JPH0665562A - Mixed working fluid and heat pump apparatus using the same - Google Patents

Abstract

PURPOSE:To provide a working fluid which scarcely affects the stratospheric ozone layer and can substitute for R22. CONSTITUTION:This mixed working fluid is prepd. by mixing 15-90wt.% perfluorodimethyl ether with one or two fluorodimethyl ethers selected from the group consisting of 85wt.% or lower pentafluorodimethyl ether, 50wt.% or lower dimethyl ether, 60wt.% or lower trifluorodimethyl ether, 60wt.% or lower tetrafluorodimethyl ether, and 50wt.% or lower difluorodimethyl ether.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a working fluid and a heat pump device such as an air conditioner and a refrigerator using the working fluid.

[0002]

2. Description of the Related Art Conventionally, in heat pump devices such as air conditioners and refrigerators, CFCs (hereinafter referred to as R ○
Methane called ◯ or R ○○○)
Alternatively, halogenated halocarbons derived from ethane are known, and the condensation temperature and / or the evaporation temperature are about 0 to about 5 as utilization temperatures.
It is usually used in the range of 0 ° C. Among them, chlorodifluoromethane (CHClF ₂ , R22, boiling point -40.8
C) is widely used as a working fluid for home air conditioners, building air conditioners, large refrigerators, etc.

[0003]

However, in recent years, the depletion of the stratospheric ozone layer by CFCs has become a global environmental problem, and some fully halogenated hydrocarbons (which have large stratospheric ozone depletion capacity) CFCs) have already been regulated in terms of usage and production by the International Convention on Montreal, and in the future CFCs
There is a movement to abolish the use and production of. Well, R
22 is ozone depletion ability (trichlorofluoromethane (C
Cl ₃ F, R11) has a stratospheric ozone depletion capacity of 1, and the stratospheric ozone depletion capacity (hereinafter referred to as ODP) is 0.
Although it is as small as 05, it is not CFCs, but it is expected that the usage will increase in the future, and now that refrigeration and air-conditioning equipment has become widespread, the increase in the usage and production of R22 will have a large impact on the human living environment. Is expected to be. Therefore, there is a strong demand for early development of a working fluid that is a substitute for R22, which has a small ozone depletion ability in the stratosphere but is said to have some depletion ability.

The present invention has been tried in view of the above-mentioned problems, and has almost no effect on the stratospheric ozone layer.
22 to provide an alternative working fluid.

In order to almost eliminate the influence on the stratospheric ozone layer, it is required that the molecular structure does not contain chlorine, and as a possibility, there is no chlorine-containing fluorohydrocarbon. However, the present invention intends to propose a mixture of chlorine-free fluorinated dimethyl ethers. Here, dimethyl ethers are referred to as E ○○○, and the 100th position is the number of carbon atoms-
The 1st and 10th positions represent the number of hydrogen atoms + 1, and the 1st position represents the number of fluorine atoms. The single candidate for these alternative working fluids is WLKopko, 'B
eyond CFCs: Extending the Search for New Refrigera
nrs'ASHRAE's 1989 CFC Conf. p.39-46 (1989.9) with boiling point.

Prior art patents for chlorine-free fluorinated ethers include the following. USP2,06
In 6,905, trifluorodimethyl ether trifl
_{uorodimethylether (E143, C 2 H 3} F 3 O) is disclosed. In USP 2,500,388, perfluorodimethyl ether (E1
16, CF ₃ —O—CF ₃ , boiling point −59 ° C.) and the like are disclosed. In USP 3,362,180, pentafluorodimethyl ether (E12
5, CF ₃ —O—CHF ₂ , boiling point −35 ° C.), tetrafluorodimethyl ether (E1)
34a, CF ₃ —O—CH ₂ F, boiling point −20 ° C.) and the like. In USP 3,394,878, trifluorodimethyl ether (E14
3a, CF ₃ —O—CH ₃ , boiling point −23 ° C.) and perfluorodimethyl ether (E11)
_{6, CF 3 -O-CF 3} , azeotrope boiling point -59 ° C.) is disclosed. In USP 3,409,555, trifluoromethyl-trifluoroethyl ether trifluoro
methyl-trifluoroethylether (CF ₃ -O-CH ₂ -C
F ₃ , boiling point + 5.6 ° C) and dichlorofluoromethane dich
A minimum boiling azeotrope of lorofluoromethane (R21, boiling point + 9 ° C) is disclosed. In USP 3,922,228, pentafluorodimethyl ether (E12
_{5, CF 3 -O-CHF 2} , boiling point -35 ° C.) and dimethyl ether _{dimethylether (E170, CH 3 -O-} CH 3, maximum boiling azeotrope of boiling point -24 ℃) maximum boiling a
zeotrope is disclosed. USP 4,041,14
In 8, bis-difluoromethyl ether bis-difluor
omethylether (E134, CHF ₂ -CHF ₂ , boiling point +5
℃) and perfluorodimethyl ether
_{ether (E116, CF 3 -O-} CF 3, boiling point -59 ° C.) mixture have been disclosed. In USP 4,139,607, bis-difluoromethyl ether bis-difluoromet
hylether (E134, CHF ₂ -CHF ₂ , boiling point + 5 ° C)
A mixture of carbon dioxide and carbon dioxide (CO ₂ ) is disclosed. In USP 4,783,276, dimethyl ether (E170, CH ₃ -O-CH ₃ ,
Boiling point -24 ℃) and dichlorodifluoromethane dichlorod
An azeotropic mixture of ifluoromethane (R12, boiling point -30 ° C) is disclosed. In USP 4,961,321,
Bis-difluoromethyle
ther (E134, CHF ₂ -CHF ₂ , boiling point + 5 ° C) and chlorine-free fluorohydrocarbons fluorinated halocarbo
Mixtures of ns are disclosed. USP 5,061,3
In 94, dimethyl ether (E17
_{0, CH 3 -O-CH 3} , boiling point -24 ° C.) and chlorotetrafluoroethane chlorotetrafluoroethane (R124,
The highest boiling azeotrope (boiling point -10 ° C) is disclosed. In EP443,912A, dimethyl ether dim
_{ethylether (E170, CH 3 -O-} CH 3, boiling point -24
℃) and 1,1,1,2-tetrafluoroethane 1,1,1,2
The highest boiling azeotrope of -tetrafluoroethane (R134a, boiling point -27 ° C) is disclosed. However, these working fluids are chlorodifluoromethanes.
The boiling point differs greatly from that of luoromethane (R22, boiling point -40.8 ° C), and it cannot be used as is for current equipment that uses R22.

[0007]

In order to solve the above problems, the present invention is a mixed working fluid composed of dimethyl ethers, which contains at least perfluorodimethyl ether and contains 2 carbon atoms, 1 oxygen atom and hydrogen atom. It includes one or two selected from fluorinated dimethyl ethers consisting only of fluorine atoms. The present invention is also a heat pump device using the working fluid.

[0008]

According to the present invention, the working fluid is combined with perfluorodimethyl ether (ODP = 0), which is an ether having almost no ozone depletion ability and containing no chlorine in its molecular structure, under atmospheric pressure by the above combination. By having a boiling point of 40 ° C. or higher, almost no ozone depletion ability, and a mixture of one or two ethers (ODP = 0) selected from chlorine-free molecular structures, The effect on the stratospheric ozone layer is smaller than that of R22 and can be almost eliminated.

Further, according to the present invention, by specifying the composition range, it has a vapor pressure similar to that of R22 at about 0 to about 50 ° C. which is a use temperature of a heat pump device such as an air conditioner / refrigerator. As a result, it is possible to provide a working fluid that can be used in current equipment.

In particular, the ODP in the above-mentioned combination and in the specified composition range is also expected to be 0, which is a very promising working fluid as an alternative to R22. Moreover, since such a mixture is expected to be a non-azeotropic mixture and has a temperature gradient in the condensation process and the evaporation process, a coefficient of performance higher than that of R22 can be obtained by constructing a Lorentz cycle in which the temperature difference with the heat source fluid is close. A (COP) heat pump device can be constructed.

[0011]

The working fluid of the present invention is a mixed working fluid composed of dimethyl ethers, and contains at least perfluorodimethyl ether, and is fluorinated dimethyl ether containing only 2 carbon atoms, 1 oxygen atom, hydrogen atom and fluorine atom. Includes one or two selected from the class. Further, the composition range of these mixtures is specified so that the vapor pressure of the mixture becomes almost equal to R22.

Here, perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.) is an ether having almost no ozone depletion ability and containing no chlorine in its molecular structure. Further, perfluorodimethyl ether (E116) has a boiling point under atmospheric pressure of about −59 ° C., and is the only dimethyl ether having a lower boiling point than R22. However, the critical temperature is estimated to be about 50 ° C. or lower, the vapor pressure is high, and it cannot be used alone in a refrigerator, a heat pump or the like having a use temperature of about 0 to about 50 ° C.

In the present invention, by mixing perfluorodimethyl ether (E116) with a similar dimethyl ether having a boiling point higher than that of R22, the vapor pressure of the mixture is almost equal to that of R22, and there is almost no ODP. It is possible to obtain a fluid.

Fluorinated dimethyl ethers composed of only two carbon atoms, one oxygen atom, one hydrogen atom and one fluorine atom are ethers containing no chlorine in their molecular structure, and therefore have almost no ozone depleting ability. It is a thing. In particular,
Since ethers containing a hydrogen atom have a boiling point of -40 ° C or higher under atmospheric pressure, they can be mixed with perfluorodimethyl ether to form a mixture having a boiling point equivalent to that of chlorodifluoromethane (R22). Is. Fluorinated dimethyl ethers include pentafluorodimethyl ether (E125, CF ₃ —O—CHF ₂ , boiling point −35 ° C.), or dimethyl ether (E170, CH
₃ -O-CH _3, boiling point -24 ° C.), or trifluoromethyl ether _{(E143a, CF 3 -O-CH} 3, boiling -2
3 ° C) or tetrafluorodimethyl ether (E1
34a, CF ₃ -O-CH ₂ F, boiling point -20 ° C), or difuluorodimethylether
(E152a, CHF ₂ —O—CH ₃ , boiling point −5 ° C.) It is desirable that it is one or two selected from any of the above.

Examples of working fluids according to the present invention will be described below with reference to vapor pressure diagrams. FIG. 1 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), pentafluorodimethyl ether (E1
_{25, CF 3 -O-CHF 2} , boiling point -35 ° C.), dimethyl ether (the _{E170, CH 3 -O-CH 3} , boiling point -24 ° C.) working fluid constituted by a mixture of three kinds of ethers, constant temperature・ The equilibrium state at constant pressure is shown using triangular coordinates.

In the present triangular coordinates, a single substance is arranged counterclockwise at each vertex of the triangle in the counterclockwise direction from the lower vertex, and the composition ratio of each component at a certain point on the coordinate plane ( The weight ratio) is represented by the ratio of the distance between the point and each side of the triangle. At this time, the distance between the point and the side of the triangle corresponds to the composition ratio of the substance described at the apex of the triangular coordinate on the side opposite to the side.

In FIG. 1, 1 indicates a temperature of 0 ° C. and a pressure of 4.0.
It is a vapor-liquid equilibrium line of the mixture at 44 kg / cm ² G, and this temperature / pressure corresponds to the saturated state of R22. The upper line of the vapor-liquid equilibrium line (corresponding to R22 0 ° C.) 1 represents the saturated vapor phase line, and the lower line of the vapor-liquid equilibrium line (R22 0 ° C. equivalent) 1 represents the saturated liquid phase line. The vapor-liquid equilibrium state is reached in the range that is set. 2 is temperature 50 ℃, pressure 1
It is a vapor-liquid equilibrium line of the mixture at 8.782 kg / cm ² G, and this temperature / pressure also corresponds to the saturated state of R22.

The composition on the saturated vapor phase vaporizes at a pressure higher than R22 and liquefies at the same pressure as R22. The composition on the saturated liquidus line vaporizes at the same pressure as R22 and liquefies at a pressure lower than R22. The composition in the area between these two lines vaporizes above R22 and liquefies below R22. That is, 50 ° C vapor-liquid equilibrium line 2
The composition in the area between
At a lower pressure, the gas phase changes to a liquid phase, and at the same pressure as R22, a gas phase higher than 50 ° C condenses and changes to a liquid phase lower than 50 ° C. The composition in the area between the vapor-liquid equilibrium line 1 at 0 ° C changes from the liquid phase to the vapor phase at a pressure higher than R22 at 0 ° C, and the liquid phase lower than 0 ° C evaporates at the same pressure as R22. Then, the gas phase changes to a temperature higher than 0 ° C.

When E116 is used alone, it may exceed the critical temperature at 50 ° C., but when it is made into such a mixture, a saturated state exists, and about 0 to about 5 are obtained.
It can be used for heat pump devices such as air conditioners and refrigerators having a use temperature of 0 ° C.

As can be seen from the figure, E116, E125
And E170 are in the range of about 15 to about 80% by weight, 0 to about 85% by weight, and 0 to about 50% by weight, respectively, and the vapor pressure is almost the same as that of R22 at a use temperature of about 0 to about 50 ° C. Desirable because it has Furthermore, E116,
The composition range in which E125 and E170 are approximately 15 to approximately 75% by weight, 0 to approximately 85% by weight, and 0 to approximately 45% by weight, respectively, is almost the same as R22 at all use temperatures between 0 ° C and 50 ° C. It is particularly desirable because it has comparable vapor pressure. In particular, the ODP in the above-mentioned combination and composition range is also expected to be 0, which is a very promising working fluid as a substitute for R22.

FIG. 2 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), pentafluorodimethyl ether (E125, CF ₃ —O—CH).
F ₂ , boiling point −35 ° C.), a working fluid composed of a mixture of three ethers of trifluorodimethyl ether (E143a, CF ₃ —O—CH ₃ , boiling point −23 ° C.),
The equilibrium state at constant temperature and constant pressure is shown using triangular coordinates. In FIG. 2, 1 is a vapor-liquid equilibrium line of the mixture at a temperature of 0 ° C. and a pressure of 4.044 kg / cm ² G, and 2 is a temperature of 50 ° C. and a pressure of 18.782 k.
3 is a vapor-liquid equilibrium line of the mixture at g / cm ² G.

In this case, E116, E125 and E
143a is approximately 15 to approximately 70% by weight, and 0 to approximately 85, respectively.
The composition range such that the weight% is 0 to approximately 60% by weight is R
22 is desirable because it has almost the same vapor pressure as E22.
6, E125 and E143a are approximately 15 to approximately 65, respectively.
A composition range of 0% to about 85% by weight, 0% to about 55% by weight is particularly desirable.

FIG. 3 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), pentafluorodimethyl ether (E125, CF ₃ —O—CH).
F ₂ , boiling point −35 ° C., tetrafluorodimethyl ether (E134a, CF ₃ —O—CH ₂ F, boiling point −20 ° C.) at a constant temperature and a constant pressure of a working fluid composed of a mixture of three ethers. The equilibrium state is shown using triangular coordinates. In FIG. 3, 1 is the temperature 0 °
-Vapor-liquid equilibrium line of the mixture at a pressure of 4.044 kg / cm ² G, and 2 is a temperature of 50 ° C and a pressure of 18.78
3 is a vapor-liquid equilibrium line of the mixture at ² kg / cm ² G.

In this case, E116, E125 and E
134a is approximately 15 to approximately 70% by weight, and 0 to approximately 85, respectively.
The composition range such that the weight% is 0 to approximately 60% by weight is R
22 is desirable because it has almost the same vapor pressure as E22.
6, E125 and E134a are approximately 15 to approximately 65, respectively.
A composition range of 0% to about 85% by weight, 0% to about 55% by weight is particularly desirable.

FIG. 4 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), pentafluorodimethyl ether (E125, CF ₃ —O—CH).
F ₂ , boiling point −35 ° C.), a working fluid composed of a mixture of three ethers of difluorodimethyl ether (E152a, CHF ₂ —O—CH ₃ , boiling point −5 ° C.),
The equilibrium state at constant temperature and constant pressure is shown using triangular coordinates. In FIG. 4, 1 is a vapor-liquid equilibrium line of the mixture at a temperature of 0 ° C. and a pressure of 4.044 kg / cm ² G, and 2 is a temperature of 50 ° C. and a pressure of 18.782 k.
3 is a vapor-liquid equilibrium line of the mixture at g / cm ² G.

In this case, E116, E125 and E
152a is approximately 15 to approximately 90% by weight, and 0 to approximately 85, respectively.
The composition range such that the weight% is 0 to approximately 50% by weight is R
22 is desirable because it has almost the same vapor pressure as E22.
6, E125 and E152a are approximately 15 to approximately 85, respectively.
A composition range of 0% to about 85% by weight, 0% to about 40% by weight is particularly desirable.

FIG. 5 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), dimethyl ether (E170, CH ₃ —O—CH ₃ , boiling point −24).
° C), trifluorodimethyl ether (E143a, C
FIG. 3 shows the equilibrium state at a constant temperature and a constant pressure of a working fluid composed of a mixture of three ethers (F ₃ —O—CH ₃ , boiling point −23 ° C.) using triangular coordinates. In FIG. 5, 1 indicates a temperature of 0 ° C. and a pressure of 4.044 kg.
/ Cm ² G is the vapor-liquid equilibrium line of the mixture, and 2
Is a vapor-liquid equilibrium line of the mixture at a temperature of 50 ° C. and a pressure of 18.782 kg / cm ² G.

In this case, E116, E170 and E
143a is approximately 40 to approximately 80% by weight, and 0 to approximately 50, respectively.
The composition range such that the weight% is 0 to approximately 60% by weight is R
22 is desirable because it has almost the same vapor pressure as E22.
6, E170 and E143a are approximately 45 to approximately 75, respectively.
A composition range of 0% to about 45% by weight, 0% to about 55% by weight is particularly desirable.

FIG. 6 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), dimethyl ether (E170, CH ₃ —O—CH ₃ , boiling point −24).
° C), tetrafluorodimethyl ether (E134a,
₃ shows the equilibrium state of a working fluid composed of a mixture of three kinds of ethers (CF ₃ —O—CH ₂ F, boiling point −20 ° C.) at constant temperature and constant pressure by using triangular coordinates. In FIG. 6, 1 indicates a temperature of 0 ° C. and a pressure of 4.044.
² is a vapor-liquid equilibrium line of the mixture at kg / cm ² G, and 2 is a temperature of 50 ° C. and a pressure of 18.782 kg / cm ² G
3 is a vapor-liquid equilibrium line of the mixture in FIG.

In this case, E116, E170 and E
134a is approximately 40 to approximately 80% by weight and 0 to approximately 50%, respectively.
The composition range such that the weight% is 0 to approximately 60% by weight is R
22 is desirable because it has almost the same vapor pressure as E22.
6, E170 and E134a are approximately 45 to approximately 75, respectively.
A composition range of 0% to about 45% by weight, 0% to about 55% by weight is particularly desirable.

FIG. 7 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), dimethyl ether (E170, CH ₃ —O—CH ₃ , boiling point −24).
° C), difluorodimethyl ether (E152a, CH
FIG. 3 shows the equilibrium state of a working fluid composed of a mixture of three kinds of ethers (F ₂ —O—CH ₃ , boiling point −5 ° C.) at constant temperature and constant pressure by using triangular coordinates. In FIG. 7, 1 indicates a temperature of 0 ° C. and a pressure of 4.044 kg.
/ Cm ² G is the vapor-liquid equilibrium line of the mixture, and 2
Is a vapor-liquid equilibrium line of the mixture at a temperature of 50 ° C. and a pressure of 18.782 kg / cm ² G.

In this case, E116, E170 and E
152a is approximately 50 to approximately 90% by weight, and 0 to approximately 50, respectively.
The composition range such that the weight% is 0 to approximately 50% by weight is R
22 is desirable because it has almost the same vapor pressure as E22.
6, E170 and E152a are approximately 60 to approximately 85, respectively.
A composition range of 0% to about 45% by weight, 0% to about 40% by weight is particularly desirable.

FIG. 8 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), trifluorodimethyl ether (E143a, CF ₃ —O—C).
H _3, boiling point -23 ° C.), tetrafluoro ether (E134a, of CF ₃ -O-CH ₂ F, the working fluid constituted by a mixture of three kinds of ethers having a boiling point of -20 ° C.), at a constant temperature and constant pressure The equilibrium state is shown using triangular coordinates. In FIG. 8, 1 indicates a temperature of 0 ° C.
-Vapor-liquid equilibrium line of the mixture at a pressure of 4.044 kg / cm ² G, and 2 is a temperature of 50 ° C and a pressure of 18.78
3 is a vapor-liquid equilibrium line of the mixture at ² kg / cm ² G.

In this case, E116, E143a and E134a are approximately 40 to approximately 70% by weight and 0 to approximately 6 respectively.
The composition range such that 0% by weight, 0 to approximately 60% by weight,
E1 is desirable because it has almost the same vapor pressure as R22.
A composition range in which 16, E143a, and E134a are approximately 45 to approximately 65% by weight, 0 to approximately 55% by weight, and 0 to approximately 55% by weight, respectively, is particularly desirable.

FIG. 9 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), trifluorodimethyl ether (E143a, CF ₃ —O—C).
H _3, boiling point -23 ° C.), difluoro dimethyl ether _{(E152a, CHF 2 -O-CH} 3, the working fluid constituted by a mixture of three kinds of ethers having a boiling point of -5 ° C.),
The equilibrium state at constant temperature and constant pressure is shown using triangular coordinates. In FIG. 9, 1 is a vapor-liquid equilibrium line of the mixture at a temperature of 0 ° C. and a pressure of 4.044 kg / cm ² G, and 2 is a temperature of 50 ° C. and a pressure of 18.782 k.
3 is a vapor-liquid equilibrium line of the mixture at g / cm ² G.

In this case, E116, E143a and E152a are approximately 40 to approximately 90% by weight and 0 to approximately 6 respectively.
The composition range of 0% by weight, 0 to about 50% by weight,
E1 is desirable because it has almost the same vapor pressure as R22.
A composition range in which 16, E143a, and E152a are approximately 45 to approximately 85% by weight, 0 to approximately 55% by weight, and 0 to approximately 40% by weight, respectively, is particularly desirable.

FIG. 10 shows perfluorodimethyl ether (E116, CF ₃ —O—CF ₃ , boiling point −59 ° C.), tetrafluorodimethyl ether (E134a, CF ₃ —O—C).
H ₂ F, boiling point −20 ° C.), a working fluid composed of a mixture of three ethers of difluorodimethyl ether (E152a, CHF ₂ —O—CH ₃ , boiling point −5 ° C.),
The equilibrium state at constant temperature and constant pressure is shown using triangular coordinates. In FIG. 10, 1 indicates a temperature of 0 ° C.
² is a vapor-liquid equilibrium line of the mixture at a pressure of 4.044 kg / cm ² G, and 2 is a temperature of 50 ° C. and a pressure of 18.782
3 is a vapor-liquid equilibrium line of the mixture at kg / cm ² G.

In this case, E116, E134a and E152a are approximately 40 to approximately 90% by weight, and 0 to approximately 6 respectively.
The composition range of 0% by weight, 0 to about 50% by weight,
E1 is desirable because it has almost the same vapor pressure as R22.
A composition range in which 16, E134a, and E152a are approximately 45 to approximately 85% by weight, 0 to approximately 55% by weight, and 0 to approximately 40% by weight, respectively, is particularly desirable.

In total, these are 15 to 90% by weight of perfluorodimethyl ether, and 85% by weight or less of pentafluorodimethyl ether as fluorinated dimethyl ethers containing only 2 carbon atoms, 1 oxygen atom, 1 hydrogen atom and 1 fluorine atom. Also, a mixed working fluid containing 50% by weight or less of dimethyl ether, 60% by weight or less of trifluorodimethyl ether, 60% by weight or less of tetrafluorodimethyl ether, or 50% by weight or less of difluorodimethyl ether is preferable.

As a more preferable composition range, 15 to 85% by weight of perfluorodimethyl ether, 85% by weight or less of pentafluorodimethyl ether or 45% by weight or less of dimethyl ether, 55% by weight or less of trifluorodimethylether or 55% by weight or less of tetrafluorodimethyl ether, or Difluorodimethyl ether 4
A mixed working fluid containing one or two selected from 0 wt% or less is particularly desirable.

When only one kind is selected as the fluorinated dimethyl ethers consisting only of 2 carbon atoms, 1 oxygen atom, hydrogen atom and fluorine atom, a mixed operation consisting of 2 components of perfluorodimethyl ether. The composition range for becoming a fluid and having a vapor pressure equivalent to that of R22 at this time is preferably a range on each side of each triangular coordinate, but also in a mixture derived from the above specified composition range,
It is considered that there is no problem in practical use because it shows a slightly higher vapor pressure than R22.

In the above embodiments, the working fluid is composed of a mixture of two or three kinds of ethers. However, the working fluid is composed of a mixture of trifluorodimethyl ether, tetrafluorodimethyl ether and difluorodimethyl ether structural isomers geometrical isomar. It is of course possible to constitute the working fluid by a mixture of at least one ether.

Further, with perfluorodimethyl ether,
In addition to fluorinated dimethyl ethers consisting only of 2 carbon atoms, 1 oxygen atom, 1 hydrogen atom and 1 fluorine atom, it is also possible to add fluorocarbons which do not contain chlorine. In this case, difluoromethane (CH ₂
F _2, R32, boiling point -52 ° C.), pentafluoroethane
_{pentafluoroethane (CF 3 -CHF 2, R125} , boiling point -48 ° C.), 1,1,1-trifluoroethane 1, 1, 1-t
_{rifluoroehtane (CF 3 -CH 3, R143a} , boiling point -
48 ° C.), 1,1,1,2-tetrafluoroethane 1,
_{1,1,2-tetrafluoroethane (CF 3 -CH 2} F, R134
a, boiling point -27 ° C), 1,1-difluoroethane 1,1-d
_{ifluoroethane (CHF 2 -CH 3, R152a} , boiling point -
It is desirable to mix chlorine-containing fluorohydrocarbons having a boiling point close to R22, such as 25 ° C.).

Furthermore, since such a mixture is expected to be almost a non-azeotropic mixture and has a temperature gradient in the condensation process and the evaporation process, by forming a Lorentz cycle in which the temperature difference with the heat source fluid is close, Is expected to have a high coefficient of performance.

[0045]

As is apparent from the above description, in the working fluid and heat pump device of the present invention, (1)
The influence on the stratospheric ozone layer is smaller than that of R22, and it is possible to expand the range of choice of working fluid that makes it almost none. (2) At the operating temperature of equipment that is difficult to use with perfluorodimethyl ether alone R
It has a vapor pressure similar to that of R22 and can be used in current equipment as an alternative to R22. Furthermore, by utilizing the property of the temperature gradient of the non-azeotropic mixture (3), a higher coefficient of performance than that of R22 can be expected. And so on.

[Brief description of drawings]

FIG. 1 is a triangular coordinate diagram showing an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E125, and E170 at a constant temperature and a constant pressure.

FIG. 2 is a triangular coordinate diagram showing the equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E125, and E143a at a constant temperature and a constant pressure.

FIG. 3 is a triangular coordinate diagram showing an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E125, and E134a at a constant temperature and a constant pressure.

FIG. 4 is a triangular coordinate diagram showing an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E125, and E152a at a constant temperature and a constant pressure.

FIG. 5 is a triangular coordinate diagram showing an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E170, and E143a at a constant temperature and a constant pressure.

FIG. 6 is a trigonometric coordinate diagram showing trigonometric coordinates of an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E170, and E134a at a constant temperature and a constant pressure.

FIG. 7 is a triangular coordinate diagram showing an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E170, and E152a at a constant temperature and a constant pressure.

FIG. 8 is a triangular coordinate diagram showing an equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E143a, and E134a at a constant temperature and a constant pressure.

FIG. 9 is a triangular coordinate diagram showing the equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E143a, and E152a at a constant temperature and a constant pressure.

FIG. 10 is a triangular coordinate diagram showing the equilibrium state of a working fluid composed of a mixture of three kinds of ethers E116, E134a, and E152a at a constant temperature and a constant pressure.

[Explanation of symbols]

 1 Gas-liquid equilibrium line (equivalent to R22 0 ° C) 2 Gas-liquid equilibrium line (equivalent to R22 50 ° C)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Tagashira 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (4)

[Claims] 1. Perfluorodimethyl ether 15-90
A mixed working fluid containing, by weight, one or two selected from fluorinated dimethyl ethers consisting only of 2 carbon atoms, 1 oxygen atom, 1 hydrogen atom and 1 fluorine atom,
Fluorinated dimethyl ethers consisting only of 2 carbon atoms, 1 oxygen atom, hydrogen atom and fluorine atom are pentafluorodimethyl ether 85 wt% or less, dimethyl ether 50 wt% or less, trifluorodimethyl ether 60 wt% or less, or tetrafluorodimethyl ether. 60% by weight or less or difluorodimethyl ether 5
A mixed working fluid characterized by being one or two selected from 0% by weight or less. 2. Perfluorodimethyl ether 15-90
Fluorinated dimethyl ethers containing only 1% by weight, 2 carbon atoms, 1 oxygen atom, hydrogen atom, and fluorine atom, and difluoromethane, pentafluoroethane, 1,1 as chlorine-free fluorohydrocarbons. The mixed working fluid according to claim 1, wherein any one of 1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane is mixed. 3. Perfluorodimethyl ether 15-90
The dimethyl ether-based mixed working fluid according to claim 1, containing 1% or 2% by weight, selected from fluorinated dimethyl ethers containing only 2 carbon atoms, 1 oxygen atom, 1 hydrogen atom and 1 fluorine atom. The heat pump device used. 4. Perfluorodimethyl ether 15-90
% By weight, fluorinated dimethyl ethers consisting only of 2 carbon atoms, 1 oxygen atom, hydrogen atom and fluorine atom, and difluoromethane, pentafluoroethane, 1,1 as chlorine-free fluorohydrocarbons. , 1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,
The heat pump device using the dimethyl ether-based mixed working fluid according to claim 2, wherein any one of 1-difluoroethane is mixed.