A heat transfer composition and its application

Abstract

The present application discloses a heat transfer composition, which includes HFC-32, HFC-125, HFC-134a, HFO-1234yf, HFC-152a; or includes HFC-32, HFC-125, HFC-134a, HFO-1234yf, CF3I, and has a GWP value of less than 1500. It can directly replace R-404A in a heat transfer system designed for R-404A without changing any components, and has excellent refrigeration effect in low-temperature freezing, fast cooling rate and low energy consumption.

Description

Technical Field

[0001] The present application relates to the field of refrigeration, and in particular to a heat transfer composition and its application and a heat transfer system. Background Art

[0002] Refrigerants are the medium used to complete energy conversion in various heat engines, mainly fluorine-containing refrigerants. Fluorine refrigerants are made from hydrofluoric acid and chlorinated hydrocarbons as raw materials. They are important organic fluorine chemical products with strong chemical stability and excellent thermodynamic properties. They are mainly used in refrigerators, household air conditioners, automotive air conditioners, low-temperature refrigeration and other refrigeration fields, driving and supporting trillions of related industries.

[0003] Due to environmental issues, hydrofluorocarbons (HFCs) and their compositions used today are gradually being replaced because of their relatively high GWP values ​​(global warming potential). More and more low GWP fluids, such as hydrofluoroolefins (HFOs), are being studied and applied. Many governments have signed the Kyoto Protocol to protect the global environment and propose to reduce CO2 emissions. Therefore, alternatives to HFCs with high GWP values ​​are needed.

[0004] Low temperature refrigeration systems are particularly important for the food manufacturing, distribution and retail industries, as they ensure that the food delivered to consumers is fresh and suitable for consumption. In such low temperature refrigeration systems, the commonly used refrigerant is R-404A, which has the composition of R125 / 143a / 134a44 / 52 / 4%. The GWP value of R-404A is 3922. The Kyoto Protocol proposes a reduction in this high GWP refrigerant. Since 2015, developed countries and regions such as the European Union and Japan have proposed a motion to ban its use.

[0005] At present, there are many kinds of mixed refrigerants that can replace R-404A, with GWP values ​​ranging from below 150 to around 2000. For example, R-407 series and R-448~R-454, etc., through comparison, it is found that the compositions with GWP values ​​below 150 are flammable and belong to the A2 level. There are certain safety risks when the charge volume is large. Refrigerants with GWP values ​​between 1000 and 1500 belong to the A1 level, which is safe and reliable, and will not be eliminated in the short term. It is the focus of research and development, and many companies have important layouts.

[0006] The composition of the present application contains five components, which has R134a and R152a in addition to the four components R32, R125, R1234yf and CF3I mentioned in the CN111788277A patent. Adding them can reduce the exhaust temperature of the system. The low exhaust temperature can protect the compressor without causing high pressure and high temperature alarm protection, and can avoid the use of expensive control measures for monitoring.

[0007] Compared with the four-component composition of R32, R125, R1234yf and R134a mentioned in the comparative document CN102947410A, the present application adds R152a or CF3I, which can reduce the GWP value of the composition, improve the flammability of the composition, and make it safer and more environmentally friendly. Summary of the invention

[0008] In view of the above situation, the purpose of the present application is to provide a heat transfer composition and its application and a heat transfer system, which can directly replace R-404A in a heat transfer system designed for R-404A without changing any components, and has excellent refrigeration effect in low-temperature freezing, fast cooling rate and low energy consumption.

[0009] An embodiment of the present application provides a heat transfer composition, which includes HFC-32, HFC-125, HFC-134a, HFO-1234yf, HFC-152a; or includes HFC-32, HFC-125, HFC-134a, HFO-1234yf, and CF3I.

[0010] Preferably, the heat transfer composition comprises the following components in percentage by weight:

[0011] HFC-32 16.0%-27.0%,

[0012] HFC-125 27.0%-38.5%,

[0013] HFC-134a 14.0%-24.5%,

[0014] HFO-1234yf 15.0%-32.0%,

[0015] HFC-152a 1.0%-4.0%;

[0016] The sum of the mass percentages of the above components is 100%.

[0017] Preferably, the heat transfer composition comprises the following components in percentage by weight:

[0018] HFC-32 19.0%-26.5%,

[0019] HFC-125 19.5%-30.0%,

[0020] HFC-134a 20.0%-28.0%,

[0021] HFO-1234yf 15.0%-30.0%,

[0022] CF3I 3.0%-8.0%;

[0023] The sum of the mass percentages of the above components is 100%.

[0024] Preferably, the heat transfer composition consists of the following components in percentage by weight: HFC-32 16.0%, HFC-125 38.0%, HFC-134a 14.0%, HFO-1234yf 31.0%, and HFC-152a 1.0%.

[0025] Preferably, the heat transfer composition consists of the following components in percentage by weight: HFC-32 20.0%, HFC-125 27.0%, HFC-134a 19.0%, HFO-1234yf 32.0%, and HFC-152a 2.0%.

[0026] Preferably, the heat transfer composition consists of the following components in percentage by weight: HFC-32 26.0%, HFC-125 31.0%, HFC-134a 24.0%, HFO-1234yf 15.0%, and HFC-152a 4.0%.

[0027] Preferably, the heat transfer composition consists of the following components in percentage by weight: HFC-32 20.0%, HFC-125 26.0%, HFC-134a 21.0%, HFO-1234yf 30.0%, and CF3I 3.0%.

[0028] Preferably, the heat transfer composition consists of the following components in percentage by weight: HFC-32 24.0%, HFC-125 29.0%, HFC-134a 24.0%, HFO-1234yf 16.0%, and CF3I 7.0%.

[0029] Preferably, the heat transfer composition consists of the following components in percentage by weight: HFC-32 26.0%, HFC-125 20.0%, HFC-134a 28.0%, HFO-1234yf 21.0%, and CF3I 5.0%.

[0030] Preferably, the heat transfer composition is used as a replacement refrigerant for R-404A.

[0031] The present application also provides the use of the heat transfer composition in a heat transfer system of R-404A to replace R-404A.

[0032] The embodiment of the present application also provides a heat transfer system, which uses the above-mentioned heat transfer composition as the heat transfer medium, and has a better effect when the lubricating oil is a mixture of mineral oil and polyol ester (POE) oil.

[0033] One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:

[0034] 1. The heat transfer composition provided in this application has an ODP value of zero and a GWP of <1500. It is an environmentally friendly refrigerant and is non-flammable, belonging to Class A1 refrigerant.

[0035] 2. The heat transfer composition provided in this application can be used to replace R-404A. The temperature and pressure in each area during system operation are close to those of R-404A. It can perfectly replace the operation of R-404A in the system, shorten the cooling time, and reduce energy consumption.

[0036] 3. The heat transfer composition provided in the present application can be used to replace R-404A, and the COP under the same working conditions is increased by more than 10% compared with R404A.

[0037] 4. The heat transfer composition provided in the present application can be used in place of R-404A, and can reduce the exhaust temperature of the compressor during system operation, thereby better protecting the compressor and the system.

[0038] 5. When the lubricating oil in the system of the heat transfer composition provided by the present application is a mixture of mineral oil and polyol ester (POE) oil, the heat transfer system runs more smoothly and is more energy-efficient. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a temperature-gas-liquid phase pressure comparison diagram of the heat transfer composition in Example 1 of the present application and R-404A;

[0040] Figure 2 This is a temperature-gas-liquid phase pressure comparison diagram of the heat transfer composition in Example 2 of the present application and R-404A;

[0041] Figure 3 A temperature-gas-liquid phase pressure comparison diagram of the heat transfer composition in Example 3 of the present application and R-404A;

[0042] Figure 4 This is a temperature-gas-liquid phase pressure comparison diagram of the heat transfer composition in Example 4 of the present application and R-404A;

[0043] Figure 5 This is a temperature-gas-liquid phase pressure comparison diagram of the heat transfer composition in Example 5 of the present application and R-404A;

[0044] Figure 6 This is a temperature-gas-liquid phase pressure comparison diagram of the heat transfer composition in Example 6 of the present application and R-404A; DETAILED DESCRIPTION

[0045] In order to facilitate the understanding of the present application scheme by those skilled in the art, the present application scheme is further elaborated below in conjunction with specific embodiments. It should be understood that the embodiments of the present application are explanations of the present application scheme and are not intended to limit the scope of protection of the present application.

[0046] The embodiment of the present application provides a heat transfer composition, which can directly replace R-404A and does not require any components to be changed during the replacement process. The heat transfer composition has an excellent refrigeration effect in low-temperature freezing, a fast cooling rate and low energy consumption.

[0047] The technical solution in the embodiment of the present application is to solve the above problems, and the overall idea is as follows:

[0048] An embodiment of the present application provides a heat transfer composition, which includes HFC-32, HFC-125, HFC-134a, HFO-1234yf, HFC-152a; or includes HFC-32, HFC-125, HFC-134a, HFO-1234yf, and CF3I.

[0049] In a preferred embodiment of the present application, the heat transfer composition comprises the following components in percentage by weight:

[0050] HFC-32 16.0%-27.0%,

[0051] HFC-125 27.0%-38.5%,

[0052] HFC-134a 14.0%-24.5%,

[0053] HFO-1234yf 15.0%-32.0%,

[0054] HFC-152a 1.0%-4.0%;

[0055] The sum of the mass percentages of the above components is 100%.

[0056] In a preferred embodiment of the present application, the heat transfer composition comprises the following components in percentage by mass:

[0057] HFC-32 19.0%-26.5%,

[0058] HFC-125 19.5%-30.0%,

[0059] HFC-134a 20.0%-28.0%,

[0060] HFO-1234yf 15.0%-30.0%,

[0061] CF3I 3.0%-8.0%;

[0062] The sum of the mass percentages of the above components is 100%.

[0063] In a preferred embodiment of the present application, the heat transfer composition is composed of the following components in percentage by mass: HFC-32 16.0%, HFC-125 38.0%, HFC-134a 14.0%, HFO-1234yf 31.0%, and HFC-152a 1.0%.

[0064] Or the heat transfer composition is composed of the following components in percentage by weight: HFC-32 20.0%, HFC-125 27.0%, HFC-134a 19.0%, HFO-1234yf 32.0%, and HFC-152a 2.0%.

[0065] Or the heat transfer composition is composed of the following components in percentage by weight: HFC-32 26.0%, HFC-125 31.0%, HFC-134a 24.0%, HFO-1234yf 15.0%, and HFC-152a 4.0%.

[0066] Or the heat transfer composition is composed of the following components in percentage by weight: HFC-32 20.0%, HFC-125 26.0%, HFC-134a 21.0%, HFO-1234yf 30.0%, and CF3I 3.0%.

[0067] Or the heat transfer composition is composed of the following components in percentage by weight: HFC-32 24.0%, HFC-125 29.0%, HFC-134a 24.0%, HFO-1234yf 16.0%, and CF3I 7.0%.

[0068] Or the heat transfer composition is composed of the following components in percentage by weight: HFC-32 26.0%, HFC-125 20.0%, HFC-134a 28.0%, HFO-1234yf 21.0%, and CF3I 5.0%.

[0069] The heat transfer composition provided in the embodiments of the present application is used as a replacement refrigerant for R-404A.

[0070] The heat transfer composition provided in the embodiments of the present application can be used to replace R-404A in the heat transfer system of R-404A.

[0071] The embodiment of the present application also provides a heat transfer system, which uses the above-mentioned heat transfer composition as the heat transfer medium, and has a better effect when the lubricating oil is a mixture of mineral oil and polyol ester (POE) oil.

[0072] The heat transfer composition provided in the present application can be obtained by physically mixing the above-mentioned various components according to corresponding proportions in a liquid phase state.

[0073] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods, but it does not serve as a limitation to the present application.

[0074] Example

[0075] Table 1 Component ratio of heat transfer composition

[0076]

[0077]

[0078] The heat transfer compositions in Examples 1-6 and R-404A in Comparative Example 1 were tested for temperature-liquid phase pressure change and temperature-gas phase pressure change, and the results were as follows: Figure 1-6 The temperature-gas-liquid phase pressure comparison diagrams are shown in the figures. It can be seen from these figures that the temperature-gas-liquid phase pressure variation curves of the heat transfer composition provided in the present application are extremely close to those of R-404A, that is, the temperature and pressure of each region when operating in the refrigeration system are relatively close to those of R-404A. Therefore, it can perfectly replace R-404A in the refrigeration system designed for R-404A and operate in the system.

[0079] Comparative Examples 2-5 are compositions with the same components as the present invention, but with a composition ratio outside the scope of the claims, and Comparative Examples 6 and 7 are heat transfer compositions disclosed in the prior art CN102947410A and CN111788277A. The following tests will be compared under the same operating conditions.

[0080] Refrigeration performance test:

[0081] The refrigeration performance of Examples 1-6 and Comparative Examples 1-7 was tested on a loaded ultra-low temperature freezer. Three parallel experiments were conducted for each formulation, and the average value was taken to compare the cooling rate and power consumption. Test conditions: ambient temperature 30°C, ultra-low temperature freezer load and set temperature of -45°C, evaporation temperature of -55°C. The test results are shown in Tables 2 and 3.

[0082] Table 2 Time taken for the temperature in the ultra-low temperature freezer to drop to the specified temperature

[0083]

[0084] Table 3 Power consumption when the temperature in the ultra-low temperature freezer drops to a specified temperature

[0085]

[0086] According to the experimental data in Table 2 and Table 3, it can be seen that when the temperature in the loaded ultra-low temperature freezer is reduced to -45°C, the average cooling time when the heat transfer composition of Examples 1-6 is used is shortened by 13% to 20% compared with R-404A in Comparative Example 1, which significantly shortens the cooling time; the power consumption is also reduced by 12% to 19%, which has a significant effect of improving efficiency and saving energy. Compared with Comparative Examples 2-7, Examples 1-6 also shorten the cooling time and are more energy-efficient.

[0087] Examples 1-6 and comparative examples 1-7 were tested on a refrigerant performance test platform. The test conditions were condensing end temperature / evaporating end temperature of 25°C / -20°C, 30°C / -20°C, and 40°C / -20°C. The cooling capacity and COP were tested respectively. The test results are shown in Tables 4, 5 and 6.

[0088] Table 4 Comparison of refrigeration capacity and COP of different compositions at 25℃

[0089]

[0090]

[0091] According to the experimental data in Table 4, when the ambient temperature on the condensing side is 25°C, the temperature is reduced to -20°C and remains stable. Compared with Comparative Example 1, the refrigeration capacity of Examples 1-6 is increased by 4% to 9%, and the COP is increased by 7% to 14%. Compared with Comparative Examples 2-7, the refrigeration capacity and COP of Examples 1-6 are also improved to varying degrees. The exhaust temperature of Examples 1-6 is about 10°C lower than that of Comparative Example 1, and more than 20°C lower than that of Comparative Example 7, which can better protect the compressor.

[0092] Table 5 Comparison of refrigeration capacity and COP of different compositions at 30℃

[0093]

[0094] According to the experimental data in Table 5, when the ambient temperature on the condensing side is 30°C, the temperature is reduced to -20°C and remains stable. Compared with Comparative Example 1, the refrigeration capacity of Examples 1-6 is increased by 3% to 8%, and the COP is increased by 4% to 11%. Compared with Comparative Examples 2-7, the refrigeration capacity and COP of Examples 1-6 are also improved to varying degrees. The exhaust temperature of Examples 1-6 is more than 10°C lower than that of Comparative Example 1, and about 25°C lower than that of Comparative Example 7, which can better protect the compressor.

[0095] Table 6 Comparison of refrigeration capacity and COP of different compositions at 40℃

[0096]

[0097] According to the experimental data in Table 6, when the ambient temperature on the condensing side is 40°C, the temperature is reduced to -20°C and remains stable. Compared with Comparative Example 1, the cooling capacity of Examples 1-6 is increased by 2% to 7%, and the COP is increased by 3% to 10%. Compared with Comparative Examples 2-7, the cooling capacity and COP of Examples 1-6 are also improved to varying degrees. The exhaust temperature of Examples 1-6 is about 15°C lower than that of Comparative Example 1, and more than 25°C lower than that of Comparative Example 7, which can better protect the compressor.

[0098] Since CF3I is more miscible with mineral oil, Examples 4-6 will generate more foam when running in the equipment. Therefore, different lubricating oils are mixed and used. Example 4 continues to be tested on the refrigerant performance test platform. The test conditions are: condensing end temperature / evaporating end temperature: 30°C / -20°C, respectively. The cooling capacity and COP are also tested. The test results are shown in Table 7.

[0099] Table 7 Comparison of refrigeration capacity and COP of Example 4 at different lubricating oil compositions at 30°C

[0100]

[0101] According to the experimental data in Table 7, it can be seen that when the ambient temperature on the condensing side is 30°C, it is cooled to -20°C and remains stable. When different mixed lubricants are used, the refrigeration capacity does not change much, the compressor power will drop significantly, and the COP is increased by 5%, 8% and 2% respectively compared with Example 4; compared with Comparative Example 1, the COP is increased by 17%, 20% and 14%, and the energy-saving effect is obvious.

[0102] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application and are not intended to limit it. Although the present application has been described in detail with reference to the preferred embodiments, a person of ordinary skill in the art should understand that the technical solution of the present application can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution of the present application, which should be included in the scope of the claims of the present application.

Claims

1. A heat transfer composition, characterized in that: The heat transfer composition is composed of the following components in percentage by mass: The sum of the mass percentages of the above components is 100%; Or the heat transfer composition consists of the following components in percentage by mass: The sum of the mass percentages of the above components is 100%.

2. The heat transfer composition according to claim 1, characterized in that The heat transfer composition is composed of the following components in percentage by mass: HFC-32 16.0%, HFC-125 38.0%, HFC-134a 14.0%, HFO-1234yf 31.0%, HFC-152a 1.0%; or HFC-32 20.0%, HFC-125 27.0%, HFC-134a 19.0%, HFO-1234yf 32.0%, HFC-152a 2.0%; or HFC-32 26.0%, HFC-125 31.0%, HFC-134a 24.0%, HFO-1234yf 15.0%, HFC-152a 4.0%; or HFC-32 20.0%, HFC-125 26.0%, HFC-134a 21.0%, HFO-1234yf 30.0%, CF3I 3.0%; or HFC-32 24.0%, HFC-125 29.0%, HFC-134a 24.0%, HFO-1234yf16.0%, CF3I 7.0%; or HFC-32 26.0%, HFC-125 20.0%, HFC-134a 28.0%, HFO-1234yf21.0%, CF3I 5.0%.

3. The heat transfer composition according to any one of claims 1 to 2, characterized in that The heat transfer composition is used as a substitute refrigerant for R-404A, and the COP under the same working conditions is increased by more than 10% compared with R404A, and the cooling time can be shortened and the energy consumption can be reduced.

4. Use of the heat transfer composition according to any one of claims 1 to 3 to replace R-404A in a heat transfer system of R-404A.

5. A heat transfer system using the heat transfer composition of claims 1-3.

6. The heat transfer system according to claim 5, characterized in that The heat transfer system is a heat transfer system designed for R-404A, and the R-404A in the heat transfer system is replaced by the heat transfer composition.

7. A composition, characterized in that The invention comprises the heat transfer composition according to claims 1 to 3 and lubricating oil.

8. The composition according to claim 7, characterized in that The lubricating oil is mineral oil and / or polyol ester (POE) oil.

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