to 30% by weight or 1% to 20% by weight, such as about 3% to 15% by weight of 1,1-difluoroethylene (R-1132a), based on the total weight of the refrigerant composition.

[0019] In the embodiments, the refrigerant composition comprises 1,1-difluoroethylene (R-1132a), at least one tetrafluoropropylene refrigerant compound selected from the group consisting of 2,3,3,3-tetrafluoropropylene (R-1234yf) and 1,3,3,3-tetrafluoropropylene (R-1234ze(E)), and optionally difluoromethane (R-32). In this embodiment, R-1132a is preferably present in an amount of 1% to 20% by weight of the total weight of the refrigerant composition. In the case of difluoromethane, R-1132a is preferably present in an amount of 1% to 21% by weight of the total weight of the refrigerant composition. Regardless of whether the composition of this first embodiment is a binary or ternary composition, the selected tetrafluoropropylene provides a balance to the refrigerant composition.

[0020] The preferred composition of this first embodiment comprises the following:

[0021] (i) A binary refrigerant composition comprising 1 wt% to 20 wt% of 1,1-difluoroethylene (R-1132a) and 99 wt% to 80 wt% of 2,3,3,3-tetrafluoropropylene (R-1234yf).

[0022] (ii) A binary refrigerant composition comprising 1 wt% to 20 wt% of 1,1-difluoroethylene (R-1132a) and 99 wt% to 80 wt% of 1,3,3,3-tetrafluoropropylene (R-1234ze(E)).

[0023] (iii) A ternary refrigerant composition comprising 1 wt% to 20 wt% of 1,1-difluoroethylene (R-1132a), 1 wt% to 21 wt% of difluoromethane (R-32), and 59 wt% to 98 wt% of 2,3,3,3-tetrafluoropropylene (R-1234yf).

[0024] (iv) A ternary refrigerant composition comprising 1 wt% to 20 wt% of 1,1-difluoroethylene (R-1132a), 1 wt% to 21 wt% of difluoromethane (R-32) and 59 wt% to 98 wt% of 1,3,3,3-tetrafluoropropylene (R-1234ze(E)).

[0025] When trifluoroiodomethane (CF3I) is included in the compositions of the present invention, it is typically present in amounts less than R-1234yf or R-1234ze(E). Preferred CF3I-containing compositions of the present invention include R-1132a, R-32, R-1234yf, and CF3I, such as 1% to 20% by weight of R-1132a, 1% to 21% by weight of R-32, 5% to 40% by weight of CF3I, and 19% to 93% by weight of R-1234yf.

[0026] When carbon dioxide (CO2) is included in the compositions of the present invention, the content of R-1132a and CO2 in the combination is typically less than about 30% by weight, such as less than about 20% by weight. Preferred CO2-containing compositions of the present invention include R-1132a, R-32, R-1234yf and CO2.

[0027] In another embodiment, the refrigerant composition includes R-1132a, R-152a, and optionally R-32. A preferred composition of this embodiment comprises the following:

[0028] (i) A binary refrigerant composition comprising 1 wt% to 30 wt% of R-1132a and 99 wt% to 70 wt% of R-152a.

[0029] (ii) A ternary refrigerant composition comprising 1 wt% to 20 wt% of R-1132a, 1 wt% to 10 wt% of R-32 and 70 wt% to 98 wt% of R-152a.

[0030] In another embodiment, the refrigerant composition comprises, optionally, primarily R-1132a, R-152a, and R-1234yf. Typically, the amount of R-1132a present in such compositions ranges from 1 wt% to 20 wt%. A preferred composition of this embodiment comprises a composition including 2 wt% to 14 wt% R-1132a (e.g., 4 wt% to 10 wt%), 2 wt% to 96 wt% R-152a, and 2 wt% to 96 wt% R-1234yf. Preferably, R-152a is present in such compositions in an amount from 4 wt% to 80 wt%, such as 5 wt% to 30 wt%. Preferably, R-1234yf is present in such compositions in an amount from 4 wt% to 96 wt%, or 60 wt% to 94 wt%.

[0031] In another embodiment, the refrigerant composition comprises R-1132a, R-32, R-152a, and at least one tetrafluoropropylene refrigerant compound selected from the group consisting of R-1234yf and R-1234ze(E). A preferred composition of this third embodiment comprises the following:

[0032] (i) A quaternary refrigerant composition comprising 1% to 20% by weight of 1,1-difluoroethylene (R-1132a), 1% to 21% by weight of difluoromethane (R-32), and 59% to 98% by weight of a mixture of 1,1-difluoroethane (R-152a) and 2,3,3,3-tetrafluoropropylene (R-1234yf) in any proportion.

[0033] (ii) A quaternary refrigerant composition comprising 1% to 20% by weight of 1,1-difluoroethylene (R-1132a), 1% to 21% by weight of difluoromethane (R-32), and 59% to 98% by weight of a mixture of 1,1-difluoroethane (R-152a) and 1,3,3,3-tetrafluoropropylene (R-1234ze(E)) in any proportion.

[0034] Based on the total weight of the refrigerant composition, the refrigerant composition of the present invention typically also contains R-134a in an amount of about 1% to about 10% by weight. Preferred R-134a-containing compositions comprise those including: R-1132a, CF3I, and R-134a; R-1132a, R-1234yf, and R-134a; R-1132a, R-1234ze(E), and R-134a; R-1132a, R-1234yf, R-32, and R-134a; R-1132a, R-1234ze(E), R-32, and R-134a; R-1132a, R-1234yf, CF3I, and R-134a; R-1132a, R-1234ze(E), CF3I, and R-134a. I and R-134a; R-1132a, R-152a and R-134a; R-1132a, R-152a, R-32 and R-134a; R-1132a, R-1234yf, R-152a and R-134a (such as about 1% to about 20% by weight of R-1132a, about 5% to about 25% by weight of R-152a, about 1% to about 10% by weight of R-134a and about 93% to about 45% by weight of R-1234yf); and R-1132a, R-1234ze(E), R-152a and R-134a.

[0035] When trifluoroethylene (R-1123) is included in the compositions of the present invention, it is typically present in amounts less than about 30% by weight, such as less than about 20% by weight. Preferred R-1123-containing compositions of the present invention include R-1132a, R-1123, and R-1234yf, preferably from about 1% to about 20% by weight of R-1132a, from about 1% to about 20% by weight of R-1123, and from about 98% to about 60% by weight of R-1234yf. Preferred R-1123-containing compositions are those in which the maximum molar content of R-1123, in blends such as those formulated and in vapors equilibrated with the blends, will be less than about 55% at temperatures of -40°C or higher. This is to reduce the risk of R-1123 disproportionation (self-reaction). The compositions described above and the listed compositions (see Examples 24 to 27 below) are predicted to meet these criteria.

[0036] Certain compositions of the present invention comprise, optionally, primarily, R-1132a and R-32, preferably from about 68% to about 99% by weight of R-1132a and from about 1% to about 32% by weight of R-32, for example, from about 72% to about 96% by weight of R-1132a and from about 4% to about 28% by weight of R-32. These compositions may be substantially free of R-1234yf.

[0037] Other compositions of the present invention include, optionally, primarily consisting of: R-1132a, R-32, and CO2, preferably from about 1 wt% to about 20 wt% of R-1132a, from about 1 wt% to about 32 wt% of R-32, and from about 50 wt% to about 95 wt% of CO2, such as from about 2 wt% to about 15 wt% of R-1132a, from about 2 wt% to about 32 wt% of R-32, and from about 55 wt% to about 93 wt% of CO2, such as from about 64 wt% to about 93 wt% of carbon dioxide, from about 2 wt% to about 25 wt% of difluoromethane, and from about 2 wt% to about 14 wt% of R-1132a, for example, from about 65 wt% to about 93 wt% of carbon dioxide, from about 2 wt% to about 22 wt% of difluoromethane, and from about 2 wt% to about 14 wt% of R-1132a. These compositions may be substantially free of R-1234yf.

[0038] "Substantially none" implies that the compositions of the present invention contain 0.5% by weight or less (preferably 0.1% by weight or less) of the components based on the total weight of the compositions.

[0039] As used herein, unless otherwise stated, all percentages mentioned in the compositions herein (including the claims) are based on the total weight of the compositions by weight.

[0040] In the embodiments, the composition may consist primarily of the aforementioned components. The term "consistently composed of" includes the meaning that the composition of the present invention is substantially free of other components, particularly other (hydrofluorine) compounds (e.g., (hydrofluorine)alkanes or (hydrofluorine)olefins) known for use in heat transfer compositions. The term "composed of" is included within the meaning of "consistently composed of".

[0041] To avoid any doubt, it should be understood that the upper and lower limits of the range of amounts of components in the compositions of the present invention described herein may be interchanged in any way, provided that the resulting range falls within the broadest scope of the invention.

[0042] When used in heat pumps or combined heat pump and air conditioning systems, the refrigerant composition is typically combined with a lubricant. Suitable lubricants comprise polyol esters, such as neopentyl polyol esters, and polyalkylene glycols, preferably with alkyl groups, such as C10, at one or both ends. 1-4 Alkyl-terminated.

[0043] The composition of the present invention has a zero ozone depletion potential.

[0044] Typically, the GWP of the compositions of the present invention is less than about 150, such as less than about 100, for example less than about 50.

[0045] Generally, the compositions of the present invention have reduced flammability hazards compared to R-1132a.

[0046] Flammability can be determined according to ASHRAE Standard 34 in conjunction with ASTM Standard E-681 and the test method according to Appendix 34p of 2004, the entire contents of which are incorporated herein by reference.

[0047] In one respect, compared to R-1132a alone, the composition has one or more of the following: (a) a higher lower flammability limit; (b) a higher ignition energy; (c) a higher autoignition temperature; or (d) a lower flame velocity. Preferably, compared to R-1132a, the composition of the present invention is less flammable in one or more of the following aspects: a lower flammability limit at 23°C; a lower flammability limit at 60°C; a wider flammability range at 23°C or 60°C; an autoignition temperature (thermal decomposition temperature); and a minimum ignition energy or combustion rate in dry air. The flammability limit and combustion rate are determined according to the method specified in ASHRAE-34, and the autoignition temperature is determined in a 500 ml glass flask according to the method of ASTM E659-78.

[0048] Preferred compositions of the present invention are those with a laminar combustion velocity of less than 10 cm / s, and particularly preferred ones: wherein the combustion velocities of both the blends and the "worst-case graded blends" are less than 10 cm / s, meaning that they would be classified as "2L" flammable articles according to ASHRAE Standard 34.

[0049] In preferred embodiments, the compositions of the present invention are non-flammable. For example, using the ASHRAE-34 method, the compositions of the present invention are non-flammable at a test temperature of 60°C. Advantageously, vapor mixtures present in equilibrium with the compositions of the present invention at any temperature between about -20°C and 60°C are also non-flammable.

[0050] In some applications, it may not be necessary to classify formulations as non-flammable using the ASHRAE-34 method. It is possible to develop fluids whose flammability limits in air are sufficiently reduced to ensure their safe use in applications, for example, if it is physically impossible to release flammable mixtures into the surrounding environment through leaky refrigeration equipment.

[0051] In one embodiment, according to the ASHRAE Standard 34 classification method, the flammability of the compositions of the present invention can be classified as 1 or 2L, which indicates non-flammability (Class 1) or weakly flammable fluid with a flame velocity of less than 10 cm / s (Class 2L).

[0052] The temperature glide of the composition of the present invention in the evaporator or condenser is preferably less than about 15 K, even more preferably less than about 10 K, and even more preferably less than about 5 K.

[0053] The compositions of the present invention can be used in mobile applications, such as automotive heat pump applications, and also exhibit acceptable performance in mobile air conditioning applications. The compositions can provide particular benefits when used in electric vehicles, whether pure electric or hybrid.

[0054] Unless otherwise stated, it should be understood that the term "electric vehicle" refers to both pure electric vehicles and vehicles that use electricity as one of several means of propulsion, such as hybrid vehicles.

[0055] Preferably, in the application of the invention, the refrigerant composition evaporates at a temperature below about -30°C, thereby enabling the heat pump to operate at ambient air temperatures as low as -25°C to -30°C.

[0056] Therefore, in another aspect, the present invention provides an electric vehicle having a heat pump and / or air conditioning system that uses the refrigerant composition of the first aspect of the invention. The refrigerant composition may be as described in any of the embodiments discussed above.

[0057] Therefore, the present invention also provides (i) a method for generating cooling in an electric vehicle, the method comprising evaporating a refrigerant composition of the present invention near a vehicle body to be cooled; and (ii) a method for generating heating in an electric vehicle, the method comprising condensing a refrigerant composition of the present invention near a vehicle body to be heated.

[0058] The invention is illustrated by the following non-limiting examples. Attached Figure Description

[0059] Figure 1 A schematic diagram of a modeled loop is given.

[0060] Figure 2 and3 The test results are explained as follows: Based on SAE standard J2765, the system performance was tested under three test conditions using the same refrigerant fill size for the blend as R-1234yf, operating in cooling mode (air conditioning). Following standard practice for comparing different refrigerants, the compressor speed of the blend was reduced to achieve the same cooling capacity as R-1234yf at each test point. Detailed Implementation

[0061] Example

[0062] The invention will now be illustrated by theoretical cyclic modeling of the performance of the selected compositions in heat pump and air conditioning cycles. R-1234yf was selected as the reference refrigerant for both cycles.

[0063] Modeling was performed in Microsoft Excel using NIST REFPROP10 as the thermodynamic data source. First, the phase equilibrium of mixtures of R-1132a with R-32 and R-1234yf was studied using a constant-volume apparatus to measure the vapor pressures of binary mixtures of R-1132a / R-32 or R-1132a / R-1234yf over a temperature range of -70°C to +40°C. This data was then regressed to generate binary interaction parameters for reproducing the experimental data in REFPROP.

[0064] For a heat pump cycle, the following conditions are assumed:

[0065]

[0066] The modeled cycle incorporates medium-pressure vapor injection of refrigerant vapor to improve cycle performance. For each composition, the optimal injection pressure is determined to maximize the coefficient of performance (COP) of heating.

[0067] The results of the binary and ternary blends selected in this invention are summarized in Examples 1-8 below. It has been found that incorporating R-1132a increases the COP (energy efficiency) and the refrigerant evaporation pressure compared to R-1234yf. It also reduces the volumetric flow rate of refrigerant that needs to be pumped through the system, indicating a reduction in pressure drop losses compared to R-1234yf. For comparison, modeling performance data for two commercially available blends (R-454C and R-516A) are also provided in the table below:

[0068]

[0069] Example 1 (Binary composition of R-1132a and R-1234yf)

[0070] *Comparative performance data for compositions comprising 0% by weight of R-1132a and 100% by weight of R-1234yf (not based on the invention).

[0071] Example 2 (a ternary composition of R-1132a, 4wt% R-32 and R-1234yf)

[0072] *Comparative performance data for compositions comprising 0% by weight of R-1132a, 4% by weight of R-32, and 96% by weight of R-1234yf (not based on the invention).

[0073] Example 3 (a ternary composition of R-1132a, 12wt% R-32 and R-1234yf)

[0074] *Comparative performance data for compositions comprising 0% by weight of R-1132a, 12% by weight of R-32, and 88% by weight of R-1234yf (not based on the invention).

[0075] Example 4 (a ternary composition of R-1132a, 20wt% R-32 and R-1234yf)

[0076] *Comparative performance data for compositions comprising 0% by weight of R-1132a, 20% by weight of R-32, and 80% by weight of R-1234yf (not based on the invention).

[0077] Example 5 (Binary composition of R-1132a and R-152a)

[0078] *Comparative performance data for compositions comprising 0% by weight of R-1132a and 100% by weight of R-152a (not based on the invention).

[0079] Example 6 (a ternary composition of R-1132a, 8wt% R-32 and R-1234yf)

[0080] *Comparative performance data for compositions comprising 0% by weight of R-1132a, 8% by weight of R-32, and 92% by weight of R-1234yf (not based on the invention).

[0081] Example 7 (a ternary composition of R-1132a, 16wt% R-32 and R-1234yf)

[0082] *Comparative performance data for compositions comprising 0% by weight of R-1132a, 16% by weight of R-32, and 92% by weight of R-1234yf (not based on the invention).

[0083] Example 8 (a ternary composition of R-1132a, 21.5 wt% R-32 and R-1234yf)

[0084]

[0085] *Comparative performance data of compositions comprising 0% by weight of R-1132a, 21.5% by weight of R-32, and 78.5% by weight of R-1234yf (not based on the invention).

[0086] The air conditioning performance was then evaluated using the following theoretical cycle modeling conditions representing operation under high-temperature environmental conditions (Examples 9 and 10):

[0087]

[0088] Improved heating mode performance and cooling mode performance were found to be achievable, with the theoretical COP of cooling within approximately 10% of the COP obtained using R-1234yf. Compared to R-1234yf, the fluid of the present invention will operate at higher pressures and with reduced mass / volume flow rate, which means that efficiency losses due to pressure drop effects in real-world systems will also be reduced compared to R-1234yf.

[0089] Example 9 (Binary composition of R-1132a and R-1234yf)

[0090] *Comparative performance data for compositions comprising 0% by weight of R-1132a and 100% by weight of R-1234yf (not based on the invention).

[0091] Example 10 (a ternary composition of R-1132a, 8wt% R-32 and R-1234yf)

[0092]

[0093] *Comparative performance data for compositions comprising 0% by weight of R-1132a, 8% by weight of R-32, and 92% by weight of R-1234yf (not based on the invention).

[0094] The performance of the binary, ternary, and quaternary compositions selected in this invention in heat pump cycles is further demonstrated in Examples 11 to 34 below. Similarly, R-1234yf was selected as the reference refrigerant for the cycle.

[0095] Assume the following operating conditions:

[0096]

[0097] In summary, the modeled performance data demonstrates the following advantages of the composition according to the present invention:

[0098] (a) Compared to R-1234yf alone, it has essentially equivalent or improved energy efficiency (COP) in heated mode cycle operation.

[0099] (b) Increased evaporation pressure results in higher capacity and better ability to operate at lower outside air temperatures.

[0100] Furthermore, Examples 35 through 37 below demonstrate the performance of selected binary blends including R-1132a and R-32 and ternary blends including R-1132a, R-32 and CO2 in air conditioning cycles.

[0101] Example 11 (Binary composition of R-1132a and R-1234ze(E))

[0102]

[0103] Example 12 (Binary composition of R-1132a and CF3I)

[0104]

[0105] Example 13 (a ternary composition of 4 wt% R-1132a, R-1234yf and CF3I)

[0106]

[0107] Example 14 (a ternary composition of 8 wt% R-1132a, R-1234yf and CF3I)

[0108]

[0109] Example 15 (a ternary composition of 10 wt% R-1132a, R-1234yf and CF3I)

[0110]

[0111] Example 16 (a quaternary composition of 4 wt% R-1132a, 8 wt% R-32, R-1234yf and CF3I)

[0112]

[0113] Example 17 (A ternary composition of R-1132a, 5wt% R-32 and R-152a)

[0114]

[0115] Example 18 (a quaternary composition of 4 wt% R-1132a, 6 wt% R-32, R-1234yf and R-152a)

[0116]

[0117] Example 19 (a quaternary composition of 4 wt% R-1132a, 12 wt% R-32, R-1234yf and R-152a)

[0118]

[0119] Example 20 (a quaternary composition of 4 wt% R-1132a, 16 wt% R-32, R-1234yf and R-152a)

[0120]

[0121] Example 21 (A quaternary composition of 8 wt% R-1132a, 16 wt% R-32, R-1234yf and R-152a)

[0122]

[0123] Example 22 (a ternary composition of R-1132a, 10 wt% R-32 and R-1234ze(E) and R-1132a, 21 wt% R-32 and R-1234ze(E))

[0124]

[0125] Example 23 (a quaternary composition of 3 wt% R-1132a, 3 wt% CO2, R-32 and R-1234yf)

[0126]

[0127] Example 24 (a quaternary composition of 4 wt% R-1132a, 4 wt% CO2, R-32 and R-1234yf)

[0128]

[0129] Example 25 (a quaternary composition of 4 wt% R-1132a, 2 wt% CO2, R-32 and R-1234yf)

[0130]

[0131] Example 26 (a quaternary composition of 5 wt% R-1132a, 3 wt% CO2, R-32 and R-1234yf)

[0132]

[0133] Example 27 (a ternary composition of 4 wt% R-1132a, R-1123 and R-1234yf)

[0134]

[0135] Example 28 (a ternary composition of 6 wt% R-1132a, R-1123 and R-1234yf)

[0136]

[0137] Example 29 (a ternary composition of 8 wt% R-1132a, R-1123 and R-1234yf)

[0138]

[0139] Example 30 (a ternary composition of 10 wt% R-1132a, R-1123 and R-1234yf)

[0140]

[0141] Example 31 (a ternary composition of 4% by weight of R-1132a, R-152a and R-1234yf)

[0142]

[0143] Example 32 (a ternary composition of 6% by weight of R-1132a, R-152a and R-1234yf)

[0144]

[0145] Example 33 (a ternary composition of 8 wt% of R-1132a, R-152a and R-1234yf)

[0146]

[0147] Example 34 (a ternary composition of 10% by weight of R-1132a, R-152a and R-1234yf)

[0148]

[0149] Example 35 (4 wt% R-1132a, R-32 and CO2 ternary compositions and compositions comprising 8 wt% R-1132a, R-32 and CO2)

[0150] (ternary composition)

[0151]

[0152] Example 36 (a ternary composition comprising 10 wt% R-1132a, R-32 and CO2, and a composition comprising 14 wt% R-1132a, R-32 and CO2)

[0153] (a ternary composition of CO2)

[0154]

[0155] Example 37 (Binary composition of R-1132a and R-32)

[0156]

[0157] Example 38 shows performance data for a ternary composition comprising 8 wt% R-1132a, 11 wt% R-32 and 81 wt% R-1234yf in a mobile heat pump / air conditioning system for use in an electric vehicle.

[0158] According to SAE standard J2765, the system performance was tested under three test conditions using the same refrigerant fill size for the blend as R-1234yf, operating in cooling mode (air conditioning). Following standard practice for comparing different refrigerants, the compressor speed of the blend was reduced to achieve the same cooling capacity as R-1234yf at each test point.

[0159] The results are shown below, and in Figure 2 and 3 The results are described in the documentation. The tested composition consistently delivered improved energy efficiency at each test point, with the coefficient of performance (COP) varying between 110% and 125% of the R-1234yf value.

[0160] Example 38 (a ternary composition of 8 wt% R-1132a, 11 wt% R-32 and 81 wt% R-1234yf)

[0161]

[0162] Example 38 - Continued

[0163]

[0164] The present invention also provides the following technical solutions:

[0165] Note 1. Use of a composition as a refrigerant in a heat pump system in an electric vehicle, said composition comprising 1,1-difluoroethylene (R-1132a) and at least one fluorocarbon refrigerant compound selected from the group consisting of: 2,3,3,3-tetrafluoropropylene (R-1234yf), difluoromethane (R-32), 1,3,3,3-tetrafluoropropylene (R-1234ze(E)) and 1,1-difluoroethane (R-152a).

[0166] Note 2. According to the use described in Note 1, the refrigerant composition further comprises at least one of the following: trifluoroethylene (R-1123), trifluoroiodomethane (CF3I), carbon dioxide (R-744, CO2), and 1,1,1,2-tetrafluoroethane (R-134a).

[0167] Note 3. Use of a composition as a refrigerant in a heat pump system in an electric vehicle, said composition comprising 1,1-difluoroethylene (R-1132a) and trifluoroiodomethane (CF3I), preferably said refrigerant composition comprising about 1% to about 30% by weight of R-1132a and about 70% to about 99% by weight of CF3I.

[0168] Note 4. According to the use described in Note 1, the refrigerant composition comprises R-1132a, R-152a and R-1234yf, preferably 2% to 14% by weight of R-1132a, 2% to 96% by weight of R-152a and 2% to 96% by weight of R-1234yf, such as 4% to 10% by weight of R-1132a, 2% to 30% by weight of R-152a and 60% to 94% by weight of R-1234yf.

[0169] Note 5. According to the use described in Note 1, the refrigerant composition comprises R-1132a, at least one tetrafluoropropylene refrigerant compound selected from the group consisting of R-1234yf and R-1234ze(E), and optionally difluoromethane (R-32).

[0170] Note 6. The use according to any one of Notes 1 to 5, wherein the R-1132a is present in an amount of 1% to 30% by weight, preferably 1% to 20% by weight, such as about 3% to about 15% by weight, based on the total weight of the refrigerant composition.

[0171] Note 7. For the use described in Note 5 or 6, wherein R-32 is present in an amount of 1% to 21% by weight based on the total weight of the refrigerant composition.

[0172] Note 8. According to the use described in Note 5, the refrigerant composition comprises:

[0173] 1% to 20% by weight of R-1132a and 99% to 80% by weight of R-1234yf;

[0174] R-1132a from 1 wt% to 20 wt% and R-1234ze(E) from 99 wt% to 80 wt%;

[0175] 1% to 20% by weight of R-1132a, 1% to 21% by weight of R-32 and 59% to 98% by weight of R-1234yf; or

[0176] 1 wt% to 20 wt% of R-1132a, 1 wt% to 21 wt% of R-32 and 59 wt% to 98 wt% of R-1234ze(E).

[0177] Note 9. In accordance with any one of Notes 5 to 8, the refrigerant composition further comprises CF3I, preferably wherein the CF3I is present in an amount less than R-1234yf or R-1234ze(E).

[0178] Note 10. According to the use described in Note 9, the refrigerant composition includes R-1132a, R-32, R-1234yf and CF3I.

[0179] Note 11. For the use according to any one of Notes 5 to 8, wherein the refrigerant composition further comprises CO2 (R-744), preferably wherein the content of CO2 and R-1132a in the combination is less than about 30% by weight, such as less than about 20% by weight.

[0180] Note 12. According to the use described in Note 11, the refrigerant composition includes R-1132a, R-32, R-1234yf and CO2.

[0181] Note 13. For the use described in Notes 1, 2 or 6, the refrigerant composition includes R-1132a, R-152a and optionally R-32.

[0182] Note 14. According to the use described in Note 13, the refrigerant composition comprises:

[0183] 1% to 30% by weight of R-1132a and 99% to 70% by weight of R-152a; or

[0184] R-1132a from 1 wt% to 20 wt%, R-32 from 1 wt% to 10 wt%, and R-152a from 70 wt% to 98 wt%.

[0185] Note 15. For the use described in Notes 1, 2 or 6, the refrigerant composition comprises R-1132a, R-32, R-152a and at least one tetrafluoropropylene refrigerant compound selected from the group consisting of R-1234yf and R-1234ze(E).

[0186] Note 16. According to the use described in Note 15, the refrigerant composition comprises:

[0187] A mixture of 1% to 20% by weight of R-1132a, 1% to 21% by weight of R-32, and 59% to 98% by weight of R-152a and R-1234yf; or

[0188] A mixture of 1 wt% to 20 wt% R-1132a, 1 wt% to 21 wt% R-32, and 59 wt% to 98 wt% R-152a and R-1234ze(E).

[0189] Note 17. For the use according to any one of Notes 3 to 9 or 13 to 16, wherein the refrigerant composition preferably further comprises R-134a in an amount of about 1% to about 10% by weight of R-134a.

[0190] Note 18. According to the use described in Note 2, the refrigerant composition comprises R-1132a, R-1123 and R-1234yf, preferably from about 1 wt% to about 20 wt% of R-1132a, from about 1 wt% to about 20 wt% of R-1123 and from about 98 wt% to about 60 wt% of R-1234yf.

[0191] Note 19. According to the use described in Note 2, the refrigerant composition comprises R-1132a, R-152a, R-134a and R-1234yf, preferably from about 1 wt% to about 20 wt% of R-1132a, from about 5 wt% to about 25 wt% of R-152a, from about 1 wt% to about 10 wt% of R-134a and from about 93 wt% to about 45 wt% of R-1234yf.

[0192] Note 20. According to the use described in Note 1, the refrigerant composition comprises R-1132a and R-32, preferably from about 68% to about 99% by weight of R-1132a and from about 1% to about 32% by weight of R-32, for example from about 72% to about 96% by weight of R-1132a and from about 4% to about 28% by weight of R-32.

[0193] Note 21. According to the use described in Note 2, the refrigerant composition comprises R-1132a, R-32 and CO2, preferably from about 1 wt% to about 20 wt% of R-1132a, from about 1 wt% to about 32 wt% of R-32 and from about 50 wt% to about 95 wt% of CO2, such as from about 2 wt% to about 15 wt% of R-1132a, from about 2 wt% to about 32 wt% of R-32 and from about 55 wt% to about 93 wt% of CO2, such as from about 64 wt% to about 93 wt% of carbon dioxide, from about 2 wt% to about 25 wt% of difluoromethane and from about 2 wt% to about 14 wt% of R-1132a, such as from about 65 wt% to about 93 wt% of carbon dioxide, from about 2 wt% to about 22 wt% of difluoromethane and from about 2 wt% to about 14 wt% of R-1132a.

[0194] Note 22. For any of the preceding notes, the refrigerant composition has a global warming potential (GWP) of less than 150.

[0195] Note 23. In the use according to any one of the preceding notes, the heat pump system is also suitable for performing air conditioning.

[0196] Note 24. The use according to any one of Notes 1 to 23, wherein the composition consists primarily of the said components.

[0197] Note 25. In accordance with any of the preceding notes, the refrigerant composition is less flammable than R-1132a alone, preferably wherein, compared to R-1132a alone, the refrigerant composition has:

[0198] a. Higher flammability limit

[0199] b. Higher ignition energy; and / or

[0200] c. Lower flame speed.

[0201] Note 26. In the use according to any one of the preceding notes, the refrigerant composition is non-flammable, preferably the refrigerant composition is non-flammable at ambient temperature, or the composition is non-flammable at 60°C.

[0202] Note 27. In the use according to any one of the preceding notes, the heat pump system further includes a lubricant, preferably a polyol ester (POE) or polyalkylene glycol (PAG) lubricant.

[0203] Note 28. In the use according to any one of the preceding notes, the refrigerant composition evaporates at a temperature below -30°C, and preferably the refrigerant composition also condenses at a temperature above 40°C.

[0204] Note 29. In accordance with any of the preceding notes, the refrigerant composition is capable of operating in heat pump mode at ambient temperatures below about -15°C, preferably above -20°C.

[0205] Note 30. In the use according to any one of the preceding notes, the temperature glide of the refrigerant composition in the evaporator or condenser is less than about 15 K, preferably less than about 10 K, such as less than about 5 K.

[0206] Note 31. An electric vehicle equipped with a heat pump system and a refrigerant composition as defined in any one of Notes 1 to 30.

[0207] Note 32. A method for generating cooling in an electric vehicle, the method comprising causing a refrigerant composition as defined in any one of Notes 1 to 30 to evaporate near the vehicle body to be cooled.

[0208] Note 33. A method for generating heat in an electric vehicle, the method comprising causing a refrigerant composition as defined in any one of Notes 1 to 30 to condense near the vehicle body to be heated.

Claims

1. A refrigerant composition comprising: 3% to 30% by weight of 1,1-difluoroethylene (R-1132a). Difluoromethane (R-32) 1,1-Difluoroethane (R-152a), and At least one tetrafluoropropylene refrigerant compound selected from 2,3,3,3-tetrafluoropropylene (R-1234yf) and 1,3,3,3-tetrafluoropropylene (R-1234ze(E)).

2. The composition according to claim 1, wherein the composition comprises 3% to 20% by weight of R-1132a, 1% to 21% by weight of R-32, and 59% to 98% by weight of a mixture of R-152a and R-1234ze(E) in any proportion.

3. The composition according to claim 1, wherein the composition comprises 3% to 20% by weight of R-1132a, 1% to 21% by weight of R-32, and 59% to 98% by weight of a mixture of R-152a and R-1234yf in any proportion.

4. A refrigerant composition comprising: 3% to 30% by weight of 1,1-difluoroethylene (R-1132a). Difluoromethane (R-32), and Carbon dioxide (CO2).

5. The composition according to claim 4, wherein the composition comprises 3% to 20% by weight of R-1132a, 1% to 32% by weight of R-32 and 50% to 95% by weight of CO2.

6. The composition according to claim 5, wherein the composition comprises 3% to 15% by weight of R-1132a, 2% to 32% by weight of R-32 and 55% to 93% by weight of CO2.

7. The composition of claim 6, wherein the composition comprises 64% to 93% by weight of carbon dioxide, 2% to 25% by weight of difluoromethane, and 3% to 14% by weight of R-1132a.

8. The composition of claim 7, wherein the composition comprises 65% to 93% by weight of carbon dioxide, 2% to 22% by weight of difluoromethane, and 3% to 14% by weight of R-1132a.

9. A refrigerant composition comprising: 3% to 30% by weight of 1,1-difluoroethylene (R-1132a). 1,3,3,3-Tetrafluoropropylene (R-1234ze(E)), and Difluoromethane (R-32).

10. The composition of claim 9, wherein the composition comprises 1% to 21% by weight of R-32 based on the total weight of the composition.

11. The composition of claim 10, wherein the composition comprises 3% to 20% by weight of R-1132a, 1% to 21% by weight of R-32 and 59% to 98% by weight of R-1234ze(E).

12. The composition according to claim 9, wherein the composition further comprises trifluoroiodomethane (CF3I).

13. The composition according to claim 12, wherein the CF3I is present in an amount less than R-1234ze(E).

14. A refrigerant composition comprising: 3% to 30% by weight of 1,1-difluoroethylene (R-1132a). 1,1-Difluoroethane (R-152a), and Difluoromethane (R-32).

15. The composition of claim 14, wherein the composition comprises 3% to 20% by weight of R-1132a, 1% to 10% by weight of R-32 and 70% to 98% by weight of R-152a.

16. The composition according to any one of claims 1 to 15, wherein the R-1132a is present in an amount of 3% to 20% by weight based on the total weight of the refrigerant composition.

17. The composition of claim 16, wherein the R-1132a is present in an amount of 3% to 15% by weight based on the total weight of the refrigerant composition.

18. The composition according to any one of claims 1 to 15, wherein the refrigerant composition further comprises CO2 (R-744).

19. The composition according to claim 18, wherein the content of CO2 and R-1132a in the composition is less than 30% by weight.

20. The composition according to claim 19, wherein the content of CO2 and R-1132a in the composition is less than 20 by weight.

21. The composition according to any one of claims 1 to 15, wherein the refrigerant composition further comprises R-134a.

22. The composition of claim 21, wherein the R-134a is present in an amount of 1% to 10% by weight.

23. The composition according to any one of claims 1 to 15, wherein the composition comprises less than 0.5% by weight of other hydrofluoroalkanes or hydrofluoroolefins.

24. The composition according to any one of claims 1 to 15, wherein the composition has a global warming potential (GWP) of less than 150.

25. The composition according to any one of claims 1 to 15, wherein the composition is less flammable than R-1132a alone.

26. The composition according to claim 25, wherein, compared to R-1132a alone, the refrigerant composition has: a. Higher flammability limit; b. Higher ignition energy; and / or c. Lower flame speed.

27. The composition according to any one of claims 1 to 15, wherein the composition is non-flammable.

28. The composition of claim 27, wherein the refrigerant composition is non-flammable at ambient temperature.

29. The composition of claim 27, wherein the refrigerant composition is non-flammable at 60°C.

30. The composition according to any one of claims 1 to 15, wherein the composition is evaporated at a temperature below -30°C.

31. The composition of claim 30, wherein the refrigerant composition further condenses at a temperature above 40°C.

32. The composition according to any one of claims 1 to 15, wherein the composition is capable of operating in heat pump mode at an ambient temperature below -15°C.

33. The composition of claim 32, wherein the composition is capable of operating in heat pump mode at ambient temperatures below -20°C.

34. The composition according to any one of claims 1 to 15, wherein the temperature glide of the composition in the evaporator or condenser is less than 15 K.

35. The composition of claim 34, wherein the temperature glide of the composition in the evaporator or condenser is less than 10 K.

36. The composition of claim 35, wherein the temperature glide of the composition in the evaporator or condenser is less than 5 K.

37. Use of the composition according to any one of claims 1 to 15 as a refrigerant in a heat pump system in an electric vehicle.

38. The use according to claim 37, wherein the heat pump system is also suitable for performing air conditioning.

39. The use according to claim 37, wherein the heat pump system further comprises a lubricant.

40. The use according to claim 39, wherein the lubricant is a polyol ester (POE) or a polyalkylene glycol (PAG) lubricant.

41. An electric vehicle equipped with a refrigerant composition and a heat pump system as defined in any one of claims 1 to 15.

42. A method for generating cooling in an electric vehicle, the method comprising causing a refrigerant composition as defined in any one of claims 1 to 15 to evaporate near the vehicle body to be cooled.

43. A method for generating heat in an electric vehicle, the method comprising causing a refrigerant composition as defined in any one of claims 1 to 15 to condense near the vehicle body to be heated.

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