Heat transfer composition as well as preparation method and application thereof

Abstract

The invention discloses a heat transfer composition as well as a preparation method and application thereof. According to the total mass of the composition, the mass ratios of the first component, trans-1, 3, 3, 3-tetrafluoropropene and difluoromethane are x%, y% and z% respectively, the first component is 2, 3, 3, 3-tetrafluoropropene and 1, 1-difluoroethane, the ratios (x, y and z) of the first component, the trans-1, 3, 3, 3-tetrafluoropropene and 1, 1-difluoroethane are located in a ternary phase diagram, the x coordinate of a point A is 23.6%, the x coordinate of a point B is 90.0%, the point coordinates on a curve section AB are (x, 70.06-0.6395 x-0. 001538 x2 and 29.94-0.3605 x + 0.001538 x2), and the coordinates of a point C are (77.6, 0 and 22.4 The GWP of the composition does not exceed 150, the flammability grade reaches A2L, and the composition is a heat transfer composition which is used for replacing propane and is low in global warming potential value, high in refrigeration / heat efficiency and low in flammability and is suitable for refrigeration / heating application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of refrigeration and heating, in particular to a heat transfer composition, a preparation method and application thereof. BACKGROUND

[0002] The current trend is to gradually eliminate the ozone-depleting chlorofluorocarbons and hydrogen-containing chlorofluorocarbons, and reduce the use of high global warming potential (GWP) hydrofluorocarbons. This trend has driven the refrigeration industry to accelerate the transition to low-GWP, zero-ODP (ozone depletion potential) new environmentally friendly refrigerants.

[0003] Under this background, propane, as a natural working medium, is widely used in household refrigerators, small air conditioners, heat pump equipment, and vehicle thermal management systems, etc. due to its good thermodynamic performance, extremely low GWP value (GWP < 3), and no destruction to the ozone layer (ODP = 0), becoming one of the popular choices for low-GWP refrigerant replacement.

[0004] However, propane belongs to A3 highly flammable refrigerant, and its high combustion speed and low ignition point make it subject to strict restrictions in the design of refrigeration systems, charge control, and safety in use. In the fields of vehicle air conditioning, heat pump systems, portable refrigeration, and high-density residential areas, due to its potential fire and explosion risk, regulatory agencies and manufacturers have a reserved attitude towards its application. Therefore, developing a new low-GWP heat transfer composition with the same level of thermodynamic performance as propane and a higher safety level (such as A2L or lower) has become a key direction for the industry to upgrade technology.

[0005] Currently, there are several patents related to low-GWP mixtures, but there are still technical bottlenecks. For example: Patent ZL202010199221.1 discloses a composition composed of 2,3,3,3-tetrafluoropropene (R1234yf), 1,1-difluoroethane (R152a), and propane (R290) / isobutane (R600a) / propylene (R1270). Although it has certain low-GWP characteristics, its flammability level is A3, and it does not effectively reduce the risk of system combustion.

[0006] Patent ZL202211097550.0 discloses a composition including 1,1,2-trifluoroethylene, hexafluoropropylene, 1,1,1,2-tetrafluoroethane, and fluoroethane. Its GWP is low, but its flammability is generally A2 or A3, which is not suitable for high-safety vehicle or household scenarios.

[0007] The composition disclosed in patent ZL201880019810.8 is composed of difluoromethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene, which has good refrigeration performance, but the overall boiling point is slightly high (about -37℃), and cannot provide sufficient latent heat of evaporation under low temperature working conditions, and is not suitable for replacing propane.

[0008] The composition disclosed in patent ZL202210946335.7 involves components such as trifluoroiodomethane, 1,1,2-trifluoroethylene, propane, 1,1-difluoroethane, 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene, but the composition is incompatible with existing systems in terms of lubricating oil solubility, system sealing material adaptation and operating pressure characteristics, and requires structural modification of the equipment, increasing the difficulty of industrialization.

[0009] In addition, the above-mentioned prior art also has the following common problems: 1. The boiling point of some compositions is high, and it is difficult to provide stable cooling capacity under medium and low temperature evaporation working conditions; 2. The overall flammability level is high (A3 or A2), which cannot meet the strict system safety specifications; 3. The unit volume refrigeration capacity (CAP) and energy efficiency ratio (COP) are lower than those of propane, and the system operating efficiency is poor; 4. Poor compatibility with existing refrigeration system materials and working conditions, making it difficult to achieve seamless replacement, and increasing the modification cost.

[0010] Therefore, it is urgent to develop a new type of mixed working fluid with low GWP less than 150, excellent heat transfer performance, low flammability, high safety and propane replaceability, to meet the increasingly stringent environmental protection regulations, and be widely used in vehicle air conditioning systems, household heat pumps, refrigerators, mobile cold chain devices and high safety requirement occasions, and promote the large-scale substitution and popularization of low-carbon refrigerants in the industry. SUMMARY

[0011] In view of the above technical problems and the deficiencies in the art, the present application provides a heat transfer composition, a preparation method and application thereof. The heat transfer composition has low GWP value (GWP less than 150), good safety (flammability below A2L), excellent heat transfer performance and other advantages, and is suitable for various heat transfer working condition systems such as air conditioning, refrigeration, heat pump, etc., and is particularly suitable as a safe substitute for high flammable heat transfer fluid propane.

[0012] The specific technical solutions are as follows: In a first aspect, the present application provides a heat transfer composition consisting of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane, wherein the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane satisfies the GWP of the heat transfer composition is less than 150 and the flammability is below A2L; In the heat transfer composition, the sum of the mass ratio of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane is x%, the mass ratio of trans-1,3,3,3-tetrafluoropropene is y%, and the mass ratio of difluoromethane is z%, the coordinates (x, y, z) in the ternary phase diagram are located inside or on the boundary of the closed area surrounded by the curve segment AB, the straight line segment BC and the straight line segment CA, and y is not 0; In the ternary phase diagram, the sum of the mass ratio of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point A is 23.6%, the sum of the mass ratio of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point B is 90.0%, the coordinates of the points on the curve segment AB are (x, 70.06-0.6395x-0.001538x 2 , 29.94-0.3605x+0.001538x 2 ), and the coordinates of point C are (77.6, 0, 22.4).

[0013] In the heat transfer composition of the first aspect, the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane is preferably 1-10:1, for example 5:1, etc. In the preferred range, when the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane is 10:1, the GWP value of the composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane is the smallest. When the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane is 5:1, this ratio makes the composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane exhibit azeotropic characteristics, and the temperature glide is close to 0. In order to ensure the balance of temperature glide and performance, the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane in the range of 1-10:1 can provide the optimal operating conditions, which can ensure that the temperature glide is less than 10 K during the heat transfer process, optimize the system stability and improve the thermal efficiency. At the same time, the acceptable energy efficiency ratio (COP) and refrigeration performance are maintained to ensure the safety, reliability and economy of the system.

[0014] Further, the boiling point of the heat transfer composition of the first aspect is less than -37℃, for example -45.9~-37.9℃, which is close to that of propane, the CAP is greater than 90% of that of propane, further can be greater than 95% of that of propane, and further can be not less than 100% of that of propane, and both the heating COP and the refrigeration COP are greater than that of propane.

[0015] In a second aspect, the present application provides a heat transfer composition consisting of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane, wherein the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane satisfies the GWP of the heat transfer composition being less than 150 and the flammability being below A2L; In the heat transfer composition, the sum of the mass ratio of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane is x%, the mass ratio of trans-1,3,3,3-tetrafluoropropene is y%, and the mass ratio of difluoromethane is z%, the coordinates (x, y, z) in the ternary phase diagram are located inside or on the boundary of the closed region formed by the curve segment A'B', the straight line segment B'C and the straight line segment CA', and y is not 0; In the ternary phase diagram, the sum of the mass ratio of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point A' is 38.7%, the sum of the mass ratio of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point B' is 85.8%, the coordinates of the points on the curve segment A'B' are (x, 65.88-0.6348x-0.001548x 2 , 34.12-0.3653x+0.001548x 2 ), and the coordinates of point C are (77.6, 0, 22.4).

[0016] The heat transfer composition of the second aspect can achieve low environmental impact and high safety, the CAP of the composition is at least greater than 95% of that of propane in the whole range, and further can be not less than 100% of that of propane, showing equivalent or even better refrigeration capacity than propane. At the same time, the composition exceeds propane in both heating COP and refrigeration COP, providing higher energy efficiency performance.

[0017] In the heat transfer composition of the second aspect, the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane is preferably 1-10:1, for example 5:1, etc. In the preferred range, when the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane is 10:1, the GWP value of the composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane is the smallest. When the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane is 5:1, the ratio makes the composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane exhibit azeotropic characteristics, with a temperature glide close to 0. In order to ensure the balance of temperature glide and performance, the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane in the range of 1-10:1 can provide the optimal operating conditions, which can ensure that the temperature glide is less than 10 K in the heat transfer process, optimize the system stability and improve the thermal efficiency. At the same time, the acceptable energy efficiency ratio (COP) and refrigeration performance are maintained, ensuring the safety, reliability and economy of the system.

[0018] Further, the heat transfer composition has a boiling point less than -37℃, for example -45.9 ~ -37.9℃, close to that of propane, a CAP greater than 90% of that of propane, further greater than 95% of that of propane, and more further not less than 100% of that of propane, and both the heating COP and the refrigeration COP are greater than that of propane.

[0019] The heat transfer composition has x+y+z=100, x can be selected from 23.6 ~ 90.0, for example 25, 30, 35, 40, 45, 46, 50, 51, 52, 56, 57, 58, 62, 63, 68, 69, 71, 72, 75, 76, 78, 79, 80, 83, etc., y can be selected from 1 ~ 55, for example 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, etc., for example x is 78, 79 or 83, y is 2; or, x is 75, 76 or 80, y is 5; or, x is 71, 72 or 75, y is 10; or, x is 68 or 69, y is 15; or, x is 62 or 63, y is 20; or, x is 56, 57 or 68, y is 25; or, x is 51 or 52, y is 30; or, x is 45 or 46, y is 35; or, x is 40, y is 40; or, x is 35, y is 45.

[0020] In a third aspect, the present application provides a preparation method of the heat transfer composition of the first aspect or the second aspect, comprising: mixing 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane in a liquid phase state to obtain the heat transfer composition.

[0021] In a fourth aspect, the present application provides a composition for heat transfer, which is composed of 80% ~ 99.9% (for example 82%, 84%, 85%, 86%, 88%, 89%, 90%, 92%, 94%, 96%, 97%, 98%, 99%, 99.5%, etc.) of the heat transfer composition of the first aspect or the second aspect and 0.1% ~ 20% (for example 0.5%, 1%, 2%, 3%, 4%, 6%, 8%, 10%, 11%, 12%, 14%, 15%, 16%, 18%, etc.) of component M, wherein component M is selected from one or more than two of C1 ~ C4 fluorinated hydrocarbon, C1 ~ C4 hydrocarbon, trifluoroiodomethane, carbon dioxide, dimethyl ether other than 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane; the GWP of the composition for heat transfer is less than 150 and the flammability is below A2L.

[0022] The composition for heat transfer according to the fourth aspect, the C1-C4 fluorinated hydrocarbon is preferably selected from one or more of 1,1,1,2-tetrafluoroethane, pentafluoroethane, 3,3,3-trifluoropropene, trifluoroethene, hexafluoropropene, trans-1,2-difluoroethene.

[0023] The composition for heat transfer according to the fourth aspect, the C1-C4 hydrocarbon is preferably selected from one or more of propane, propylene, isobutane.

[0024] Further, the composition for heat transfer according to the fourth aspect has a boiling point less than -37℃, for example, -45.9 to -37.9℃, close to that of propane, a CAP greater than 90% of that of propane, further greater than 95% of that of propane, and further not less than 100% of that of propane, and both the heating COP and the refrigeration COP are greater than that of propane.

[0025] In the fifth aspect, the present application provides a preparation method of the composition for heat transfer according to the fourth aspect, comprising: mixing 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene, difluoromethane, and component M in a liquid phase state to obtain the composition for heat transfer.

[0026] In the sixth aspect, the present application provides an application of the composition for heat transfer according to the fourth aspect in a heat exchange device. The composition for heat transfer can circulate in the heat exchange device as a heat transfer fluid (refrigerant, heat transfer working medium, etc.). The composition for heat transfer can be used to replace propane, chlorodifluoromethane, R410A, R404A, or other traditional refrigerants with high GWP, and is particularly suitable for occasions with higher requirements for system safety level and pursuit of high energy efficiency and low carbon emission. The heat exchange device has no special requirements, and can be a household heat exchange device, a commercial heat exchange device, a heat pump system heat exchange device, a cold storage equipment heat exchange device, an industrial refrigeration heat exchange device, an automobile heat exchange device, a data center heat exchange device, or a mobile refrigeration equipment heat exchange device, etc., such as various heat exchangers, household air conditioners, refrigerators, heat pump water heaters, vehicle air conditioners, vehicle heat pump systems (automobile thermal management systems), commercial refrigerators, cold chain logistics equipment, and other small and medium-sized closed systems.

[0027] In the application process according to the sixth aspect, the composition for heat transfer can be adapted to various heat exchange devices, and can realize direct replacement of the composition for heat transfer propane without modification or replacement of the original heat exchange device, thereby reducing the application cost.

[0028] In a seventh aspect, the present application provides a heat transfer method, which uses the heat transfer composition according to the first aspect or the second aspect or the composition for heat transfer according to the fourth aspect to transfer heat.

[0029] The specific use scenarios, further selection and optimization of the technical solutions of the heat transfer method according to the seventh aspect can refer to the application according to the sixth aspect.

[0030] The heat transfer composition and the composition for heat transfer according to the present application have the characteristics of low GWP, low flammability, high performance, etc., are environmentally friendly, have good refrigeration (heat) effect, are suitable for replacing propane and the like in household and commercial refrigeration devices, and have good environmental compatibility, energy efficiency performance and system adaptation ability.

[0031] The heat transfer composition according to the present application uses a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane as the first component, trans-1,3,3,3-tetrafluoropropene as the second component, and difluoromethane as the third component, and the total mass of the first component, the second component and the third component is 100%.

[0032] Figure 1 The three-phase diagram of the first component, the second component and the third component of the heat transfer composition according to the first aspect in a ternary coordinate system is shown in the enclosed area formed by the curve segment AB, the straight line segment BC and the straight line segment CA.

[0033] Figure 2 The three-phase diagram of the first component, the second component and the third component of the heat transfer composition according to the second aspect in a ternary coordinate system is shown in the enclosed area formed by the curve segment A'B', the straight line segment B'C and the straight line segment CA'.

[0034] The heat transfer composition according to the present application, for example, the coordinate (x, y, z) position corresponding to the composition includes but is not limited to the point (80, 5, 15), the point (75, 10, 15), the point (70, 15, 15), the point (65, 20, 15), the point (60, 25, 15), the point (75, 5, 20), the point (70, 10, 20), the point (65, 15, 20), the point (60, 20, 20), the point (55, 25, 20), the point (50, 30, 20), the point (45, 35, 20), the point (40, 40, 20), the point (35, 45, 20) and the like. Here, taking the coordinate (x, y, z) at the point (60, 25, 15) as an example, it can be understood as: the mass content of the first component is 60%, the mass content of the second component is 25%, and the mass content of the third component is 15% based on the total mass of the first component, the second component and the third component being 100%.

[0035] The ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane in the first component of the heat transfer composition can be flexibly adjusted according to system performance, safety and environmental index requirements, and the specific ratio range is relatively wide. Exemplarily, the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane in the first component can be 1:1, 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc. The specific ratio can be optimized and adjusted according to factors such as the global warming potential value, condensation pressure, flammability limit, lubricating oil compatibility, etc. of the target system.

[0036] In order to further improve the CAP and COP of the composition and make the heat exchange effect better, the present application proposes a composition for heat transfer, which further introduces component M on the basis of the heat transfer composition in the first aspect or the second aspect, for adjusting system pressure, condensation temperature, flammability level or improving material compatibility and other performance parameters.

[0037] The present application has no special requirements for the preparation method of the heat transfer composition and the composition for heat transfer, for example: the first component, the second component and the third component are mixed in a liquid phase state, and the heat transfer composition of the present application can be obtained; the first component, the second component, the third component and the component M are mixed in a liquid phase state, and the composition for heat transfer of the present application can be obtained.

[0038] Compared with the prior art, the present application has the following beneficial effects: The heat transfer composition and the composition for heat transfer of the present application have significant environmental protection and system adaptability, and are particularly suitable for replacing the traditional high-flammability refrigerant propane. Compared with propane, the heat transfer composition and the composition for heat transfer of the present application have similar latent heat of evaporation and operating pressure characteristics, and can be directly replaced without significantly modifying the original system. At the same time, the global warming potential (GWP) of the composition is less than 150, and the ozone depletion potential (ODP) is 0, which helps to achieve the greenhouse gas emission reduction target. In terms of safety performance, by reasonably adjusting the ratio of low-flammability hydrofluoroolefin and hydrofluoroalkane, the maximum burning speed and flame propagation speed of the composition are effectively reduced, so that the overall flammability of the heat transfer composition reaches A2L level or below, which is significantly better than A3 level propane, and meets the use requirements of higher safety level scenes (such as household air conditioners, vehicle-mounted heat pump systems, heat pump water heaters, etc.).

[0039] In addition, the heat transfer composition and the composition for heat transfer of the present application exhibit excellent thermodynamic performance, and have a unit volume refrigeration capacity (CAP) comparable to that of propane and a higher energy efficiency ratio (COP), which helps to improve the overall efficiency of the system and reduce the operating energy consumption. The components have good compatibility with common lubricating oils (such as polyester oil POE, polyether oil PAG and polyvinyl ether PVE) and system materials, and have the basis for industrial promotion. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 The three-phase diagram of the first component, the second component and the third component of the heat transfer composition of the first aspect of the present application in a ternary coordinate system is shown in Figure 1. The closed area surrounded by the curve segment AB, the straight line segment BC and the straight line segment CA represents the feasible component range.

[0041] Figure 2 The three-phase diagram of the first component, the second component and the third component of the heat transfer composition of the second aspect of the present application in a ternary coordinate system is shown in Figure 2. The closed area surrounded by the curve segment A'B', the straight line segment B'C and the straight line segment CA' represents the feasible component range.

[0042] Figure 3 The temperature-pressure (T-P) curve diagram of the heat transfer composition of Example 2 and propane in the evaporation temperature range is shown in Figure 3. DETAILED DESCRIPTION

[0043] The present application will be further described below in conjunction with the accompanying drawings and specific examples. It should be understood that these examples are only used to illustrate the present application and are not used to limit the scope of the present application.

[0044] In the present application, the disclosure of numerical ranges includes all values and further subdivided ranges within the entire range, including the endpoints given for these ranges, the point values given for the examples and the subranges formed by any combination of these points.

[0045] The term "line segment" refers to a finite portion of a straight line or a curve between two points (including the two endpoints), including on the line segment at the two endpoints and on the line connecting the two endpoints. For example, the coordinate (x, y, z) is on the line segment AB, which means that the coordinate (x, y, z) is on the point A, the point B or the line connecting them.

[0046] Example 1: A composition of 75 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (62.5 g of 2,3,3,3-tetrafluoropropene, 12.5 g of 1,1-difluoroethane composition), 5 g of trans-1,3,3,3-tetrafluoropropene and 20 g of difluoromethane were mixed in a liquid phase to obtain the heat transfer composition of the present example.

[0047] Example 2: A heat transfer composition of the present example was obtained by mixing 71 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (60.9 g of 2,3,3,3-tetrafluoropropene, 10.1 g of 1,1-difluoroethane composition), 10 g of trans-1,3,3,3-tetrafluoropropene, and 19 g of difluoromethane in a liquid phase state. Figure 3 A temperature-pressure (T-P) diagram of the heat transfer composition of the present example and propane in the evaporation temperature range is shown.

[0048] Example 3: A heat transfer composition of the present example was obtained by mixing 69 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (41.4 g of 2,3,3,3-tetrafluoropropene, 27.6 g of 1,1-difluoroethane composition), 15 g of trans-1,3,3,3-tetrafluoropropene, and 16 g of difluoromethane in a liquid phase state.

[0049] Example 4: A heat transfer composition of the present example was obtained by mixing 62 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (55.1 g of 2,3,3,3-tetrafluoropropene, 6.9 g of 1,1-difluoroethane composition), 20 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane in a liquid phase state.

[0050] Example 5: A heat transfer composition of the present example was obtained by mixing 56 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (49.8 g of 2,3,3,3-tetrafluoropropene, 6.2 g of 1,1-difluoroethane composition), 25 g of trans-1,3,3,3-tetrafluoropropene, and 19 g of difluoromethane in a liquid phase state.

[0051] Example 6: A heat transfer composition of the present example was obtained by mixing 52 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (39.0 g of 2,3,3,3-tetrafluoropropene, 13.0 g of 1,1-difluoroethane composition), 30 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane in a liquid phase state.

[0052] Example 7: A heat transfer composition of the present example was obtained by mixing 45 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (40.5 g of 2,3,3,3-tetrafluoropropene, 4.5 g of 1,1-difluoroethane composition), 35 g of trans-1,3,3,3-tetrafluoropropene, and 20 g of difluoromethane in a liquid phase state.

[0053] Example 8: A composition of 40 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (32.0 g of 2,3,3,3-tetrafluoropropene, 8.0 g of 1,1-difluoroethane composition), 40 g of trans-1,3,3,3-tetrafluoropropene, and 20 g of difluoromethane was mixed in a liquid phase state to obtain the heat transfer composition of the present example.

[0054] Example 9: A composition of 35 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (29.2 g of 2,3,3,3-tetrafluoropropene, 5.8 g of 1,1-difluoroethane composition), 45 g of trans-1,3,3,3-tetrafluoropropene, and 20 g of difluoromethane was mixed in a liquid phase state to obtain the heat transfer composition of the present example.

[0055] Example 10: A composition of 76 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (68.4 g of 2,3,3,3-tetrafluoropropene, 7.6 g of 1,1-difluoroethane composition), 5 g of trans-1,3,3,3-tetrafluoropropene, and 19 g of difluoromethane was mixed in a liquid phase state to obtain the heat transfer composition of the present example.

[0056] Example 11: A composition of 72 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (60.0 g of 2,3,3,3-tetrafluoropropene, 12.0 g of 1,1-difluoroethane composition), 10 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane was mixed in a liquid phase state to obtain the heat transfer composition of the present example.

[0057] Example 12: A composition of 68 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (61.2 g of 2,3,3,3-tetrafluoropropene, 6.8 g of 1,1-difluoroethane composition), 15 g of trans-1,3,3,3-tetrafluoropropene, and 17 g of difluoromethane was mixed in a liquid phase state to obtain the heat transfer composition of the present example.

[0058] Example 13: A composition of 62 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (49.6 g of 2,3,3,3-tetrafluoropropene, 12.4 g of 1,1-difluoroethane composition), 20 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane was mixed in a liquid phase state to obtain the heat transfer composition of the present example.

[0059] Example 14: A heat transfer composition of the present example was obtained by mixing 58 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (43.5 g of 2,3,3,3-tetrafluoropropene, 14.5 g of 1,1-difluoroethane composition), 25 g of trans-1,3,3,3-tetrafluoropropene, and 17 g of difluoromethane in a liquid phase state.

[0060] Example 15: A heat transfer composition of the present example was obtained by mixing 52 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (44.6 g of 2,3,3,3-tetrafluoropropene, 7.4 g of 1,1-difluoroethane composition), 30 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane in a liquid phase state.

[0061] Example 16: A heat transfer composition of the present example was obtained by mixing 46 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (41.4 g of 2,3,3,3-tetrafluoropropene, 4.6 g of 1,1-difluoroethane composition), 35 g of trans-1,3,3,3-tetrafluoropropene, and 19 g of difluoromethane in a liquid phase state.

[0062] Example 17: A heat transfer composition of the present example was obtained by mixing 80 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (70.0 g of 2,3,3,3-tetrafluoropropene, 10.0 g of 1,1-difluoroethane composition), 5 g of trans-1,3,3,3-tetrafluoropropene, and 15 g of difluoromethane in a liquid phase state.

[0063] Example 18: A heat transfer composition of the present example was obtained by mixing 75 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (60.0 g of 2,3,3,3-tetrafluoropropene, 15.0 g of 1,1-difluoroethane composition), 10 g of trans-1,3,3,3-tetrafluoropropene, and 15 g of difluoromethane in a liquid phase state.

[0064] Example 19: A heat transfer composition of the present example was obtained by mixing 78 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (66.9 g of 2,3,3,3-tetrafluoropropene, 11.1 g of 1,1-difluoroethane composition), 2 g of trans-1,3,3,3-tetrafluoropropene, and 20 g of difluoromethane in a liquid phase state.

[0065] Example 20: A heat transfer composition of the present example was obtained by mixing 79 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (69.1 g of 2,3,3,3-tetrafluoropropene, 9.9 g of 1,1-difluoroethane composition), 2 g of trans-1,3,3,3-tetrafluoropropene, and 19 g of difluoromethane in a liquid phase state.

[0066] Example 21: A heat transfer composition of the present example was obtained by mixing 83 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (45.3 g of 2,3,3,3-tetrafluoropropene, 37.7 g of 1,1-difluoroethane composition), 2 g of trans-1,3,3,3-tetrafluoropropene, and 15 g of difluoromethane in a liquid phase state.

[0067] Example 22: A heat transfer composition of the present example was obtained by mixing 52 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (43.3 g of 2,3,3,3-tetrafluoropropene, 8.7 g of 1,1-difluoroethane composition), 30 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane in a liquid phase state.

[0068] Example 23: A heat transfer composition of the present example was obtained by mixing 63 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (53.3 g of 2,3,3,3-tetrafluoropropene, 9.7 g of 1,1-difluoroethane composition), 20 g of trans-1,3,3,3-tetrafluoropropene, and 17 g of difluoromethane in a liquid phase state.

[0069] Example 24: A heat transfer composition of the present example was obtained by mixing 57 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (48.2 g of 2,3,3,3-tetrafluoropropene, 8.8 g of 1,1-difluoroethane composition), 25 g of trans-1,3,3,3-tetrafluoropropene, and 18 g of difluoromethane in a liquid phase state.

[0070] Example 25: A heat transfer composition of the present example was obtained by mixing 51 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (43.2 g of 2,3,3,3-tetrafluoropropene, 7.8 g of 1,1-difluoroethane composition), 30 g of trans-1,3,3,3-tetrafluoropropene, and 19 g of difluoromethane in a liquid phase state.

[0071] Example 26: A composition of 70 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (62.2 g of 2,3,3,3-tetrafluoropropene, 7.8 g of 1,1-difluoroethane composition), 15 g of trans-1,3,3,3-tetrafluoropropene, 15 g of difluoromethane, and 11 g of trifluoroethylene was mixed in a liquid phase state to obtain the composition for heat transfer of the present example.

[0072] Example 27: A composition of 64 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (56.9 g of 2,3,3,3-tetrafluoropropene, 7.1 g of 1,1-difluoroethane composition), 16 g of trans-1,3,3,3-tetrafluoropropene, 20 g of difluoromethane, and 8 g of trans-1,2-difluoroethylene was mixed in a liquid phase state to obtain the composition for heat transfer of the present example.

[0073] Example 28: A composition of 70 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (52.5 g of 2,3,3,3-tetrafluoropropene, 17.5 g of 1,1-difluoroethane composition), 13 g of trans-1,3,3,3-tetrafluoropropene, 17 g of difluoromethane, and 2 g of carbon dioxide was mixed in a liquid phase state to obtain the composition for heat transfer of the present example.

[0074] Example 29: A composition of 62 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (53.1 g of 2,3,3,3-tetrafluoropropene, 8.9 g of 1,1-difluoroethane composition), 20 g of trans-1,3,3,3-tetrafluoropropene, 18 g of difluoromethane, and 15 g of 3,3,3-trifluoropropene was mixed in a liquid phase state to obtain the composition for heat transfer of the present example.

[0075] Example 30: A composition of 60 g of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (45 g of 2,3,3,3-tetrafluoropropene, 15 g of 1,1-difluoroethane composition), 25 g of trans-1,3,3,3-tetrafluoropropene, 15 g of difluoromethane, and 2 g of 1,1,1,2-tetrafluoroethane was mixed in a liquid phase state to obtain the composition for heat transfer of the present example.

[0076] Example 31: 56 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (42 g of 2,3,3,3-tetrafluoropropene and 14 g of 1,1-difluoroethane), 25 g of trans-1,3,3,3-tetrafluoropropene, 19 g of difluoromethane, and 3 g of isobutane were mixed in a liquid phase to obtain a composition that can be used for heat transfer in this example.

[0077] Comparative Example 1: The heat transfer fluid is propane.

[0078] Comparative Example 2: 32 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (16.0 g of 2,3,3,3-tetrafluoropropene and 16.0 g of 1,1-difluoroethane), 34 g of trans-1,3,3,3-tetrafluoropropene and 34 g of difluoromethane were mixed in a liquid phase to obtain a heat transfer composition of this comparative example.

[0079] Comparative Example 3: 30 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (20.0 g of 2,3,3,3-tetrafluoropropene and 10.0 g of 1,1-difluoroethane), 63 g of trans-1,3,3,3-tetrafluoropropene and 7 g of difluoromethane were mixed in a liquid phase to obtain a heat transfer composition of this comparative example.

[0080] Comparative Example 4: 50 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (43.8 g of 2,3,3,3-tetrafluoropropene and 6.2 g of 1,1-difluoroethane), 40 g of trans-1,3,3,3-tetrafluoropropene and 10 g of difluoromethane were mixed in a liquid phase to obtain a heat transfer composition of this comparative example.

[0081] Comparative Example 5: 53 g of a composition of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane (17.7 g of 2,3,3,3-tetrafluoropropene and 35.3 g of 1,1-difluoroethane), 27 g of trans-1,3,3,3-tetrafluoropropene and 20 g of difluoromethane were mixed in a liquid phase to obtain a heat transfer composition of this comparative example.

[0082] Performance testing: The boiling point, relative refrigeration capacity per unit volume (CAP) and relative coefficient of performance (COP) of the compositions of the embodiments or comparative examples were obtained through theoretical calculations using Refprop 10.0, a fluid thermodynamics and transport properties database of the National Institute of Standards and Technology of the United States.

[0083] CAP: the product of the latent heat value of the heat transfer composition and the vapor density under refrigeration and heating cycle conditions.

[0084] COP: the ratio of the refrigeration capacity (or heating capacity) of the heat transfer composition to the power consumption of the compressor under refrigeration (or heating) cycle conditions with an evaporation temperature of 5℃, a condensation temperature of 45℃, a superheat temperature of 10 K, a subcooling temperature of 5 K, and a compressor efficiency of 70%.

[0085] Relative CAP, Relative COP: the ratio of the CAP, COP of the composition to the CAP, COP of propane.

[0086] The GWP value of the composition of each example or comparative example is calculated by the weighted average of the GWP value of each component of the composition by mass fraction. The GWP value of each component is taken from the Fourth Report of the Intergovernmental Panel on Climate Change.

[0087] The flammability performance of the composition of each example or comparative example is evaluated by determining the lower flammable limit and the flammable rate under standard conditions. The test is carried out in accordance with the GB / T 7778 standard "Refrigerant Numbering Method and Safety Classification". The safety classification results of the compositions of each example and comparative example are shown in Table 1.

[0088] The average boiling point, relative CAP, relative COP, and GWP value calculation results of the compositions of each example and comparative example are shown in Table 1.

[0089] Table 1 As can be seen from Table 1, the compositions of each example of the present application have a boiling point close to that of propane (-45.9~ -37.9℃), lower flammability (below A2L), similar CAP and higher COP, and a GWP value lower than 150. At the same time, the comparative examples and comparative examples show that the heat transfer composition and the composition useful for heat transfer of the present application can achieve a high energy efficiency ratio COP higher than that of propane, a boiling point close to that of propane, a GWP lower than 150, a safety level of A2L, and can achieve the environmental protection replacement of propane. When the heat transfer composition is not the formula required by the present application, such as comparative examples 2~4, it is not possible to simultaneously achieve a high energy efficiency ratio COP higher than that of propane, a GWP lower than 150, and a boiling point close to that of propane. When the mass ratio of the first component 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane exceeds the range defined by the present application, such as comparative example 5, although the refrigeration efficiency COP is higher than that of propane and the GWP is lower than 150, the safety level is A2.

[0090] In this disclosure, the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" mean that a particular feature, structure, material, or characteristic is included in at least one embodiment or example of the present application. The illustrative appearances of the above-mentioned terms in various places in the specification are not necessarily referred to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics can be combined in any suitable manner in one or more embodiments or examples. Moreover, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It is also possible in the present application that additional or fewer features than those explicitly described above are present in the claims.

[0091] In addition, the terms "first", "second", etc. are used herein only to describe various features, and do not imply a relative importance or a specific order of the features. Thus, a feature defined with "first" or "second" can implicitly or explicitly include at least one of the feature. In the description of the present application, the meaning of "a plurality" is at least two, such as two, three, etc., unless otherwise specifically defined.

[0092] It is to be understood that the above description is intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reading the above description. The scope of the application should, therefore, be determined not with reference to the above description, but instead with reference to the appended claims, along with their full scope of equivalents.

Claims

1. A heat transfer composition, characterized in that Composed of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane, wherein the mass ratio of 2,3,3,3-tetrafluoropropene to 1,1-difluoroethane satisfies the GWP of the heat transfer composition to be less than 150 and the flammability to be below A2L; In the heat transfer composition, the sum of the mass of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane accounts for x%, the mass of trans-1,3,3,3-tetrafluoropropene accounts for y%, and the mass of difluoromethane accounts for z%. In the ternary phase diagram, the coordinates (x, y, z) are located inside or on the boundary of the closed region enclosed by the curve segment AB, the straight line segment BC, and the straight line segment CA, and y is not 0. In the ternary phase diagram, the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point A accounts for 23.6%, and the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point B accounts for 90.0%. The coordinates of the points on the curve segment AB are (x,70.06-0.6395x-0.001538x 2 ,29.94-0.3605x+0.001538x 2 ), the coordinates of point C are (77.6,0,22.4).

2. The heat transfer composition according to claim 1, characterized in that The coordinates (x, y, z) in the ternary phase diagram are located inside or on the boundary of the closed region enclosed by the curve segment A'B', the straight line segment B'C, and the straight line segment CA'; In the ternary phase diagram, the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point A' accounts for 38.7%, and the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane corresponding to point B' accounts for 85.8%. The coordinates of the points on the curve segment A'B' are (x,65.88-0.6348x-0.001548x 2 ,34.12-0.3653x+0.001548x 2 ).

3. The heat transfer composition according to claim 1 or 2, characterized in that The mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is 1~10:

1.

4. The heat transfer composition according to claim 1 or 2, characterized in that The heat transfer composition has a boiling point lower than -37°C, a CAP greater than 90% of propane, and a heating COP and a cooling COP greater than propane.

5. The heat transfer composition according to claim 2, characterized in that The heat transfer composition has a boiling point lower than -37°C, a CAP greater than 95% of propane, and a heating COP and a cooling COP greater than propane.

6. The heat transfer composition according to claim 4, characterized in that The boiling point of the heat transfer composition is -45.9 to -37.9°C.

7. The method for preparing the heat transfer composition according to any one of claims 1 to 6, characterized in that: include: The heat transfer composition is obtained by mixing 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene and difluoromethane in a liquid phase.

8. A composition useful for heat transfer, characterized in that: The heat transfer composition comprises, by mass percentage, 80% to 99.9% of the heat transfer composition according to any one of claims 1 to 6 and 0.1% to 20% of component M, wherein component M is selected from one or more of C1 to C4 fluorocarbons other than 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane, C1 to C4 hydrocarbons, trifluoroiodomethane, carbon dioxide, and dimethyl ether; the GWP of the heat transfer composition is less than 150 and the flammability is below A2L.

9. The heat transfer composition according to claim 8, characterized in that The C1-C4 fluorohydrocarbon is selected from one or more of 1,1,1,2-tetrafluoroethane, pentafluoroethane, 3,3,3-trifluoropropylene, trifluoroethylene, hexafluoropropylene, and trans-1,2-difluoroethylene.

10. The heat transfer composition according to claim 8, characterized in that The C1-C4 hydrocarbon is selected from one or more of propane, propylene and isobutane.

11. The heat transfer composition according to any one of claims 8 to 10, characterized in that The composition that can be used for heat transfer has a boiling point lower than -37°C, a CAP greater than 90% of propane, and a heating COP and a cooling COP both greater than propane.

12. The heat transfer composition according to claim 11, characterized in that The boiling point of the composition that can be used for heat transfer is -45.9 to -37.9°C.

13. The method for preparing a composition that can be used for heat transfer according to any one of claims 8 to 12, characterized in that: include: 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene, difluoromethane and component M are mixed in a liquid phase to obtain the composition that can be used for heat transfer.

14. Use of the heat transfer composition according to any one of claims 1 to 6 or the composition useful for heat transfer according to any one of claims 8 to 12 in a heat exchange device.

15. The use according to claim 14, characterized in that The heat transfer composition or the composition usable for heat transfer circulates in the heat exchange device as a heat transfer fluid.

16. The use according to claim 14 or 15, characterized in that The heat transfer composition or the composition usable for heat transfer is used to replace propane, chlorodifluoromethane, R410A or R404A.

17. The use according to claim 14, characterized in that The heat exchange device is a household heat exchange device, a commercial heat exchange device, a heat exchange device for a heat pump system, a heat exchange device for a refrigeration device, a heat exchange device for an industrial refrigeration device, a heat exchange device for an automobile, a heat exchange device for a data center, or a heat exchange device for a mobile refrigeration device.

18. A heat transfer method, characterized in that: Heat transfer is performed using the heat transfer composition according to any one of claims 1 to 6 or the composition usable for heat transfer according to any one of claims 8 to 12.

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