# Patent

## Title
Refrigerant composition

## Abstract

A composition which comprises or consists of more than 75 to less than 80 wt. % of pentafluoroethane (HFC-125); more than 17 to less than 22.7 wt. % of 1,1,1,2-tetrafluoroethane (HFC-134a); and more than 2.3 to less than 3.0 wt. % of n-butane (R600).

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims the priority benefit under 35 U.S.C. §119(a)-(d) of European Application No. 09162579.8 filed Jun. 12, 2009, the whole content of this application being incorporated herein by reference for all purposes.
FIELD OF THE INVENTION
The present invention relates to refrigerant compositions, which are suitable, in particular as replacement or drop-in substitute for chlorodifluoromethane (HCFC-22).
BACKGROUND OF THE INVENTION
HCFC-22 is due to be phased out in certain countries for cooling and air conditioning applications to address Ozone Depletion Potential concerns related to that compound. Different replacement compositions for HCFC-22 (also known as R22) have been suggested, for example R417A which consists of 46.6 wt. % pentafluoroethane (HFC-125), 50 wt. % 1,1,1,2-tetrafluoroethane (HFC-134a) and 3.4 wt. % n-butane (R-600).
A specific field of application of HCFC-22 is low temperature refrigeration.
WO-A-01/23493 discloses a refrigerant composition comprising HFC-125, HFC-134a and an additive selected from a saturated hydrocarbon or a mixture thereof boiling in the range of −5 to 70° C. wherein the weights of HFC-125 to R134a is in the ranges 50-80 wt. % HFC-125, 50-20% wt % HFC-134a.
WO-A-2004/033582 discloses in particular compositions consisting of 85 wt. % HFC-125, 11.5 wt. % HFC-134a and 3.5 wt. % of n-butane or isobutane.
SUMMARY OF THE INVENTION
The invention makes now available refrigerant compositions having zero ozone depletion potential, which are suitable as HCFC-22 drop-in substitutes,
especially for low-temperature refrigeration applications, and present advantages in particular regarding their volumetric cooling capacity. Also, generally, the refrigerant compositions found are and remain non-flammable in case of a worst case fractionation scenario.
The invention relates in consequence to a composition which comprises or consists of

    HFC-125: more than 75 to less than 80 wt. %
    HFC-134a: more than 17 to less than 22.7 wt. %
    R600: more than 2.3 to less than 3.0 wt. %.


The percentages herein are relative to the total weight of the composition.
It has been found, surprisingly, that the composition according to the invention when used to replace R22 in existing refrigeration systems offer good oil return characteristics while maintaining good performance, in particular concerning volumetric cooling capacity, heat transfer and, consequently, energy consumption. The temperature glide of the composition according to the invention is relatively small, thereby, when the compositions are used as refrigerant, the superheat at the end of the evaporation process can be significantly decreased and hence the evaporation temperature lifted. Furthermore the small temperature glide allows for a higher medium temperature in the evaporator and a lower condensing temperature in the condenser. The pressure of the composition is generally slightly higher compared to R22 but the compositions can be safely used with refrigeration equipment designed for use with R22.


DETAILED DESCRIPTION OF THE INVENTION
The composition according to the invention preferably comprises or consists of

    HFC-125: 78.5-79.5 wt. %
    HFC-134a: 17.4-19.0 wt. %
    R600: 2.5-2.9 wt. %.


More preferably the composition according to the invention comprises or consists of

    HFC-125: 78.5-79.5 wt. %
    HFC-134a: 17.75-18.75 wt. %
    R600: about 2.75 wt. %.


A composition according to the invention, which comprises or consists of

    HFC-125: about 79 wt. %
    HFC-134a: about 18.25 wt. %
    R600: about 2.75 wt. %.

is more particularly preferred. Herein after the composition according to the invention consisting of 79 wt. % HFC-125, 18.25 wt. % HFC-134a and 2.75 wt. % R600 will be also referred to as “Mix A”.



The compositions according to the invention are generally non-flammable, especially when tested in accordance with ASHRAE Standard 34-2007. Non flammability is generally found both in liquid and vapor phases. Preferred compositions are non flammable both in liquid and vapor phases in case of worst case fractionation scenario, for example tested according to ASHRAE Standard 34-2007.
The compositions according to the invention have generally a vapor pressure measured at 55° C. equal or lower than about 25 bars absolute pressure. Often this pressure is in a range from 23 to 25 bars, preferably from 24 to 25 bars. It has been found that the compositions having this pressure have particular heat transfer efficiency.
The compositions according to the invention have generally a temperature glide, defined as the temperature difference between the bubble point and the dew point at the boiling temperature and corresponding boiling pressure of the composition, which is less than 4° C., often equal to or less than 3.5° C., preferably equal to or less than 3.0° C. The temperature glide is generally equal to or more than 0.5° C., often equal to or more than 1.0° C.
Table 1 here after gives the pressure temperature behavior and glide of Mix A. The pressure temperature behavior of R22 is given for reference.











TABLE 1







Bubble





Boiling point
point
Dew point


pressure
(R22, reference)
(Mix A)
(Mix A)
Glide


bar
° C.
° C.
° C.
° C.



















0.79
−45.94
−50
−46.27
3.73


1.01
−40.83
−45
−41.37
3.63


1.28
−35.71
−40
−36.48
3.52


1.60
−30.60
−35
−31.58
3.42


1.97
−25.49
−30
−26.68
3.32


2.42
−20.39
−25
−21.77
3.23


2.93
−15.28
−20
−16.87
3.13


3.53
−10.18
−15
−11.97
3.03


4.21
−5.08
−10
−7.06
2.94


4.98
0.02
−5
−2.16
2.84


5.86
5.12
0
2.75
2.75


6.85
10.22
5
7.65
2.65


7.97
15.32
10
12.55
2.55


9.21
20.42
15
17.45
2.45


10.59
25.52
20
22.35
2.35


12.12
30.63
25
27.25
2.25


13.80
35.74
30
32.14
2.14


15.66
40.85
35
37.02
2.02


17.69
45.97
40
41.90
1.90


19.92
51.10
45
46.78
1.78


22.35
56.23
50
51.64
1.64


25.00
61.37
55
56.49
1.49


27.89
66.53
60
61.32
1.32


31.03
71.70
65
66.11
1.11


34.46
76.89
70
70.83
0.83









The compositions according to the invention may be combined for example, with additives or auxiliaries used in refrigeration such as in particular a lubricant. Suitable lubricants include in particular those which are suitable for use with HCFC-22. Examples of lubricants which can suitably be combined with the composition according to the invention are selected from mineral oil, for example napthtenic mineral oils alkylbenzene oils lubricants, and polyol ester oils or mixtures thereof.
When the composition according to the invention is combined with an additive, in particular a lubricant as described here before the weight ratio composition/additive is generally from equal to or greater than 99:1 to equal to or less than 80:20 (weight/weight) preferably from equal to or greater than 98.5:1.5 to equal to or less than 95:5 (weight/weight).
The invention relates also to the combination of the composition according to the invention with an additive as described here before.
The invention relates also to a refrigeration apparatus containing a composition according to the invention or a combination according to the invention. A preferred refrigeration apparatus according to the invention is designed for use with R22. The refrigeration apparatus according to the invention is preferably suitable for providing low-temperature refrigeration.
“Low temperature refrigeration” is understood to denote in particular cooling a body to be cooled to a temperature of from −45° C. to −20° C. The compositions according to the invention and the refrigeration apparatus according to the invention are particularly suitable for cooling a body to be cooled to a temperature of from −35° C. to −20° C.
The compositions according to the invention and the refrigeration apparatus according to the invention are also suitable for “normal refrigeration”, understood to denote in particular cooling a body to be cooled to a temperature of from greater than −20° C. to +5° C.
In a particular embodiment, the refrigeration apparatus according to the invention has been used with R22 and R22 has been replaced by the composition according to the invention. In a particular aspect of the refrigeration apparatus according to this embodiment, a lubricant, in particular as described above was used with R22 and said lubricant has been at least partially kept in the apparatus for use with the composition according to the invention.
The invention relates also to the use of the composition according to the invention as refrigerant, such as a method for refrigeration which comprises utilizing any of the compositions according to the invention. The composition according to the invention is preferably used as replacement for R22, in particular as drop-in replacement for R22.
EXAMPLES
The examples here after are intended to illustrate the invention without however limiting it.
Example 1
Refrigeration with a Composition According to the Invention
In an apparatus working with simple refrigeration cycle containing Mix A, evaporation of the refrigerant composition is carried out at −30° C. and condensation is carried out at variable temperatures (30/35/40/45° C.). Superheat is 5K and subcooling is 2K. The compressor efficiency at the different temperatures is given in the table here after.
Example 2
(Comparison): Refrigeration with Prior Art Refrigerants
Following the same procedure as in example 1, the volumetric cooling capacity of R22, R417A and the composition HFC-125/HFC-134a/pentane 76.8/19.2/4.0 (% wt.) disclosed in WO-A-01/23493 (here after “Mix B”) are determined at different temperatures.
The results of examples 1 and 2 are shown in Table 2. It is apparent that the composition according to the invention comes the closest to the volumetric cooling capacity of R22 and is superior to the prior art non-ozone depleting R22 replacements.














TABLE 2










Isentropic





T. evap.
T cond.
p evap.
Ratio
compressor


Refrigerant
° C.
° C.
bar
p cond./p. evap
efficiency
COP
Qvol, kJ/m3






















R22
−30
30
1.64
7.27
0.745
2.33
1165



−30
35
1.64
8.26
0.734
2.06
1662



−30
40
1.64
9.35
0.723
1.82
1072



−30
45
1.64
10.55
0.71
1.61
1024


Mix A
−30
30
1.71
8.03
0.737
1.93
979



−30
35
1.71
9.11
0.725
1.66
907



−30
40
1.71
10.3
0.713
1.42
832



−30
45
1.71
11.6
0.699
1.21
756


Mix B
−30
30
0.7
18.33
0.628
1.17
417



−30
35
0.7
20.78
0.603
1
388



−30
40
0.7
23.46
0.575
0.84
359



−30
45
0.7
26.38
0.544
0.71
330


R417A
−30
30
1.23
9.17
0.725
1.96
783



−30
35
1.23
10.44
0.711
1.7
734



−30
40
1.23
11.83
0.697
1.47
685



−30
45
1.23
13.36
0.681
1.27
634





T. evap. Evaporation Temperature


T cond. Condensation Temperature


p evap. Evaporation pressure


p cond. Condensing pressure


COP Coefficient of Performance


Qvol. Volumetric Capacity






Example 3
Flammability of a Composition According to the Invention
Mix A was determined to be non-flammable in accordance with ASHRAE Standard 34-2007.
Example 4
Worst Case Fractionation Scenario of a Composition According to the Invention
Concentration of refrigerant components after vapor leakage of Mix A with 90% liquid as worst case start condition is determined in accordance with ASHRAE Standard 34-2007. The maximum R600 content is reached after 93% vapor leakage with the evaporation of the last liquid. The full composition of vapor and liquid phases at this point is given in Table 3 the components being indicated in the same order as in the “Refrigerant” column. The maximum R600 concentration is in this point about 3.7 wt. % in the vapor phase and about 4.1 wt. % in the liquid phase. Both liquid and vapor phases are non-flammable.
Example 5
(Comparison)
As in example 4, concentration of refrigerant components after vapor leakage, but of refrigerant mix B, with 90% liquid as worst case start condition is determined. The maximum Pentane content is reached at the end of the liquid phase. The full composition of vapor and liquid phases at this point is given in Table 3 the components being indicated in the same order as in the “Refrigerant” column. The maximum Pentane concentration is in this point about 96.3 wt % in the liquid phase and 52.6 wt. % in the vapor phase. Both liquid and vapor phases are highly flammable.
Example 6
(Comparison)
As in example 4, concentration of refrigerant components after vapor leakage, but of a R125/R134a/n-butane blend with 75.02/21.48/3.5 with 90% liquid as worst case start condition is determined. The maximum n-butane content is reached at the end of the liquid phase. The full composition of vapor and liquid phases at this point is given in Table 3 the components being indicated in the same order as in the “Refrigerant” column. The maximum butane concentration is in this point about 5.37 wt. % in the liquid phase and 5.05 wt. % in the vapor phase. Both liquid and vapor phases are flammable.










TABLE 3






Amount of





leaked
Liquid



Refrigerant
Gas, %
(wt. %)
Vapor phase







R125/R134a/n-Butane
  93%
50.3/45.6/4.1
63.3/33.0/3.7


(79.0/18.25/2.75


wt. %) (invention)


(Mix A)


R125/R134a/Pentane
  98%
1.0/2.7/96.3
18.9/28.5/52.6


(76.8/19.2/4.0 wt %)


(comparison) (Mix B)


R125/R134a/Pentane
 91.5%
14.2/8.4/77.4
64.0/22.2/13.85


(76.8/19.2/4.0 wt %)


(comparison) (Mix B)


R125/R134a/n-Butane
95.54%
38.33/56.30/5.37
51.82/43.14/5.05


(75.02/21.48/3.5


wt. %) (comparison)









Example 7
Drop-in Substitution of R22 by the Composition According to the Invention
A cooling system for the food storage room and display cases of a company restaurant operated to cool the room to about 0° C. and the display cases to about −5° C. was monitored when working with R22. Over a given time period the compressor was either in working state, when the room and display cases needed to be cooled or in stand-by, when they were at an acceptable temperature. The percentage of compressor working time required to cool the room and display cases was taken as a benchmark for the efficiency of R22 in the cooling system. Subsequently, a drop-in substitution of the R22 by Mix A according to the invention was carried out. The compressor working time was monitored as described here before for R22, under similar conditions and for a similar period of time. The comparison of the percentages of compressor working time required with Mix A and with R22 respectively showed that Mix A was as efficient as R22.

## Claims

1. A composition which is non-flammable and which comprises
more than 75 to less than 80 wt. % of pentafluoroethane (HFC-125);
more than 17 to less than 22.7 wt. % of 1,1,1,2-tetrafluoroethane (HFC-134a); and
more than 2.3 to less than 3.0 wt. % of n-butane (R600).

2. The composition of claim 1, which comprises
78.5-79.5 wt. % of HFC-125;
17.4-19.0 wt. % of HFC-134a; and
2.5-2.9 wt. % of R600.

3. The composition of claim 2, which comprises
78.5-79.5 wt. % of HFC-125;
17.75-18.75 wt. % of HFC-134a; and
about 2.75 wt. % of R600.

4. The composition of claim 3, which comprises
about 79 wt. % of HFC-125;
about 18.25 wt. % of HFC-134a; and
about 2.75 wt. % of R600.

5. The composition according to claim 1, which has a vapor pressure measured at 55° C. below 25 bars.

6. The composition according to claim 1 which has a temperature glide from 0.5° C. to less than 4° C.

7. A combination comprising the composition according to claim 1 and a lubricant.

8. The combination according to claim 7, wherein the lubricant is selected from the group consisting of mineral oil and alkylbenzene oil.

9. The combination according to claim 7 wherein the weight ratio composition/lubricant is from 99:1 to 80:20 (weight/weight).

10. A refrigeration apparatus containing the composition according to claim 1.

11. The refrigeration apparatus according to claim 10, which is designed for use with R22.

12. The refrigeration apparatus according to claim 10, which is suitable for providing low-temperature refrigeration.

13. A method for refrigeration comprising utilizing the composition according to claim 1 as a refrigerant.

14. The method for refrigeration according to claim 13, wherein said composition is used as drop-in replacement for R22.

15. A refrigeration apparatus containing the combination according to claim 7.

16. A composition which is non-flammable and which consists of
more than 75 to less than 80 wt. % of pentafluoroethane (HFC-125);
more than 17 to less than 22.7 wt. % of 1,1,1,2-tetrafluoroethane (HFC-134a); and
more than 2.3 to less than 3.0 wt. % of n-butane (R600).

17. A combination comprising the composition according to claim 16 and a lubricant.

18. A refrigeration apparatus containing the composition according to claim 16, which is designed for use with R22.

19. A refrigeration apparatus containing the composition according to claim 16, which is suitable for providing low-temperature refrigeration.