JPS59117579A - Refrigerant composition - Google Patents

Abstract

PURPOSE:To provide the titled composition consisting of a non-azeotropic mixture of a refrigerant having lower boiling point than flon 12 and a refrigerant having higher boiling point than flon 12 at a ratio within a specific range, and capable of improving the efficiency of a heat pump keeping the refrigeration capacity without modification of the heat pump. CONSTITUTION:The objective composition is composed of a non-azeotropic mixture of (A) a refrigerant having lower boiling point than flon 12 (hereinafter called as R12) (preferably R503, R23, R13, etc.) and (B) a refrigerant having higher boiling point than R12 (preferably R152a, R124, etc.). The boiling temperature difference between the refrigerants is preferably 20-60 deg.C. The boiling point of the saturated liquid is lower than that of R12, and the condensation point of the saturated vapor of the composition is higher than R12 under arbitrary pressure, or the boiling pressure of the saturated liquid of the composition is higher than that of R12 and the condensation pressure of the saturated vapor is lower than R12 at an arbitrary temperature. USE:Heat pump for utilization of small-scale cold heat in a refrigerator, dehumidifier, etc., and for utilization of high-temperature heat in a hot water supplier.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a refrigerant composition suitable for heat pump devices, particularly for small-capacity cold heat utilization in refrigerators, dehumidifiers, etc., and high-temperature heat utilization in water heaters, etc. .

(Conventional structure and its problems) Conventionally, as a refrigerant for heat pump equipment for the purpose of using small capacity cold energy such as refrigerators and dehumidifiers, and high temperature heat utilization such as water heaters,
For the former, due to problems in manufacturing the compressor, etc., and for the latter, due to problems in high temperature and pressure resistance, halogenated hydrocarbons such as Freon 12 (dichlorodifluoromethane, boiling point -29
, 8°C, R12 (hereinafter abbreviated as R-) has been widely used. However, the efficiency of heat pump equipment is naturally limited by the thermodynamic properties of the refrigerant, which is determined by the heat source temperature.In order to save energy, the higher the boiling point of the refrigerant, the higher the latent heat of vaporization. Since the efficiency is also high, it is considered to use a refrigerant with a higher boiling point than R12 (R114, R21, etc.). However, since a refrigerant with a higher boiling point than R12 has a large suction specific volume of the compressor, the amount of refrigerant circulated during the refrigeration cycle in the same compressor is reduced, and the refrigeration capacity is also significantly reduced. On the other hand, since high efficiency is not an objective, in order to obtain the same capacity as R12, it is necessary to increase the heat transfer area of the compressor and heat exchanger, which is contrary to the desire to use the component parts for general purpose. It was something to do.

(Objective of the Invention) The object of the present invention is to provide a heat pump system that has conventionally used R12 with higher efficiency than R12, while requiring major modifications to the compressor, heat transfer area, etc. of the current heat pump system. The aim is to provide a new refrigerant composition free from the above, and to achieve this by using a mixed refrigerant of two or more components.

(Structure of the Invention) The refrigerant composition according to the present invention is a non-azeotropic mixed refrigerant consisting of a combination of a tower medium with a lower boiling point than R12 and a refrigerant with a higher boiling point than R12, and is realized in an appropriate composition range. It is. A particularly desirable composition range is defined as the boiling point line and the R12 Preferably, the range is larger than the composition where the boiling point intersects, and smaller than the composition where the dew point line intersects the R12 boiling point. The boiling point line in the T-X diagram represents the relationship between the composition and temperature at which the mixed refrigerant saturated liquid begins to boil, and the dew point line represents the relationship between the composition and temperature at which the mixed refrigerant saturated gas begins to condense. It is something.

In addition, it is preferable that the boiling point difference between a refrigerant with a lower boiling point than R12 and a refrigerant with a higher boiling point than R12 to be combined is about 60 deg at the maximum, and conversely, if the boiling point difference is 20 deg or less, The effect is diminished, and in some cases, the mixed refrigerant forms an azeotropic composition, which is undesirable.

(Description of Examples) Hereinafter, the refrigerant composition according to the present invention will be illustrated together with Examples.

Example 1 FIG. 1 shows a heat pump device to which a refrigerant composition according to the present invention is applied. 1 is a compressor, 2 is a refrigerant-to-water double-pipe condenser, 3 is a manual expansion valve, and 4 is a refrigerant-to-water double-pipe evaporator. In the first example, R22 (boiling point -40.8°C) is used as a refrigerant with a lower boiling point than R12, R114 (boiling point 3.8°C) is used as a refrigerant with a higher boiling point than R12, and R22
The mole fraction X was made variable from θ to 1. In addition, the experiment was conducted for the purpose of water heater use, and water was flowed in the condenser 2 and evaporator 4 so that the refrigerant and water were in counterflow. Inlet water temperature 25℃
The amount of water and the opening degree of the manual expansion valve 3 were adjusted so that the outlet water temperature was 10°C. Comparing these results (5) with the case where R12 is applied using the same heat pump device, the coefficient of performance (=condenser 2 heating capacity/compressor 1
The relationship shown in Figure 2 was obtained for heating capacity (manpower) and heating capacity. In this case, the coefficient of performance is better than R12 in almost all composition ranges, with the highest efficiency being about 20% or more at around x = 0.2, and the heating capacity being about 50% of R12. ing. This is thought to be due to the fact that the loss in the heat exchange process was reduced by making the refrigerant and water flow in opposite directions.

Further, in the R22/R114 mixed refrigerant, the vapor pressure of the saturated solution was measured while changing the composition of R22 as appropriate, and the T-X diagram at atmospheric pressure was estimated using these data, which is shown in FIG. In Figure 3, R12 boiling point (-29
, 8° C.), it is possible to specify the desirable composition range of the mixed refrigerant to replace R12. That is, R12
From the composition where the boiling point line intersects (x-=0.36), R12
In the composition range where the and dew point lines intersect (X20.84), the coefficient of performance is 1.21 to 1.04 times that of R12, and the heating capacity is 0.67 to 1.36 times that of R12. , R1
]4(6) Both the coefficient of performance and heating capacity are improved compared to the single unit (x=0.0). Therefore, although it cannot be said that the maximum efficiency is achieved in this composition range, the coefficient of performance can be improved without major modification of the thermoponzo device.

Example 2 A second example, like the first example, was conducted using the same experimental method in the heat pump apparatus shown in FIG. The mixed refrigerant used here is a combination of R13B1 (boiling point -57.8°C) as a refrigerant with a lower boiling point than R12, and R]2B1 (boiling point -3.5°C) as a refrigerant with a higher boiling point than R12. . The results at this time were only around x = 0.7 due to the increase in condensation pressure, but R12
When compared with the case of , the same relationship as shown in Fig. 4 was obtained. In this case as well, in almost all the composition ranges tested,
The coefficient of performance has improved for R]2 as well, and the highest efficiency is around 30 coefficients at around X20.2, and the heating capacity is around 70% of R12.

Also, as in the first embodiment, an estimated T-X diagram is shown in FIG. 5. In FIG.
, 8° C.), it is possible to specify the desirable composition range of the mixed refrigerant to replace R12. That is, R12
In the range from the composition where R12 and the dew point line intersect (x = 0.15) to the composition where R12 and the dew point line intersect (x = 0.72), the coefficient of performance is 1.28 to 0.97 times that of R12, and the heating capacity is is 0.70 to 129 times that of R12. Therefore, this composition range includes the composition that provides the maximum efficiency, and the coefficient of performance can be improved without major modification of the heat pump device.

As can be seen from the above examples, the refrigerant composition according to the present invention is a non-azeotropic mixed refrigerant consisting of a combination of a refrigerant with a polymorphic boiling point than R12 and a refrigerant with a higher boiling point than R12, and its desirable composition range is #Hills can be identified as follows.

The first method, as shown in Figure 6, is that the boiling temperature of the saturated liquid at an arbitrary pressure of the mixed refrigerant is lower than R12,
Moreover, it can be specified as a composition range in which the condensation temperature of the saturated gas is higher than R12. It is convenient to use atmospheric pressure as the arbitrary pressure. Also, the second method is the seventh method.
As shown in the figure, it can be specified as a composition range in which the boiling pressure of the saturated liquid at any temperature is higher than R12, and the condensing pressure of the saturated liquid is lower than RI2. Note that there is no significant difference in the range whether the first or second method for specifying the composition range is used.

Next, as a combination of mixed refrigerants, the boiling point difference is 20 to 5 Q
A refrigerant with a boiling point lower than R12 is preferable, and R503, R23, R13°R13B1.
R32, R125, R502, R22゜R500 etc., R
R152a, R1,2 are refrigerants with higher boiling points than R12.
4, R142b, R12B1.

Examples include R114, RI33a, R21, and R11. When selecting a mixed refrigerant to replace R12 from these combinations, refrigerants with very low boiling points such as R503 and R23°R13 are suitable for use in low-temperature heat sources such as refrigerators and dehumidifiers, but they are not suitable for use in water heaters. This is not necessarily preferable when using high-temperature heat such as, because it induces a large pressure increase.

(9) In addition, in the combination of a refrigerant with a lower boiling point than R12 and a refrigerant with a higher boiling point than R12, the composition range based on the low boiling point refrigerant is that the lower the boiling point of the low boiling point refrigerant, the lower the boiling point. The higher the boiling point of the high-boiling point refrigerant, the more the amount of the low-boiling point refrigerant is shifted.

(Effect of the invention) The mixed refrigerant and its composition range specified in the present invention do not have the same boiling point and dew point like a single refrigerant, but the average value thereof is almost the same boiling point as R12. The compressor suction specific volume is almost the same as R12, making it possible to improve efficiency while maintaining refrigeration (heating) capacity without major modification of the heat pump device. It is particularly suitable for heat pump devices that utilize small-capacity cold heat such as refrigerators and dehumidifiers, and high-temperature heat such as water heaters.

[Brief explanation of the drawing]

Figure 1 shows an example of a heat pump device to which the refrigerant composition of the present invention is applied, and Figures 2 and (10) 4 show the mixed refrigerant composition, coefficient of performance and heating capacity compared to R112. Figures 3 and 5 are diagrams showing the relationship between the mixed refrigerant composition and temperature at atmospheric pressure, and Figures 6 and 7 are diagrams for specifying the composition range of the refrigerant composition according to the present invention. It is a figure explaining the method. 1. Compressor, 2. Condenser, 3. Manual expansion valve, 4. Evaporator. (11) Figure 1 Figure 3 The mole of R22 in R22/R114 Figure 4 R13 day 1/R12B1 Ya's R13B1 hair 1 figure Figure 5 R13B1/R12B1 Ya R13BI Q LAi Yisendai Figure 6 shows the number of people in the 4th ward, Figure 7

Claims (3)

[Claims] (1) In a non-azeotropic mixed refrigerant consisting of two or more components, which is a combination of a refrigerant with a lower boiling point than R12 and a refrigerant with a higher boiling point than R12, A. The boiling temperature of the saturated liquid at any pressure is lower than that of R12, and It is specified by a composition in which the condensation temperature of saturated gas is higher than R12, or (B) a composition in which the boiling pressure of saturated liquid at any temperature is higher than R12 and the condensation pressure of saturated gas is lower than R12. Refrigerator with a composition range. A refrigerant composition used in heat pump devices that utilize small-capacity cold heat, such as dehumidifiers, and high-temperature heat, such as water heaters. (2) R12! D Low boiling point refrigerant Te R503, R
23°R13, R13B1. R125, R502, R2
2° R500 contains at least one, R12
R152a-R124 as higher boiling point refrigerants. R142b, R12B1, R114, R133a
, R21°R11. (3) The refrigerant composition according to claim (1), characterized in that it consists of two components with a boiling point difference of 20 to 60 degrees.