A mixed refrigerant, its preparation method and uses

Abstract

This invention provides a mixed refrigerant, its preparation method, and its uses. The mixed refrigerant comprises a first component, a second component, and a third component; the first component is trans-1,2-difluoroethylene (HFO-1132(E)), the second component is monofluoroethane (HFC-161), and the third component is trifluoromethyl ether (HFE-143a). Compared with the existing R290 refrigerant, the mixed refrigerant has reduced combustion and explosion hazards; the mixed refrigerant has low GWP (Gross Potential) and is environmentally friendly, with a GWP ≤ 150, meeting environmental protection requirements; the thermophysical properties, refrigeration, and / or heating cycle performance of the mixed refrigerant are similar to or better than those of R290; the mixed refrigerant can directly replace R290 refrigerant.

Description

Technical Field

[0001] This invention belongs to the field of refrigerant technology, specifically relating to a mixed refrigerant, its preparation method, and its uses. Background Technology

[0002] Currently, low GWP values ​​have become a regulatory requirement for the development of new refrigerants. R32 (GWP 677) and R410A (GWP 2100) used in household air conditioners are both within controlled limits. In the promotion and application of next-generation environmentally friendly refrigerants, propane (R290), a natural working medium, possesses excellent flowability and heat transfer properties, low exhaust temperature, small charge quantity, and low pressure ratio, making it commonly used in household air conditioning systems and thus one of the refrigerants with the potential for widespread application. However, due to its high heat of combustion (50 MJ / kg) and the immaturity of existing industrial chain application technologies, R290 poses safety risks in confined spaces such as automotive air conditioning systems, and its safety is significantly insufficient in high-charge conditions such as those found in household air conditioners (3P and above). Furthermore, the development and widespread adoption of heat pump technology require refrigerants to not only have excellent cooling capacity but also outstanding heating performance.

[0003] Therefore, there is an urgent need for a refrigerant with good environmental performance, better combustion performance than R290, and cooling and heating capacity comparable to or even better than R290 as a substitute. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention provides a mixed refrigerant, its preparation method and uses; the mixed refrigerant includes trans-1,2-difluoroethylene (HFO-1132(E)), monofluoroethane (HFC-161) and trifluoromethyl methyl ether (HFE-143a); the mixed refrigerant has a GWP ≤ 150, and the mixed refrigerant can replace R290 as a refrigerant.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] A mixed refrigerant, the mixed refrigerant comprising a first component, a second component and a third component; the first component is trans-1,2-difluoroethylene (HFO-1132(E)), the second component is monofluoroethane (HFC-161), and the third component is trifluoromethyl ether (HFE-143a).

[0007] The first component accounts for 0%-45% of the total mass of the mixed refrigerant, excluding 0%; the second component accounts for 27%-100% of the total mass of the mixed refrigerant, excluding 100%; and the third component accounts for 0%-28% of the total mass of the mixed refrigerant, excluding 0%.

[0008] According to an embodiment of the present invention, the first component accounts for 0.5%-44% of the total mass of the mixed refrigerant, the second component accounts for 28%-99% of the total mass of the mixed refrigerant, and the third component accounts for 0.5%-28% of the total mass of the mixed refrigerant.

[0009] According to an embodiment of the present invention, the first component accounts for 5%-43% of the total mass of the mixed refrigerant, the second component accounts for 29%-92% of the total mass of the mixed refrigerant, and the third component accounts for 3%-28% of the total mass of the mixed refrigerant.

[0010] According to an embodiment of the present invention, the first component accounts for 8%-42% of the total mass of the mixed refrigerant, the second component accounts for 30%-88% of the total mass of the mixed refrigerant, and the third component accounts for 4%-28% of the total mass of the mixed refrigerant.

[0011] According to an embodiment of the present invention, the first component accounts for 10%-40% of the total mass of the mixed refrigerant, the second component accounts for 32%-85% of the total mass of the mixed refrigerant, and the third component accounts for 5%-28% of the total mass of the mixed refrigerant.

[0012] According to an embodiment of the present invention, the first component accounts for 15%-38% of the total mass of the mixed refrigerant, the second component accounts for 34%-79% of the total mass of the mixed refrigerant, and the third component accounts for 6%-28% of the total mass of the mixed refrigerant.

[0013] According to an embodiment of the present invention, the first component accounts for 18%-36% of the total mass of the mixed refrigerant, the second component accounts for 36%-75% of the total mass of the mixed refrigerant, and the third component accounts for 7%-28% of the total mass of the mixed refrigerant.

[0014] According to an embodiment of the present invention, the first component accounts for 20%-35% of the total mass of the mixed refrigerant, the second component accounts for 37%-72% of the total mass of the mixed refrigerant, and the third component accounts for 8%-28% of the total mass of the mixed refrigerant.

[0015] According to an embodiment of the present invention, the first component accounts for 22%-34% of the total mass of the mixed refrigerant, the second component accounts for 38%-68% of the total mass of the mixed refrigerant, and the third component accounts for 10%-28% of the total mass of the mixed refrigerant.

[0016] According to an embodiment of the present invention, the first component accounts for 25%-33% of the total mass of the mixed refrigerant, the second component accounts for 39%-63% of the total mass of the mixed refrigerant, and the third component accounts for 12%-28% of the total mass of the mixed refrigerant.

[0017] According to an embodiment of the present invention, the first component accounts for 27%-32% of the total mass of the mixed refrigerant, the second component accounts for 40%-59% of the total mass of the mixed refrigerant, and the third component accounts for 14%-28% of the total mass of the mixed refrigerant.

[0018] According to an embodiment of the present invention, the first component accounts for 27% of the total mass of the mixed refrigerant, the second component accounts for 59% of the total mass of the mixed refrigerant, and the third component accounts for 14% of the total mass of the mixed refrigerant.

[0019] According to an embodiment of the present invention, the first component accounts for 29% of the total mass of the mixed refrigerant, the second component accounts for 55% of the total mass of the mixed refrigerant, and the third component accounts for 16% of the total mass of the mixed refrigerant.

[0020] According to an embodiment of the present invention, the first component accounts for 28% of the total mass of the mixed refrigerant, the second component accounts for 54% of the total mass of the mixed refrigerant, and the third component accounts for 18% of the total mass of the mixed refrigerant.

[0021] According to an embodiment of the present invention, the first component accounts for 32% of the total mass of the mixed refrigerant, the second component accounts for 40% of the total mass of the mixed refrigerant, and the third component accounts for 28% of the total mass of the mixed refrigerant.

[0022] According to an embodiment of the present invention, the mass of the first component accounts for 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, or 45% of the total mass of the mixed refrigerant.

[0023] According to an embodiment of the present invention, the mass of the second component accounts for 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% of the total mass of the mixed refrigerant.

[0024] According to an embodiment of the present invention, the mass of the third component accounts for 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, or 28% of the total mass of the mixed refrigerant.

[0025] According to an embodiment of the present invention, the sum of the masses of the first component, the second combination, and the third component accounts for 100% of the total mass of the mixed refrigerant.

[0026] According to an embodiment of the present invention, the mixed refrigerant is composed of a first component, a second component and a third component; the first component is trans-1,2-difluoroethylene (HFO-1132(E)), the second component is monofluoroethane (HFC-161), and the third component is trifluoromethyl ether (HFE-143a).

[0027] According to embodiments of the present invention, the trans-1,2-difluoroethylene (HFO-1132(E)), monofluoroethane (HFC-161), and trifluoromethyl methyl ether (HFE-143a) are prepared by methods known in the art or obtained through commercial purchase.

[0028] According to an embodiment of the present invention, the mixed refrigerant does not include flammable hydrocarbons; the flammable hydrocarbons are flammable organic compounds composed of carbon and hydrogen elements; the flammable hydrocarbons are exemplary propane, propylene, cyclopropane, isobutene, isobutane, n-butene, etc.

[0029] According to an embodiment of the present invention, the GWP of the mixed refrigerant is ≤150, indicating that the mixed refrigerant has good environmental performance and meets environmental protection requirements.

[0030] According to an embodiment of the present invention, the ODP of the mixed refrigerant is 0, indicating that the mixed refrigerant has good environmental performance and meets environmental protection requirements.

[0031] According to an embodiment of the present invention, the ratio of the volumetric cooling capacity of the mixed refrigerant to that of R290 is not less than 1.00; the ratio of the volumetric heating capacity of the mixed refrigerant to that of R290 is not less than 0.95; indicating that the volumetric cooling capacity and volumetric heating capacity of the mixed refrigerant are comparable to those of R290, and can be used to directly replace R290 as a refrigerant for long-term use without requiring changes to the refrigeration and / or heating system.

[0032] According to an embodiment of the present invention, the ratio of the coefficient of performance (COP) of the mixed refrigerant to that of R290 is not less than 1.00; the ratio of the coefficient of performance (COP) of the mixed refrigerant to that of R290 is not less than 0.95; indicating that the COP of the mixed refrigerant is comparable to that of R290, and can be used to directly replace R290 as a refrigerant for long-term use without requiring changes to the refrigeration and / or heating system.

[0033] According to an embodiment of the present invention, the lower flammability limit (LFL) of the mixed refrigerant is ≥3.5%; indicating that the mixed refrigerant is safer to use and can be used to directly replace R290 as a refrigerant for long-term use without requiring changes to the refrigeration and / or heating system.

[0034] According to an embodiment of the present invention, the heat of combustion (HOC) of the mixed refrigerant is ≤28.0 MJ·kg⁻¹. -1 This indicates that the mixed refrigerant is safer to use and can be used to directly replace R290 as a refrigerant for long-term use without requiring changes to the refrigeration and / or heating system.

[0035] According to an embodiment of the present invention, the mixed refrigerant has excellent thermodynamic properties and good cooling and heating effects, making it suitable for use in low-temperature heat pumps (room air conditioners and automotive air conditioners); the heating temperature of the low-temperature heat pump is less than 60°C.

[0036] According to an embodiment of the present invention, the mixed refrigerant can be used to directly replace R290 as a refrigerant.

[0037] The present invention also provides a composition containing a refrigerant, the composition comprising the above-described mixed refrigerant.

[0038] According to an embodiment of the present invention, the refrigerant-containing composition may contain at least one of the following other components as needed.

[0039] According to an embodiment of the present invention, the refrigerant-containing composition includes refrigeration oil.

[0040] According to an embodiment of the present invention, the content of the refrigeration oil relative to the composition containing refrigerant is preferably 10% by mass or less, more preferably 8% by mass or less; for example, when used in an automotive air conditioner, the content of the refrigeration oil relative to the composition containing refrigerant is preferably 7% by mass or less; when used in a room air conditioner, the content of the refrigeration oil relative to the composition containing refrigerant is preferably 1% by mass or less.

[0041] According to an embodiment of the present invention, the refrigerant-containing composition includes water.

[0042] According to an embodiment of the present invention, the content of water relative to the composition containing refrigerant is preferably 0.1% by mass or less, more preferably 0.05% by mass or less; the addition of trace amounts of water can stabilize the intramolecular double bonds of unsaturated fluorocarbon compounds in the refrigerant, and also makes it less prone to oxidation of unsaturated fluorocarbon compounds, thus improving the stability of the composition containing refrigerant.

[0043] According to an embodiment of the present invention, the refrigerant-containing composition comprises an ultraviolet fluorescent dye.

[0044] According to an embodiment of the present invention, the content of the ultraviolet fluorescent dye relative to the composition containing the refrigerant is preferably 1% by mass or less, more preferably 0.1% by mass or less.

[0045] According to embodiments of the present invention, the refrigerant-containing composition of the present invention may contain a single refrigerant or two or more refrigerants as ultraviolet fluorescent dyes. There are no particular limitations on the ultraviolet fluorescent dye; it can be appropriately selected from commonly used ultraviolet fluorescent dyes. Examples of ultraviolet fluorescent dyes include naphthalenediimide, coumarin, anthracene, phenanthrene, xanthracene, thioxanthracene, benzoxanthracene, and fluorescein, as well as their derivatives. Either or both of naphthalenediimide and coumarin are particularly preferred as ultraviolet fluorescent dyes.

[0046] According to an embodiment of the present invention, the refrigerant-containing composition includes an oligomerization / polymerization inhibitor or a chain transfer agent.

[0047] According to an embodiment of the present invention, the oligomerization / polymerization inhibitor or chain transfer agent is selected from at least one of hydrocarbons and aromatic hydrocarbons, terpenes and terpenoids, phenols and hindered phenols.

[0048] According to embodiments of the present invention, the hydrocarbons and aromatic hydrocarbons include at least one of C2-C5 hydrocarbons (such as ethane, propane, butane, isobutene, etc.), m-xylene, o-xylene, p-xylene, and α-methylstyrene (such as α-m-methylstyrene, α-o-methylstyrene, and α-p-methylstyrene); preferably at least one of m-xylene, o-xylene, p-xylene, and α-methylstyrene.

[0049] According to embodiments of the present invention, the terpenes and terpenoids include at least one of limonene, terpinene, pinene, myrcene, p-cymene, terpineol, farnesene, and carvone; preferably at least one of limonene, α-terpinene, and α-pinene; more preferably limonene and / or α-terpinene.

[0050] According to embodiments of the present invention, the phenols and hindered phenols include at least one of butylated hydroxytoluene (BHT), α-tocopherol, 4-methoxyphenol, butylated hydroxyanisole (BHA), and tert-butylhydroquinone (TBHQ); preferably at least one of butylated hydroxytoluene (BHT), α-tocopherol, butylated hydroxyanisole (BHA), and tert-butylhydroquinone (TBHQ).

[0051] According to embodiments of the present invention, the content of the oligomerization / polymerization inhibitor or chain transfer agent relative to the composition containing the refrigerant is preferably 5% by mass or less, more preferably 2% by mass or less. The content of the stabilizer relative to the composition containing the refrigerant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

[0052] According to an embodiment of the present invention, the refrigerant-containing composition includes a stabilizer.

[0053] According to an embodiment of the present invention, the content of the stabilizer relative to the composition containing the refrigerant is preferably 5% by mass or less, more preferably 2% by mass or less. The content of the stabilizer relative to the composition containing the refrigerant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

[0054] According to embodiments of the present invention, the refrigerant-containing composition of the present invention may contain only one type of stabilizer or two or more types. There are no particular limitations on the stabilizer; it can be appropriately selected from commonly used stabilizers. Examples of stabilizers include nitro compounds, ethers, and amines. Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitrobenzene, and aromatic nitro compounds such as nitrobenzene and nitrostyrene. Examples of ethers include 1,4-dioxane. Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine. Furthermore, butylated hydroxyxylene and benzotriazole may also be included.

[0055] According to an embodiment of the present invention, the refrigerant-containing composition includes a polymerization inhibitor.

[0056] According to an embodiment of the present invention, the content of the polymerization inhibitor relative to the composition containing the refrigerant is preferably 5% by mass or less, more preferably 2% by mass or less. The content of the stabilizer relative to the composition containing the refrigerant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

[0057] According to embodiments of the present invention, the refrigerant-containing composition of the present invention may contain only one type of polymerization inhibitor or two or more types. There are no particular limitations on the polymerization inhibitor, and it can be appropriately selected from commonly used polymerization inhibitors. Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl tert-butylphenol, 2,6-di-tert-butyl-p-cresol, benzotriazole, etc.

[0058] According to an embodiment of the present invention, the refrigerant-containing composition can be used to directly replace R290 as a refrigerant.

[0059] The present invention also provides a method for preparing the above-mentioned mixed refrigerant, the method comprising the following steps:

[0060] The first component, the second component, and the third component are mixed and stirred in a low-temperature, normal-pressure liquid phase to obtain the mixed refrigerant; wherein, the first component is trans-1,2-difluoroethylene (HFO-1132(E)), the second component is monofluoroethane (HFC-161), and the third component is trifluoromethyl ether (HFE-143a).

[0061] According to an embodiment of the present invention, the low temperature refers to a temperature range of -60℃ to -50℃.

[0062] The present invention also provides a method for preparing the above-mentioned composition containing refrigerant, the method comprising the following steps:

[0063] The components of the refrigerant-containing composition are mixed and stirred in a low-temperature, normal-pressure liquid phase to obtain the refrigerant-containing composition.

[0064] According to an embodiment of the present invention, the low temperature refers to a temperature range of -60℃ to -50℃.

[0065] The present invention also provides the use of the above-mentioned mixed refrigerant for direct replacement of R290 as a refrigerant.

[0066] According to an embodiment of the present invention, the mixed refrigerant is used to directly replace R290 as a refrigerant in refrigeration and / or heating systems.

[0067] The present invention also provides a refrigeration and / or heating system comprising the above-described mixed refrigerant or the above-described composition containing refrigerant.

[0068] According to an embodiment of the present invention, the refrigeration and / or heating system uses the above-described mixed refrigerant or the above-described refrigerant-containing composition as the working fluid.

[0069] According to an embodiment of the present invention, the refrigeration and / or heating system is an automotive air conditioner and / or a room air conditioner.

[0070] According to an embodiment of the present invention, the automotive air conditioner is, for example, a plug-in hybrid vehicle air conditioner or an electric vehicle air conditioner.

[0071] The present invention also provides a method for operating a refrigeration and / or heating system, the method comprising the step of using the above-described mixed refrigerant or the above-described composition containing refrigerant as a working fluid to circulate in the refrigeration and / or heating system.

[0072] The beneficial effects of this invention are:

[0073] This invention provides a mixed refrigerant, its preparation method, and its uses. Compared with R290 refrigerant in the prior art, the mixed refrigerant has reduced combustion and explosion hazards; the mixed refrigerant has low GWP environmental characteristics, with a GWP ≤ 150, meeting environmental protection requirements; the thermophysical properties, refrigeration and / or heating cycle performance of the mixed refrigerant are similar to or better than those of R290; the mixed refrigerant can directly replace R290 refrigerant. Detailed Implementation

[0074] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0075] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0076] In the description of this invention, it should be noted that the terms "first," "second," "third," etc., are used for descriptive purposes only and are not intended to indicate or imply relative importance.

[0077] The method for preparing the mixed refrigerant in the embodiments and comparative examples of the present invention is to physically mix and stir the components in the mixed refrigerant according to their respective mass percentages in a liquid phase state at -60°C and atmospheric pressure (0.1MPa).

[0078] The basic parameters of each component in the mixed refrigerant of the present invention embodiments and comparative examples are shown in Table 1.

[0079] Table 1. Basic parameters of each component in the mixed refrigerant of the examples and comparative examples.

[0080]

[0081] The mass percentage of each component in the mixed refrigerant of the embodiments and comparative examples of the present invention is shown in Table 2.

[0082] Table 2 Composition of the mixed refrigerants in the examples and comparative examples

[0083]

[0084] Test Example 1: Thermal Properties

[0085] The thermophysical parameters of the mixed refrigerants in the examples and comparative examples were obtained through theoretical calculations, and the calculation results are shown in Table 3.

[0086] Table 3. Thermophysical properties of the Examples, Comparative Examples, and R290 refrigerant

[0087]

[0088] As shown in Table 3, the GWP of the mixed refrigerant provided by this invention is <150, which meets environmental protection standards. The ODP value of the mixed refrigerant provided by this invention is 0, which also indicates that it is more environmentally friendly.

[0089] The test results in Table 3 also show that the critical temperature, critical pressure and standard boiling point of the mixed refrigerant provided by the present invention are close to those of R290, indicating that the mixed refrigerant provided by the present invention can be used as a long-term replacement for R290 without the need to redesign the refrigeration and / or heating system.

[0090] The GWP values ​​of the mixed refrigerants in Comparative Examples 1 and 4 exceeded 150. The mixed refrigerants in Comparative Examples 2, 5, and 6 used the HFO-1234yf component, which has a higher preparation cost and more complex production process. Compared to HFO-1234yf, the HFC-161 component of this invention has a lower preparation cost and simpler production process. Therefore, the use of HFC-161 component makes the preparation cost of the mixed refrigerant of this invention lower and the requirements for the production process less stringent. Furthermore, studies have shown that the HFO-1234yf component decomposes upon contact with water in the atmosphere to produce trifluoroformic acid (TFA), posing an environmental risk. Therefore, the mixed refrigerant of this invention has greater application prospects as a long-term alternative to R290.

[0091] Test Example 2 Performance Test

[0092] The performance of the mixed refrigerants in the examples and comparative examples was tested to obtain the COP ratio, cooling capacity ratio and heating capacity ratio based on R290.

[0093] The refrigeration conditions selected for the test were: evaporation temperature of 1.0℃, condensation temperature of 54.5℃, suction superheat of 10℃, pre-expansion temperature of 50.0℃, and compressor adiabatic efficiency of 0.75.

[0094] The heating conditions selected for the test were: evaporation temperature of -15.0℃, condensation temperature of 45.0℃, suction superheat of 10℃, pre-expansion temperature of 37.0℃, and compressor adiabatic efficiency of 0.75.

[0095] The cycle performance parameters of the above-described embodiments, comparative examples, and R290 refrigerant in the refrigeration system were tested and calculated, and the relative volumetric cooling capacity Q was compared. vc (Ratio of cooling capacity per unit volume to R290), relative heating capacity per unit volume Q vh (Ratio of heating capacity per unit volume to R290), relative coefficient of performance (COP) c (Ratio of cooling performance coefficient to R290), relative heating performance coefficient (COP) h The following parameters are recorded in Tables 4 and 5: (ratio of heating performance coefficient to R290), evaporation pressure, condensation pressure, pressure ratio, and exhaust temperature.

[0096] Table 4 Refrigeration performance parameters of the examples, comparative examples, and R290 refrigerant

[0097]

[0098] As shown in Table 4, under refrigeration conditions, the evaporation pressure, condensation pressure, and pressure ratio of the mixed refrigerant of this invention are quite similar to those of R290, indicating that the mixed refrigerant of this invention can directly replace R290 without significant modifications to the refrigeration system. The relative COP of the mixed refrigerant of this invention... c Relative unit volume cooling capacity Q vc All values ​​are higher than those of R290, indicating that the refrigeration performance of the mixed refrigerant of the present invention completely exceeds that of R290. Replacing R290 with R290 as a refrigerant will not only not reduce the refrigeration performance of the refrigeration system, but will also improve the refrigeration performance of the refrigeration system.

[0099] The relative Q of the mixed refrigerant in Comparative Example 2 vc and relative COP c The results were all lower than in Example 1, indicating that the mixed refrigerant of the present invention has superior refrigeration performance. This also demonstrates a more significant synergistic effect between HFO-1132(E), HFE-143a, and HFC-161, with the synergistic effect far exceeding that between HFO-1132(E), HFE-143a, and HFO-1234yf. Furthermore, the addition of the HFO-1234yf component to the mixed refrigerants of Comparative Examples 2, 5, and 6 resulted in significantly higher preparation costs than the mixed refrigerant of the present invention. Additionally, the HFO-1234yf component decomposes upon contact with water in the atmosphere to produce trifluoroformic acid (TFA), posing an environmental risk.

[0100] Although the relative Q of the mixed refrigerant in Comparative Example 3 vc Slightly higher, but its relative COP c The improvement in efficiency was significantly lower than in Example 1, and the evaporation pressure, condensation pressure, and exhaust temperature were all higher than in Example 1. This indicates that the mixed refrigerant in Comparative Example 3 exhibited a relatively lower Q under refrigeration conditions. vc The increase comes at the cost of system cost; in fact, the mixed refrigerant in ratio 3 does not show a significant improvement in energy efficiency (COP).

[0101] Table 5 Heating performance parameters of the examples, comparative examples, and R290 refrigerant

[0102]

[0103] As shown in Table 5, under heating conditions, the evaporation and condensation pressures of the mixed refrigerant of this invention are closer to those of R290, indicating that the mixed refrigerant of this invention can directly replace R290 without significant system modifications; the pressure ratio is significantly lower than that of R290, indicating that the mixed refrigerant of this invention can reduce compressor power consumption and is beneficial for long-term compressor operation; the relative COP of the mixed refrigerant of this invention... h Relative heat capacity per unit volume Qvh The performance is superior to or comparable to that of R290 refrigerant, indicating that the mixed refrigerant of the present invention can be used to directly replace R290 as a refrigerant.

[0104] As can be seen from the comparison of Example 1 and Comparative Example 2, there is a more significant synergistic effect among HFO-1132(E), HFE-143a, and HFC-161, with an effect far exceeding that among HFO-1132(E), HFE-143a, and HFO-1234yf. Specifically, compared to the combination of HFO-1132(E), HFE-143a, and HFO-1234yf, the combination of HFO-1132(E), HFE-143a, and HFC-161 has a relatively high COP. h Under essentially the same conditions, a higher relative volumetric heating capacity Q can be achieved. vh Meanwhile, the addition of the HFO-1234yf component to the mixed refrigerants of Comparative Examples 2, 5, and 6 resulted in a significantly higher preparation cost than the mixed refrigerant of this invention. Furthermore, the HFO-1234yf component decomposes upon contact with water in the atmosphere to produce trifluoroformic acid (TFA), posing an environmental risk.

[0105] Although the relative Q of the mixed refrigerant in Comparative Example 3 vh High, but its relative COP h The improvement in efficiency was significantly lower than in Example 1, and the evaporation pressure, condensation pressure, and exhaust temperature were all higher than in Example 1. This indicates that the mixed refrigerant in Comparative Example 3 exhibits better relative Q under heating conditions. vh The increase in efficiency comes at the cost of system cost; in fact, the mixed refrigerant in ratio 3 does not show a significant improvement in energy efficiency (COP).

[0106] Test Example 3 Combustion Performance

[0107] The combustion performance of the mixed refrigerants in the examples and comparative examples was obtained through theoretical calculations.

[0108] The heat of combustion is calculated from the standard enthalpy of formation of components such as HFO-1132(E), HFC-161, HFE-143a, HFC-32, HFO-1234yf, CO2, HF, COF2, and H2O to obtain the standard enthalpy of combustion.

[0109] Table 6 Combustion parameters of the examples, comparative examples, and R290 refrigerant

[0110]

[0111] As can be seen from the comparison in Table 6, the lower flammability limit (LFL) of the mixed refrigerant in the embodiments is >3.5%, and the heat of combustion (HOC) is less than 60% of that of R290. Furthermore, embodiments 4 and 15 have reached flammability level 2. This indicates that the flammability safety of the mixed refrigerant of the present invention is far superior to that of R290, and it can be directly used to replace R290 refrigerant without requiring any safety performance modifications to the refrigeration and / or heating systems.

[0112] In summary, the mixed refrigerant provided by this invention not only has the environmentally friendly characteristic of low GWP, but also has thermal and flammability properties that are comparable to or even better than R290, making it a good substitute for R290.

[0113] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A mixed refrigerant, wherein, The mixed refrigerant includes a first component, a second component, and a third component; the first component is trans-1,2-difluoroethylene (HFO-1132(E)), the second component is monofluoroethane (HFC-161), and the third component is trifluoromethyl ether (HFE-143a). The first component accounts for 0.5%-45% of the total mass of the mixed refrigerant; The second component accounts for 27%-98% of the total mass of the mixed refrigerant; The third component accounts for 0.5%-28% of the total mass of the mixed refrigerant; The mixed refrigerant does not include flammable hydrocarbons.

2. The mixed refrigerant according to claim 1, wherein, The first component accounts for 0.5%-44% of the total mass of the mixed refrigerant, the second component accounts for 28%-98% of the total mass of the mixed refrigerant, and the third component accounts for 0.5%-28% of the total mass of the mixed refrigerant.

3. The mixed refrigerant according to claim 2, wherein, The first component accounts for 5%-43% of the total mass of the mixed refrigerant, the second component accounts for 29%-92% of the total mass of the mixed refrigerant, and the third component accounts for 3%-28% of the total mass of the mixed refrigerant.

4. The mixed refrigerant according to claim 3, wherein, The first component accounts for 8%-42% of the total mass of the mixed refrigerant, the second component accounts for 30%-88% of the total mass of the mixed refrigerant, and the third component accounts for 4%-28% of the total mass of the mixed refrigerant.

5. The mixed refrigerant according to claim 4, wherein, The first component accounts for 10%-40% of the total mass of the mixed refrigerant, the second component accounts for 32%-85% of the total mass of the mixed refrigerant, and the third component accounts for 5%-28% of the total mass of the mixed refrigerant.

6. The mixed refrigerant according to claim 5, wherein, The first component accounts for 15%-38% of the total mass of the mixed refrigerant, the second component accounts for 34%-79% of the total mass of the mixed refrigerant, and the third component accounts for 6%-28% of the total mass of the mixed refrigerant.

7. The mixed refrigerant according to claim 6, wherein, The first component accounts for 18%-36% of the total mass of the mixed refrigerant, the second component accounts for 36%-75% of the total mass of the mixed refrigerant, and the third component accounts for 7%-28% of the total mass of the mixed refrigerant.

8. The mixed refrigerant according to claim 7, wherein, The first component accounts for 20%-35% of the total mass of the mixed refrigerant, the second component accounts for 37%-72% of the total mass of the mixed refrigerant, and the third component accounts for 8%-28% of the total mass of the mixed refrigerant.

9. The mixed refrigerant according to claim 8, wherein, The first component accounts for 22%-34% of the total mass of the mixed refrigerant, the second component accounts for 38%-68% of the total mass of the mixed refrigerant, and the third component accounts for 10%-28% of the total mass of the mixed refrigerant.

10. The mixed refrigerant according to claim 9, wherein, The first component accounts for 25%-33% of the total mass of the mixed refrigerant, the second component accounts for 39%-63% of the total mass of the mixed refrigerant, and the third component accounts for 12%-28% of the total mass of the mixed refrigerant.

11. The mixed refrigerant according to claim 10, wherein, The first component accounts for 27%-32% of the total mass of the mixed refrigerant, the second component accounts for 40%-59% of the total mass of the mixed refrigerant, and the third component accounts for 14%-28% of the total mass of the mixed refrigerant.

12. The mixed refrigerant according to claim 11, wherein, The first component accounts for 27% of the total mass of the mixed refrigerant, the second component accounts for 59% of the total mass of the mixed refrigerant, and the third component accounts for 14% of the total mass of the mixed refrigerant. Alternatively, the first component accounts for 29% of the total mass of the mixed refrigerant, the second component accounts for 55% of the total mass of the mixed refrigerant, and the third component accounts for 16% of the total mass of the mixed refrigerant. Alternatively, the first component accounts for 28% of the total mass of the mixed refrigerant, the second component accounts for 54% of the total mass of the mixed refrigerant, and the third component accounts for 18% of the total mass of the mixed refrigerant. Alternatively, the first component accounts for 32% of the total mass of the mixed refrigerant, the second component accounts for 40% of the total mass of the mixed refrigerant, and the third component accounts for 28% of the total mass of the mixed refrigerant.

13. The mixed refrigerant according to any one of claims 1-12, wherein, The ratio of the volumetric cooling capacity of the mixed refrigerant to that of R290 is not less than 1.00; the ratio of the volumetric heating capacity of the mixed refrigerant to that of R290 is not less than 0.

95. And / or, the ratio of the coefficient of performance (COP) of the mixed refrigerant to that of R290 is not less than 1.00; the ratio of the coefficient of performance (COP) of the mixed refrigerant to that of R290 is not less than 0.

95.

14. A composition containing a refrigerant, said composition comprising the mixed refrigerant according to any one of claims 1-13.

15. The composition according to claim 14, wherein, The composition containing refrigerant includes refrigeration oil; And / or, the refrigerant-containing composition includes water; And / or, the refrigerant-containing composition includes an ultraviolet fluorescent dye; And / or, the refrigerant-containing composition includes oligomerization / polymerization inhibitors or chain transfer agents; And / or, the refrigerant-containing composition includes a stabilizer; And / or, the refrigerant-containing composition includes a polymerization inhibitor.

16. Use of the mixed refrigerant according to any one of claims 1-13, for direct replacement of R290 as a refrigerant.

17. A refrigeration and / or heating system, the refrigeration and / or heating system comprising a mixed refrigerant as described in any one of claims 1-13 or a composition containing a refrigerant as described in claim 14 or 15; the refrigeration and / or heating system being an automotive air conditioner and / or a room air conditioner.

18. A method of operating a refrigeration and / or heating system, the method comprising the step of circulating a mixed refrigerant as described in any one of claims 1-13 or a refrigerant-containing composition as described in claims 14 or 15 as a working fluid in the refrigeration and / or heating system.

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