# Patent

## Title
Refrigerant composition

## Abstract

Refrigerant fluids that can be used in different types of compression systems. A composition including between 36 and 39 wt. % of difluromethane (HFC-32), between 28 and 32 wt. % of pentafluoroethane (HFC-125), and between 31 and 35 wt. % of tetrafluoroethane (HFC-134a). The composition may be used as a replacement for R-404A.

## Background
The present invention relates to liquid refrigerants capable of being used in various types of compression systems as a replacement for the refrigerant R-404A.
The use of liquid refrigerant in compression refrigeration systems is very widespread in the fields of industrial, commercial and domestic refrigeration.
The problems presented by substances which deplete the atmospheric ozone layer (ODP: ozone depletion potential) were dealt with at Montreal, where the protocol was signed imposing a reduction in the production and use of chlorofluorocarbons (CFCs). This protocol has formed the subject of amendments which have required the abandoning of CFCs and have extended regulation to other products, including hydrochlorofluorocarbons (HCFCs).
The refrigeration industry and the industry for the production of air conditioning have invested a great deal in the replacement of these liquid refrigerants and it is because of this that hydrofluorocarbons (HFCs) have been marketed.
The contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP (Global Warming Potential), which summarizes the heating power by taking a reference value of 1 for carbon dioxide.
The liquid refrigerant R-404A is a mixture of fluoroethanes, i.e. R-143a, R-125 and R-134a, having a GWP of 3944. This fluid has a high GWP, predominantly because of the presence of R-143a, which has a GWP of 4470.
A fluid having a high GWP requires being replaced. There thus exists a major need to develop a replacement fluid for R-404A which can operate in the same compression systems.


According to a first aspect, the invention thus relates to compositions comprising at least from 36 to 39% by weight of difluoromethane (HFC-32), from 28 to 32% by weight of pentafluoroethane (HFC-125) and from 31 to 35% by weight of tetrafluoroethane (HFC-134a).
Preferably, the compositions according to the invention are characterized in that the sum of the weights of the compounds HFC-32, HFC-125 and HFC-134a is equal to 100%.
In one embodiment according to the invention, preference is given to the composition consisting of 37% by weight of difluoromethane (HFC-32), 30% by weight of pentafluoroethane (HFC-125), and 33% by weight of tetrafluoroethane (HFC-134a).
One possibility offered by the present invention is the use of the abovementioned compositions as liquid refrigerant.
In a preferred embodiment, the compositions according to the invention are used as a replacement for R-404A.
The invention also relates to a refrigeration process comprising at least one stage of condensation followed by one stage of evaporation of a composition described above.
In a preferred embodiment, the process according to the invention comprises a stage of condensation carried out at a temperature of greater than 13° C., preferably of greater than 24° C.
According to a very particularly preferred embodiment, the process according to the invention comprises a stage of evaporation carried out at a temperature of less than or equal to −10° C.
Another subject matter of the invention is a device for transfer of heat in a compression cycle including a composition described above.
The performance of the mixture, denoted “Mixture 1”, consisting of 37% by weight of difluoromethane (HFC-32), 30% by weight of pentafluoroethane (HFC-125) and 33% by weight of tetrafluoroethane (HFC-134a), is compared with that of R-404A by simulating the performances with the Cycle D, NIST, version 5.0, software under the following operating conditions and are presented below:

    
    
        Evaporation temperature: −32° C.
        Condensation temperature: 43° C.
        Subcooling: 5° C.
        Superheat: 5° C.
        Refrigerating capacity: 10 kW
        Isentropic coefficient of the compressor: 0.7

The GWP is calculated according to the 4th report of the IPCC (2007).

    
    

















Refrigerant
R-404A
Mixture 1




















GWP
3922
1722



Evaporation pressure (bar)
1.8
1.6



Condensation pressure (bar)
19.3
20.6



Volumetric refrigerating capacity
912
998



(kJ/m3)



Coefficient of performance
1.4
1.5



Flow rate by weight (kg/h)
375
233










The performance of the “Mixture 1” at different condensation and evaporation temperatures is presented below and compared with that of R404A:















Refrigerant



R-404A





GWP
3922











Condensation temperature (° C.)
13
24
35
43















Evaporation temperature (° C.)
−32
−32
−10
−20
−32
−10
−20
−32


Evaporation pressure (bar)
1.8
1.8
4.3
3.0
1.8
4.3
3.0
1.8


Condensation pressure (bar)
8.8
12.0
15.9
15.9
15.9
19.3
19.3
19.3


Volumetric refrigerating capacity (kJ/m3)
1343
1191
2589
1738
1032
2318
1547
912


Coefficient of performance
3.1
2.3
3.2
2.3
1.7
2.5
1.9
1.4


Flow rate by weight (kg/h)
254
287
296
310
331
330
349
375


Volumetric refrigerating capacity with
—
—
—
—
—
—
—
—


respect to R-404A (%)


COP with respect to R-404A (%)
—
—
—
—
—
—
—
—












Refrigerant



Mixture 1





GWP
1722











Condensation temperature (° C.)
13
24
35
43















Evaporation temperature (° C.)
−32
−32
−10
−20
−32
−10
−20
−32


Evaporation pressure (bar)
1.6
1.6
3.9
2.7
1.6
3.9
2.7
1.6


Condensation pressure (bar)
9.2
12.6
16.9
16.9
16.9
20.6
20.6
20.6


Volumetric refrigerating capacity (kJ/m3)
1308
1199
2746
1838
1084
2541
1697
998


Coefficient of performance
2.9
2.2
3.1
2.4
1.7
2.5
1.9
1.5


Flow rate by weight (kg/h)
178
194
201
207
215
217
224
233


Volumetric refrigerating capacity with
97
101
106
106
105
110
110
109


respect to R-404A (%)


COP with respect to R-404A (%)
95
99
98
100
102
101
104
106

## Claims

1. A composition comprising:
a. from 36 to 39% by weight of difluoromethane (HFC-32);
b. from 28 to 32% by weight of pentafluoroethane (HFC-125);
c. from 31 to 35% by weight of tetrafluoroethane (HFC-134a).

2. The composition as claimed in claim 1, in which the sum of the weights of the compounds HFC-32, HFC-125 and HFC-134a is equal to 100%.

3. The composition as claimed in claim 1, consisting of:
a. 37% by weight of difluoromethane (HFC-32);
b. 30% by weight of pentafluoroethane (HFC-125);
c. 33% by weight of tetrafluoroethane (HFC-134a).

4. A refrigeration process comprising the use of a composition as claimed in claim 1 as refrigerant.

5. The refrigeration process use as claimed in claim 4, wherein the refrigerant is a replacement for R-404A.

6. A refrigeration process comprising the following stages:
a. condensation of a composition as claimed in claim 1;
b. evaporation of said composition.

7. The process as claimed in claim 6, in which the condensation stage is carried out at a temperature of greater than 13° C.

8. The process as claimed in claim 6, in which the evaporation stage is carried out at a temperature of less than or equal to −10° C.

9. A device for transfer of heat in a compression cycle including the composition as claimed in claim 1.

10. The process as claimed in claim 6, in which the condensation stage is carried out at a temperature of greater than 24° C.

11. The process as claimed in claim 10, in which the evaporation stage is carried out at a temperature of less than or equal to −10° C.

12. The process as claimed in claim 7, in which the evaporation stage is carried out at a temperature of less than or equal to −10° C.