Composite refrigerants, their preparation methods and applications, and refrigeration devices containing composite refrigerants.

Abstract

This invention relates to a composite refrigerant comprising a first component and a second component. The first component is N,N,1,1-tetrafluoromethylamine, and the second component is difluoromethane, or a mixture of difluoromethane and 2,3,3,3-tetrafluoropropylene. The composite refrigerant provided by this invention selects specific components for combination, resulting in a GWP < 150, a temperature glide of less than 5°C, and a bubble point temperature below -30°C at atmospheric pressure. It also possesses significant environmental advantages and excellent refrigeration and heating performance. This invention further relates to a method for preparing and applying the aforementioned composite refrigerant, as well as a refrigeration device comprising the aforementioned composite refrigerant.

Description

Technical Field

[0001] This invention relates to the field of refrigeration technology, and in particular to a composite refrigerant, its preparation method and application, and a refrigeration device containing the composite refrigerant. Background Technology

[0002] To meet the requirements of environmental protection, safety, and efficiency, refrigerants are constantly being developed. From a molecular composition perspective, first-generation refrigerants are mainly readily available natural working fluids, such as CO2 and NH3. These have relatively low cooling or heating efficiency or poor safety. Second-generation refrigerants are mainly chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) composed of C, H, F, and Cl atoms, such as R12 (difluorodichloromethane) and R22 (difluorochloromethane). However, the presence of Cl atoms depletes the ozone layer and is environmentally unfriendly. Third-generation refrigerants are mainly hydrofluorocarbons (HFCs) composed of C, H, and F atoms, such as tetrafluoroethane (R134a) and difluoromethane (R32). However, the presence of F atoms results in a high global warming potential (GWP), which exacerbates global warming. Fourth-generation refrigerants are mainly hydrofluoroolefins (HFOs) and mixtures thereof composed of C=C, H, and F atoms, such as 2,3,3,3-tetrafluoropropylene (R1234yf) and R454B (a mixture of R32 and R1234yf). Although they reduce GWP, HFOs are unstable and have poor performance. Furthermore, while R454C has a GWP of 146, its temperature glide is large, resulting in poor performance.

[0003] N,N,1,1-tetrafluoromethylamine (CHF2NF2), composed of C, H, F, and N atoms, has a low volumetric refrigeration capacity as a refrigerant. R32 is a commonly used refrigerant in household applications, but its high GWP (Gross Potential) fails to meet the requirement of next-generation refrigerants (GWP < 150). R1234yf is a fourth-generation refrigerant, currently used in automotive air conditioning, but its heating performance is poor.

[0004] For the reasons mentioned above, there is an urgent need for an environmentally friendly refrigerant with a GWP of less than 150 and good cooling and low-temperature heating performance. Summary of the Invention

[0005] To address the problems in the prior art, one objective of this invention is to provide a composite refrigerant. This composite refrigerant can balance environmental friendliness and performance indicators, while possessing the advantages of being environmentally friendly, having high-efficiency cooling, and providing low-temperature heating performance.

[0006] The second objective of this invention is to provide a method for preparing the above-mentioned composite refrigerant, which has simple synthesis steps and good repeatability.

[0007] The third objective of this invention is to provide an application of the above-mentioned composite refrigerant or the composite refrigerant prepared by the above-mentioned preparation method.

[0008] The fourth objective of this invention is to provide a refrigeration device that uses the above-mentioned composite refrigerant or the composite refrigerant prepared by the above-mentioned method as the heat transfer fluid.

[0009] For composite refrigerants, the key to finding new refrigerants lies in how to select different components and weigh the characteristics of each component to obtain a refrigerant composition with balanced physical properties, environmental friendliness, excellent and stable refrigeration performance, and excellent and stable low-temperature heating performance. Based on extensive basic research, this invention selects specific components and proposes the following composite refrigerant with low GWP, high refrigeration performance, and high and low temperature heating performance.

[0010] Therefore, in a first aspect, the present invention provides a composite refrigerant comprising a first component and a second component, wherein the first component is N,N,1,1-tetrafluoromethylamine, and the second component is difluoromethane (R32), or difluoromethane and 2,3,3,3-tetrafluoropropylene (R1234yf); by weight percentage, the content of the first component is 60%-99%, the content of difluoromethane in the second component is 1%-20%, and the content of 2,3,3,3-tetrafluoropropylene in the second component is 0-20%.

[0011] Specifically, the composite refrigerant provided by this invention selects specific components for combination. The composite refrigerant has a low GWP, a temperature glide of less than 5°C, and a normal pressure bubble point temperature of less than -30°C. At the same time, it has obvious environmental advantages and excellent cooling and heating performance.

[0012] In some preferred embodiments of the present invention, the content of the first component by weight percentage may be 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98% or 99%.

[0013] In some preferred embodiments of the present invention, the content of difluoromethane may be 1%, 3%, 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19% or 20% by weight percentage.

[0014] In some preferred embodiments of the present invention, the content of 2,3,3,3-tetrafluoropropylene may be 0, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20% by weight percentage.

[0015] In some preferred embodiments of the present invention, the content of the first component is 60%-99% by weight, the content of difluoromethane in the second component is 1%-19%, and the content of 2,3,3,3-tetrafluoropropylene in the second component is 0-20%, preferably 5%-20%.

[0016] Specifically, the composite refrigerant provided by this invention selects specific components for combination. The composite refrigerant has a GWP < 150, a temperature glide of less than 5°C, and a normal pressure bubble point temperature of less than -30°C. It also has significant environmental advantages and excellent cooling and heating performance.

[0017] In some preferred embodiments of the present invention, the composite refrigerant comprises 80-99% N,N,1,1-tetrafluoromethylamine and 1-20% difluoromethane by weight percentage. Controlling the proportions of the components within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition has a lower glide temperature, avoiding the adverse effects of glide temperature.

[0018] In some preferred embodiments of the present invention, the composite refrigerant comprises 81%-99% N,N,1,1-tetrafluoromethylamine and 1%-19% difluoromethane by weight percentage. Controlling the proportions of the components within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition has a lower glide temperature, avoiding the adverse effects of glide temperature.

[0019] In some preferred embodiments of the present invention, the composite refrigerant comprises 81%-90% N,N,1,1-tetrafluoromethylamine and 10%-19% difluoromethane by weight percentage. Controlling the proportions of the components within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition has a lower glide temperature, avoiding the adverse effects of glide temperature.

[0020] In some preferred embodiments of the present invention, the composite refrigerant comprises, by weight percentage, 60%-90% N,N,1,1-tetrafluoromethylamine, 5%-20% difluoromethane, and 5%-20% 2,3,3,3-tetrafluoropropylene. Controlling the proportions of each component within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition exhibits a lower glide temperature, avoiding the adverse effects of glide temperature.

[0021] In some preferred embodiments of the present invention, the composite refrigerant comprises, by weight percentage, 60%-80% N,N,1,1-tetrafluoromethylamine, 10%-20% difluoromethane, and 10%-20% 2,3,3,3-tetrafluoropropylene. Controlling the proportions of each component within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition exhibits a lower glide temperature, avoiding the adverse effects of glide temperature.

[0022] In some preferred embodiments of the present invention, the composite refrigerant comprises, by weight percentage, 65%-80% N,N,1,1-tetrafluoromethylamine, 10%-20% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene. Controlling the proportions of each component within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition exhibits a lower glide temperature, avoiding the adverse effects of glide temperature.

[0023] In some preferred embodiments of the present invention, the composite refrigerant comprises, by weight percentage, 70%-80% N,N,1,1-tetrafluoromethylamine, 10%-15% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene. Controlling the proportions of each component within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition exhibits a lower glide temperature, avoiding the adverse effects of glide temperature.

[0024] In some preferred embodiments of the present invention, the composite refrigerant comprises, by weight percentage, 70%-75% N,N,1,1-tetrafluoromethylamine, 10%-15% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene. Controlling the proportions of each component within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition exhibits a lower glide temperature, avoiding the adverse effects of glide temperature.

[0025] In some preferred embodiments of the present invention, the composite refrigerant comprises, by weight percentage, 75%-80% N,N,1,1-tetrafluoromethylamine, 10%-15% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene. Controlling the proportions of each component within the above range enables the refrigerant composition to have a lower GWP and better cooling and low-temperature heating performance. Simultaneously, the refrigerant composition exhibits a lower glide temperature, avoiding the adverse effects of glide temperature.

[0026] In some preferred embodiments of the present invention, the GWP of the composite refrigerant is <150. A GWP <150 in the composite refrigerant results in a low global warming potential (GWP), thus avoiding exacerbating global warming.

[0027] In some preferred embodiments of the present invention, the composite refrigerant has a GWP of 20 < GWP < 150. A GWP < 150 in the composite refrigerant results in a low Global Warming Potential (GWP), thus avoiding exacerbating global warming.

[0028] In some preferred embodiments of the present invention, the GWP of the composite refrigerant is <120.

[0029] In some preferred embodiments of the present invention, the composite refrigerant has a concentration of 25 < GWP < 120.

[0030] In some preferred embodiments of the present invention, the atmospheric pressure bubble point temperature of the composite refrigerant is below -30°C. The composite refrigerant, with an atmospheric pressure bubble point temperature below -30°C, possesses excellent cooling and heating performance.

[0031] In some preferred embodiments of the present invention, the atmospheric pressure bubble point temperature of the composite refrigerant is lower than or equal to -35°C.

[0032] In some preferred embodiments of the present invention, the temperature glide of the composite refrigerant is less than 5°C. This temperature glide of less than 5°C avoids the adverse effects of temperature glide.

[0033] In some preferred embodiments of the present invention, the temperature glide of the composite refrigerant is less than or equal to 4°C.

[0034] Therefore, in a second aspect, the present invention provides a method for preparing the above-mentioned composite refrigerant, comprising the following steps: mixing the components of the composite refrigerant uniformly in a liquid phase to obtain the composite refrigerant.

[0035] In some preferred embodiments of the present invention, the conditions for uniform mixing include: a temperature of 20 to 40°C, preferably room temperature (25°C).

[0036] Therefore, in a third aspect, the present invention provides the application of the above-described composite refrigerant or the composite refrigerant prepared by the above-described preparation method in the preparation of a refrigeration device.

[0037] In some preferred embodiments of the present invention, the refrigeration device is an air conditioner or a refrigerator.

[0038] Therefore, in a fourth aspect, the present invention provides a refrigeration device comprising the above-described composite refrigerant or the composite refrigerant prepared by the above-described preparation method as a heat transfer fluid.

[0039] In some preferred embodiments of the present invention, the refrigeration device is an air conditioner or a refrigerator.

[0040] The present invention has the following beneficial effects:

[0041] The composite refrigerant provided by this invention has a relatively simple composition, with a GWP < 150, a temperature glide of less than 5°C, and a normal pressure bubble point temperature below -30°C. It also has significant environmental advantages and excellent cooling and heating performance. Detailed Implementation

[0042] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0043] As described in the background section, existing refrigerants suffer from problems such as excessively high GWP and insufficient low-temperature heating performance. To address this issue, the present invention provides a composite refrigerant comprising a first component and a second component. The first component is N,N,1,1-tetrafluoromethylamine, and the second component is difluoromethane (R32), or difluoromethane and 2,3,3,3-tetrafluoropropylene (R1234yf). By weight percentage, the content of the first component is 60%-99%, the content of difluoromethane in the second component is 1%-20%, and the content of 2,3,3,3-tetrafluoropropylene in the second component is 0-20%.

[0044] The composite refrigerant provided by this invention selects specific components for combination. The composite refrigerant has a low GWP, a temperature glide of less than 5°C, and a normal pressure bubble point temperature of less than -30°C. At the same time, it has obvious environmental advantages and excellent cooling and heating performance.

[0045] In some preferred embodiments of the present invention, the content of the first component is 60%-99% by weight, the content of difluoromethane in the second component is 1%-19%, and the content of 2,3,3,3-tetrafluoropropylene in the second component is 0-20%, preferably 5%-20%.

[0046] The composite refrigerant provided by this invention selects specific components for combination. The composite refrigerant has a GWP < 150, a temperature glide of less than 5°C, and a normal pressure bubble point temperature of less than -30°C. It also has significant environmental advantages and excellent cooling and heating performance.

[0047] In the composite refrigerant provided by this invention, N,N,1,1-tetrafluoromethylamine alone has the problem of low volumetric refrigeration capacity.

[0048] In the composite refrigerant provided by this invention, difluoromethane alone, as a refrigerant, has a GWP that is too high to meet the requirement of GWP<150 for the next generation of refrigerants.

[0049] In the composite refrigerant provided by this invention, 2,3,3,3-tetrafluoropropylene alone has poor heating performance as a refrigerant.

[0050] In order to further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises 80%-99% N,N,1,1-tetrafluoromethylamine and 1%-20% R32 by weight percentage.

[0051] In order to further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises 81%-99% N,N,1,1-tetrafluoromethylamine and 1%-19% difluoromethane by weight percentage.

[0052] In order to further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises 81%-90% N,N,1,1-tetrafluoromethylamine and 10%-19% difluoromethane by weight percentage.

[0053] To further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises, by weight percentage, 60%-90% N,N,1,1-tetrafluoromethylamine, 5%-20% difluoromethane, and 5%-20% 2,3,3,3-tetrafluoropropylene.

[0054] To further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises, by weight percentage, 60%-80% N,N,1,1-tetrafluoromethylamine, 10%-20% difluoromethane, and 10%-20% 2,3,3,3-tetrafluoropropylene.

[0055] To further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises, by weight percentage, 65%-80% N,N,1,1-tetrafluoromethylamine, 10%-20% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene.

[0056] To further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises, by weight percentage, 70%-80% N,N,1,1-tetrafluoromethylamine, 10%-15% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene.

[0057] To further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises, by weight percentage, 70%-75% N,N,1,1-tetrafluoromethylamine, 10%-15% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene.

[0058] To further balance the refrigerant properties of each component, thereby further reducing the GWP of the refrigerant composition and improving its low-temperature heating performance, in a preferred embodiment, the composite refrigerant comprises, by weight percentage, 75%-80% N,N,1,1-tetrafluoromethylamine, 10%-15% difluoromethane, and 10%-15% 2,3,3,3-tetrafluoropropylene.

[0059] In a preferred embodiment, the GWP of the composite refrigerant is <150. A GWP <150 results in a low global warming potential (GWP), thus avoiding exacerbating global warming.

[0060] In some preferred embodiments of the present invention, the composite refrigerant has a GWP of 20 < GWP < 150. A GWP < 150 in the composite refrigerant results in a low Global Warming Potential (GWP), thus avoiding exacerbating global warming.

[0061] In a preferred embodiment, the GWP of the composite refrigerant is <120.

[0062] In some preferred embodiments of the present invention, the composite refrigerant has a concentration of 25 < GWP < 120.

[0063] In a preferred embodiment, the composite refrigerant has a normal pressure bubble point temperature below -30°C. The composite refrigerant, with a normal pressure bubble point temperature below -30°C, possesses excellent cooling and heating performance.

[0064] In a preferred embodiment, the atmospheric pressure bubble point temperature of the composite refrigerant is less than or equal to -35°C.

[0065] In a preferred embodiment, the temperature glide of the composite refrigerant is less than 5°C. This temperature glide of less than 5°C avoids the adverse effects of temperature glide.

[0066] In a preferred embodiment, the temperature glide of the composite refrigerant is less than or equal to 4°C.

[0067] According to another aspect of the present invention, a method for preparing the above-mentioned composite refrigerant is also provided, comprising the following steps: mixing the components of the refrigerant composition uniformly in a liquid phase state to obtain the refrigerant composition.

[0068] In a preferred embodiment, the conditions for uniform mixing in the above preparation method include a temperature of 20–40°C.

[0069] In a preferred embodiment, the conditions for uniform mixing in the above preparation method include: room temperature (25°C).

[0070] According to another aspect of the present invention, the application of the above-described composite refrigerant or the composite refrigerant prepared by the above-described preparation method in the preparation of a refrigeration device is also provided.

[0071] In a preferred embodiment, the refrigeration device described above is an air conditioner or a refrigerator.

[0072] According to another aspect of the present invention, a refrigeration device is also provided, wherein the composite refrigerant described above or the composite refrigerant prepared by the above preparation method is used as the heat transfer fluid.

[0073] In a preferred embodiment, the refrigeration device is an air conditioner or a refrigerator.

[0074] This invention does not have special requirements for the structure or materials of the refrigeration device, and any known conventional structure and materials in the field can be used.

[0075] The raw materials and their basic parameters used in the following embodiments and comparative examples are shown in Table 1.

[0076] Table 1

[0077]

[0078] Several specific examples are given below, where the proportions of the components are all by mass percentage, and the sum of the mass percentages of all components in each refrigerant composition is 100%.

[0079] Example 1

[0080] N,N,1,1-tetrafluoromethylamine and R32 were physically mixed in the liquid phase at room temperature at a weight percentage of 0.81:0.19 to form a composite refrigerant.

[0081] Example 2

[0082] N,N,1,1-tetrafluoromethylamine and R32 were physically mixed in the liquid phase at room temperature at a weight percentage of 0.90:0.10 to form a composite refrigerant.

[0083] Example 3

[0084] N,N,1,1-tetrafluoromethylamine and R32 were physically mixed in the liquid phase at room temperature at a weight percentage of 0.99:0.01 to form a composite refrigerant.

[0085] Example 4

[0086] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.60:0.20:0.20 to form a composite refrigerant.

[0087] Example 5

[0088] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.65:0.20:0.15 to form a composite refrigerant.

[0089] Example 6

[0090] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.70:0.15:0.15 to form a composite refrigerant.

[0091] Example 7

[0092] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.75:0.15:0.10 to form a composite refrigerant.

[0093] Example 8

[0094] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.80:0.10:0.10 to form a composite refrigerant.

[0095] Example 9

[0096] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage ratio of 0.85:0.05:0.10 to form a composite refrigerant.

[0097] Example 10

[0098] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.90:0.05:0.05 to form a composite refrigerant.

[0099] Comparative Example 1

[0100] Propane (R290) is used as the refrigerant.

[0101] Comparative Example 2

[0102] R1234yf refrigerant was used as the refrigerant.

[0103] Comparative Example 3

[0104] R32 refrigerant is used as the refrigerant.

[0105] Comparative Example 4

[0106] R454C refrigerant is used as the refrigerant. R454C refrigerant is a mixture of R32 and R1234yf physically mixed in the liquid phase at room temperature, with a mass ratio of 21.5:78.5.

[0107] Comparative Example 5

[0108] R454B refrigerant is used as the refrigerant. R454B refrigerant is a mixture of R32 and R1234yf physically mixed in the liquid phase at room temperature, with a mass ratio of 68.9:31.1.

[0109] Comparative Example 6

[0110] CHF2NF2 refrigerant was used as the refrigerant.

[0111] Comparative Example 7

[0112] N,N,1,1-tetrafluoromethylamine and R32 were physically mixed at room temperature in the liquid phase at a weight percentage of 0.75:0.25 to form a composite refrigerant.

[0113] Comparative Example 8

[0114] The three components N,N,1,1-tetrafluoromethylamine, R32 and R1234yf were physically mixed in the liquid phase at room temperature in a weight percentage of 0.50:0.25:0.25 to form a composite refrigerant.

[0115] Comparative Example 9

[0116] The two components, R32 and R1234yf, were physically mixed at room temperature in the liquid phase at a weight percentage of 0.60:0.40 to form a composite refrigerant.

[0117] Comparative Example 10

[0118] N,N,1,1-tetrafluoromethylamine and R1234yf were physically mixed in the liquid phase at room temperature at a weight percentage of 0.90:0.10 to form a composite refrigerant.

[0119] Comparative Example 11

[0120] N,N,1,1-tetrafluoromethylamine and R1234yf were physically mixed at room temperature in the liquid phase at a weight percentage of 0.80:0.20 to form a composite refrigerant.

[0121] Example 11

[0122] Performance characterization:

[0123] The basic and refrigeration properties of the refrigerants prepared in the above embodiments and comparative examples were characterized. The refrigeration properties were obtained under the following refrigeration conditions: evaporator evaporation temperature of 10°C, condenser condensation temperature of 40°C, gas phase at evaporator outlet in a superheated state with a superheat of 5°C, liquid phase at condenser outlet in a subcooled state with a subcooling of 5°C, and compressor adiabatic efficiency of 0.75.

[0124] The theoretical calculations were performed using the cycle performance parameters of the refrigerants in the refrigeration system in the above examples and comparative examples. Among them, GWP (calculated by linear summation of mass percentages), relative volumetric cooling / heating capacity Qv (ratio of volumetric cooling / heating capacity to R290), relative coefficient of performance COP (ratio of coefficient of performance to R290), atmospheric boiling point (bubble point temperature), and temperature glide were calculated. The results are shown in Table 3.

[0125] Table 2

[0126]

[0127] Table 3

[0128]

[0129] In Table 3, the glide temperature is the difference between the dew point temperature and the bubble point temperature at 1 standard atmosphere.

[0130] As shown in Table 3, the GWP of the composite refrigerants in Examples 1-10 is less than 150, which is environmentally friendly. Conversely, the GWP of Comparative Example 3 (using R32 alone as the refrigerant, without the first component, N,N,1,1-tetrafluoromethylamine) and Comparative Example 5 (R454B, using a mixture of R32 and R1234yf as the composite refrigerant, without the first component, N,N,1,1-tetrafluoromethylamine) is greater than 150. This excessively high GWP fails to meet the requirement of GWP < 150 for next-generation refrigerants. The relative Qv of the composite refrigerants in Examples 1-10 is greater than that of Comparative Example 1 (using R290 alone as the refrigerant, without...). Comparative Examples 1-10 (containing both the first and second components), Comparative Example 2 (using R1234yf alone as the refrigerant, without the first component N,N,1,1-tetrafluoromethylamine and the second component R32), Comparative Example 4 (R454C, using a mixture of R32 and R1234yf as the composite refrigerant, without the first component N,N,1,1-tetrafluoromethylamine), and Comparative Example 6 (using CHF2NF2 alone as the refrigerant, containing only the first component and not the second component) demonstrate that the composite refrigerants of Examples 1-10 possess significant environmental advantages and excellent cooling and heating performance compared to the refrigerants of the comparative examples.

[0131] In Comparative Example 7, the amount of difluoromethane in the second component of the composite refrigerant is higher than 20%, which is excessive. In Comparative Example 8, the amount of the first component is less than 60%, which is insufficient, exceeding the specific proportion range of each component in the composite refrigerant provided by this invention. As shown in Table 3, comparing Comparative Example 7 with Example 1 and Comparative Example 8 with Example 4, it can be seen that each component needs to be within this proportion range for the composite refrigerant to meet the requirement of GWP < 150; otherwise, an excessively high GWP will not meet the requirement of GWP < 150 for the next generation of refrigerants.

[0132] As can be seen from the comparison of Comparative Examples 9-11 in Table 3 (Comparative Example 9 does not contain the first component, and Comparative Examples 10 and 11 do not contain difluoromethane in the second component) with Examples 4, 10 and 8 respectively, the composite refrigerant provided by the present invention, which is composed of N,N,1,1-tetrafluoromethylamine and difluoromethane, or composed of N,N,1,1-tetrafluoromethylamine, difluoromethane and 2,3,3,3-tetrafluoropropylene, is superior to the combination of N,N,1,1-tetrafluoromethylamine and 2,3,3,3-tetrafluoropropylene and the combination of difluoromethane and 2,3,3,3-tetrafluoropropylene.

[0133] As shown in Table 3, the composite refrigerant provided by this invention has better overall performance than R290 and can be used to replace R290.

[0134] As shown in Table 3, the GWP of the composite refrigerants provided by the present invention is less than 150, and the environmental performance is excellent. The relative volumetric cooling capacity of all refrigerant formulations is greater than 1.18, and the highest is 33% higher than that of Comparative Example 1 (R290). The relative performance coefficients are all greater than 0.9, the atmospheric pressure bubble point temperature is lower than -30℃, and the temperature glide is less than 5℃.

[0135] The above description of the embodiments is provided to enable those skilled in the art to understand and apply the present invention. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A composite refrigerant, characterized in that, It comprises a first component and a second component, wherein the first component is N,N,1,1-tetrafluoromethylamine, and the second component is difluoromethane, or difluoromethane and 2,3,3,3-tetrafluoropropylene; by weight percentage, the content of the first component is 60%-99%, the content of difluoromethane in the second component is 1%-20%, the content of 2,3,3,3-tetrafluoropropylene in the second component is 0-20%, and the sum of the weight percentages of the first component and the second component is 100%.

2. The composite refrigerant according to claim 1, characterized in that, The first component has a content of 60%-99% by weight, the second component has a content of 1%-19% of difluoromethane, and the second component has a content of 0-20% of 2,3,3,3-tetrafluoropropylene.

3. The composite refrigerant according to claim 2, characterized in that, The content of 2,3,3,3-tetrafluoropropylene in the second component is 5-20%.

4. The composite refrigerant according to claim 1, characterized in that, By weight percentage, the composite refrigerant comprises 80-99% N,N,1,1-tetrafluoromethylamine and 1-20% difluoromethane; or, The composite refrigerant comprises, by weight percentage, 60%-90% N,N,1,1-tetrafluoromethylamine, 5%-20% difluoromethane, and 5%-20% 2,3,3,3-tetrafluoropropylene.

5. The composite refrigerant according to claim 4, characterized in that, The composite refrigerant comprises 81-99% N,N,1,1-tetrafluoromethylamine and 1-19% difluoromethane; or, The composite refrigerant comprises 60%-80% N,N,1,1-tetrafluoromethylamine, 10%-20% difluoromethane, and 10%-20% 2,3,3,3-tetrafluoropropylene.

6. The composite refrigerant according to claim 5, characterized in that, The composite refrigerant comprises 81-90% N,N,1,1-tetrafluoromethylamine and 10-19% difluoromethane.

7. The composite refrigerant according to any one of claims 1-3, characterized in that, The composite refrigerant has a GWP < 150; and / or a bubble point temperature below -30°C at atmospheric pressure; and / or a temperature glide of less than 5°C.

8. The composite refrigerant according to claim 7, characterized in that, The composite refrigerant has a GWP < 120; and / or a bubble point temperature at atmospheric pressure less than or equal to -35°C; and / or a temperature glide less than or equal to 4°C.

9. A method for preparing a composite refrigerant according to any one of claims 1 to 8, characterized in that, The process includes the following steps: mixing the components of the composite refrigerant uniformly in the liquid phase to obtain the composite refrigerant.

10. The preparation method according to claim 9, characterized in that, The conditions for uniform mixing include a temperature of 20–40°C.

11. The application of a composite refrigerant according to any one of claims 1-8 or a composite refrigerant prepared by the preparation method according to claim 9 or 10 in the preparation of a refrigeration device.

12. The application according to claim 11, characterized in that, The refrigeration device is an air conditioner or a refrigerator.

13. A refrigeration device, characterized in that, The composite refrigerant described in any one of claims 1-8 or the composite refrigerant prepared by the preparation method described in claim 9 or 10 is a heat transfer fluid.

14. The refrigeration device according to claim 13, characterized in that, The refrigeration device is an air conditioner or a refrigerator.

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