# Patent

## Title
Azeotropic or quasi-azeotropic composition of chloromethane

## Abstract

Quasi-azeotropic or azeotropic compositions containing chloromethane and at least one or more compound(s) selected from 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, E/Z-1,2,3,3,3-pentafluoropropene, 1,1-difluoroethane and E-1,3,3,3-tetrafluoropropene. The composition may include either from 0.5 to 70 mol % of chloromethane and at least from 99.5 to 30 mol % of a compound selected from 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, 3,3,3-trifluoropropene and 1,1,1,2-tetrafluoroethane, or from 55 to 95 mol % of chloromethane and at least from 45 to 5 mol % of one or more compound(s) selected from 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, E/Z-1,2,3,3,3-pentafluoropropene and E-1,3,3,3-tetrafluoropropene.

## Background
The present invention relates to azeotropic or quasi-azeotropic compositions comprising chloromethane.


Fluids based on halocarbons have found many applications in various industrial fields, in particular as heat transfer fluid, propellants, foaming agents, blowing agents, gaseous dielectrics, monomer or polymerization medium, support fluids, agents for abrasives, drying agents and fluids for energy production units.
Particular importance is given to fluids that have a low impact on the environment.
The advantage of using azeotropic or quasi-azeotropic fluids is that they do not fractionate during evaporation processes and act (almost) as a pure body. However, it is difficult to identify novel fluids that meet these characteristics, since azeotropes cannot be predicted.
The invention thus relates to an azeotropic or quasi-azeotropic composition comprising chloromethane and at least one or more compound(s) selected from 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, E/Z-1,2,3,3,3-pentafluoro-propene, 1,1-difluoroethane and E-1,3,3,3-tetrafluoropropene.
The expression “quasi-azeotropic” has a broad meaning and is intended to include the compositions that are strictly azeotropic and those that behave as an azeotropic mixture.
A mixture is azeotropic when the pressure at the dew point is equal to that at the bubble point, which means that the vapor composition is equal to that of the condensed liquid.
A mixture is considered to be quasi-azeotropic when the pressure difference between the pressure at the dew point and the pressure at the bubble point is less than or equal to 5%, on the basis of the pressure at the bubble point.
According to one embodiment, the composition according to the invention comprises, preferably essentially consisting of, either (from) 0.5 to 70 mol % of chloromethane and from 99.5 to 30 mol % of at least one compound selected from 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, 3,3,3-trifluoropropene and 1,1,1,2-tetrafluoroethane, or (from) 55 to 95 mol % of chloromethane and (from) 45 to 5 mol % of at least one compound selected from 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, E/Z-1,2,3,3,3-pentafluoropropene and E-1,3,3,3-tetrafluoro-propene.
According to one preferred embodiment, the composition according to the invention comprises, preferably essentially consisting of, chloromethane, preferably from 10 to 50 mol %, and at least compound(s) selected from 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, E/Z-1,1,3,3,3-pentafluoropropene, E/Z-1,2,3,3,3-pentafluoropropene and E-1,3,3,3-tetrafluoropropene, preferably 2,3,3,3-tetrafluoropropene, preferably representing 50 to 90 mol %.
According to one particularly preferred embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 10 to 45 mol % of chloromethane and (from) 90 to 55 mol % of 2,3,3,3-tetrafluoropropene.
In one embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 0.5 to 50 mol % of chloromethane and (from) 95.5 to 50 mol % of 1,1,1,2-tetrafluoroethane.
In another embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 35 to 65 mol % of chloromethane and (from) 65 to 35 mol % of 3,3,3-trifluoropropene.
According to one embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 60 to 90 mol % of chloromethane and (from) 40 to 10 mol % of 1,1,1,2,2-pentafluoropropane.
According to another embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 55 to 85 mol % of chloromethane and (from) 45 to 15 mol % of E/Z-1,1,3,3,3-pentafluoropropene.
According to one possibility offered by the invention, the composition according to the invention comprises, preferably essentially consisting of, (from) 60 to 90 mol % of chloromethane and (from) 40 to 10 mol % of E/Z-1,2,3,3,3-pentafluoropropene.
In one embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 5 to 70 mol %, preferably from 10 to 60 mol % of chloromethane and (from) 95 to 30 mol %, preferably 40 to 90 mol % of 1,1-difluoroethane.
In another embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 65 to 95 mol % of chloromethane and (from) 35 to 5 mol % of E-1,3,3,3-tetrafluoropropene.
According to one possibility offered by the invention, the composition may also comprise hydrogen fluoride.
According to one particularly preferred possibility offered by the invention, the composition according to the invention comprises, preferably essentially consisting of, (from) 20 to 45 mol % of HF, 5 to 20 mol % of chloromethane and 35 to 70 mol % of 2,3,3,3-tetrafluoropropene.
According to one embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 15 to 45 mol % of HF, 35 to 60 mol % of chloromethane and 15 to 30 mol % of 1,1,1,2,2-pentafluoropropane.
According to another embodiment, the composition according to the invention is characterized in that it comprises, preferably essentially consisting of, (from) 15 to 45 mol % of HF, 1 to 30 mol % of chloromethane and 30 to 85 mol % of 1,1-difluoroethane.
According to one embodiment, the composition according to the invention comprises, preferably essentially consisting of, (from) 15 to 40 mol % of HF, 40 to 70 mol % of chloromethane and 10 to 30 mol % of E/Z-1,3,3,3-tetrafluoropropene.
According to another embodiment, the composition according to the invention has a boiling point between from −40° C. to 70° C. at a pressure of between 1 and 15 bar.
The invention also relates to the use of a fluid comprising the composition according to the invention as heat transfer fluid, propellants, foaming agents, blowing agents, gaseous dielectrics, monomer or polymerization medium, support fluids, agents for abrasives, drying agents and fluids for energy production units.
Preferably, the invention relates to the use of a fluid comprising the composition according to the invention as heat transfer fluid in a heat pump or refrigeration plant.
The invention also relates to a heat transfer plant comprising a vapor compression circuit containing a fluid comprising a composition according to the invention as heat transfer fluid or containing a heat transfer fluid as described above.
According to one embodiment, the plant is selected from mobile or stationary plants for heating via a heat pump, for air conditioning, and in particular for motor vehicle air conditioning or for centralized stationary air conditioning, for refrigeration or for freezing and Rankine cycles; and which is preferably an air conditioning plant.
The invention also relates to a process for heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid, said process successively comprising the evaporation of the heat transfer fluid, the compression of the heat transfer fluid, the condensation of the heat fluid and the expansion of the heat transfer fluid, in which the heat transfer fluid is a fluid comprising a composition according to the invention.
The expression “heat transfer fluid” is understood to mean a fluid capable of absorbing heat by evaporating at low temperature and low pressure and of releasing heat by condensing at high temperature and high pressure, in a vapor compression circuit.
A heat transfer fluid optionally comprises one or more additives which are not heat transfer compounds for the envisaged application. The additives may in particular be selected from lubricants, nanoparticles, stabilizers, surfactants, tracers, fluorescent agents, odorous agents and solubilizing agents, as are well known to a person skilled in the art.
In what follows, the following compounds represent:

    
    
        chloromethane: HCC-40 or F40
        2,3,3,3-tetrafluoropropene: HFO-1234yf or F1234yf
        3,3,3-trifluoropropene: HFO-1243zf or F1243zf
        1,1,1,2-tetrafluoroethane: HFC-134a or F134a
        1,1,1,2,2-pentafluoropropane: HFC-245cb or F245cb
        E/Z-1,1,3,3,3-pentafluoropropene: HFO-1225zc or F1225zc
        E/Z-1,2,3,3,3-pentafluoropropene: HFO-1225ye or F1225ye
        1,1-difluoroethane: HFC-152a or F152a
        E-1,3,3,3-tetrafluoropropene: HFO-1234ze-E or F1234ze-E
    
    


The azeotropic compositions representative of the invention, non-limitingly, at various temperatures and pressures, are presented in table 1 below:













TABLE 1






Temperature
Mole (%)
Mole (%) of
Temperature
Mole (%)
Mole (%) of


Azeotrope
(° C.)
of F40
Compound 2
° C.
of F40
Compound 2


















Pressure: 1 bar absolute
Pressure 3 bar absolute













F40/F1234yf
−30
34
66
−2.0
34
66


F40/F1243zf
−27
53
47
1
54
46


F40/F134a
−28
35
65
0
22
78


F40/F245cb
−26
76
24
3
76
24


F40/F1225zc
−25
70
30
3
69
31


F40/F1225ye
−25
74
26
3.0
72
28


F40/F152a
−25
54
46
3.0
42
58


F40/F1234ze-E
−24
80
20
4.0
81
19










Pressure 10 bar absolute
Pressure 15 bar absolute













F40/F1234yf
38
66
34
55
65
35


F40/F1243zf
40
55
45
59
56
44


F40/F134a
39
3
97
—
—
—


F40/F245cb
44
78
22
60
78
22


F40/F1225zc
44
68
32
60
68
32


F40/F1225ye
43
70
30
60
69
31


F40/F152a
43
27
73
59
21
79


F40/F1234ze-E
45
83
17
62
84
16

## Claims

1. An azeotropic or quasi-azeotropic composition comprising chloromethane and at least one or more compound(s) selected from 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, E/Z-1,2,3,3,3-pentafluoropropene, and 1,1-difluoroethane, wherein the composition comprises either
from 0.5 to 70 mol % of chloromethane and from 99.5 to 30 mol % of at least one or more compound(s) selected from 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, and 3,3,3-trifluoropropene, or
from 55 to 95 mol % of chloromethane and from 45 to 5 mol % of at least one or more compound(s) selected from 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, and E/Z-1,2,3,3,3-pentafluoropropene.

2. The composition as claimed in claim 1, wherein the composition comprises either from 20 to 50 mol % of chloromethane and from 80 to 50 mol % of 2,3,3,3-tetrafluoropropene.

3. The composition as claimed in claim 1, wherein the composition comprises from 35 to 65 mol % of chloromethane and from 65 to 35 mol % of 3,3,3-trifluoropropene.

4. The composition as claimed in claim 1, wherein the composition comprises from 60 to 90 mol % of chloromethane and from 40 to 10 mol % of 1,1,1,2,2-pentafluoropropane.

5. The composition as claimed in claim 1, wherein the composition comprises from 55 to 85 mol % of chloromethane and from 45 to 15 mol % of E/Z-1,1,3,3,3-pentafluoropropene.

6. The composition as claimed in claim 1, wherein the composition comprises from 60 to 90 mol % of chloromethane and from 40 to 10 mol % of E/Z-1,2,3,3,3-pentafluoropropene.

7. The composition as claimed in claim 1, wherein the composition comprises from 5 to 70 mol % of chloromethane and from 95 to 30 mol % of 1,1-difluoroethane.

8. The composition as claimed in claim 1, wherein the composition further comprises hydrogen fluoride.

9. The composition as claimed in claim 8, wherein the composition comprises from 20 to 45 mol % of HF, 5 to 20 mol % of chloromethane and 35 to 70 mol % of 2,3,3,3-tetrafluoropropene.

10. The composition as claimed in claim 8, wherein the composition comprises from 15 to 45 mol % of HF, 35 to 60 mol % of chloromethane and 15 to 30 mol % of 1,1,1,2,2-pentafluoropropane.

11. The composition as claimed in claim 8, wherein the composition comprises from 15 to 45 mol % of HF, 1 to 30 mol % of chloromethane and 30 to 85 mol % of 1,1-difluoroethane.

12. An azeotropic or quasi-azeotropic composition comprising from 15 to 40 mol % of HF, 40 to 70 mol % of chloromethane and 10 to 30 mol % of E/Z-1,3,3,3-tetrafluoropropene.

13. The composition as claimed in claim 1, wherein the composition has a boiling point between from −40° C. to 70° C. and a pressure of between 1 and 15 bar.

14. The composition as claimed in claim 1, wherein the composition consists essentially of either
from 0.5 to 70 mol % of chloromethane and from 99.5 to 30 mol % of a at least one or more compound(s) selected from 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, and 3,3,3-trifluoropropene, or
from 55 to 95 mol % of chloromethane and from 45 to 5 mol % of at least one or more compound(s) selected from 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, and E/Z-1,2,3,3,3-pentafluoropropene.

15. The composition as claimed in claim 1, wherein the composition consists of either
from 0.5 to 70 mol % of chloromethane and from 99.5 to 30 mol % of a at least one or more compound(s) selected from 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane, and 3,3,3-trifluoropropene, or
from 55 to 95 mol % of chloromethane and from 45 to 5 mol % of at least one or more compound(s) selected from 1,1,1,2,2-pentafluoropropane, E/Z-1,1,3,3,3-pentafluoropropene, and E/Z-1,2,3,3,3-pentafluoropropene.