阅读说明：本技术 一种传热组合物及其应用与传热系统 (Heat transfer composition, application thereof and heat transfer system ) 是由 王斌辉 王树华 宓宏 李行行 童灿辉 马列军 付磊 王双双 王金明 于 2021-09-26 设计创作，主要内容包括：本申请公开了一种传热组合物及其应用以及传热系统,涉及制冷领域,该传热组合物包括HFC-32、HFC-125、HFC-134a、HFC-143a和HC-600a,其能够在为R-22或R-404A设计的传热系统中直接替换R-22或R-404A而不需要替换传热系统中的润滑油和改变任何组件,且在低温冷冻上具有优异的制冷效果,降温速率快且能耗低。(Disclosed herein are a heat transfer composition, an application thereof, and a heat transfer system, relating to the field of refrigeration, the heat transfer composition comprising HFC-32, HFC-125, HFC-134A, HFC-143a and HC-600a, capable of directly replacing R-22 or R-404A in a heat transfer system designed for R-22 or R-404A without replacing lubricating oil in the heat transfer system and changing any components, and having excellent refrigeration effect on low temperature freezing, fast cooling rate and low energy consumption.)

1. A heat transfer composition comprising HFC-32, HFC-125, HFC-134a, HFC-143a and HC-600 a.

2. The heat transfer composition of claim 1, wherein the heat transfer composition comprises the following components in percent by mass:

HFC-32 6.0％-23.0％，

HFC-125 41.5％-60.0％，

HFC-134a 23.0％-40.0％，

HFC-143a 1.0％-7.0％，

HC-600a 1.0％-4.0％；

the sum of the mass percentages of the components is 100 percent.

3. The heat transfer composition of claim 1, wherein the heat transfer composition comprises the following components in percent by mass:

HFC-32 7％-21.2％，

HFC-125 42.1％-57％，

HFC-134a 24.6％-39.5％，

HFC-143a 1％-6％，

HC-600a 1％-3％；

the sum of the mass percentages of the components is 100 percent.

4. The heat transfer composition of claim 1, wherein the heat transfer composition is comprised of the following components in mass percent: HFC-327.0%, HFC-12545.5%, HFC-134a 39.5%, HFC-143a 6.0%, HC-600a 2.0%.

5. The heat transfer composition of claim 1, wherein the heat transfer composition is comprised of the following components in mass percent: HFC-3219.6%, HFC-12549%, HFC-134a 24.6%, HFC-143a 5.1%, HC-600a 1.7%.

6. The heat transfer composition of claim 1, wherein the heat transfer composition is comprised of the following components in mass percent: HFC-3210.0%, HFC-12557%, HFC-134a 25%, HFC-143a 6%, HC-600a 2%.

7. The heat transfer composition of claim 1, wherein the heat transfer composition is comprised of the following components in mass percent: HFC-3221.2%, HFC-12542.1%, HFC-134a 33.7%, HFC-143a 1%, HC-600a 2%.

8. A heat transfer composition according to any of claims 1-7 wherein said heat transfer composition is used as a replacement refrigerant for R-22 or R-404A.

9. Use of a heat transfer composition according to any one of claims 1 to 7 in a heat transfer system for R-22 or R-404A in place of R-22 or R-404A.

10. A heat transfer system comprising the heat transfer composition of any of claims 1-7 as a heat transfer medium.

11. A heat transfer system according to claim 10 wherein the heat transfer system is an automotive air conditioning system, a domestic air conditioner, a commercial air conditioner, a domestic refrigeration system, a commercial refrigeration system, a heat pump or a chiller cooling system.

12. The heat transfer system of claim 10 wherein the heat transfer system is a heat transfer system designed for R-22 or R-404A and wherein R-22 or R-404A in the heat transfer system is replaced by the heat transfer composition.

13. The heat transfer system of claim 12 wherein the heat transfer composition has a fill mass in the range of 85% to 90% of the fill mass of R-22 in a heat transfer system designed for R-22.

14. The heat transfer system of claim 12 wherein the fill mass of said heat transfer composition in a heat transfer system designed for R-404A is 90-95% of the fill mass of R-404A.

Technical Field

The application relates to the field of refrigeration, in particular to a heat transfer composition, application thereof and a heat transfer system.

Background

R-22 (chlorodifluoromethane) is a HCFC (hydrochlorofluorocarbon) type refrigerant widely used for heat transfer, including stationary air conditioning, commercial and industrial refrigeration, heat pump and air conditioning. There are many heat exchange systems designed for R-22. Although R-22 has a very low Ozone Depletion Potential (ODP), its use is limited and is phased out. R-404A is also a commonly used low temperature freezing system, but has a GWP of as high as 3922, which is environmentally undesirable. The kyoto protocol proposed a reduction in this high GWP refrigerant. Since 2015, the use of the drug has been prohibited in developed countries and regions such as the european union and japan.

The refrigerating product based on HFC (hydrofluorocarbon) is newly developed, has zero ODP value, does not damage the ozone layer and is environment-friendly. Such as HFC product R-407C, which has been developed so far, can replace R-22 in air conditioning applications. The product comprises the following components in percentage by weight: 25: 52 of R-32 (difluoromethane), R-125 (pentafluoroethane) and R-134a (1, 1, 1, 2-tetrafluoroethane). R-407C has thermodynamic properties very similar to R-22 and can be used in older systems designed for use with R-22. However, these new HFC-based products (especially R-407C) are not compatible with mineral oils or alkylbenzene oils used in R-22 operating systems, especially with insufficient oil return, in terms of lubrication of mechanical parts. Therefore, systems using HFC products require the use of new oils such as polyol ester (POE) and polyalkylene glycol (PAG) types as lubricating oils. In many existing heat transfer systems operating with R-22, in addition to the need to replace the refrigerant, changes to the lubrication oil are required, and even changes to certain components of the refrigeration circuit, such as connecting piping work and seals, etc. In essence, for some widely used types of compression devices (e.g., hermetic compressors), such a conversion process is not possible. In any case, such a conversion process is long, difficult and expensive. In order to remove all the oil in the system and piping, it is necessary to flush with fresh oil several times, and the cleaning process is cumbersome and time consuming.

Disclosure of Invention

In view of the above, it is an object of the present application to provide a heat transfer composition, which is capable of directly replacing R-22 or R-404A in a heat transfer system designed for R-22 or R-404A without replacing lubricating oil in the heat transfer system and changing any components, and has excellent refrigeration effect on low-temperature freezing, a fast cooling rate and low power consumption, and applications thereof, and a heat transfer system.

Embodiments of the present application provide a heat transfer composition comprising HFC-32, HFC-125, HFC-134a, HFC-143a and HC-600 a.

Preferably, the heat transfer composition comprises the following components in percentage by mass:

HFC-32 6.0％-23.0％，

HFC-125 41.5％-60.0％，

HFC-134a 23.0％-40.0％，

HFC-143a 1.0％-7.0％，

HC-600a 1.0％-4.0％；

the sum of the mass percentages of the components is 100 percent.

Preferably, the heat transfer composition comprises the following components in percentage by mass:

HFC-32 7％-21.2％，

HFC-125 42.1％-57％，

HFC-134a 24.6％-39.5％，

HFC-143a 1％-6％，

HC-600a 1％-3％；

the sum of the mass percentages of the components is 100 percent.

Preferably, the heat transfer composition consists of the following components in percentage by mass: HFC-327.0%, HFC-12545.5%, HFC-134a 39.5%, HFC-143a 6.0%, HC-600a 2.0%.

Preferably, the heat transfer composition consists of the following components in percentage by mass: HFC-3219.6%, HFC-12549%, HFC-134a 24.6%, HFC-143a 5.1%, HC-600a 1.7%.

Preferably, the heat transfer composition consists of the following components in percentage by mass: HFC-3210.0%, HFC-12557%, HFC-134a 25%, HFC-143a 6%, HC-600a 2%.

Preferably, the heat transfer composition consists of the following components in percentage by mass: HFC-3221.2%, HFC-12542.1%, HFC-134a 33.7%, HFC-143a 1%, HC-600a 2%.

Preferably, the heat transfer composition is used in a replacement refrigerant for R-22 or R-404A.

The present embodiments also provide for the use of the above-described heat transfer compositions in heat transfer systems for R-22 or R-404A in place of R-22 or R-404A.

Embodiments of the present application also provide a heat transfer system that uses the heat transfer composition described above as a heat transfer medium.

Preferably, the heat transfer system is an automotive air conditioning system, a domestic air conditioner, a commercial air conditioner, a domestic refrigeration system, a commercial refrigeration system, a heat pump or a chiller cooling system.

Preferably, the heat transfer system is one designed for R-22 or R-404A and R-22 or R-404A in the heat transfer system is replaced by the heat transfer composition.

Preferably, the heat transfer composition has a fill mass in a heat transfer system designed for R-22 of from 85% to 90% of the fill mass of R-22.

Preferably, the heat transfer composition has a fill mass in a heat transfer system designed for R-404A of 90-95% of the fill mass of R-404A.

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

1. the heat transfer composition provided by the application has an ODP value of zero, is an environment-friendly refrigerant and is non-flammable, and belongs to A1-grade refrigerants.

2. The heat transfer composition provided by the application can replace R-22 to be used, the temperature and pressure of each area in the system operation are relatively close to that of R-22, the heat transfer composition can perfectly replace the operation of R-22 in the system, the compatibility with lubricating oil of the R-22 system is good, the lubricating oil does not need to be replaced, the filling amount of the heat transfer composition is only equal to 85% -90% of that of R-22 when a liquid storage tank is not provided, the cooling time can be shortened, and the energy consumption can be reduced.

3. The heat transfer composition provided by the application can replace R-404A to be used, the temperature and pressure of each area in the system operation are closer to that of R-404A, the operation of R-404A in the system can be perfectly replaced, the filling amount is only equal to 90% -95% of that of R-404A when no liquid storage tank is arranged, the cooling time can be shortened, and the energy consumption can be reduced.

Drawings

FIG. 1 is a graph of temperature versus liquid phase pressure of the heat transfer compositions of examples 1 and 2 of the present application, in comparison to R-22;

FIG. 2 is a graph of temperature versus vapor pressure for the heat transfer compositions of examples 1 and 2 of the present application, in comparison to R-22;

FIG. 3 is a graph of temperature versus liquid phase pressure of the heat transfer compositions of examples 3 and 4 of the present application compared to R-404A;

FIG. 4 is a graph of temperature versus vapor pressure of the heat transfer compositions of examples 3 and 4 of the present application versus R-404A;

FIG. 5 is a graph of the time to cool down the refrigerator versus the amount of R-125 in the heat transfer composition for the examples and comparative examples of the present application;

FIG. 6 is a graph of the variation of the cooling time of a refrigerator versus the amount of R-134a in a heat transfer composition in examples and comparative examples of the present application;

FIG. 7 is a graph comparing the temperature to target versus the average cool down time for a refrigerator employing the heat transfer compositions of example 1 and comparative example 7 of the present application;

FIG. 8 is a graph comparing the temperature to target for a refrigerator versus the average power consumption using the heat transfer compositions of example 1 and comparative example 7 of the present application;

FIG. 9 is a graph comparing the temperature to target versus the average cool down time for a refrigerator employing the heat transfer compositions of example 4 and comparative example 6 of the present application;

FIG. 10 is a graph comparing the temperature to target for a refrigerator versus the average power consumption using the heat transfer compositions of example 4 and comparative example 6 of the present application.

Detailed Description

In order to facilitate the understanding of the scheme of the present application by those skilled in the art, the following further description is provided with specific examples, and it should be understood that the examples are illustrative of the scheme of the present application and are not intended to limit the scope of the present application.

The embodiment of the application provides a heat transfer composition, which can directly replace R-22 or R-404A, does not need to replace lubricating oil in a heat transfer system and change any component in the replacement process, has excellent refrigeration effect on low-temperature refrigeration, and has high cooling rate and low energy consumption.

In order to solve the above problems, the technical solution in the embodiment of the present application has the following general idea:

embodiments of the present application provide a heat transfer composition comprising HFC-32, HFC-125, HFC-134a, HFC-143a and HC-600 a.

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

HFC-32 6.0％-23.0％，

HFC-125 41.5％-60.0％，

HFC-134a 23.0％-40.0％，

HFC-143a 1.0％-7.0％，

HC-600a 1.0％-4.0％；

the sum of the mass percentages of the components is 100 percent.

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

HFC-32 7％-21.2％，

HFC-125 42.1％-57％，

HFC-134a 24.6％-39.5％，

HFC-143a 1％-6％，

HC-600a 1％-3％；

the sum of the mass percentages of the components is 100 percent.

In a preferred embodiment of the present application, the heat transfer composition comprises the following components in percentage by mass: HFC-327.0%, HFC-12545.5%, HFC-134a 39.5%, HFC-143a 6.0% and HC-600a 2.0%;

or the heat transfer composition comprises the following components in percentage by mass: HFC-3219.6%, HFC-12549%, HFC-134a 24.6%, HFC-143a 5.1%, HC-600a 1.7%;

or the heat transfer composition comprises the following components in percentage by mass: HFC-3210.0%, HFC-12557%, HFC-134a 25%, HFC-143a 6%, HC-600a 2%;

or the heat transfer composition comprises the following components in percentage by mass: HFC-3221.2%, HFC-12542.1%, HFC-134a 33.7%, HFC-143a 1%, HC-600a 2%.

The heat transfer compositions provided by the embodiments herein are useful as replacement refrigerants for R-22 or R-404A.

The heat transfer compositions described above as provided by the examples herein can be used in place of R-22 or R-404A in heat transfer systems for R-22 or R-404A.

The embodiments of the present application also provide a heat transfer system that uses the heat transfer composition described above as a heat transfer medium.

In a preferred embodiment of the present application, the heat transfer system is an automotive air conditioning system, a domestic air conditioner, a commercial air conditioner, a domestic refrigeration system, a commercial refrigeration system, a heat pump, or a chiller cooling system.

In a preferred embodiment of the present application, the heat transfer system described above is a heat transfer system designed for R-22 or R-404A, and R-22 or R-404A in the heat transfer system is replaced with the heat transfer composition.

In a preferred embodiment of the present application, the charge mass of the above-described heat transfer composition in a heat transfer system designed for R-22 is from 85% to 90% of the charge mass of R-22.

In a preferred embodiment of the present application, the charge mass of the above-described heat transfer composition in a heat transfer system designed for R-404A is 90-95% of the charge mass of R-404A.

The heat transfer composition provided by the application can be obtained by physically mixing the components in a liquid phase state according to corresponding proportions.

For better understanding of the above technical solutions, the following detailed descriptions will be provided with reference to the drawings and specific embodiments of the specification, but the present invention is not limited thereto.

Examples

TABLE 1 component ratios of Heat transfer compositions

The heat transfer compositions of examples 1 and 2 were tested for temperature-liquid phase pressure change and temperature-vapor phase pressure change, respectively, with respect to R-22 of comparative example 5, to provide the temperature-liquid phase pressure comparison graph of fig. 1 and the temperature-vapor phase pressure comparison graph of fig. 2, from which it can be seen that the heat transfer compositions provided herein are very close to the temperature-liquid phase pressure change curve and the temperature-vapor phase pressure change curve of R-22, i.e., the temperature and pressure in each zone are relatively close to R-22 when operating in a refrigeration system, and thus can be operated in the system in place of R-22 in a refrigeration system designed for R-22.

The heat transfer compositions of examples 3 and 4 were tested for temperature-liquid phase pressure change and temperature-vapor phase pressure change, respectively, with respect to R-404A of comparative example 6, to provide the temperature-liquid phase pressure comparison graph of fig. 3 and the temperature-vapor phase pressure comparison graph of fig. 4. from these graphs, it can be seen that the heat transfer compositions provided herein also provide a temperature-liquid phase pressure change curve and a temperature-vapor phase pressure change curve that are very close to R-404A, i.e., the temperature and pressure in each zone are relatively close to R-404A when operating in a refrigeration system, and thus can be used in a system designed for R-404A in place of R-404A perfectly.

And (3) testing the refrigeration performance:

the heat transfer compositions of examples 1-4 and comparative examples 1-6 in table 1 were subjected to charge capacity testing and refrigeration performance testing on an unloaded refrigerator. The refrigerator model is as follows: copeland ZF18K 4E-TFD. And (3) testing conditions are as follows: the ambient temperature is 30 ℃, the set temperature of the refrigerator is-55 ℃, the refrigerator is unloaded, and the evaporation temperature is-65 to-70 ℃. The results of the resulting charge tests are shown in Table 2 and the results of the performance tests are shown in tables 3 and 4.

Table 2 shows the results of testing the optimum charge for the different heat transfer compositions of examples 1-4 and comparative examples 1-6. As can be seen from the table, the optimum charge for the heat transfer compositions provided in the examples herein are all lower than the optimum charge for the comparative examples, particularly significantly lower than the optimum charges for R-22 and R-404A. In particular, the heat transfer composition of example 4 had an optimum charge of only 5380g, which is 13.2% less than the charge for R-22 and 8.7% less than the charge for R-404A, reducing the cost of refrigeration equipment.

TABLE 2 optimum charge of heat transfer composition

TABLE 3 time spent in the case that the temperature in the refrigerator is lowered to a designated temperature

TABLE 4 compressor Current level when temperature in refrigerator drops to specified temperature

As can be seen from the experimental data in tables 3 and 4, the time taken for the heat transfer composition provided in the examples of the present application to reach the target temperature in the refrigerator is lower than that in the comparative example, particularly, when the heat transfer composition of example 3 is used, the cooling rate of the refrigerator is fastest, the time taken for the temperature of the refrigerator to decrease to-55 ℃ is 49.6min, which is 16% higher than that of R-22, and is 14% higher than that of R-404A. And when the heat transfer composition of example 3 was used, the compressor current was also much lower than when R-404A was used, indicating that the heat transfer composition provided in the examples of the present application had higher cooling efficiency and was more energy efficient, and had a higher COP value. In addition, when the heat transfer compositions of comparative example 1, comparative example 2 and comparative example 7 are adopted, the refrigerator can not be cooled to-55 ℃, and when the heat transfer compositions of comparative example 3 and comparative example 4 are adopted, the time for cooling the refrigerator to-55 ℃ is far more than that of examples 1-4, which shows that the heat transfer composition with a specific mixture ratio provided by the examples of the application has excellent low-temperature refrigeration effect, and the low-temperature refrigeration effect is greatly reduced when the mixture ratio of the heat transfer composition provided by the examples of the application is beyond the range of the mixture ratio of the heat transfer composition provided by the examples of the application.

Based on the time taken for the refrigerator temperature to be lowered to-50 ℃ in examples 1 to 4 and comparative examples 1 to 4 in Table 3, a graph showing the relationship between the time taken for lowering the temperature and the content of R-125(HFC-125) in the heat transfer composition as shown in FIG. 5 and a graph showing the relationship between the time taken for lowering the temperature and the content of R-134a (HFC-134a) in the heat transfer composition as shown in FIG. 6 were obtained. As can be seen from FIG. 5, as the component content of R125 increases, the time taken for the refrigerator to cool to-50 ℃ decreases first and then increases, and the time taken for the R125 to be between 42.1% and 57% by mass is shorter. As can be seen from FIG. 6, as the content of the component R134a is increased, the time spent on cooling the refrigerator to-50 ℃ is also increased after being decreased, and the time spent on cooling the refrigerator to-50 ℃ is shorter when the content of the component R134a is 24.6-39.5% by mass.

The heat transfer compositions of example 1 and comparative example 7 were tested for refrigeration performance on a load-bearing refrigerator, with 3 parallel runs for each formulation. The refrigerator model is as follows: copeland ZF18K4E-TFD, test conditions: the ambient temperature was 30 ℃, the refrigerator load was set at-50 ℃ and the evaporation temperature was-60 ℃. The results of the tests obtained are shown in tables 5 and 6.

TABLE 5 time spent in cooling to a designated temperature in the refrigerator

TABLE 6 Power consumption when the temperature in the refrigerator falls to a given temperature

From the experimental data in tables 5 and 6, a comparison graph of the target temperature and the average temperature-decreasing time shown in fig. 7 and a comparison graph of the target temperature and the average power consumption shown in fig. 8 were obtained. As can be seen from fig. 7 and 8, the average cool-down time with the heat transfer composition of example 1 is significantly lower than that of comparative example 7 and the average power consumption is significantly lower than that of comparative example 7 at the cryogenic stage below-40 ℃. In particular, when the load refrigerator was brought to-50 ℃, the average required time was 40% lower with the heat transfer composition of example 1 than with the heat transfer composition of comparative example 7, and the average power consumption was 39% lower than that of comparative example 7, greatly shortening the refrigeration time in the cryogenic stage and having a significant energy saving effect.

The heat transfer composition provided by the embodiment of the application is added with the R-600a, so that the compatibility of the mixed heat transfer composition and mineral oil can be increased, and the mixed heat transfer composition can be directly used in an R-22 system. Compared with other hydrocarbon refrigerants such as R-600, R601a and the like, the boiling point of R-600a is lower, the temperature slippage of the mixed heat transfer composition is smaller, and the refrigeration performance is more excellent; the boiling point of 600a is higher than that of R290, which can reduce the temperature of the exhaust gas of the compressor in the system and make the system operate more stably. In sum, R-600a is the more preferred hydrocarbon working fluid component of the compounded heat transfer composition. To reduce the flammability of the heat transfer composition, the mass percent of R-600a in the heat transfer composition is controlled to be less than 4%, more preferably less than 3%. Considering the compatibility of the heat transfer composition with mineral oil and the safety level of the heat transfer composition, the content of R-600a is preferably 1 to 4% by mass, more preferably 1 to 3% by mass.

The heat transfer compositions of example 4 and comparative example 6 were tested for refrigeration performance on a load-bearing refrigerator, with 3 parallel runs for each formulation. The refrigerator model is as follows: copeland ZF18K4E-TFD, test conditions: the ambient temperature was 30 ℃, the refrigerator load was set at-45 ℃ and the evaporation temperature was-55 ℃. The results of the tests obtained are shown in tables 7 and 8.

TABLE 7 time spent in cooling to a designated temperature in the refrigerator

TABLE 8 power consumption when the temperature in the refrigerator falls to a given temperature

From the experimental data in tables 9 and 10, a comparison graph of the target temperature and the average temperature-decreasing time shown in fig. 9 and a comparison graph of the target temperature and the average power consumption shown in fig. 10 were obtained. As can be seen from FIGS. 9 and 10, when the temperature in the loaded refrigerator is lowered to-45 ℃, the average cooling time is shortened by about 6% and the power consumption is reduced by about 8% compared with that of R-404A of comparative example 6 in the heat transfer composition of example 4, which has a significant effect-enhancing and energy-saving effect.

Finally, the above embodiments are only used for illustrating the technical solutions of the present application and not for limiting, although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application, and all the technical solutions of the present application should be covered by the claims of the present application.