Environmentally friendly mixed refrigerant containing co2

Abstract

The application belongs to the technical field of refrigerants, and discloses an environmentally-friendly mixed refrigerant containing CO2, which is formed by mixing at least one of three components, propylene, 1,1-difluoroethane and trifluoroethylene, with carbon dioxide, and specifically can be composed of two components, carbon dioxide and propylene, or three components, carbon dioxide, propylene and 1,1-difluoroethane, or three components, carbon dioxide, propylene and trifluoroethylene. Through improvement on the component composition of the mixed refrigerant and the proportion of each component, the obtained mixed refrigerant has high energy efficiency, low exhaust temperature and large refrigerating capacity per unit volume, and can solve the actual problems of high GWP value and high exhaust temperature of the existing R32 refrigerant, and low refrigerating capacity per unit volume, low energy efficiency and poor heating performance of the existing R290 refrigerant.

Description

Technical Field

[0001] The present invention belongs to the technical field of refrigerants, and more specifically, relates to an environmentally friendly mixed refrigerant containing CO2. The mixed refrigerant is an environmentally friendly mixed refrigerant that can replace R32, R410A and R290, and can be used as an air-conditioning refrigerant in particular. Its comprehensive performance is superior to that of existing R32 air conditioners and R290 air conditioners that have not yet been fully promoted and applied. Background Art

[0002] As people pay more attention to the depletion of the ozone layer and the intensification of the greenhouse effect, countries around the world have gradually phased out chlorine-containing refrigerants with an ODP greater than zero and have begun to restrict the use of hydrofluorocarbon (HFC) refrigerants with high global warming potential (GWP). In October 2016, the Kigali Amendment to the Montreal Protocol clarified the control of 18 HFCs. The task of finding alternative refrigerants with excellent performance is urgent.

[0003] In recent years, difluoromethane (R32) has been widely used in residential air conditioning as a transitional replacement for R410A. It offers high cooling capacity per unit volume, a high coefficient of performance (COP) for system applications, and a low global warming potential (GWP). However, according to the Intergovernmental Panel on Climate Change's Sixth Assessment Report (IPCC AR6), R32's GWP has been revised to 771, exceeding the limit for refrigerants used in residential air conditioners under the European Parliament's Fluorinated Gases Regulation (F-gas). According to the European Parliament's regulations, after 2025, fluorinated greenhouse gases with a GWP of 750 or higher will be banned in split air conditioning systems with a charge of less than 3 kg. Therefore, research on alternatives to R32 used in air conditioners is urgent.

[0004] Currently, the natural refrigerant propane (R290) is one of the main approaches to replacing R32. However, the unit cooling capacity of air conditioning systems using R290 is too low, at only about 50% of that of R32. This results in larger compressors and higher vibration and noise levels. Furthermore, due to R290's low unit cooling capacity, the compressor has a high suction volume, resulting in high evaporator flow rates and high flow resistance. Consequently, the heating capacity of R290 air conditioning systems is far lower than that of R32 systems.

[0005] Mixed refrigerants are an effective solution to the aforementioned R32 replacement problem and the practical challenges encountered in the application of single-component hydrocarbon refrigerants such as R290. Mixed refrigerants can be created by combining multiple refrigerants with varying performance characteristics. This approach leverages the strengths of each refrigerant to tailor various aspects of the blend, mitigating the shortcomings of single-component refrigerants. This results in a blend with excellent overall properties, addressing the challenges of refrigerant replacement in the refrigeration and air conditioning sector. Summary of the Invention

[0006] In response to the above-mentioned defects or improvement needs of R32 refrigerant replacement and existing technologies, the purpose of the present invention is to provide an environmentally friendly mixed refrigerant containing CO2, wherein by improving the composition of the mixed refrigerant and the proportion of each component, compared with the existing technology, it can solve the practical problems of the existing R32 refrigerant with a high GWP value and high exhaust temperature, and the R290 refrigerant with a low unit volume cooling capacity, low energy efficiency, and poor heating performance. The mixed refrigerant obtained by the present invention has high energy efficiency, low exhaust temperature, and large unit volume cooling capacity, and can be used in the following occasions: (1) The unit volume cooling capacity is higher than that of R32 air conditioners, and no compressor replacement is required when replacing R32; (2) When used in newly developed air conditioners, the unit volume cooling capacity is higher, and the cooling and heating COP is higher than that of existing R32 air conditioners, with significant energy-saving effects. It is applicable to refrigeration equipment such as household and commercial air conditioning systems, heat pump water heaters, and automotive air conditioners.

[0007] To achieve the above object, according to one aspect of the present invention, there is provided an environmentally friendly mixed refrigerant containing CO2, characterized in that it is a mixture of at least one of the three components of propylene, 1,1-difluoroethane, and trifluoroethylene with carbon dioxide;

[0008] The mixed refrigerant is composed of two components: carbon dioxide and propylene, wherein the mass percentage of carbon dioxide in the mixed refrigerant is 5% to 12%, and the mass percentage of propylene in the mixed refrigerant is 88% to 95%; the GWP value of the mixed refrigerant is less than 150;

[0009] Alternatively, the mixed refrigerant is composed of three components: carbon dioxide, propylene, and 1,1-difluoroethane, wherein the mass percentage of carbon dioxide in the mixed refrigerant is 5% to 15%, the mass percentage of propylene in the mixed refrigerant is 33% to 85%, and the mass percentage of 1,1-difluoroethane in the mixed refrigerant is 10% to 55%; the GWP value of the mixed refrigerant is less than 150;

[0010] Alternatively, the mixed refrigerant is composed of three components: carbon dioxide, propylene and trifluoroethylene, wherein the mass percentage of carbon dioxide in the mixed refrigerant is 5% to 15%, the mass percentage of propylene in the mixed refrigerant is 20% to 70%, and the mass percentage of trifluoroethylene in the mixed refrigerant is 20% to 65%; the GWP value of the mixed refrigerant is less than 150.

[0011] As a further preferred embodiment of the present invention, the mixed refrigerant is composed of two components: carbon dioxide and propylene. The mass ratio of carbon dioxide to propylene in the mixed refrigerant is 0.05:0.95, or 0.08:0.92, or 0.1:0.9, or 0.12:0.88.

[0012] As a further preferred embodiment of the present invention, the mixed refrigerant is composed of three components: carbon dioxide, propylene and 1,1-difluoroethane. The mass ratio of carbon dioxide, propylene and 1,1-difluoroethane in the mixed refrigerant is 0.1:0.8:0.1, or 0.1:0.75:0.15, or 0.1:0.7:0.2, or 0.1:0.65:0.25, or 0.1:0.6:0.3, or 0.1:0.55:0.35, or 0.1:0.5:0.4, or 0.1:0.45:0.45, or 0.1:0.4:0.5, or 0.12:0.78:0.1, or 0.12:0.68:0.2, or 0.12:0.63:0.25, or 0.12:0.58:0.3, or 0.12:0.53:0.35, or 0.12:0.48:0.4, or 0.12:0.43:0.45, or 0.12:0.38:0.5, or 0.12:0.33:0.55, or 0.15:0.75:0.1, or 0.15:0.7:0.15, or 0.15:0.65:0.2, or 0.15:0.6:0.25, or 0.15:0.55:0.3, or 0.15:0.5:0.35, or 0.15:0.45:0.4, or 0.15:0.4:0.45, or The ratio is 0.15:0.35:0.5, or 0.05:0.85:0.1, or 0.05:0.8:0.15, or 0.05:0.75:0.2, or 0.05:0.7:0.25, or 0.05:0.65:0.3, or 0.05:0.6:0.35, or 0.05:0.55:0.4, or 0.05:0.5:0.45, or 0.05:0.45:0.5.

[0013] As a further preferred aspect of the present application, the mixed refrigerant is composed of carbon dioxide, propylene and trifluoroethylene, and the mass ratio of carbon dioxide, propylene and trifluoroethylene in the mixed refrigerant is 0.05:0.4:0.55, or 0.05:0.45:0.5, or 0.05:0.5:0.45, or 0.05:0.55:0.4, or 0.05:0.6:0.35, or 0.05:0.65:0.3, or 0.1:0.4:0.5, or 0.1:0.45:0.45, or 0.1:0.5:0.4, or 0.1:0.55:0.35, or 0.1:0.6:0.3, or 0.1:0.65:0.25, or 0.1:0.7:0.2, or 0.08:0.42:0.5, or 0.08:0.47:0.45, or 0.08:0.52:0.4, or 0.08:0.57:0.35, or 0.08:0.62:0.3, or 0.15:0.2:0.65, or 0.15:0.25:0.6, or 0.15:0.3:0.55, or 0.15:0.35:0.5, or 0.15:0.4:0.45, or 0.15:0.45:0.4, or 0.15:0.5:0.35.

[0014] According to another aspect of the present application, the present application provides the use of the above-mentioned environmentally friendly mixed refrigerant containing CO2 as a refrigerant.

[0015] As a further preferred aspect of the present application, the use is specifically as a refrigerant for household air conditioners, central air conditioners, heat pump water heaters or automobile air conditioners.

[0016] As a further preferred aspect of the present application, the use is specifically for replacing R32, R410A or R290.

[0017] According to the above technical scheme conceived by the present application, compared with the prior art, the mixed refrigerant in the present application is mixed from at least one of propylene, 1,1-difluoroethane and trifluoroethylene (the sum of the mass percentage concentrations of the components in the mixed refrigerant is 100%), and the advantages and disadvantages of each component as a refrigerant are as follows:

[0018] Carbon dioxide (R744): advantages are large refrigerating capacity per unit volume, non-flammable, safe and environmentally friendly; disadvantages are low COP for refrigeration and heating, high pressure and high exhaust temperature.

[0019] Propylene (R1270): Its advantages are high COP for cooling and heating, environmental protection, moderate pressure and exhaust temperature; its disadvantages are A3 safety level, flammability and explosiveness, and low cooling capacity per unit volume, which is about 60-70% of R32.

[0020] 1,1-Difluoroethane (R152a): Its advantages are high COP for cooling and heating, environmental protection, moderate pressure, and low exhaust temperature. Its disadvantages are its safety level of A2, flammability and explosiveness, and low cooling capacity per unit volume, which is about 30-40% of R32.

[0021] Trifluoroethylene (R1123): The advantage is its large cooling capacity per unit volume; its cooling capacity per unit volume is comparable to that of R32. The disadvantage is its low cooling and heating COP, which is about 10% lower than that of R32. Its safety level is A2L and it is flammable.

[0022] The present invention utilizes at least one of the three components of propylene, 1,1-difluoroethane, and trifluoroethylene to mix with carbon dioxide to form a mixed refrigerant:

[0023] (1) When CO2 is mixed with propylene, or CO2 with propylene and 1,1-difluoroethane, by controlling the ratio of CO2, propylene and 1,1-difluoroethane, the corresponding mixed refrigerant has better cooling and heating COP and unit volume cooling capacity, and can be used to replace R32 and R290 in air conditioning or other refrigeration systems, and achieve the following goals: 1) The cooling and heating COP is higher than that of single-component R32 and R290 air conditioning systems; 2) The unit volume cooling capacity is higher than that of R290 air conditioning systems and reaches 85% or more of R32 air conditioning systems; 3) The flammability of the mixed refrigerant is lower than that of R290 refrigerant; 4) The GWP value of the mixed refrigerant is lower than 150; 5) The exhaust temperature is lower than that of R32 air conditioning systems.

[0024] (2) When CO2 is mixed with R1123, propylene, by controlling the proportion of each component, the corresponding mixed refrigerant has high unit volume refrigeration capacity, and the temperature glide is small. Moreover, when propylene is involved in the system, in addition to the advantages of high unit volume refrigeration capacity, it also has the advantage of high refrigeration and heating COP, which can make up for the low COP of R1123 refrigerant, and the mixed refrigerant has very low GWP value. Based on the present application, the mixed refrigerant obtained by mixing CO2 with R1123 and propylene in a specific mass ratio has the excellent characteristics of high COP, high unit volume refrigeration capacity and low GWP, and is used to replace R32 and applied to air conditioners or other refrigeration systems, and the following goals are achieved: 1) The refrigeration and heating COP is higher than that of the single-component R32 air conditioner system; 2) The unit volume refrigeration capacity is higher than that of the R290 air conditioner, and is higher than or equivalent to that of the R32 air conditioner system; 3) The flammability of the mixed refrigerant is lower than that of the R290 refrigerant; 4) The GWP value of the mixed refrigerant is less than 150; 5) The discharge temperature is lower than that of the R32 air conditioner system.

[0025] The ODP value of the present application is 0, and the GWP value is less than 150, which has outstanding environmental protection advantages. In addition, the mixed refrigerant formed by CO2, flammable refrigerant propylene, 1,1-difluoroethane and trifluoroethylene improves the safety of the mixed refrigerant by using the flame retardant property of CO2.

[0026] Specifically, the mixed refrigerant in the present application can achieve the following beneficial effects:

[0027] 1. The refrigerant used in the present application has a low GWP value. Within the mass concentration range of the mixture involved in the present application, the GWP value of the mixture is not more than 150, which meets the requirements of the F-gas regulation of the European Union for alternative refrigerants, and is used to replace R32 in household air conditioners and automobile air conditioners. According to the existing conventional air conditioner test and application conditions, the refrigeration evaporation temperature is in the range of about 7-13℃, with slight fluctuations under different working conditions; the heating evaporation temperature is about 2℃. If it is a refrigeration and refrigeration application, such as a refrigerator, the evaporation temperature can be as low as -15℃ (for example, a self-recovery refrigerator). The mixed refrigerant obtained by the present application contains CO2. When mixed with other components, if the boiling points of each component differ greatly (that is, the glide temperature is large), the mixed refrigerant in the system needs to be fractionated. The mixed refrigerant for air conditioning application needs to have as low a glide temperature as possible, so as to meet the application conditions of the air conditioner (that is, a refrigerant with too large a glide temperature, such as a mixed refrigerant used in a self-recovery refrigerator, cannot be applied to an air conditioning device). In the present application, at least one of CO2, propylene, 1,1-difluoroethane and trifluoroethylene is mixed, and the proportion of each component is controlled, so that the glide temperature is small, which is very suitable for application in air conditioning systems.

[0028] The refrigerant replacement is one of the bottleneck problems of the air conditioning industry. The currently widely used R32 refrigerant has a high GWP value and belongs to the controlled refrigerant. However, the air conditioning industry widely uses R32, so that the compressor, heat exchanger, throttling mechanism and control method of the air conditioning system are closely matched with R32, and the most important ones are the compressor and the heat exchanger. The R32 has a small size due to a high unit volume refrigerating capacity, so that the R32 air conditioner generally has the characteristics of low cost, low noise and high capacity. At the same time, the heat exchanger of R32 has a small resistance due to a small volume flow and a small specific volume of R32, so that the structure of the heat exchanger does not need to be optimized too much when the heat exchanger is designed. Until now, a replacement refrigerant with similar properties to R32 has not yet appeared.

[0029] In the process of replacing R32 in the current air conditioning industry, R290 is used as a potential replacement, but the physical properties of R290 are too different from those of R32, which are as follows: the unit volume refrigerating capacity of R290 is only about 50% of that of R32. This leads to a large compressor displacement of the R290 air conditioner and a large number of branches of the heat exchanger. This results in high cost, high vibration and noise and poor thermal performance of the R290 air conditioner, especially in the heating performance. R290 has a high flow resistance, so the heat exchanger needs to be designed with multiple branches, which sacrifices the heat transfer performance.

[0030] However, the CO2 refrigerant in the prior art is difficult to be applied to the air conditioner, because: CO2 has a high unit volume refrigerating capacity, but the low critical temperature characteristic of CO2 leads to a low cycle thermodynamic coefficient of the CO2 refrigerant applied in the air conditioning system, which is difficult to meet the requirements of the national standard for the energy efficiency grade of the air conditioner.

[0031] In view of the above problems, how to find a refrigerant with a high unit volume refrigerating capacity (comparable to or not much different from R32) and a high cycle thermodynamic coefficient (meeting the requirements of the national standard for the energy efficiency grade) is the main problem encountered by the air conditioning industry at present.

[0032] The present application uses at least one of propylene, 1,1-difluoroethane and trifluoroethylene to form a mixed refrigerant with carbon dioxide, controls the ratio of each component, realizes a compromise between the thermodynamic coefficient and the unit volume refrigerating capacity, and correspondingly obtains a mixed refrigerant with appropriate temperature glide characteristics, so that the temperature difference between the air conditioner and the cold and heat source is reduced, and the disadvantage of the low thermodynamic characteristic of CO2 is compensated. The mixed refrigerant obtained by the present application has the characteristics of high unit volume refrigerating capacity, high thermodynamic coefficient and appropriate temperature glide, and due to these characteristics, the mixed refrigerant obtained by the present application can be applied to the air conditioning system.

[0033] 2. The refrigerant used in the present application has a low GWP value, and the GWP value of the mixture is not more than 750 in the mass concentration range of the mixture involved in the present application, which meets the requirements of the F-gas regulation of the European Union for alternative refrigerants, and is used to replace R32 and R410A in refrigeration equipment with a refrigeration capacity greater than 12kW.

[0034] 3. The COP value of the refrigerant provided by the present application is higher than that of R32, R410A and R290, and has a significant energy saving advantage.

[0035] 4. The unit volume refrigeration capacity of the refrigerant provided by the present application is close to that of R32 and R410A, and higher than that of R290, which can be directly applied to replace R32 and R410A without changing too many parts, or only changing part of the parts.

[0036] 5. The unit volume refrigeration capacity of the refrigerant provided by the present application is higher than that of R32 under the condition of a specific component ratio.

[0037] 6. The system charging amount of the refrigerant provided by the present application is much smaller than that of R32 and R410A, which can save the amount of refrigerant and reduce the risk of refrigerant leakage.

[0038] 7. The refrigerant provided by the present application has a lower exhaust temperature than R32, which is beneficial to improve the low-temperature heating capacity, and is also beneficial to the operation of the refrigeration compressor, so that the refrigeration compressor has higher reliability.

[0039] 8. The CO2 component of the refrigerant of the present application can reduce the combustion characteristics of the mixed refrigerant and improve the safety of the refrigerant application.

[0040] In summary, the refrigerant provided by the present application is a mixed refrigerant, which has high energy efficiency, can be used to directly replace R32 without changing the refrigeration parts, has high COP, low exhaust temperature, large unit volume refrigeration capacity and small refrigerant charging amount. The ODP value of the present application is 0, and the GWP value is less than 150, which has outstanding environmental protection advantages and wide application prospects, and can be used to replace high GWP refrigerants such as R32 and R410A. It is applicable to household and commercial air conditioning systems, heat pump water heaters, automobile air conditioners and other refrigeration equipment. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and not to limit the present application. In addition, the technical features involved in each embodiment of the present application described below can be combined with each other as long as they do not conflict with each other.

[0042] The mixed refrigerant in the present application is composed of two, three or more of carbon dioxide (R744), propylene (R1270), trifluoroethylene (R1123) and 1,1-difluoroethane (R152a), wherein the proportion of carbon dioxide is 1-30%, which is a necessary component.

[0043] The basic physical properties of the four components are shown in Table 1.

[0044] Table 1: Basic physical properties of the four components

[0045]

[0046]

[0047] Based on the present application, the mixed refrigerant formed by the above components can be prepared by using the conventional method of the prior art, for example, comprising the following steps: mixing gaseous carbon dioxide, gaseous trifluoroethylene, gaseous propylene and gaseous 1,1-difluoroethane in proportion to obtain the mixed refrigerant.

[0048] For another example, the preparation method can also comprise the following steps: mixing liquid carbon dioxide, liquid trifluoroethylene, liquid propylene and liquid 1,1-difluoroethane in proportion to obtain the mixed refrigerant.

[0049] The above refrigerant can be mutually dissolved according to the principle of similar dissolves similar, so that it can be physically mixed in the refrigerant tank according to the weight ratio in the order of boiling point from high to low. Or according to the weight ratio, pour into the compressor in the order of boiling point from high to low, and mix uniformly for use.

[0050] The following are specific examples:

[0051] Example 1: Take pure carbon dioxide and pure propylene refrigerant, in liquid phase, take 8% of carbon dioxide, 92% of propylene in mass percentage to physically mix thoroughly, and obtain the mixed refrigerant.

[0052] Example 2: Take pure carbon dioxide, pure propylene and pure 1,1-difluoroethane refrigerant, in liquid phase, take 10% of carbon dioxide, 60% of propylene and 30% of 1,1-difluoroethane in mass percentage to physically mix thoroughly, and obtain the mixed refrigerant.

[0053] Example 3: Take pure carbon dioxide, pure propylene and pure 1,1-difluoroethane refrigerant, in liquid phase, take 12% of carbon dioxide, 58% of propylene and 30% of 1,1-difluoroethane in mass percentage to physically mix thoroughly, and obtain the mixed refrigerant.

[0054] Example 4: Take pure carbon dioxide, pure propylene and pure trifluoroethylene refrigerant, in liquid phase, take 8% of carbon dioxide, 42% of propylene and 50% of trifluoroethylene by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0055] Example 5: Take pure carbon dioxide, pure propylene and pure trifluoroethylene refrigerant, in liquid phase, take 10% of carbon dioxide, 30% of propylene and 60% of trifluoroethylene by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0056] Example 6: Take pure carbon dioxide and pure propylene refrigerant, in liquid phase, take 5% of carbon dioxide and 95% of propylene by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0057] Example 7: Take pure carbon dioxide and pure propylene refrigerant, in liquid phase, take 12% of carbon dioxide and 88% of propylene by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0058] Example 8: Take pure carbon dioxide, pure propylene and 1,1-difluoroethane refrigerant, in liquid phase, take 5% of carbon dioxide, 45% of propylene and 50% of 1,1-difluoroethane by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0059] Example 9: Take pure carbon dioxide, pure propylene and 1,1-difluoroethane refrigerant, in liquid phase, take 10% of carbon dioxide, 80% of propylene and 10% of 1,1-difluoroethane by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0060] Example 10: Take pure carbon dioxide, pure propylene and 1,1-difluoroethane refrigerant, in liquid phase, take 10% of carbon dioxide, 40% of propylene and 50% of 1,1-difluoroethane by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0061] Example 11: Take pure carbon dioxide, pure propylene and 1,1-difluoroethane refrigerant, in liquid phase, take 15% of carbon dioxide, 33% of propylene and 52% of 1,1-difluoroethane by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0062] Example 12: Take pure carbon dioxide, pure propylene and 1,1-difluoroethane refrigerant, in liquid phase, take 15% of carbon dioxide, 30% of propylene and 55% of 1,1-difluoroethane by mass percentage to carry out sufficient physical mixing, and obtain a mixed refrigerant.

[0063] Example 13: Take pure carbon dioxide, pure propylene and 1,1-difluoroethane refrigerant, in liquid phase, take 15% of carbon dioxide, 75% of propylene, 10% of 1,1-difluoroethane for sufficient physical mixing, obtain mixed refrigerant.

[0064] Example 14: Take pure carbon dioxide, pure propylene and trifluoroethylene refrigerant, in liquid phase, take 5% of carbon dioxide, 40% of propylene, 55% of trifluoroethylene for sufficient physical mixing, obtain mixed refrigerant.

[0065] Example 15: Take pure carbon dioxide, pure propylene and trifluoroethylene refrigerant, in liquid phase, take 5% of carbon dioxide, 65% of propylene, 30% of trifluoroethylene for sufficient physical mixing, obtain mixed refrigerant.

[0066] Example 16: Take pure carbon dioxide, pure propylene and trifluoroethylene refrigerant, in liquid phase, take 10% of carbon dioxide, 40% of propylene, 50% of trifluoroethylene for sufficient physical mixing, obtain mixed refrigerant.

[0067] Example 17: Take pure carbon dioxide, pure propylene and trifluoroethylene refrigerant, in liquid phase, take 10% of carbon dioxide, 70% of propylene, 20% of trifluoroethylene for sufficient physical mixing, obtain mixed refrigerant.

[0068] Example 18: Take pure carbon dioxide, pure propylene and trifluoroethylene refrigerant, in liquid phase, take 15% of carbon dioxide, 20% of propylene, 65% of trifluoroethylene for sufficient physical mixing, obtain mixed refrigerant.

[0069] Example 19: Take pure carbon dioxide, pure propylene and trifluoroethylene refrigerant, in liquid phase, take 15% of carbon dioxide, 50% of propylene, 35% of trifluoroethylene for sufficient physical mixing, obtain mixed refrigerant.

[0070] For comparison of performance, the above examples are calculated with R32 and R290 in the theoretical cycle of air conditioning system, taking the refrigeration working condition of air conditioner as: the evaporation temperature is 10℃, the condensation temperature is 47.5℃, the condenser outlet temperature is 38℃, the compressor inlet temperature is 20℃, the compressor isentropic efficiency is 0.7; the heating working condition is: the evaporation temperature is 2℃, the condensation temperature is 45℃, the condenser outlet temperature is 35℃, the compressor inlet temperature is 5℃, the compressor isentropic efficiency is 0.7. The obtained calculation parameters are shown in Table 2 and Table 3.

[0071] Table 2: Refrigeration cycle performance parameters of R32, R290 and examples 1-5

[0072]

[0073] Table 3: Heating cycle performance parameters of R32, R290 and Examples 1-5

[0074]

[0075] According to the theoretical calculation results of the above working conditions, it can be concluded that:

[0076] 1. The mixed refrigerant in Example 1 has a GWP of approximately 20, a COP 11% higher than that of an R32 direct cooling cycle, and a unit volumetric cooling capacity of 80.7% of that of an R32 system. The exhaust temperature is 73.27°C, approximately 30°C lower than that of an R32 system. The heating COP is 2.2% higher than that of an R32 system, and the volumetric heating capacity is 75.9% of that of an R32 system. This eliminates the need for compressor replacement in R32 air conditioning applications.

[0077] 2. The mixed refrigerant in Example 2 has a GWP of approximately 49.3, a COP 18.9% higher than that of the R32 direct cooling cycle, and a unit volumetric cooling capacity of 87.9% of that of the R32 system. The exhaust temperature is 70.43°C, approximately 32°C lower than that of the R32 system. The heating COP is 2.4% higher than that of the R32 system, and the volumetric heating capacity is 78.1% of that of the R32 system. This eliminates the need for compressor replacement in R32 air conditioning applications.

[0078] 3. The mixed refrigerant in Example 3 has a GWP of approximately 48.92, a COP 13.9% higher than that of the R32 direct cooling cycle, and a unit volumetric cooling capacity of 90.1% of that of the R32 system. The exhaust temperature is 72.6°C, approximately 30°C lower than that of the R32 system. The heating COP is approximately 1.5% lower than that of the R32 system, and the volumetric heating capacity is 79.8% of that of the R32 system. This eliminates the need for compressor replacement in R32 air conditioning applications.

[0079] 4. The mixed refrigerant in Example 4 has a GWP value of <3, a COP 15.8% higher than the R32 direct cooling cycle, and a unit volumetric cooling capacity 7.4% higher than that of the R32 system. The exhaust temperature is 65.72°C, approximately 37°C lower than that of the R32 system. The heating COP and volumetric heating capacity are comparable to those of the R32 system. When replacing R32 in air conditioning applications, the compressor size can remain unchanged, resulting in higher energy efficiency.

[0080] 5. The mixed refrigerant in Example 5 has a GWP value of <3, a COP 12.5% ​​higher than the R32 direct cooling cycle, and a unit volumetric cooling capacity 13.5% higher than that of the R32 system. The exhaust temperature is 65.33°C, approximately 37°C lower than that of the R32 system. The heating COP is 2.8% higher than that of the R32 system, and the volumetric heating capacity is 9% higher. When replacing R32 in air conditioning applications, the compressor size can be further reduced, achieving higher energy efficiency.

[0081] In addition, the mixed refrigerants obtained in Examples 6-19 also have relatively good thermal performance (of course, the overall performance is slightly inferior to that of Examples 1-5), as shown in Tables 4 to 6.

[0082] Table 4: Thermodynamic properties of the mixed refrigerants obtained in Examples 6-7

[0083]

[0084]

[0085] Table 5: Thermodynamic properties of the mixed refrigerants obtained in Examples 8-13

[0086]

[0087] Table 6: Thermodynamic properties of the mixed refrigerants obtained in Examples 14-19

[0088]

[0089]

[0090] As can be seen, the mixed refrigerant of the present invention is environmentally friendly, has no ozone-damaging effects, and exhibits a very low greenhouse effect. The GWP of each of the above embodiments does not exceed 150, meeting the EU F-gas regulations for environmentally friendly refrigerants for household air conditioners. The present invention can be widely used in various refrigeration applications, particularly in household air conditioners, central air conditioners, heat pump water heaters, automotive air conditioners, and other refrigeration systems.

[0091] It will be easily understood by those skilled in the art that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An environmentally friendly mixed refrigerant containing CO2, characterized in that: The mixed refrigerant is composed of three components: carbon dioxide, propylene, and 1,1-difluoroethane, wherein the mass percentage of carbon dioxide in the mixed refrigerant is 5% to 15%, the mass percentage of propylene in the mixed refrigerant is 33% to 85%, and the mass percentage of 1,1-difluoroethane in the mixed refrigerant is 10% to 55%; the GWP value of the mixed refrigerant is less than 150; Alternatively, the mixed refrigerant is composed of three components: carbon dioxide, propylene and trifluoroethylene, wherein the mass percentage of carbon dioxide in the mixed refrigerant is 5% to 15%, the mass percentage of propylene in the mixed refrigerant is 20% to 70%, and the mass percentage of trifluoroethylene in the mixed refrigerant is 20% to 65%; the GWP value of the mixed refrigerant is less than 150.

2. The environmentally friendly mixed refrigerant containing CO2 as claimed in claim 1, characterized in that: The mixed refrigerant is composed of three components: carbon dioxide, propylene and 1,1-difluoroethane. The mass ratio of carbon dioxide, propylene and 1,1-difluoroethane in the mixed refrigerant is 0.1:0.8:0.1, or 0.1:0.75:0.15, or 0.1:0.7:0.2, or 0.1:0.65:0.25, or 0.1:0.6:0.3, or 0.1:0.55:0.35, or 0.1:0.5:0 .4, or 0.1:0.45:0.45, or 0.1:0.4:0.5, or 0.12:0.78:0.1, or 0.12:0.68:0.2, or 0.12:0.63:0.25, or 0.12:0.58:0.3, or 0.12:0.53:0.35, or 0.12:0.48:0.4, or 0.12:0.43:0.45, or 0.12:0 .38:0.5, or 0.12:0.33:0.55, or 0.15:0.75:0.1, or 0.15:0.7:0.15, or 0.15:0.65:0.2, or 0.15:0.6:0.25, or 0.15:0.55:0.3, or 0.15:0.5:0.35, or 0.15:0.45:0.4, or 0.15:0.4:0.45, or 0 .15:0.35:0.5, or 0.05:0.85:0.1, or 0.05:0.8:0.15, or 0.05:0.75:0.2, or 0.05:0.7:0.25, or 0.05:0.65:0.3, or 0.05:0.6:0.35, or 0.05:0.55:0.4, or 0.05:0.5:0.45, or 0.05:0.45:0.

5.

3. The environmentally friendly mixed refrigerant containing CO2 as claimed in claim 1, characterized in that: The mixed refrigerant is composed of three components: carbon dioxide, propylene and trifluoroethylene. The mass ratio of carbon dioxide, propylene and trifluoroethylene in the mixed refrigerant is 0.05:0.4:0.55, or 0.05:0.45:0.5, or 0.05:0.5:0.45, or 0.05:0.55:0.4, or 0.05:0.6:0.35, or 0.05:0.65:0.3, or 0.1:0.4:0.5, or 0.1:0.45:0.45, or 0.1:0.5:0.4, or 0.1:0.55:0.35, or 0.1:0.6:0.3, or 0.1:0.65:0.25, or 0.1:0.7:0.2, or 0.08:0.42:0.5, or 0.08:0.47:0.45, or 0.08:0.52:0.4, or 0.08:0.57:0.35, or 0.08:0.62:0.3, or 0.15:0.2:0.65, or 0.15:0.25:0.6, or 0.15:0.3:0.55, or 0.15:0.35:0.5, or 0.15:0.4:0.45, or 0.15:0.45:0.4, or 0.15:0.5:0.

35.

4. Use of the environmentally friendly mixed refrigerant containing CO2 as claimed in any one of claims 1 to 3 as a refrigerant.

5. The use according to claim 4, characterized in that The application is specifically as a refrigerant for household air conditioners, central air conditioners, heat pump water heaters or automobile air conditioners.

6. The use according to claim 4, characterized in that The application is specifically to replace R32, R410A or R290.

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