Ternary azeotropic mixture and preparation method thereof

Abstract

The invention relates to a ternary azeotropic mixture and a preparation method thereof. Comprising a first component, a second component and a third component, the first component is heptafluoro-1-methoxypropane, the second component is trans-dichloroethylene, and the third component is Z-hexafluorobutene; the preparation method comprises the following steps: preliminarily mixing heptafluoro-1-methoxypropane, trans-dichloroethylene and Z-hexafluorobutene in a low-temperature environment, and injecting the mixture into a pressurized nano-bubble fluidized bed for continuous mixing; filtering the mixed liquid, and standing in a normal-pressure storage tank to obtain a ternary mixed composition; the ternary mixture prepared by the invention has an azeotropic phenomenon when the first component is 31.3 parts by weight, the second component is 23.6 parts by weight, and the third component is 45.1 parts by weight. The prepared composition has the advantages of environmental friendliness, high latent heat, good chemical stability, high safety and the like. Except the azeotropic point, all the components which are close to the azeotropic point and have the respective change within 0.5% by weight are azeotrope-like mixtures.

Description

Technical Field

[0001] The present invention relates to the field of refrigeration, and in particular to a method for preparing a ternary and azeotropic mixed refrigeration medium. Background Art

[0002] In the field of refrigeration technology, refrigerants, as the key heat transfer fluid in the refrigeration cycle, have a direct impact on the efficiency, energy consumption, and environmental performance of refrigeration systems. Since the advent of refrigeration technology, refrigerants have undergone numerous changes and developments. Early refrigerants such as ammonia and sulfur dioxide, while capable of cooling, suffered from toxicity and corrosiveness, severely limiting their application. With technological advancements, halogenated hydrocarbon refrigerants, such as Freon, have long been the mainstream choice in the refrigeration industry due to their non-toxic, non-flammable, and stable cooling performance.

[0003] However, subsequent studies have found that traditional halogenated hydrocarbon refrigerants can cause serious damage to the ozone layer and have a high global warming potential, which is extremely harmful to the environment. In response to these problems, the international community has adopted a series of agreements such as the Montreal Protocol and the Kyoto Protocol to strictly restrict and gradually phase out the use of refrigerants with high environmental impacts. Against this background, researchers are committed to developing more environmentally friendly and efficient new refrigerants, such as hydrofluorocarbon (HFCs) alternatives. However, new refrigerants with a single component have limitations in terms of refrigeration performance, cost control, and applicable operating conditions, making it difficult to fully meet the complex and diverse refrigeration needs.

[0004] Patent TW515840 describes a compound composed of C3F7-OCH3 (heptafluoro-1-methoxypropane) and a second component selected from an unsubstituted alkane having 5-7 carbon atoms, methyl formate, acetone, methanol, hexafluoro-2-propanol, dichloromethane, and trans-1,2-dichloroethylene. It mentions a binary azeotrope. However, in the examples mentioned, the proportion of heptafluoro-1-methoxypropane forming an azeotrope with trans-1,2-dichloroethylene is as high as 77.6%, and its GWP is as high as 420, meaning the azeotrope is still not friendly, exceeding the defined GWP of 150.

[0005] Patent US20220025146 describes the existence of azeotropic and azeotrope-like phenomena between C3F7-OCH3 (heptafluoro-1-methoxypropane) and Z-hexafluorobutene components. As can be seen from the graph obtained in the patent, when the molar ratio of Z-hexafluorobutene is about 58%, the two have the highest boiling point, which is the possibility of azeotropy. However, the mass ratio of Z-hexafluorobutene is about 52%, which means that the GWP of the mixture is still relatively high.

[0006] To meet these requirements while also improving heat exchange, the present invention has developed a ternary refrigerant. This refrigerant, which combines three different refrigerant components in a specific ratio, combines the advantages of each component and is expected to achieve breakthroughs in environmental performance, cooling efficiency, energy consumption, and other aspects. However, the preparation of ternary refrigerants currently faces challenges such as precise proportioning, component compatibility, and complex and costly preparation processes. Therefore, the development of a scientific, efficient, and low-cost method for preparing ternary refrigerants is of great practical significance and crucial to promoting the sustainable development of the refrigeration industry. Summary of the Invention

[0007] To address the above-mentioned issues, the present invention provides a ternary mixed refrigerant, characterized in that the ternary mixed refrigerant comprises a first component, a second component, and a third component, wherein the first component is heptafluoro-1-methoxypropane, the second component is trans-dichloroethylene, and the third component is Z-hexafluorobutene. Furthermore, the present invention provides that these three components exhibit azeotropic behavior at specific ratios, and that each component exhibits azeotrope-like behavior when the change in the ratio is 0.5% or less.

[0008] A method for preparing a ternary mixed refrigerant is as follows:

[0009] S1: Premix

[0010] Heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene are weighed in a specific weight ratio, and then preliminarily mixed at a low temperature of -20 to 0°C; magnetic stirring is used for stirring at a speed of 50 to 200 rpm for 5 to 15 minutes;

[0011] S2: Pressurized nanobubble fluidized bed mixing

[0012] The premixed liquid obtained in S1 is injected into a pressurized nanobubble fluidized bed device with a special structure, which includes a bubble generating device, a mixing chamber, and a gas circulation system. The bubble generating device uses ultrasonic vibration combined with microporous dispersion technology to produce nanobubbles with uniform size in the range of 50-500nm. The mixing chamber is equipped with multiple layers of staggered spoilers to increase the turbulence of the liquid and improve the mixing effect. The gas circulation system can recycle the introduced neon gas to reduce gas consumption.

[0013] S3: Post-processing

[0014] Before placing the S2 mixed liquid into a normal pressure storage tank, the mixed liquid is first filtered using a filter with a pore size of 0.1-1 μm. The filtered liquid is then placed into a normal pressure storage tank, the temperature in the tank is controlled to be between -20°C and 0°C, and the mixed liquid is allowed to stand at this temperature for 50-100 hours to completely remove the neon gas therein, thereby finally obtaining the ternary mixed refrigerant.

[0015] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 20-45 parts of heptafluoro-1-methoxypropane, 20-30 parts of trans-dichloroethylene, and 25-60 parts of Z-hexafluorobutene.

[0016] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 23-41 parts of heptafluoro-1-methoxypropane, 22-28 parts of trans-dichloroethylene, and 31-55 parts of Z-hexafluorobutene.

[0017] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 25-35 parts of heptafluoro-1-methoxypropane, 23-26 parts of trans-dichloroethylene, and 39-52 parts of Z-hexafluorobutene.

[0018] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 30-33 parts of heptafluoro-1-methoxypropane, 23-25 parts of trans-dichloroethylene, and 42-49 parts of Z-hexafluorobutene.

[0019] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 30-32 parts of heptafluoro-1-methoxypropane, 23-25 parts of trans-dichloroethylene, and 43-47 parts of Z-hexafluorobutene.

[0020] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 31.3 parts of heptafluoro-1-methoxypropane, 23.6 parts of trans-dichloroethylene, and 45.1 parts of Z-hexafluorobutene.

[0021] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 31.8 parts of heptafluoro-1-methoxypropane, 23.6 parts of trans-dichloroethylene, and 44.6 parts of Z-hexafluorobutene.

[0022] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 30.8 parts of heptafluoro-1-methoxypropane, 24.1 parts of trans-dichloroethylene, and 45.1 parts of Z-hexafluorobutene.

[0023] Furthermore, the weight proportions of the components in the ternary mixed refrigerant are: 31.3 parts of heptafluoro-1-methoxypropane, 23.1 parts of trans-dichloroethylene, and 45.6 parts of Z-hexafluorobutene.

[0024] Furthermore, in the bubble generating device of the pressurized nanobubble fluidized bed equipment, the ultrasonic oscillation frequency is 20kHz-100kHz, and the micropore diameter is 10-50μm.

[0025] Furthermore, the angle between the spoiler in the mixing chamber of the pressurized nanobubble fluidized bed equipment and the wall of the mixing chamber is 30°-60°, and the vertical distance between two adjacent layers of spoilers is 5-15 cm.

[0026] Furthermore, the process parameters of the pressurized nanobubble fluidized bed are: pressure of 0.5-2.0 MPa, temperature of -20°C to 0°C, gas flow rate of 0.1-5 L / min, bubble size of 50-500 nm, mixing time of 10-60 minutes, and stirring speed of 100-500 rpm.

[0027] Reaction mechanism

[0028] The ternary mixed heat exchange medium consists of heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene. These three compounds are physically mixed at room temperature and pressure to form a mixture. The following is a detailed explanation of its reaction mechanism:

[0029] Intermolecular forces: Heptafluoro-1-methoxypropane and Z-hexafluorobutene form fluorinated hydrocarbons, while trans-dichloroethylene is a fluorochlorocarbon. When these three components are mixed, the intermolecular forces between them allow them to mix evenly. Furthermore, heptafluoro-1-methoxypropane and Z-hexafluorobutene quench the flash point of trans-dichloroethylene, making the mixture safer.

[0030] Azeotropic phenomenon: Heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene can form an azeotrope at specific weight ratios. The boiling point of the azeotrope is lower than the boiling point of any individual component, and this phenomenon is called azeotropy.

[0031] Thermodynamic equilibrium: At the azeotropic point of 29.5°C, the three components in the mixed working fluid reach a vapor-liquid equilibrium state. At this point, the weight fractions of each component in the gas phase and the liquid phase are equal, and the total pressure is equal to the sum of the vapor pressures of the components.

[0032] Evaporation and condensation: During the refrigeration process, when the mixed heat exchange medium absorbs heat, it changes from liquid to gas (evaporation), thereby removing heat. When the heat is released, the gaseous heat exchange medium condenses back into liquid (condensation), completing a refrigeration cycle.

[0033] Technical Effects

[0034] The present invention provides a method for preparing a ternary mixed refrigerant. Compared with the prior art, the present invention has the following significant effects:

[0035] 1. Environmentally friendly: The global warming potential (GWP) of heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene is relatively low. Compared with traditional high-GWP refrigerants, such as some hydrofluorocarbons (HFCs), they stay in the atmosphere for a shorter time and have less impact on global warming.

[0036] 2. High-Efficiency Refrigeration: The ternary mixed refrigerant of the present invention has a suitable boiling point and vapor pressure, enabling efficient heat transfer in the refrigeration cycle. It rapidly evaporates and absorbs heat in the evaporator, and rapidly condenses and releases heat in the condenser, thereby improving the refrigeration efficiency of the refrigeration system and reducing energy consumption. Trans-dichloroethylene in the present invention has a high latent heat, and after mixing, it can increase the cooling capacity per unit volume of the mixed working fluid, achieving more efficient heat exchange capacity.

[0037] 3. Chemical stability: Heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene are chemically stable under normal refrigeration system operating conditions and are not prone to decomposition reactions; this helps ensure the performance stability of the refrigerant during long-term use and reduces the impact of impurities generated by refrigerant decomposition on the refrigeration system.

[0038] 4. Safety: Both heptafluoro-1-methoxypropane and Z-hexafluorobutene are non-flammable and non-explosive. They suppress the flash point of trans-dichloroethylene, reduce the risk of fire and explosion during the operation of the refrigeration system, and improve the safety of refrigeration equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The diagram of the test device is as follows:

[0040] 1. Dynamic balancer - Xiaxi VLE1000; 2. Pump; 3. Manual two-position valve; 4. Pipe adapter; 5. Electronic flow controller; 6. Chromatographic six-port injection valve; 7. Vaporization chamber; 8. Chromatographic column; 9. Detector; 10. Agilent gas chromatograph 8890; V. Gas phase area for analytical samples; L. Liquid phase area for analytical samples.

[0041] Figure 2 1. It is a test diagram of the deviation of the gas-liquid phase ratio of each component when the ternary mixed component ratio of the embodiment and the comparative example is in dynamic equilibrium. DETAILED DESCRIPTION

[0042] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention object, the following is a detailed description in conjunction with examples and comparative examples:

[0043] The test method is a cyclic analysis method. This involves placing an unknown analyte in a closed equilibrium reactor. A liquid, gas, or gas-liquid circulation pump is used to force two-phase flow to equilibrium. Samples are then taken from both the gas and liquid phases for component analysis. Sampling is typically performed using a six-way valve. The instrument used is the Xiaxi VLE1000.

[0044] Example 1

[0045] A ternary mixed refrigerant comprises a first component, a second component and a third component, wherein the first component is heptafluoro-1-methoxypropane, the second component is trans-dichloroethylene, and the third component is Z-hexafluorobutene.

[0046] The preparation method of the ternary mixed refrigerant is as follows:

[0047] S1: Premix

[0048] Heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene were weighed in a specific weight ratio and then preliminarily mixed at a low temperature of -20°C. The mixture was stirred using a magnetic stirrer at a speed of 50 rpm for 15 minutes.

[0049] S2: Pressurized nanobubble fluidized bed mixing

[0050] The premixed liquid obtained in S1 is injected into a pressurized nanobubble fluidized bed device with a special structure, which includes a bubble generating device, a mixing chamber, and a gas circulation system. The bubble generating device uses ultrasonic vibration combined with microporous dispersion technology to produce nanobubbles with uniform size within the range of 50nm. The mixing chamber is equipped with multiple layers of staggered spoilers to increase the turbulence of the liquid and improve the mixing effect. The gas circulation system can recycle the introduced neon gas to reduce gas consumption.

[0051] S3: Post-processing

[0052] Before placing the S2 mixed liquid into a normal pressure storage tank, the mixed liquid is first filtered using a filter with a pore size of 0.1 μm. The filtered liquid is then placed into a normal pressure storage tank, the temperature in the tank is controlled to be within a range of -20°C, and the mixed liquid is allowed to stand at this temperature for 50 hours to completely remove the neon gas therein, thereby finally obtaining the ternary mixed refrigerant.

[0053] The components of the ternary mixed refrigerant are: 31.3g heptafluoro-1-methoxypropane, 23.6g trans-dichloroethylene, and 45.1g Z-hexafluorobutene.

[0054] In the bubble generating device of the pressurized nanobubble fluidized bed equipment, the ultrasonic oscillation frequency is 20 kHz and the micropore diameter is 10 μm.

[0055] The angle between the spoiler in the mixing chamber of the pressurized nanobubble fluidized bed equipment and the wall of the mixing chamber is 30°, and the vertical distance between two adjacent layers of spoilers is 5 cm.

[0056] The process parameters of the pressurized nanobubble fluidized bed are: pressure of 0.5 MPa, temperature of -20°C, gas flow rate of 0.1 L / min, bubble size of 50 nm, mixing time of 60 minutes, and stirring speed of 500 rpm.

[0057] Example 2

[0058] The components of the ternary mixed refrigerant are: 31.8 g of heptafluoro-1-methoxypropane, 23.6 g of trans-dichloroethylene, and 44.6 g of Z-hexafluorobutene. Other components are the same as those in Example 1.

[0059] Example 3

[0060] The components of the ternary mixed refrigerant are: 30.8 g of heptafluoro-1-methoxypropane, 24.1 g of trans-dichloroethylene, and 45.1 g of Z-hexafluorobutene. Other components are the same as those in Example 1.

[0061] Example 4

[0062] The components of the ternary mixed refrigerant are: 31.3 g of heptafluoro-1-methoxypropane, 23.1 g of trans-dichloroethylene, and 45.6 g of Z-hexafluorobutene. Other components are the same as those in Example 1.

[0063] Comparative Example 1

[0064] The weight percentages of the components in the ternary mixed refrigerant are: 40 g heptafluoro-1-methoxypropane, 20 g trans-dichloroethylene, and 40 g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0065] Comparative Example 2

[0066] The weight percentages of the components in the ternary mixed refrigerant are: 38g heptafluoro-1-methoxypropane, 24g trans-dichloroethylene, and 38g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0067] Comparative Example 3

[0068] The weight percentages of the components in the ternary mixed refrigerant are: 25g heptafluoro-1-methoxypropane, 25g trans-dichloroethylene, and 50g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0069] Comparative Example 4

[0070] The weight percentages of the components in the ternary mixed refrigerant are: 39g heptafluoro-1-methoxypropane, 25g trans-dichloroethylene, and 36g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0071] Comparative Example 5

[0072] The weight percentages of the components in the ternary mixed refrigerant are: 42g heptafluoro-1-methoxypropane, 23g trans-dichloroethylene, and 35g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0073] Comparative Example 6

[0074] The weight percentages of the components in the ternary mixed refrigerant are: 36g heptafluoro-1-methoxypropane, 24g trans-dichloroethylene, and 40g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0075] Comparative Example 7

[0076] The weight percentages of the components in the ternary mixed refrigerant are: 40 g heptafluoro-1-methoxypropane, 25 g trans-dichloroethylene, and 35 g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0077] Comparative Example 8

[0078] The weight percentages of the components in the ternary mixed refrigerant are: 45g heptafluoro-1-methoxypropane, 25g trans-dichloroethylene, and 30g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0079] Comparative Example 9

[0080] The weight percentages of the components in the ternary mixed refrigerant are: 43g heptafluoro-1-methoxypropane, 24g trans-dichloroethylene, and 33g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0081] Comparative Example 10

[0082] The weight percentages of the components in the ternary mixed refrigerant are: 35g heptafluoro-1-methoxypropane, 30g trans-dichloroethylene, and 35g Z-hexafluorobutene. Other components are the same as those in Example 1.

[0083] Table 1 Gas-liquid deviation of the embodiment and the comparative example

[0084] Trans-dichloroethylene / % Z-hexafluorobutene / % Heptafluoro-1-methoxypropane / % Example 1 -0.0527 0.0971 -0.0443 Example 2 -0.0919 0.2830 -0.1911 Example 3 0.3188 0.0838 -0.4026 Example 4 0.2339 0.1586 -0.3925 Comparative Example 1 -3.1032 0.1018 3.0014 Comparative Example 2 -0.521 -0.9887 1.5097 Comparative Example 3 -1.4402 0.4848 0.9555 Comparative Example 4 -0.1993 -1.0962 1.2956 Comparative Example 5 -0.3008 0.1088 1.192 Comparative Example 6 0.2826 -1.3569 1.0743 Comparative Example 7 0.0572 -1.6274 1.5701 Comparative Example 8 0.0558 -1.662 1.6062 Comparative Example 9 0.0853 -1.8916 2.0159 Comparative Example 10 1.7948 -2.2121 0.4213

[0085] Table 2 Physical properties of Example 1

[0086]

[0087] Analysis of the data from the above examples and comparative examples shows that only Example 1 forms an azeotrope. The gas-liquid compositions of Examples 2, 3, and 4, each varying by ±0.5% based on Example 1, are within a quasi-azeotrope range.

[0088] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, make some changes or modifications to equivalent embodiments using the technical contents disclosed above. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A ternary mixed refrigerant, characterized in that: The ternary mixed refrigerant includes a first component, a second component and a third component, wherein the first component is heptafluoro-1-methoxypropane, the second component is trans-dichloroethylene, and the third component is Z-hexafluorobutene.

2. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The preparation method is: S1: Premix Heptafluoro-1-methoxypropane, trans-dichloroethylene, and Z-hexafluorobutene are weighed in a specific weight ratio, and then preliminarily mixed at a low temperature of -20 to 0°C; magnetic stirring is used for stirring at a speed of 50 to 200 rpm for 5 to 15 minutes; S2: Pressurized nanobubble fluidized bed mixing The premixed liquid obtained in S1 is injected into a pressurized nanobubble fluidized bed device with a special structure, which includes a bubble generating device, a mixing chamber, and a gas circulation system. The bubble generating device uses ultrasonic vibration combined with microporous dispersion technology to produce nanobubbles with uniform size in the range of 50-500nm. The mixing chamber is equipped with multiple layers of staggered spoilers to increase the turbulence of the liquid and improve the mixing effect. The gas circulation system can recycle the introduced neon gas to reduce gas consumption. S3: Post-processing Before placing the S2 mixed liquid into a normal pressure storage tank, the mixed liquid is first filtered using a filter with a pore size of 0.1-1 μm. The filtered liquid is then placed into a normal pressure storage tank, the temperature in the tank is controlled to be between -20°C and 0°C, and the mixed liquid is allowed to stand at this temperature for 50-100 hours to completely remove the neon gas therein, thereby finally obtaining the ternary mixed refrigerant.

3. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 20-45 parts of heptafluoro-1-methoxypropane, 20-30 parts of trans-dichloroethylene, and 25-60 parts of Z-hexafluorobutene.

4. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 23-41 parts of heptafluoro-1-methoxypropane, 22-28 parts of trans-dichloroethylene, and 31-55 parts of Z-hexafluorobutene.

5. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 25-35 parts of heptafluoro-1-methoxypropane, 23-26 parts of trans-dichloroethylene, and 39-52 parts of Z-hexafluorobutene.

6. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 30-33 parts of heptafluoro-1-methoxypropane, 23-25 parts of trans-dichloroethylene, and 42-49 parts of Z-hexafluorobutene.

7. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 30-32 parts of heptafluoro-1-methoxypropane, 23-25 parts of trans-dichloroethylene, and 43-47 parts of Z-hexafluorobutene.

8. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 31.3 parts of heptafluoro-1-methoxypropane, 23.6 parts of trans-dichloroethylene, and 45.1 parts of Z-hexafluorobutene. The obtained composition has an azeotropic phenomenon.

9. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 31.8 parts of heptafluoro-1-methoxypropane, 23.6 parts of trans-dichloroethylene, and 44.6 parts of Z-hexafluorobutene.

10. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 30.8 parts of heptafluoro-1-methoxypropane, 24.1 parts of trans-dichloroethylene, and 45.1 parts of Z-hexafluorobutene.

11. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: The weight proportions of the components in the ternary mixed refrigerant are: 31.3 parts of heptafluoro-1-methoxypropane, 23.1 parts of trans-dichloroethylene, and 45.6 parts of Z-hexafluorobutene.

12. The method for preparing a ternary mixed refrigerant according to claim 1, characterized in that: In the bubble generating device of the pressurized nanobubble fluidized bed equipment, the ultrasonic oscillation frequency is 20kHz-100kHz, and the micropore diameter is 10-50μm.

13. The method for preparing a ternary mixed refrigerant according to claim 2, characterized in that: The angle between the spoiler in the mixing chamber of the pressurized nanobubble fluidized bed equipment and the wall of the mixing chamber is 30°-60°, and the vertical distance between two adjacent layers of spoilers is 5-15 cm.

14. The method for preparing a ternary mixed refrigerant according to claim 2, characterized in that: The process parameters of the pressurized nanobubble fluidized bed are: pressure of 0.5-2.0 MPa, temperature of -20°C to 0°C, gas flow rate of 0.1-5 L / min, bubble size of 50-500 nm, mixing time of 10-60 minutes, and stirring speed of 100-500 rpm.

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