Heat transfer compositions, methods of making and using the same

Abstract

The application discloses a heat transfer composition and a preparation method and application thereof. According to the total mass of the composition, the mass proportions of a 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 proportions (x, y, z) of the three are located in a ternary phase diagram, the x coordinate of point A is 23.6%, the x coordinate of point B is 90.0%, the coordinates of 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). The composition has a GWP of not more than 150 and a flammability level of A2L, is a low-global-warming-potential, high-refrigeration / heat-efficiency and low-flammability heat transfer composition for replacing propane, and is suitable for refrigeration / heat application.

Description

Technical Field

[0001] This invention relates to the field of refrigeration and heating technology, specifically to a heat transfer composition, its preparation method, and its application. Background Technology

[0002] The current trend is to phase out ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), and to reduce the use of HFCs with high global warming potential (GWP). This trend is driving the refrigeration industry to accelerate its transition to new, environmentally friendly refrigerants with low GWP and zero ODP (ozone depletion potential).

[0003] Against this backdrop, propane, as a natural working fluid, is widely used in household refrigerators, small air conditioners, heat pump equipment, and automotive thermal management systems due to its excellent thermodynamic properties, extremely low GWP value (GWP<3), and no ozone-depleting effect (ODP=0), making it one of the popular choices for low-GWP refrigerant replacements.

[0004] However, propane is a Group A3 highly flammable refrigerant. Its high combustion rate and low ignition point severely limit its use in refrigeration systems, including design, charge control, and safety. Regulatory agencies and manufacturers have reservations about its application in automotive air conditioning, heat pump systems, portable refrigeration, and medium- to high-density residential applications due to its potential fire and explosion risks. Therefore, developing a novel low-GWP heat transfer composition that combines propane-level thermodynamic performance with a higher safety rating (such as A2L or lower) has become a key direction for technological upgrading in the industry.

[0005] Several patented technologies related to low GWP mixtures have been proposed, but technical bottlenecks still exist. For example:

[0006] Patent ZL202010199221.1 discloses a composition consisting of 2,3,3,3-tetrafluoropropylene (R1234yf), 1,1-difluoroethane (R152a), and propane (R290) / isobutane (R600a) / propylene (R1270). Although it has certain low GWP characteristics, its flammability rating is A3, which does not effectively reduce the risk of system combustion.

[0007] The composition disclosed in patent ZL202211097550.0 includes 1,1,2-trifluoroethylene, hexafluoropropylene, 1,1,1,2-tetrafluoroethane and fluoroethane. It has a low GWP, but its flammability is generally A2 or A3, which is not suitable for automotive or household applications where safety requirements are high.

[0008] The composition proposed in patent ZL201880019810.8 consists of difluoromethane, pentafluoroethane and 2,3,3,3-tetrafluoropropylene. Although it has good refrigeration performance, its overall boiling point is slightly high (about -37°C), and it cannot provide sufficient latent heat of vaporization under low temperature conditions, making it unsuitable as a substitute for propane.

[0009] The composition disclosed in patent ZL202210946335.7 involves components such as trifluoroiodomethane, 1,1,2-trifluoroethylene, propane, 1,1-difluoroethane, 2,3,3,3-tetrafluoropropylene, and trans-1,3,3,3-tetrafluoropropylene. However, this composition is incompatible with existing systems in terms of lubricant solubility, system sealing material compatibility, and operating pressure characteristics, requiring structural modifications to the equipment and increasing the difficulty of industrialization.

[0010] In addition, many of the above-mentioned existing technologies also have the following common problems:

[0011] 1. Some compositions have high boiling points, making it difficult to provide stable cooling capacity under medium and low temperature evaporation conditions;

[0012] 2. The overall flammability rating is high (A3 or A2), which fails to meet stringent system safety specifications;

[0013] 3. The volumetric cooling capacity (CAP) and coefficient of performance (COP) are lower than those of propane, resulting in poor system operating efficiency;

[0014] 4. Poor compatibility with existing refrigeration system materials and operating conditions makes seamless replacement difficult and increases modification costs.

[0015] Therefore, there is an urgent need to develop a new type of mixed working fluid that has excellent heat transfer performance, low flammability, high safety, and is a substitute for propane, while having a GWP of less than 150. This is to meet increasingly stringent environmental regulations and be widely used in automotive air conditioning systems, household heat pumps, refrigerators, mobile cold chain devices, and other applications with high safety requirements, thereby promoting the large-scale replacement and promotion of low-carbon refrigerants across the industry. Summary of the Invention

[0016] To address the aforementioned technical problems and shortcomings in the field, this invention provides a heat transfer composition, its preparation method, and its application. This heat transfer composition has advantages such as low GWP value (GWP less than 150), good safety (flammability below A2L), and excellent heat transfer performance. It is suitable for various heat transfer systems such as air conditioning, refrigeration, and heat pumps, and is particularly suitable as a safe alternative to propane, a highly flammable heat transfer fluid.

[0017] The specific technical solution is as follows:

[0018] In a first aspect, the present invention provides a heat transfer composition comprising 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene and difluoromethane, wherein the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane satisfies that the heat transfer composition has a GWP of less than 150 and a flammability of less than A2L.

[0019] In the heat transfer composition, the sum of the masses of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane accounts for x%, the mass of trans-1,3,3,3-tetrafluoropropylene accounts for y%, the mass of difluoromethane accounts for z%, and 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 AB, the straight line segment BC and the straight line segment CA, and y is not 0;

[0020] In the ternary phase diagram, the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point A accounts for 23.6%, and the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point B accounts for 90.0%. The coordinates of the point on 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).

[0021] In the heat transfer composition described in the first aspect, the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is preferably 1 to 10:1, for example, 5:1. Within this preferred range, the composition exhibits the lowest GWP value when the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is 10:1. When the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is 5:1, this ratio results in an azeotropic composition with a temperature glide close to 0. To ensure a balance between temperature glide and performance, a mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane ranging from 1 to 10:1 provides optimal operating conditions. This characteristic ensures a temperature glide below 10 K during heat transfer, optimizing system stability and improving thermal efficiency. At the same time, maintain an acceptable coefficient of performance (COP) and cooling performance to ensure the safety, reliability and economy of the system.

[0022] Furthermore, the heat transfer composition described in the first aspect has a boiling point of less than -37°C, for example -45.9 to -37.9°C, which is close to that of propane, and a CAP greater than 90% of propane, further greater than 95% of propane, and even further not less than 100% of propane, with both heating COP and cooling COP greater than propane.

[0023] In a second aspect, the present invention provides a heat transfer composition comprising 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene and difluoromethane, wherein the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane satisfies that the GWP of the heat transfer composition is less than 150 and the flammability is less than A2L.

[0024] In the heat transfer composition, the sum of the masses of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane accounts for x%, the mass of trans-1,3,3,3-tetrafluoropropylene accounts for y%, the mass of difluoromethane accounts for z%, and 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', and y is not 0;

[0025] In the ternary phase diagram, the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point A' accounts for 38.7%, and the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point B' accounts for 85.8%. The coordinates of the point on the curve segment A'B' are (x, 65.88 - 0.6348x - 0.001548x). 2 34.12-0.3653x+0.001548x 2 The coordinates of point C are (77.6, 0, 22.4).

[0026] The heat transfer composition described in the second aspect achieves low environmental impact and high safety. The CAP of this composition is at least greater than 95% of that of propane throughout the entire range, and further not less than 100% of that of propane, exhibiting cooling capacity comparable to or even superior to propane. Simultaneously, this composition surpasses propane in both heating and cooling COP, providing higher energy efficiency.

[0027] In the heat transfer composition described in the second aspect, the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is preferably 1 to 10:1, for example, 5:1. Within this preferred range, the composition exhibits the lowest GWP value when the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is 10:1. A mass ratio of 5:1 results in an azeotropic composition with a temperature glide close to 0. To ensure a balance between temperature glide and performance, a mass ratio of 1 to 10:1 for 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane provides optimal operating conditions. This characteristic ensures a temperature glide below 10 K during heat transfer, optimizing system stability and improving thermal efficiency. At the same time, maintain an acceptable coefficient of performance (COP) and cooling performance to ensure the safety, reliability and economy of the system.

[0028] Furthermore, the heat transfer composition described in the second aspect has a boiling point of less than -37°C, for example -45.9 to -37.9°C, which is close to that of propane, and its COP is greater than 90% of that of propane, further greater than 95% of that of propane, and even further not less than 100% of that of propane. Both its heating COP and cooling COP are greater than those of propane.

[0029] The heat transfer composition of this invention has x+y+z=100, where x can be selected from 23.6 to 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., and y can be selected from 1 to 55, for example 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, etc. Example: x The x is 78, 79, or 83, and the y is 2; or the x is 75, 76, or 80, and the y is 5; or the x is 71, 72, or 75, and the y is 10; or the x is 68 or 69, and the y is 15; or the x is 62 or 63, and the y is 20; or the x is 56, 57, or 68, and the y is 25; or the x is 51 or 52, and the y is 30; or the x is 45 or 46, and the y is 35; or the x is 40, and the y is 40; or the x is 35, and the y is 45.

[0030] Thirdly, the present invention provides a method for preparing the heat transfer composition described in the first or second aspect, comprising: mixing 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene and difluoromethane in a liquid phase to obtain the heat transfer composition.

[0031] Fourthly, the present invention provides a heat transfer composition comprising, by mass percentage, 80% to 99.9% (e.g., 82%, 84%, 85%, 86%, 88%, 89%, 90%, 92%, 94%, 96%, 97%, 98%, 99%, 99.5%, etc.) of the heat transfer composition described in the first or second aspect and 0.1% to 20% (e.g., 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 of C1-C4 fluorocarbons, C1-C4 hydrocarbons, trifluoroiodomethane, carbon dioxide, and dimethyl ether, excluding 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene, and difluoromethane; the heat transfer composition having a GWP of less than 150 and a flammability of less than A2L.

[0032] The heat transfer composition described in the fourth aspect preferably comprises one or more of 1,1,1,2-tetrafluoroethane, pentafluoroethane, 3,3,3-trifluoropropylene, trifluoroethylene, hexafluoropropylene, and trans-1,2-difluoroethylene.

[0033] The composition for heat transfer described in the fourth aspect, wherein the C1-C4 hydrocarbon is preferably selected from one or more of propane, propylene, and isobutane.

[0034] Furthermore, the composition described in the fourth aspect that can be used for heat transfer has a boiling point of less than -37°C, for example -45.9 to -37.9°C, which is close to that of propane, and a CAP greater than 90% of propane, further greater than 95% of propane, and even further not less than 100% of propane, with both heating COP and cooling COP greater than propane.

[0035] Fifthly, the present invention provides a method for preparing the heat transfer composition described in the fourth aspect, comprising: mixing 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene, difluoromethane and component M in a liquid phase to obtain the heat transfer composition.

[0036] In a sixth aspect, the present invention provides the application of the heat transfer composition described in the first or second aspect, or the heat transfer-compatible composition described in the fourth aspect, in a heat exchange device. The heat transfer composition or the heat transfer-compatible composition can circulate as a heat transfer fluid (refrigerant, heat transfer medium, etc.) in the heat exchange device. The heat transfer composition or the heat transfer-compatible composition can be used to replace other high-GWP conventional refrigerants such as propane, dichlorofluoromethane, R410A, or R404A, and is particularly suitable for applications requiring higher system safety levels while pursuing high energy efficiency and low carbon emissions. 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 refrigeration equipment heat exchange device, an industrial refrigeration heat exchange device, an automotive 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; automotive air conditioners, automotive heat pump systems (automotive thermal management systems); commercial freezers, cold chain logistics equipment, and other small and medium-sized closed systems, etc.

[0037] In the application process described in the sixth aspect, the heat transfer composition or the composition that can be used for heat transfer can be adapted to a variety of heat exchange devices, and can directly replace the heat transfer composition with propane without modifying or replacing the original heat exchange device, resulting in low application cost.

[0038] In a seventh aspect, the present invention provides a heat transfer method for transferring heat using the heat transfer composition described in the first or second aspect or the heat transfer composition described in the fourth aspect.

[0039] For specific application scenarios, further selection and optimization of technical solutions for the heat transfer methods described in the seventh aspect, please refer to the applications described in the sixth aspect.

[0040] The heat transfer composition of the present invention, and the composition that can be used for heat transfer, has the characteristics of low GWP, low flammability, high performance, etc. It is environmentally friendly and has good cooling (heating) effect. It is suitable for replacing propane and other materials in household and commercial refrigeration devices, and has good environmental compatibility, energy efficiency and system adaptability.

[0041] The heat transfer composition of the present invention uses a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane as the first component, trans-1,3,3,3-tetrafluoropropylene as the second component, and difluoromethane as the third component, wherein the total mass of the first component, the second component, and the third component is 100%.

[0042] Figure 1The three-phase diagram of the first, second, and third components of the heat transfer composition described in the first aspect in a ternary coordinate system shows the feasible component range within the closed region enclosed by curve segment AB, straight line segment BC, and straight line segment CA.

[0043] Figure 2 The diagram shows the first, second, and third components of the heat transfer composition according to the second aspect of the present invention in a ternary coordinate system. The closed region enclosed by the curve segment A'B', the straight line segment B'C, and the straight line segment CA' represents the feasible component range.

[0044] The heat transfer composition of the present invention, exemplarily, includes, but is not limited to, the coordinate (x,y,z) positions corresponding to its components, including but not limited to points (80,5,15), (75,10,15), (70,15,15), (65,20,15), (60,25,15), (75,5,20), (70,10,20), (65,15,20), (60,20,20), (55,25,20), and (50, Points (30,20), (45,35,20), (40,40,20), and (35,45,20) are used. Taking the coordinates (x,y,z) at point (60,25,15) as an example, it can be understood as follows: with the total mass of the first component, the second component, and the third component being 100%, 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%.

[0045] The ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane in the first component of the heat transfer composition of this invention can be flexibly adjusted according to system performance, safety, and environmental requirements, and its specific ratio range is relatively wide. Exemplarily, the mass ratio of 2,3,3,3-tetrafluoropropylene 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., and the specific ratio can be optimized according to factors such as the global warming potential, condensation pressure, combustion limit, and lubricant compatibility required by the target system.

[0046] To further improve the CAP and COP of the composition and enhance the heat exchange effect, this invention proposes a composition that can be used for heat transfer. Based on the heat transfer composition described in the first or second aspect, a component M is further introduced to adjust performance parameters such as system pressure, condensation temperature, flammability rating, or improve material compatibility.

[0047] The present invention does not have any special requirements for the preparation method of the heat transfer composition or the composition that can be used for heat transfer. For example, the heat transfer composition of the present invention can be obtained by mixing the first component, the second component, and the third component in the liquid phase; the composition that can be used for heat transfer of the present invention can be obtained by mixing the first component, the second component, the third component, and component M in the liquid phase.

[0048] Compared with the prior art, the beneficial effects of this invention are as follows:

[0049] The heat transfer compositions and applicable compositions of this invention exhibit significant environmental friendliness and system adaptability, and are particularly suitable for replacing the traditional highly flammable refrigerant propane. Compared to propane, the heat transfer compositions and applicable compositions of this invention possess similar latent heat of vaporization and operating pressure characteristics, allowing for direct replacement without significant modifications to the original system. Furthermore, the compositions have a global warming potential (GWP) of less than 150 and an ozone depletion potential (ODP) of 0, contributing to achieving greenhouse gas emission reduction targets. Regarding safety performance, this invention effectively reduces the maximum combustion rate and flame propagation speed of the composition by rationally adjusting the ratio of low-flammability hydrofluoroolefins and hydrofluoroalkanes, bringing the overall flammability of the heat transfer composition to below the A2L level, significantly superior to the A3 level propane, meeting the usage requirements of higher safety-level scenarios (such as household air conditioners, vehicle heat pump systems, and heat pump water heaters).

[0050] Furthermore, the heat transfer compositions of this invention, and compositions applicable to heat transfer, exhibit excellent thermodynamic properties. Compared to propane, they offer comparable volumetric cooling capacity (CAP) and superior coefficient of performance (COP), contributing to improved overall system efficiency and reduced operating energy consumption. Their components demonstrate good compatibility with common lubricants (such as polyester oil POE, polyether oil PAG, and polyethylene ether PVE) and system materials, providing a foundation for industrial-scale application. Attached Figure Description

[0051] Figure 1 The diagram shows the first, second, and third components of the heat transfer composition according to the first aspect of the present invention in a ternary coordinate system. The closed region enclosed by the curve segment AB, the straight line segment BC, and the straight line segment CA represents the feasible component range.

[0052] Figure 2 The diagram shows the first, second, and third components of the heat transfer composition according to the second aspect of the present invention in a ternary coordinate system. The closed region enclosed by the curve segment A'B', the straight line segment B'C, and the straight line segment CA' represents the feasible component range.

[0053] Figure 3 This is a temperature-pressure (TP) curve of the heat transfer composition of Example 2 with propane within the evaporation temperature range. Detailed Implementation

[0054] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0055] In this invention, the disclosure of numerical ranges includes all values ​​throughout the range and the disclosure of further subdivisions of the range, including endpoints, intermediate points, point values ​​given in the embodiments, and subranges arbitrarily composed of these points.

[0056] The term "line segment" refers to a finite portion (including the two endpoints) between two points on a straight line or curve. A line segment includes the two endpoints and the line connecting them. For example, coordinates (x, y, z) on line segment AB means that coordinates (x, y, z) lie at points A, B, or the line connecting them.

[0057] Example 1:

[0058] The heat transfer composition of this embodiment was obtained by mixing 75g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (62.5g of the 2,3,3,3-tetrafluoropropylene and 12.5g of the 1,1-difluoroethane composition), 5g of trans-1,3,3,3-tetrafluoropropylene and 20g of difluoromethane in the liquid phase.

[0059] Example 2:

[0060] The heat transfer composition of this embodiment was obtained by mixing 71g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (60.9g of the 2,3,3,3-tetrafluoropropylene and 10.1g of the 1,1-difluoroethane composition), 10g of trans-1,3,3,3-tetrafluoropropylene and 19g of difluoromethane in the liquid phase. Figure 3 The temperature-pressure (TP) curves of the heat transfer composition of this embodiment with propane are shown in the evaporation temperature range.

[0061] Example 3:

[0062] The heat transfer composition of this embodiment was obtained by mixing 69g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (41.4g of the 2,3,3,3-tetrafluoropropylene and 27.6g of the 1,1-difluoroethane composition), 15g of trans-1,3,3,3-tetrafluoropropylene and 16g of difluoromethane in the liquid phase.

[0063] Example 4:

[0064] The heat transfer composition of this embodiment was obtained by mixing 62g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (55.1g of the 2,3,3,3-tetrafluoropropylene and 6.9g of the 1,1-difluoroethane composition), 20g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0065] Example 5:

[0066] The heat transfer composition of this embodiment was obtained by mixing 56g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (49.8g of the 2,3,3,3-tetrafluoropropylene and 6.2g of the 1,1-difluoroethane composition), 25g of trans-1,3,3,3-tetrafluoropropylene and 19g of difluoromethane in the liquid phase.

[0067] Example 6:

[0068] The heat transfer composition of this embodiment was obtained by mixing 52g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (39.0g of the 2,3,3,3-tetrafluoropropylene and 13.0g of the 1,1-difluoroethane composition), 30g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0069] Example 7:

[0070] The heat transfer composition of this embodiment was obtained by mixing 45g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (40.5g of the 2,3,3,3-tetrafluoropropylene and 4.5g of the 1,1-difluoroethane composition), 35g of trans-1,3,3,3-tetrafluoropropylene and 20g of difluoromethane in the liquid phase.

[0071] Example 8:

[0072] The heat transfer composition of this embodiment was obtained by mixing 40g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (32.0g of the 2,3,3,3-tetrafluoropropylene and 8.0g of the 1,1-difluoroethane composition), 40g of trans-1,3,3,3-tetrafluoropropylene and 20g of difluoromethane in the liquid phase.

[0073] Example 9:

[0074] The heat transfer composition of this embodiment was obtained by mixing 35g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (29.2g of the 2,3,3,3-tetrafluoropropylene and 5.8g of the 1,1-difluoroethane composition), 45g of trans-1,3,3,3-tetrafluoropropylene and 20g of difluoromethane in the liquid phase.

[0075] Example 10:

[0076] The heat transfer composition of this embodiment was obtained by mixing 76g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (68.4g of the 2,3,3,3-tetrafluoropropylene and 7.6g of the 1,1-difluoroethane composition), 5g of trans-1,3,3,3-tetrafluoropropylene and 19g of difluoromethane in the liquid phase.

[0077] Example 11:

[0078] The heat transfer composition of this embodiment was obtained by mixing 72g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (60.0g of the 2,3,3,3-tetrafluoropropylene and 12.0g of the 1,1-difluoroethane composition), 10g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0079] Example 12:

[0080] The heat transfer composition of this embodiment was obtained by mixing 68g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (61.2g of the 2,3,3,3-tetrafluoropropylene and 6.8g of the 1,1-difluoroethane composition), 15g of trans-1,3,3,3-tetrafluoropropylene and 17g of difluoromethane in the liquid phase.

[0081] Example 13:

[0082] The heat transfer composition of this embodiment was obtained by mixing 62g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (49.6g of the 2,3,3,3-tetrafluoropropylene and 12.4g of the 1,1-difluoroethane composition), 20g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0083] Example 14:

[0084] The heat transfer composition of this embodiment was obtained by mixing 58g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (43.5g of the 2,3,3,3-tetrafluoropropylene and 14.5g of the 1,1-difluoroethane composition), 25g of trans-1,3,3,3-tetrafluoropropylene and 17g of difluoromethane in the liquid phase.

[0085] Example 15:

[0086] The heat transfer composition of this embodiment was obtained by mixing 52g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (44.6g of the 2,3,3,3-tetrafluoropropylene and 7.4g of the 1,1-difluoroethane composition), 30g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0087] Example 16:

[0088] The heat transfer composition of this embodiment was obtained by mixing 46g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (41.4g of the 2,3,3,3-tetrafluoropropylene and 4.6g of the 1,1-difluoroethane composition), 35g of trans-1,3,3,3-tetrafluoropropylene and 19g of difluoromethane in the liquid phase.

[0089] Example 17:

[0090] The heat transfer composition of this embodiment was obtained by mixing 80g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (70.0g of 2,3,3,3-tetrafluoropropylene and 10.0g of 1,1-difluoroethane), 5g of trans-1,3,3,3-tetrafluoropropylene and 15g of difluoromethane in the liquid phase.

[0091] Example 18:

[0092] The heat transfer composition of this embodiment was obtained by mixing 75g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (60.0g of the 2,3,3,3-tetrafluoropropylene and 15.0g of the 1,1-difluoroethane composition), 10g of trans-1,3,3,3-tetrafluoropropylene and 15g of difluoromethane in the liquid phase.

[0093] Example 19:

[0094] The heat transfer composition of this embodiment was obtained by mixing 78g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (66.9g of the 2,3,3,3-tetrafluoropropylene and 11.1g of the 1,1-difluoroethane composition), 2g of trans-1,3,3,3-tetrafluoropropylene and 20g of difluoromethane in the liquid phase.

[0095] Example 20:

[0096] The heat transfer composition of this embodiment was obtained by mixing 79g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (69.1g of 2,3,3,3-tetrafluoropropylene and 9.9g of 1,1-difluoroethane), 2g of trans-1,3,3,3-tetrafluoropropylene and 19g of difluoromethane in the liquid phase.

[0097] Example 21:

[0098] The heat transfer composition of this embodiment was obtained by mixing 83g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (45.3g of the 2,3,3,3-tetrafluoropropylene and 37.7g of the 1,1-difluoroethane composition), 2g of trans-1,3,3,3-tetrafluoropropylene and 15g of difluoromethane in the liquid phase.

[0099] Example 22:

[0100] The heat transfer composition of this embodiment was obtained by mixing 52g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (43.3g of the 2,3,3,3-tetrafluoropropylene and 8.7g of the 1,1-difluoroethane composition), 30g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0101] Example 23:

[0102] The heat transfer composition of this embodiment was obtained by mixing 63g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (53.3g of the 2,3,3,3-tetrafluoropropylene and 9.7g of the 1,1-difluoroethane composition), 20g of trans-1,3,3,3-tetrafluoropropylene and 17g of difluoromethane in the liquid phase.

[0103] Example 24:

[0104] The heat transfer composition of this embodiment was obtained by mixing 57g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (48.2g of the 2,3,3,3-tetrafluoropropylene and 8.8g of the 1,1-difluoroethane composition), 25g of trans-1,3,3,3-tetrafluoropropylene and 18g of difluoromethane in the liquid phase.

[0105] Example 25:

[0106] The heat transfer composition of this embodiment was obtained by mixing 51g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (43.2g of the 2,3,3,3-tetrafluoropropylene and 7.8g of the 1,1-difluoroethane composition), 30g of trans-1,3,3,3-tetrafluoropropylene and 19g of difluoromethane in the liquid phase.

[0107] Example 26:

[0108] The composition of 70g of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (62.2g of 2,3,3,3-tetrafluoropropylene and 7.8g of 1,1-difluoroethane), 15g of trans-1,3,3,3-tetrafluoropropylene, 15g of difluoromethane and 11g of trifluoroethylene were mixed in the liquid phase to obtain the composition that can be used for heat transfer in this embodiment.

[0109] Example 27:

[0110] The composition of 64g of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (56.9g of the 2,3,3,3-tetrafluoropropylene and 7.1g of the 1,1-difluoroethane composition), 16g of trans-1,3,3,3-tetrafluoropropylene, 20g of difluoromethane and 8g of trans-1,2-difluoroethylene were mixed in the liquid phase to obtain the composition that can be used for heat transfer in this embodiment.

[0111] Example 28:

[0112] The composition of 70g of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (52.5g of 2,3,3,3-tetrafluoropropylene and 17.5g of 1,1-difluoroethane), 13g of trans-1,3,3,3-tetrafluoropropylene, 17g of difluoromethane and 2g of carbon dioxide were mixed in the liquid phase to obtain the composition that can be used for heat transfer in this embodiment.

[0113] Example 29:

[0114] The composition of 62g of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (53.1g of 2,3,3,3-tetrafluoropropylene and 8.9g of 1,1-difluoroethane composition), 20g of trans-1,3,3,3-tetrafluoropropylene, 18g of difluoromethane and 15g of 3,3,3-trifluoropropylene were mixed in the liquid phase to obtain the composition that can be used for heat transfer in this embodiment.

[0115] Example 30:

[0116] The composition of 60g of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (45g of 2,3,3,3-tetrafluoropropylene and 15g of 1,1-difluoroethane), 25g of trans-1,3,3,3-tetrafluoropropylene, 15g of difluoromethane and 2g of 1,1,1,2-tetrafluoroethane were mixed in the liquid phase to obtain the composition that can be used for heat transfer in this embodiment.

[0117] Example 31:

[0118] The composition of 56g of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (42g of 2,3,3,3-tetrafluoropropylene and 14g of 1,1-difluoroethane composition), 25g of trans-1,3,3,3-tetrafluoropropylene, 19g of difluoromethane and 3g of isobutane were mixed in the liquid phase to obtain the composition that can be used for heat transfer in this embodiment.

[0119] Comparative Example 1:

[0120] The heat transfer fluid is propane.

[0121] Comparative Example 2:

[0122] The heat transfer composition of this comparative example was obtained by mixing 32g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (16.0g of the 2,3,3,3-tetrafluoropropylene and 16.0g of the 1,1-difluoroethane composition), 34g of trans-1,3,3,3-tetrafluoropropylene and 34g of difluoromethane in the liquid phase.

[0123] Comparative Example 3:

[0124] The heat transfer composition of this comparative example was obtained by mixing 30g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (20.0g of the 2,3,3,3-tetrafluoropropylene and 10.0g of the 1,1-difluoroethane composition), 63g of trans-1,3,3,3-tetrafluoropropylene and 7g of difluoromethane in the liquid phase.

[0125] Comparative Example 4:

[0126] The heat transfer composition of this comparative example was obtained by mixing 50g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (43.8g of the 2,3,3,3-tetrafluoropropylene and 6.2g of the 1,1-difluoroethane composition), 40g of trans-1,3,3,3-tetrafluoropropylene and 10g of difluoromethane in the liquid phase.

[0127] Comparative Example 5:

[0128] The heat transfer composition of this comparative example was obtained by mixing 53g of a composition of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane (17.7g of the 2,3,3,3-tetrafluoropropylene and 35.3g of the 1,1-difluoroethane composition), 27g of trans-1,3,3,3-tetrafluoropropylene and 20g of difluoromethane in the liquid phase.

[0129] Performance testing:

[0130] The boiling point, relative volumetric cooling capacity (CAP), and relative coefficient of performance (COP) of the compositions in each example or comparative example were obtained by theoretical calculation using the Refprop 10.0 database of fluid thermodynamics and transport properties from the National Institute of Standards and Technology (NIST).

[0131] CAP: The product of the latent heat of the heat transfer composition and the vapor density under refrigeration and heating cycle conditions.

[0132] COP: The ratio of the cooling capacity (or heating capacity) of the heat transfer composition to the power consumption of the compressor under the following refrigeration (or heating) cycle conditions: evaporation temperature 5°C, condensation temperature 45°C, superheating temperature 10 K, subcooling temperature 5 K, and compressor efficiency 70%.

[0133] Relative CAP, relative COP: The ratio of the CAP and COP values ​​of the composition to the CAP and COP values ​​of propane.

[0134] The GWP values ​​of the compositions in each example or comparative example were calculated as a weighted average of the GWP values ​​of the components of the composition by mass fraction. The GWP values ​​of each component were taken from the Fourth Report of the Intergovernmental Panel on Climate Change (IPCC).

[0135] The flammability of the compositions in each example or comparative example was evaluated by determining their lower flammability limit and flammability rate under standard conditions. The tests were conducted according to GB / T 7778 standard "Refrigerant Numbering Method and Safety Classification". The safety classification results of the compositions in each example and comparative example are listed in Table 1.

[0136] The calculated average boiling point, relative CAP, relative COP, and GWP values ​​of the compositions in each embodiment and comparative example are shown in Table 1.

[0137] Table 1

[0138]

[0139] As shown in Table 1, the compositions of the various embodiments of the present invention have a similar boiling point (-45.9~-37.9℃), lower flammability (below A2L), similar CAP, and higher COP compared to propane, and a GWP value below 150. Furthermore, the comparative examples and comparative cases show that the heat transfer compositions of the present invention, and the compositions that can be used for heat transfer, can achieve a higher COP than propane while maintaining a similar boiling point, a GWP below 150, and a safety level of A2L, thus achieving an environmentally friendly alternative to propane. However, when the heat transfer composition is not the formulation required by the present invention, as shown in Comparative Examples 2-4, it is impossible to simultaneously achieve a higher COP than propane, a GWP below 150, and a boiling point similar to propane. And when the mass ratio of the first component 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane exceeds the range defined by the present invention, as shown in Comparative Example 5, although the refrigeration efficiency COP is higher than propane and the GWP is below 150, the safety level is A2.

[0140] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0141] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0142] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A heat transfer composition, characterized in that, The heat transfer composition is composed of 2,3,3,3-tetrafluoropropylene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropylene, and difluoromethane, wherein the mass ratio of 2,3,3,3-tetrafluoropropylene to 1,1-difluoroethane is 1~10:

1. The composition satisfies the following conditions: the GWP of the heat transfer composition is less than 150 and the flammability is below A2L; the heating COP and cooling COP of the heat transfer composition are both greater than those of propane, the boiling point is -45.9~-37.9℃, and the CAP is greater than 90% of that of propane. In the heat transfer composition, the sum of the masses of 2,3,3,3-tetrafluoropropylene and 1,1-difluoroethane accounts for x%, the mass of trans-1,3,3,3-tetrafluoropropylene accounts for y%, the mass of difluoromethane accounts for z%, and 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 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 at point A accounts for 23.6%, and the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point B accounts for 90.0%. The coordinates of the point on 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, In the ternary phase diagram, the coordinates (x, y, z) are located inside or on the boundary of the closed region enclosed by curve segment A'B', line segment B'C, and line segment CA'. In the ternary phase diagram, the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point A' accounts for 38.7%, and the sum of the masses of 2,3,3,3-tetrafluoropropene and 1,1-difluoroethane at point B' accounts for 85.8%. The coordinates of the point 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 2, characterized in that, The CAP of the heat transfer composition is greater than 95% of that of propane.

4. The method for preparing the heat transfer composition according to any one of claims 1 to 3, 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 the liquid phase.

5. A composition that can be used for heat transfer, characterized in that, The composition comprises, by mass percentage, 80% to 99.9% of the heat transfer composition according to any one of claims 1 to 3 and 0.1% to 20% of component M, wherein component M is selected from one or more of C1 to C4 fluorocarbons, C1 to C4 hydrocarbons, trifluoroiodomethane, carbon dioxide, and dimethyl ether, excluding 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, trans-1,3,3,3-tetrafluoropropene and difluoromethane; the composition for heat transfer has a GWP of less than 150 and a flammability of less than A2L; the composition for heat transfer has a heating COP and a cooling COP greater than propane, a boiling point of -45.9 to -37.9°C, and a CAP greater than 90% of propane.

6. The composition for heat transfer according to claim 5, characterized in that, The C1-C4 fluorocarbons are selected from one or more of 1,1,1,2-tetrafluoroethane, pentafluoroethane, 3,3,3-trifluoropropylene, trifluoroethylene, hexafluoropropylene, and trans-1,2-difluoroethylene.

7. The composition for heat transfer according to claim 5, characterized in that, The C1-C4 hydrocarbons are selected from one or more of propane, propylene, and isobutane.

8. A method for preparing a heat transfer composition according to any one of claims 5 to 7, 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 the liquid phase to obtain the composition that can be used for heat transfer.

9. The use of the heat transfer composition according to any one of claims 1 to 3 or the composition for heat transfer according to any one of claims 5 to 7 in a heat exchange device.

10. The application according to claim 9, characterized in that, The heat transfer composition or the composition that can be used for heat transfer circulates as a heat transfer fluid in the heat exchange device.

11. The application according to claim 9 or 10, characterized in that, The heat transfer composition or the composition that can be used for heat transfer is used to replace propane.

12. The application according to claim 9, characterized in that, The heat exchange device can be a household heat exchange device, a commercial heat exchange device, a heat pump system heat exchange device, a refrigeration equipment heat exchange device, an industrial refrigeration heat exchange device, an automotive heat exchange device, a data center heat exchange device, or a mobile refrigeration equipment heat exchange device.

13. A heat transfer method, characterized in that, Heat transfer is performed using the heat transfer composition according to any one of claims 1 to 3 or the heat transfer composition according to any one of claims 5 to 7.

Images