Azeotropic compositions BASED FLUORIDE

D'HYDROGENE ET DE Z-3,3,3-TRIFLUORO-1 -CHLOROPROPENE

FIELD OF THE INVENTION

The present invention relates to azeotropic or near azeotropic compositions based on hydrogen fluoride and Z-3,3,3-trifluoro-1 -chloropropène.

TECHNICAL BACKGROUND

3,3,3-trifluoro-1 -chloropropène or more 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) exists as two isomers: cis isomer, namely the Z-3,3 , 3-trifluoro-1 -chloropropène (HCFO-1233zdZ), and the trans isomer, namely S-3,3,3-trifluoro-1 -chloropropène (HCFO-1233zdE). They have different boiling points, respectively 18.5 ° C for the trans compound and 39.5 ° C for the cis compound.

Fluids bases E-3,3,3-trifluoro-1 -chloropropène (HCFO-1233zdE) have found numerous applications in various industrial fields, such as heat transfer fluids, propellants, foaming agents, agents blowing, gaseous dielectrics, polymerization media or monomers, support fluids, abrasive agents, drying agents and fluids for energy production unit.

The manufacture of HCFO-1233zdE is accompanied by a multitude of by-products having a close boiling point of HCFO-1233zdE. This leads to quite complex and expensive purification steps. The difficulties encountered during the purification of HCFO-1233zdE usually involve a significant loss of desired product. In addition, the byproducts can form azeotropic compositions with HCFO-1233zdE, making it very difficult or impossible separation by simple distillation.

Document US 6013846 describes an azeotropic composition of HCFO-1233zd and hydrogen fluoride (HF). The document does not specify the isomeric form of HCFO-1233zd.

Document US 6328907 describes an azeotropic composition of 1, 1, 1, 3,3-pentafluoropropane (HFC-245fa) and HF.

Document US 8,378,158 describes a quasi-azeotropic composition HCFO-1233zdZ and HF.

Document US 7,423,188 describes an azeotropic composition

E-1 ,3,3,3-tétrafluoropropène (HFO-1234zeE) et de HF.

WO 2008/002500 describes the document azeotropic composition of Z-1, 3,3,3-tetrafluoropropene (HFO-1234zeZ) and HF.

Document US 7,183,448 describes an azeotropic composition of HFC-245fa and 1233zd-HCFO. It is stated in the document that the azeotrope is obtained with the trans isomer of HCFO-1233zd.

Document US 8075797 discloses a near-azeotropic composition of HF, HFC-245fa, and HCFO-1233zd. It is stated in the document that the azeotrope-like is obtained with the trans isomer of HCFO-1233zd.

There is still a need to provide other azeotropic compositions including azeotropic compositions based on compounds that are used in the manufacture of HCFO-1233zdE. However, in general, the azeotropes are difficult to predict.

RESUME DE L'INVENTION

The invention firstly relates to an azeotropic composition or quasi-azeotropic comprising hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène and one or more compounds (hydro) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, the compound

(Hydro) halocarbon contain 3 carbon atoms, and are preferably chosen from propane and propene partially or fully substituted by halogens.

According to one embodiment, the compound (hydro) halocarbon are selected from tétrachlorofluoropropanes, the trichlorodifluoropropanes, the dichlorotrifluoropropanes, the chlorotétrafluoropropanes, the pentafluoropropanes, the trichiorofluoropropènes, the dichlorodifluoropropènes, the chlorotrifluoropropènes and tetrafluoropropenes.

According to one embodiment, the composition of the invention comprises hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-3,3,3-trifluoro-1 and a -chloropropène or more other compounds (hydro) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention comprises hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-1, 3,3,3-tetrafluoropropene and one or more other compounds (hydro) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention comprises hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, Z-1, 3,3,3-tetrafluoropropene and one or more other compounds (hydro) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention comprises hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, 1, 1, 1, 3,3-pentafluoropropane and one or more other compounds (hydro) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention is a ternary mixture, and preferably is a mixture of hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène and E-3.3 , 3-trifluoro-1 -chloropropène.

According to one embodiment, the composition of the invention is a quaternary mixture, and preferably is a mixture of:

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-3,3,3-trifluoro-1 -chloropropène and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, Z-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane.

According to one embodiment, the composition of the invention is a quinquénaire mixture, and preferably is a mixture of:

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-3,3,3-trifluoro-1 -chloropropène, Z 1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-3,3,3-trifluoro-1 -chloropropène, E 1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, Z-1, 3,3,3-tetrafluoropropene, E-1, 3,3,3-tetrafluoropropene and

1 ,1 ,1 ,3,3-pentafluoropropane.

According to one embodiment, the composition of the invention is a senaire mixture, and preferably is a mixture of:

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-3,3,3-trifluoro-1 -chloropropène, Z-1, 3,3,3-tetrafluoropropene, E-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane.

According to one embodiment, the composition of the invention is hetero azeotropic or quasi-azeotropic hetero.

According to one embodiment, the composition of the invention comprises 1 to 85% by weight, preferably 1 to 80% by weight, more preferably 5 to 80% by weight and very particularly preferably 5 to 75% by weight of hydrogen fluoride; and / or 15 to 99% by weight, preferably 20 to 99% by weight, more preferably from 20 to 95% by weight and most preferably from 25 to 95% by weight of compounds (hydro ) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention has a boiling point of 0 to 40 ° C at a pressure of 0.5 to 9 bar absolute.

The invention also relates to a method for producing a compound (hydro) halocarbon principal, comprising:

- Forming a mixture of compounds including hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène and one or more other compounds (hydro) halocarbon;

- Distillation of this mixture, to collect on the one hand an azeotropic composition of the invention, and secondly at least one of the compounds of the mixture.

According to one embodiment, distillation is used to collect on the one hand an azeotropic composition of the invention, and secondly hydrogen fluoride; or firstly an azeotropic composition of the invention, and secondly the E-3,3,3-trifluoro-1 -chloropropène.

According to one embodiment, the method of the invention is a process for producing 3,3,3-trifluoro-1 -chloropropène, and preferably S-3,3,3-trifluoro-1 -chloropropène.

According to one embodiment, the mixture of compounds is obtained as a result of a fluorination step, comprising the reaction of a chlorinated compound with hydrogen fluoride.

According to one embodiment, the collected azeotropic composition is separated, preferably by settling into two immiscible liquid fractions, namely a fraction rich in hydrogen fluoride and a fraction low in hydrogen fluoride-rich fraction hydrogen fluoride containing a higher proportion of hydrogen fluoride that the fraction low in hydrogen fluoride; and the fraction rich in hydrogen fluoride is optionally recycled to the fluorination step. The fraction low in hydrogen fluoride may be the subject to distillation to enable to collect on the one hand an azeotropic composition of i'inven.ion and secondly the E-3.3 ( 3-trifiuoro- 1 chioropropène.

According to one embodiment, the chlorinated starting compound reacts with the hydrogen fluoride is 1, 1, 1, 3,3-pentachloropropane or 1, 1, 3,3-tetrachloropropene.

The present invention can meet the need expressed above. It provides particularly azeotropic compositions or quasi-azeotropic from compounds that are used in the manufacture of various compounds (hydro) halocarbons, particularly in the manufacture of HCFO-1233zdE.

The identification of such azeotropic or near-azeotropic compositions thus makes it possible in particular to improve the efficiency and performance of production processes of compounds (hydro) halocarbons, particularly for producing HCFO-1233zdE.

In a preferred embodiment, these compositions are hetero-azeotropic mixtures, that is to say are compositions in which the condensed liquid form two immiscible solutions that can be separated easily, for example by decantation. This has a considerable advantage for the purification operations envisaged.

BRIEF DESCRIPTION OF FIGURES

1 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention in accordance with Example 1, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B and C correspond to various compositions in compounds (hydro) halocarbon (see Example 1).

2 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention in accordance with Example 2, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C and D correspond to various compositions in compounds (hydro) halocarbon (see Example 2).

3 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention according to Example 3, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C and D correspond to various compositions in compounds (hydro) halocarbon (see Example 3).

4 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention according to Example 4, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C and D correspond to various compositions in compounds (hydro) halocarbon (see Example 4).

5 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention according to Example 5, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C, D and E correspond to various compositions in compounds (hydro) halocarbon (see Example 5).

6 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention in accordance with Example 6, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C, D and E correspond to various compositions in compounds (hydro) halocarbon (see Example 6).

Figure 7 represents the vapor pressure (ordinate, in bars absolute) mixtures according to the invention according to Example 7, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C, D and E correspond to various compositions in compounds (hydro) halocarbon (see Example 7).

8 shows the vapor pressure (ordinate, in bars absolute) mixtures according to the invention according to Example 8, to the isotherm of 25 ° C. X-axis is the mass fraction of HF in the composition. Curves A, B, C, D, E and F correspond to various compositions in compounds (hydro) halocarbon (see Example 8).

EMBODIMENTS DESCRIPTION OF THE INVENTION

The invention is now described in more detail and in a nonlimiting manner in the following description.

Unless otherwise stated, all amounts mentioned in this application are mass proportions.

The invention provides azeotropic compositions, quasi-azeotropic, hetero azeotropic and near azeotropic hetero.

A mixture is azeotropic when considered that the pressure dew point is equal to the bubble forming point, which means that the vapor composition is equal to that of the condensed liquid.

A mixture is considered quasi-azeotropic when the pressure dew point is substantially equal to that at the bubble formation point, meaning that the vapor composition is substantially equal to that of the condensed liquid, eg the pressure difference between the pressure at the dew point and the pressure at the bubble forming point is less than or equal to 5%, based on the pressure at the bubble formation point.

A hetero-azeotropic mixture is an azeotropic mixture with the condensed liquid form two immiscible solutions that can be easily separated, for example by decantation.

A quasi-hetero-azeotropic mixture is a quasi-azeotropic mixture with the condensed liquid form two immiscible solutions that can be easily separated, for example by decantation.

The compositions of the invention include HF, HCFO-1233zdZ and one or more compounds (hydro) halocarbon comprising from 1 to 3 carbon atoms.

The compounds (hydro) halocarbons are compounds based on carbon atoms, halogen (s) and optionally hydrogen; advantageously, they are compounds based on carbon atoms, chlorine and / or fluorine, and optionally hydrogen. It is advantageously alkanes or alkenes substituted partially or totally by halogen atoms, especially chlorine and / or fluorine.

In a particular embodiment, the compounds

(Hydro) halocarbon may be used in the context of the invention comprise 1 or 2 carbon atoms.

They can be chosen from:

- le chlorométhane (HCC-40) ;

- Chloropentafluoroethane (HCFC-1 15);

- Chlorotetrafluoroethane (HFCF-124) that is 1-chloro-1, 2,2,2-tetrafluoroethane and 1-chloro-1, 1, 2, 2-tetrafluoroethane;

- Le Pentafluoroethane (HFC-125);

- Chlorotrifluoroethane, namely in particular the 1-chloro-1, 2,2-trifluoroethane (HCFC-133), 1-chloro-2,2,2-trifluoroethane

(HCFC-133a) and 1-chloro-1, 1, 2-trifluoroethane (HCFC-133b); - Tetrafluoroethane, namely in particular 1,1,2,2-tetrafluoroethane (HFC-134) and 1,1,1,2-tetrafluoroethane (HFC-134a);

- Chlorodifluoroethane, namely in particular 1-chloro-2,2-difluoroethane (HCFC-142), 1-chloro-1, 2-difluoroethane

(HCFC-142a) and 1-chloro-1, 1-difluoroethane (HCFC-142b);

- The trifluoroethane, namely in particular the 1, 1, 2-trifluoroethane (HFC-143) and 1, 1, 1-trifluoroethane (HFC-143a);

- Difluoroethane, namely in particular the 1, 1-difluoroethane (HFC-152a) and 1, 2-difluoroethane (HFC-152);

- The difluoroethylene, namely 1, 2-difluoroethylene (HFO-1132) and 1,1-difluoroethylene (HFO-1132a); and

- le fluoroéthylène (HFO-1141 ).

According to a particular embodiment, the compounds (hydro) halocarbon may be used in the context of the invention comprise 3 carbon atoms.

They can be chosen from:

- The dichlorohexafluoropropane, namely in particular 1,2-dichloro-1,1,2,3,3,3-hexafluoropropane (HCFC-216ba), dichloro-1,1,2,2,3 1,3 , 3-hexafluoropropane (HCFC-216ca), 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (HCFC-216cb) and 2,2-dichloro-1, 1,1, 3 , 3,3-hexafluoropropane (HCFC-216AA);

- The chloroheptafluoropropane, namely in particular the 1-chloro-1,1,2,2,3,3,3-heptafluoropropane (HCFC-217ca) and 2-chloro-1,1,1, 2,3,3 , 3-heptafluoropropane (HCFC-217ba);

- l'octafluoropropane (HFC-218) ;

- The dichloropentafluoropropane namely especially 2,2- dichloro-1,1,1,3,3-pentafluoropropane (HCFC-225aa), 2,3-dichloro-1,1,1,2,3-pentafluoropropane ( HCFC-225ba), 1,2-dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225BB), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC 225ca), dichloro-1,1,2,2,3-pentafluoropropane 1,3 (HCFC-225cb), dichloro-1,2,2,3,3-pentafluoropropane 1,1 (HCFC-225cc) , 1,2-dichloro-1,1,3,3,3-pentafluoropropane (HCFC-225da), dichloro-1,1,2,3,3-pentafluoropropane 1,3 (HCFC-225ea) and 1,1-dichloro-1,2,3,3,3-pentafluoropropane (HCFC-225eb);

- The chlorohexafluoropropane, namely in particular 2-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ba), 3-chloro

1 ,1 ,1 ,2,2,3-hexafluoropropane (HCFC-226ca), le 1- chloro-1 ,1 ,2,2,3,3-hexafluoropropane (HCFC-226cb), le 2- chloro- 1,1,1,3,3,3-hexafluoropropane (HCFC-226da) et le 1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea) ;

heptafluoropropane, namely particularly 1,1,2,2,3,3,3-heptafluoropropane (HFC-227ca) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea );

the dichlorotétrafluoropropane, namely in particular 2,2-dichloro-1,1,3,3-tetrafluoropropane (HCFC-234aa), 2,2-dichloro-1,1,1,3-tetrafluoropropane (HCFC-234ab) , 1, 2-dichloro-1, 2,3,3-tetrafluoropropane (HCFC-234ba), 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb), 1, 2- dichloro-1, 1,2,3-tetrafluoropropane (HCFC-234bc), 1, 3-dichloro-1, 2,2,3-tetrafluoropropane (HCFC-234ca), 1,1-dichloro-2,2, 3,3-tetrafluoropropane (HCFC-234cb), 1, 3-dichloro-1, 1, 2,2-tetrafluoropropane (HCFC-234cc), 1, 1-dichloro-1, 2,2,3-tetrafluoropropane ( HCFC-234cd), 2,3-dichloro-1,1,1,3-tetrafluoropropane (HCFC-234da), 1, 3-dichloro-1, 1,3,3-tetrafluoropropane (HCFC-234fa), the 1, 1-dichloro-1, 3,3,3-tetrafluoropropane (HCFC-234fb), 1,1-dichloro-2,3,3,3-tetrafluoropropane (HCFC-234ea), 1, 3-dichloro- 1, 1,2,3-tetrafluoropropane (HCFC-234eb) 1, 1-dichloro-1, 2,3,3-tetrafluoropropane (HCFC-234ec) and 1,2-dichloro-1, 1,3,3 tétrafluoropentane (HCFC-234db);

the chloropentafluoropropane, namely in particular 1-chloro-1, 2,2,3,3-pentafluoropropane (HCFC-235ca), 3-chloro-1, 1, 1, 2,3-pentafl uoropropane (HCFC-235ea ), 1-chloro-1,1, 2,2,3-pentafl uoropropane (HCFC-235cc), 2-chloro-1,1,1,3,3-pentafl uoropropane (HCFC-235da), 1 -chloro-1,1, 3,3,3-pentafl uoropropane (HCFC-235fa), 1 - chloro-1,1, 2,3,3-pentafl uoropropane (HCFC-235eb), 3-chloro-1 , 1,1,2,2-pentafl uoropropane (HCFC-235cb), 2-chloro-1, 1, 2,3,3-pentafl uoropropane (HCFC-235ba), and 2-chloro-1,1,1 , 2,3-pentafl luoropropane (HCFC-235bb);

hexafluoropropane, namely in particular 1,1,1, 2,2,3-hexafluoropropane (HFC-236cb), 1, 1, 1, 2,3,3-hexafluoropropane (HFC-236ea), 1 , 1,1,3,3,3-hexafluoropropane (HFC-236fa) and 1,1,2,2,3,3-hexafluoropropane (HFC-236ca);

- The tétrachlorofluoropropane, namely in particular the 1-tetrachloro-1,1,3,3-fluoropropane (HCFC-241fa), 1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb), 1 , 1,3,3-tetrachloro-2-fluoropropane (HCFC-241ea), 1,1,1,3-tetrachloro-2-fluoropropane (HCFC-241eb), the 1,1,2,3-tetrachloro-3 - fluoropropane (HCFC-241da), the 1,1,2,3-tetrachloro-1-fluoropropane (HCFC-241db), 1,1,1,2-tetrachloro-3-fluoropropane (HCFC-241dc), 1 , 1,2,3-tetrachloro-2-fluoropropane (HCFC-241ba), 1,1,1, 2-fluoropropane tétrchloro-2 (HCFC-241bb), the 1,2,2,3-tetrachloro-1 - fluoropropane (HCFC-241aa), 1,1,2,2-tetrachloro-3 fluoropropane (HCFC-241ab) and 1,1,2,2-tetrachloro-1 fluoropropane (HCFC-241ac);

- The trichlorodifluoropropane, namely in particular the 1, 3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1, 3-trichloro-1, 3-difluoropropane (HCFC-242fb), 1 , 1, 1, trichloro-3,3-difluoropropane (HCFC-242fc), 1,1, 3-trichloro-2,3-difluoropropane (HCFC-242ea), 1,1, 3-trichloro-1, 2-difluoropropane (HCFC-242eb), 1,1, 1-trichloro-2,3-difluoropropane (HCFC-242ec), 1, 2,3-trichloro-1, 3-difluoropropane (HCFC-242da), the 1,1, 2-trichloro-3,3-difluoropropane (HCFC-242db), 1,2,3-trichloro-1,1-difluoropropane (HCFC-242dc), 1, 1, 2-dichloro-1, 3- difluoropropane (HCFC-242dd), 1,1, 3-trichloro-2,2-difluoropropane (HCFC-242ca), 1,1, 1-trichloro-2,2-difluoropropane (HCFC-242cb), the 1, 2,3-trichloro-1, 2-difluoropropane (HCFC-242ba), 1,1, 2-trichloro-2,3-difluoropropane (HCFC-242bb), 1,1, 2-trichloro-1, 2-difluoropropane (HCFC-242bc), 2,2,3-trichloro-1,1-difluoropropane (HCFC-242aa), 1, 2,2-trichloro-1, 3-difluoropropane (HCFC-242ab) and the 1, 2,2-trichloro-1, 1-difluoropropane (HCFC-242ac);

- The dichlorotrifluoropropane, namely in particular the 1, 1-dichloro-3,3,3-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 1 , 1-dichloro-1, 3,3-trifluoropropane (HCFC-243fc), 1,3-dichloro-1,2,3-trifluoropropane (HCFC-243ea), 1,1-dichloro-2,3,3 - trifluoropropane (HCFC-243eb), 1,3-dichloro-1,1,2

trifluoropropane (HCFC-243ec), le 1 ,1-dichloro-1 ,2,3-trifluoropropane (HCFC-243ed), le 1,2-dichloro-1,3,3-trifluoropropane (HCFC-243da), le 2,3-dichloro-1 ,1,1-trifluoropropane (HCFC-243db), le 1,2-dichloro-1,1,3-trifluoropropane (HCFC-243dc), le 1,3-dichloro-1,2,2-trifluoropropane (HCFC-243ca), le 1,1-dichloro-2,2,3-trifluoropropane (HCFC-243cb), le 1 ,1-dichloro-1 ,2,2-trifluoropropane (HCFC-243cc), le 2,3-dichloro-1,1,2-trifluoropropane (HCFC-243ba), le 1,2-dichloro-1,2,3-trifluoropropane (HCFC-243bb), le 1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc), le 2,2-dichloro-1,1,3-trifluoropropane (HCFC-243aa) et le 2,2-dichloro-3,3,3-trifluoropropane (HCFC-243ab) ;

the chlorotétrafluoropropane, namely in particular 2-chloro-1, 2,3,3-tetrafluoropropane (HCFC-244ba), 2-chloro-1, 1,1,2-tétrafl uoropropane (HCFC-244bb), 3 chloro-1, 1,2,2-tétrafl uoropropane (HCFC-244ca), 1-chloro-1, 2,2,3-tétrafl uoropropane (HCFC-244cb), 1-chloro-1, 1,2 , 2-tétrafl uoropropane (HCFC-244cc), 2-chloro-1, 1,3,3-tétrafl uoropropane (HCFC-244da), 2-chloro-1, 1,1,3-tétrafl uoropropane (HCFC 244db), 3-chloro-1, 1,2,3-tétrafl uoropropane (HCFC-244ea), 3-chloro-1, 1,1,2-tétrafl uoropropane (HCFC-244eb), 1-chloro- 1, 1,2,3-tétrafl uoropropane (HCFC-244ec), 3-chloro-1, 1,1,3-tétrafl uoropropane (HCFC-244fa) and 1-chloro-1, 1,3,3 tétrafl uoropropane (HCFC-244fb);

pentafluoropropane, namely in particular the 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,2,3,3-pentafluoropropane (HFC-245ea), 1, 1, 1, 2,3-pentafluoropropane (HFC-245eb), 1,1,1,2,2-pentafluoropropane (HFC-245cb) and 1,1,1,3,3-pentafluoropropane (HFC-245fa);

the chlorotrifluoropropane, namely in particular 2-chloro-1, 2,3-trifluoropropane (HCFC-253ba), 2-chloro-1, 1, 2-trifl uoropropane (HCFC-253bb), 1-chloro-2 , 2,3-trifluoropropane (HCFC-253ca), 1-chloro-1,2,2-trifluoropropane (HCFC-253cb), 3-chloro-1,1,2-trifluoropropane (HCFC-253ea), 1 chloro-1, 2,3-trifluoropropane (HCFC-253eb), 1-chloro-1,1,2-trifluoropropane (HCFC-253ec), 1-chloro-1,3,3-trifluoropropane (HCFC-253fa ), 3-chloro-1, 1, 1- trifluoropropane (HCFC-253fb), 1-chloro-1, 1, 3-trifluoropropane (HCFC-253fc), 2-chloro-1,1,3-trifluoropropane (HCFC-253da) and 2-chloro-1,1,1-trifluoropropane (HCFC-253db);

tetrafluoropropane, namely in particular the 1,1,2,2-tetrafluoropropane (HFC-254cb), 1,1,1,3-tetrafluoropropane (HFC-254fb), the 1,1,2,3-tetrafluoropropane ( HFC-254ea), 1,1,1,2-tetrafluoropropane (HFC-254eb), the 1,2,2,3-tetrafluoropropane (HFC-254ca) and 1,1,3,3-tetrafluoropropane (HFC 254fa);

the chlorodifluoropropane, namely in particular 1-chloro-2,2-difluoropropane (HCFC-262ca), 3-chloro-1, 1 -difluoropropane (HCFC-262fa), 1-chloro-1,3-difluoropropane ( HCFC-262fb), the

1- chloro-1,1 -difluoropropane (HCFC-262fc), le 1-chloro-2,3-difluoropropane (HCFC-262ea), le 1-chloro-1 ,2-difluoropropane (HCFC-262eb), le 2-chloro-1,3-difluoropropane (HCFC-262da), le

2- chloro-1,1 -difluoropropane (HCFC-262db) et le 2-chloro-1 ,2-difluoropropane (HCFC-262ba);

the trifluoropropane (HFC-263), namely in particular the 1,1,1-trifluoropropane (HFC-263fb), 1, 1, 3-trifluoropropane (HFC-263fa), 1, 2,3-trifluoropropane (HFC -263ea), 1,1,2-trifluoropropane (HFC-263eb) and 1,2,2-trifluoropropane (HFC-263ca);

the dichlorotétrafluoropropène (HCFO-1214), namely in particular 1,2-dichloro-1,3,3,3-tetrafluoropropene (HCFO-1214xb), 1,1-dichloro-2,3,3,3-tetrafluoropropene (HCFO-1214ya), 1,3-dichloro-1,2,3,3-tetrafluoropropene (HCFO-1214yb), 2,3-dichloro-1,1,3,3-tetrafluoropropene (HCFO-1214xc) and 3,3-dichloro-1,1,2,3-tetrafluoropropene (HCFO-1214yc);

the chloropentafluoropropene (HCFO-1215), that in particular the -chloropentafluoropropène 1, 2-and chloropentafluoropropene

3- chloropentafluoropropène ;

l'hexafluoropropène (HFO-1216) ;

the dichlorotrifluoropropène (HCFO-1223), namely in particular 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd ), 2,3-dichloro-1,3,3-trifluoropropene (HCFO-1223xe), 1, 3-dichloro-2,3,3-trifluoropropene (HCFO-1223yd), 1, 2-dichloro-1 , 3,3-trifluoropropene (HCFO-1223xb), 2,3-dichloro-1,1,3

trifluoropropène (HCFO-1223xc), le 1 ,1 -dichloro-2,3,3-trifluoropropène (HCFO-1223ya), le 1 ,3-dichloro-1 ,2,3-trifluoropropène (HCFO-1223yb), le 3,3-dichloro-1 ,1 ,2-trifluoropropène (HCFO-1223yc), le 3,3-dichloro-1 ,2,3-trifluoropropène (HCFO-1223ye), le 1 ,3-dichloro-1 ,3,3-trifluoropropène (HCFO-1223zb) et le 3,3-dichloro-1 ,1 ,3-trifluoropropène (HCFO-1223zc);

the chlorotétrafluoropropène (HCFO-1224), namely in particular the 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1 -chloro-1, 3,3,3-tetrafluoropropene (HCFO-1224zb ), 2-chloro-1, 3,3,3-tetrafluoropropene (HCFO-1224xe), 3-chloro-1, 2,3,3-tetrafluoropropene (HCFO-1224ye), 3-chloro-1, 1 , 3,3-tetrafluoropropene (HCFO-1224zc), 2-chloro-1, 1, 3,3-tetrafluoropropene (HCFO-1224xc), 1 -chloro-1, 2,3,3-tetrafluoropropene (HCFO-1224yb ) and 3-chloro-1, 1, 2,3-tetrafluoropropene (HCFO-1224yc);

pentafluoropropene, namely in particular the 1, 1, 1, 2,3-trans form pentafluoropropene (HFO-1225yeE), 1, 1, 1, 2,3-cis form pentafluoropropene (HFO-1225yeZ), the 1, 1, 3,3,3-pentafluoropropene (HFO-1225zc) and 1, 1, 2,3,3-pentafluoropropene (HFO-1225yc);

the trichlorofluoropropène (HCFO-1231), namely in particular the 1, 1, 2-trichloro-3-fluoropropene (HCFO-1231 xa), 1, 2,3-trichloro-1 -fluoropropène (HCFO-1231 xb) 1, 2,3-trichloro-3-fluoropropene (HCFO-1231 xd), 2,3,3-trichloro-1 -fluoropropène (HCFO-1231 xe), 2,3,3-trichloro-3-fluoropropene

(HCFO-1231 xf), le 1 ,1 ,3-trichloro-2-fluoropropène

(HCFO-1231 ya), le 1 ,3,3-trichloro-2-fluoropropène

(HCFO-1231 yd), 3,3,3-trichloro-2-fluoropropène (HCFO-1231 yf), le 1 ,1 ,3-trichloro-3-fluoropropène (HCFO-1231 za), le 1 ,3,3-trichloro-1 -fluoropropène (HFCO-1231 zb), 1 ,3,3-trichloro-3-fluoropropène (HCFO-1231 zd) et le 3,3,3-trichloro-1 -fluoropropène (HCFO-1231 ze) ;

the dichlorodifluoropropène (HCFO-1232), namely in particular 2,3-dichloro-3,3-difluoropropène (HCFO-1232xf), the 1, 2-dichloro-1, 3-difluoropropène (HCFO-1232xb), 2 , 3-dichloro-1, 1 -difluoropropène (HCFO-1232xc), 1, 2-dichloro-3,3-difluoropropène (HCFO-1232xd), 2,3-dichloro-1, 3-

difluoropropène (HCFO-1232xe), le 1 ,1 -dichloro-2,3-difluoropropène (HCFO-1232ya), le 1 ,3-dichloro-1 ,2-difluoropropène (HCFO-1232yb), le 1 ,3-dichloro-2,3-difluoropropène (HCFO-1232yd), le 3,3-dichloro-1 ,2-difluoropropène (HCFO-1232ye), le 3,3-dichloro-2,3-difluoropropène (HCFO-1232yf), le 1 ,1 -dichloro-3,3-difluoropropène (HCFO-1232za), le 1 ,3-dichloro-1 ,3-difluoropropène (HCFO-1232zb), le 3,3-dichloro-1 ,1 -difluoropropène (HCFO-1232zc), le 1 ,3-dichloro-3,3-difluoropropène (HCFO-1232zd) et le 3,3-dichloro-1 ,3-difluoropropène (HCFO-1232ze) ;

the chlorotrifluoropropène, namely in particular 2-chloro-1, 1, 3-trifluoropropene (HCFO-1233xc), 2-chloro-1, 3,3-trifluoropropene

(HCFO-1233xe), le 1 -chloro-1, 2,3-trifluoropropene

(HCFO-1233yb), le 3-chloro-1 ,1 ,2-trifluoropropène

(HCFO-1233yc), 1-chloro-2,3,3-trifluoropropene

(HCFO-1233yd), le 3-chloro-1 ,2,3-trifluoropropène

(HCFO-1233ye), le 3-chloro-2,3,3-trifluoropropène

(HCFO-1233yf), le 1 -chloro-1 ,3,3-trifluoropropène

(HCFO-1233zb), le 3-chloro-1, 1, 3-trifluoropropène

(HCFO-1233zc), le 3-chloro-1 ,3,3-trifluoropropène

(HCFO-1233ze), le 2-chloro-3,3,3-trifluoro-propène

(HCFO-1233xf) and 1-chloro-3,3,3-trifuloropropène trans form (HCFO-1233zdE);

the tetrafluoropropene, namely in particular the 1, 1, 2,3-tetrafluoropropene (HFO-1234yc), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1, 2,3,3-tetrafluoropropene ( HFO-1234ye), 1, 1, 3,3-tetrafluoropropene (HFO-1234zc), 1, 3,3,3-tetrafluoropropene in cis- (HFO-1234zeZ) and 1, 3,3,3-tetrafluoropropene trans form (HFO-1234zeE);

the chlorodifluoropropène (HCFO-1242), namely in particular 3-chloro-3,3-difluoropropène (HCFO-1242zf), 3-chloro-1, 3-difluoropropène (HCFO-1242ze), 2-chloro-1 , 1 -difluoropropène (HCFO-1242xc), 2-chloro-1, 3-difluoropropène (HCFO-1242xe), 2-chloro-3,3-difluoropropène (HCFO-1242xf), 1-chloro-1, 2 -difluoropropène (HCFO-1242yb), 1 -chloro-2,3-difluoropropène (HCFO-1242yd), 3-chloro-1, 2-difluoropropène (HCFO-1242ye), 3-chloro-2,3-difluoropropène (HCFO-1242yf), 1 -chloro-1, 3- difluoropropène (HCFO-1242zb), 3-chloro-1, 1 -difluoropropène (HCFO-1242zc) and 1 -chloro-3,3-difluoropropène (HCFO -1242zd);

- Trifluoropropene, namely in particular the 1, 1, 2-trifluoropropene (HFO-1243yc), 1, 2,3-trifluoropropene (HFO-1243ye), 2,3,3-trifluoropropene (HFO-1243yf), 1, 1, 3-trifluoropropene (HFO-1243zc), 1, 3,3-trifluoropropene (HFO-1243ze) and 3,3,3-trifluoropropene (HFO-1243zf);

- The chlorofluoropropène (HCFO-1251), namely in particular the 1 - chloro-3-fluoropropene (HCFO-1251 zd), 1-chloro-1 - fluoropropene (HCFO-1251 zb), 1-chloro-2- fluoropropene (HCFO-1251 yd), 2-chloro-1 -fluoropropène (HCFO-1251 xe), 2-chloro-3-fluoropropene (HCFO-1251 yf), 3-chloro-2-fluoropropene (HCFO-1251xf ), 3-chloro-1 -fluoropropène (HCFO-1251 ze and 3-chloro-3-fluoropropene (HCFO-1251 zf);

- The difluoropropène (HFO-1252), namely in particular the 1, 2- difluoropropène (HCFO-1252ye), 2,3-difluoropropène (HCFO-1252yf), 1, 1 -difluoropropène (HCFO-1252zc), the 1, 3- difluoropropène (HCFO-1252ze) and 3,3-difluoropropène (HCFO-1252zf); and

- The trifluoropropyne.

The compositions according to the invention may be of ternary mixtures, that is to say mixtures of three and only three compounds.

The compositions of the invention may be quaternary mixtures, that is to say mixtures of four and only four compounds.

The compositions of the invention may be quinquénaires mixtures, that is to say mixtures of five compounds and five only.

The compositions of the invention may be senarii mixtures, that is to say mixtures of six and only six compounds.

The compositions according to the invention may also be mixtures of seven and only seven compounds.

The compositions according to the invention may also be mixtures of compounds eight and only eight.

The compositions according to the invention may also be mixtures comprising more than eight compounds.

According to one embodiment, the compositions of the invention essentially consist of a mixture of HF, HCFO-1233zdZ and one or more compounds (hydro) halocarbon having 1 to 3 carbon atoms - the maximum amount of impurities various of these compounds, being for example 2% or 1%, or 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0, 02% or 0.01%.

According to one embodiment, the compositions according to the invention consist of a mixture of HF, HCFO-1233zdZ and one or more compounds (hydro) halocarbon having 1 to 3 carbon atoms.

According to one embodiment, compounds (hydro) halocarbons used in the aforementioned compositions of the invention are selected from tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the irichlorofluoropropènes the chlorotrifluoropropènes the tetrafluoropropenes and mixtures thereof.

According to one embodiment, compounds (hydro) halocarbons used in the aforementioned compositions of the invention are selected from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the

HFC-245fa, the HCFO-1232za the HCFO-1232zd, the HCFO-1233zdE the

HFO-1234zeZ and HFO-1234zeE.

According to one embodiment, compounds (hydro) halocarbon above used in the compositions according to the invention are selected from HFC-245fa, the HCFO-1233zdE, HFO-1234zeZ and

HFO-1234zeE.

According to one embodiment, the compositions according to the invention may consist (or essentially consist of) a mixture of HF, HCFO-1233zdE and HCFO-1233zdZ. The HF content in these compositions is advantageously from 1 to 85%, more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 4.0 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdE of HCFO-1233zdZ and one or more other compounds (hydro) halocarbons, which may be chosen from all the compounds listed above ; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the trichlorofluoropropènes the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, HFC-245fa, the HCFO-1232za the HCFO-1232zd, HFO-1234zeZ and HFO 1234zeE; and which may more particularly be selected from HFC-245fa, HFO-1234zeZ and HFO-1234zeE.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-1233zdE of HCFO-1233zdZ and HFC-245fa. The HF content in these compositions is advantageously from 1 to 85%, more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 4.4 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdE of HCFO-1233zdZ, HFC-245fa and one or more other compounds (hydro) halocarbons, which may be selected from the group of compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the trichlorofluoropropènes the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the HCFO-1232za the HCFO-1232zd, HFO-1234zeZ and HFO-1234zeE; and which may more particularly be selected from HFO-1234zeZ and HFO-1234zeE.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-1233zdZ, HFO-1234zeZ and HFC-245fa. The HF content in these compositions is advantageously from 1 to 85%, more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 4.8 bar absolute.

Alternatively the compositions of the invention may comprise a mixture of HF, HCFO-1233zdZ, HFO-1234zeZ to

HFC-245fa and one or more other compounds (hydro) halocarbons, which may be selected from the group of compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the tnchioroiluoropropènes the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the HCFO-1232za the HCFO-1232zd, the HCFO-1233zdE and HFO-1234zeE; and which may more particularly be selected from HCFO-1233zdE and HFO-1234zeE.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-1233zdZ, HFO-1234zeE and HFC-245fa. The HF content in these compositions is advantageously from 1 to 80%, more preferably from 5 to 75%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 8.6 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdZ, HFO-1234zeE, HFC-245fa and one or more other compounds (hydro) halocarbons, which may be selected from the group of compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes, the tr-ch oref uoropropènes the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the HCFO-1232za the HCFO-1232zd, the HCFO-1233zdE and HFO-1234zeZ; and which may more particularly be selected from HCFO-1233zdE and HFO-1234zeZ.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ and HFC-245fa. The HF content in these compositions is advantageously from 1 to 85%, and

more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 8.9 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ, HFC-245fa and one or more other compounds (hydro) halocarbons, which may be selected among all the compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the irlchlorofluoropropènes the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the HCFO-1232za the HCFO-1232zd and HCFO-1233zdE; and which may include the HCFO-1233zdE.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-1233zdZ of HCFO-1233zdE, HFO-1234zeE and HFC-245fa. The HF content in these compositions is advantageously from 1 to 85%, more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 8.9 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdZ of HCFO-1233zdE, HFO-1234zeE, HFC-245fa and one or more other compounds (hydro) halocarbons, which may be selected among all the compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the

Irichlorofluoropropènes, the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the HCFO-1232za the HCFO-1232zd and HFO-1234zeZ; and can be particularly HFO-1234zeZ.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-1233zdZ of HCFO-1233zdE, HFO-1234zeZ and HFC-245fa. The HF content in these compositions is advantageously from 1 to 85%, more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 4.8 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdZ of HCFO-1233zdE, HFO-1234zeZ, HFC-245fa and one or more other compounds (hydro) halocarbons, which may be selected among all the compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the trichionoffuonDpropènes the chlorotrifluoropropènes and tetrafluoropropenes; and can be chosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, the HCFO-1232za the HCFO-1232zd and HFO-1234zeE; and can be particularly HFO-1234zeE.

According to one embodiment, the compositions according to the invention may consist of (or consist essentially of) a mixture of HF, HCFO-of 1233zdZ of HCFO-1233zdE, HFO-1234zeE, HFO-1234zeZ, and HFC-245fa . The HF content in these compositions is advantageously from 1 to 85%, more preferably from 5 to 80%. The boiling point is preferably from 0 to 40 ° C to a pressure of 0.6 to 8.8 bar absolute.

Alternatively the compositions according to the invention may comprise a mixture of HF, HCFO-1233zdZ of HCFO-1233zdE, HFO-1234zeE, HFO-1234zeZ of HFC-245fa and one or more other compounds (hydro) halocarbon, which may be selected from the group of compounds listed above; and can be chosen from the propane and propenes partially or fully substituted by halogen; and can be chosen from the tétrachlorofluoropropanes the trichlorodifluoropropanes the dichlorotrifluoropropanes the chlorotétrafluoropropanes the pentafluoropropanes the dichlorodifluoropropènes the tnchforofiuonopropènes the chlorotrifluoropropènes and tetrafluoropropenes; and which can be chosen the HCFC 241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, HFO 1232za and HCFO-1232zd.

Generally, in the compositions according to the invention, the proportion of HF is preferably from 1 to 85%, especially 5 to 80% (based on the total weight of the composition), more preferably from 10 to 65%; and the proportion of compounds (hydro) halocarbons, including HCFO-1233zdZ, is 15 to 99%, especially 20 to 95%, more particularly 35 to 90%.

The boiling point of a composition according to the invention is preferably from -20 ° C to 80 ° C to a pressure of 0.1 to 44 bar absolute; preferably 0 to 40 ° C to a pressure of 0.5 to 9 bar absolute.

When the compositions according to the invention include both the HCFO-1233zdZ and HCFO-1233zdE, they may include, in weight proportions relative to the sum of these two compounds:

- From 1 to 10% HCFO-1233zdZ and 90 to 99% of

HCFO-1233zdE;

- From 10 to 20% HCFO-1233zdZ and 80 to 90% of HCFO-1233zdE;

- From 20 to 30% HCFO-1233zdZ and 70 to 80% of HCFO-1233zdE;

- From 30 to 40% HCFO-1233zdZ and 60 to 70% HCFO-1233zdE;

- From 40 to 50% HCFO-1233zdZ and 50 to 60% of HCFO-1233zdE;

- From 50 to 60% of HCFO-1233zdZ and 40 to 50%

HCFO-1233zdE;

- From 60 to 70% HCFO-1233zdZ and 30 to 40% HCFO-1233zdE;

- From 70 to 80% of HCFO-1233zdZ and 20 to 30% HCFO-1233zdE;

- From 80 to 90% of HCFO-1233zdZ and 10 to 20% HCFO-1233zdE;

- From 90 to 99% of HCFO-1233zdZ and 1 to 10% HCFO-1233zdE.

According to one embodiment, the compositions according to the invention, in the condensed state, have two liquid phases, preferably a HF-rich than the other.

The invention may in particular be particularly exploited in the context of methods for producing a fluorinated compound, wherein mixtures of the compounds described above can be produced.

Such mixtures may then be treated by distillation to collect on the one hand a composition according to the invention, and also HF, or other part of the HCFO-1233zdZ, or other hand or a several other compounds (hydro) halocarbons.

Such mixtures may be obtained in particular as a product stream after catalytic fluorination reaction of a chlorinated compound in a fluorine compound by HF.

By "chlorine-containing compound" (which is the main reactant from the catalytic fluorination reaction) is meant an organic compound comprising one or more chlorine atoms, and by "fluorinated compound" (which represents the desired product from the catalytic fluorination reaction ) shall mean an organic compound comprising one or more fluorine atoms.

It is understood that the chlorine compound can include one or more fluorine atoms, and the fluorine-containing compound can include one or more chlorine atoms. Generally, the number of chlorine atoms in the fluorinated compound is less than the number of chlorine atoms in the chlorine-containing compound; and the number of fluorine atoms of the fluorinated compound is greater than the number of fluorine atoms of the chlorinated compound.

The chlorinated compound can be an alkane or an alkene optionally having substituents selected from F, Cl, I and Br (preferably from F and Cl), and having at least one substituent Cl.

The fluorinated compound can be an alkane or an alkene optionally having substituents selected from F, Cl, I and Br (preferably from F and Cl), and having at least one substituent F

The chlorinated compound can for example be an alkane with one or more substituents chlorine (hydrochlorocarbon or chlorocarbon) or an alkane with one or more substituents chlorine and fluorine (hydrochlorofluorocarbon or chlorofluorocarbon) or an alkene with one or more substituents chlorine (chlorooléfine or hydrochlorooléfine) or alkene with one or more substituents chlorine and fluorine (or hydrochlorofluoroolefin chlorofluorooléfine).

The fluorine compound can in particular be an alkane with one or more fluorine substituents (fluorocarbon or hydrofluorocarbon) or an alkane with one or more substituents chlorine and fluorine (hydrochlorofluorocarbon or chlorofluorocarbon) or an alkene with one or more substituents fluorine (fluoroolefin or hydrofluoroolefin) or alkene with one or more substituents chlorine and fluorine (or hydrochlorofluoroolefin chlorofluorooléfine).

According to one embodiment, the chlorinated compound and the fluorinated compound comprises a single carbon atom.

According to one embodiment, the chlorinated compound and the fluorinated compound comprises two carbon atoms.

According to a particularly preferred embodiment, the chlorinated compound and the fluorinated compound comprises three carbon atoms.

The invention is particularly applicable for the following fluorination reactions:

- Fluorination of 1, 1, 1, 3,3-pentachloropropane HCFO-1233zdE;

- Fluorination of 1, 1, 3,3-tetrachloropropene in HCFO-1233zdE.

The invention may apply in particular to the determination of the stages of settling and purification needed for treatment of a gas stream leaving a fluorination reactor in the liquid phase using the 1, 1, 3,3-tetrachloropropene feedstock or a fluorination reactor in the gas phase using the 1, 1, 1, 3,3-pentachloropropane as feedstock. This gas stream may contain between 15 and 50% HF, from 15 to 50% of HCl and the balance is made up of all organic compounds resulting from the reaction.

In one embodiment there is provided a fluorination process in liquid phase using the 1, 1, 3,3-tetrachloropropene as raw material, and the distribution of organic compounds at the end of the reaction may in particular be as follows: for 85 to 95% of HCFO-1233zdE, 0 to 5% HCFO-1233zdZ, 0 to 3% of HFO-1234zeE, 0 to 3% of HFO-1234zeZ, 0 to 3% of HFC-245fa, from 0 to 3% of HCFO-1232, from 0 to 1% of HCFC-243 and from 0 to 1% of HCFC-241.

In one embodiment there is provided a gas phase fluorination process using the 1, 1, 1, 3,3-pentachloropropane as the raw material, and the distribution of organic compounds at the end of the reaction may in particular be the follows: from 65 to 85% of HCFO-1233zdE, 15 to 25% HCFO-1233zdZ, 0 to 10% HCFO-1232, from 0 to 3% of HFO-1234zeE, 0 to 3% of HFO 1234zeZ, 0 to 3% of HFC-245fa, from 0 to 3% of HCFC-243.

The compositions according to the invention have interesting properties in particular for the recycling of THF to the reaction step. Thus, the condensed phase of these compositions, optionally when subjected to a distillation step and / or a step of liquid / liquid separation, such as by decantation, forms two immiscible liquid phases. Most HF-rich phase may be recycled to the reaction step, while the less HF-rich phase may be subjected to one or more distillation steps to separate the organic compounds and allow for example to recycle to the reaction step of organic compounds which are reaction intermediates.

EXAMPLES

The following examples illustrate the invention without limiting it.

Example 1 - ternary composition HF / HCFO-1233zdE / HCFO-1233zdZ

Azeotropic and hetero-azeotropic behavior was observed for the ternary mixture HF / HCFO-1233zdE / HCFO-1233zdZ.

Figure 1 illustrates the azeotropic behavior for isotherm

25 ° C, for various proportions HCFO-1233zdE / HCFO-1233zdZ, namely:

- A: 95% of HCFO-1233zdE and 5% HCFO-1233zdZ (relative to the sum of both);

- B: 50% HCFO-1233zdE and 50% HCFO-1233zdZ (relative to the total of both);

- C: 5% HCFO-1233zdE and 95% HCFO-1233zdZ (relative to the total of both).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to 4.0 absolute bars. Thus, for a mixture of HF with 50% HCFO-1233zdZ and 50% HCFO-1233zdE (the proportions being relative to the sum of the two), the boiling point is 0 ° C to about 0.9 bar absolute, 25 ° C to about 2.1 bar absolute and 40 ° C to about 3.5 bar absolute.

Settling ranges for a mixture of HF with 50% HCFO-1233zdZ and 50% HCFO-1233zdE (the proportions being relative to the sum of both) are: 5 to 75% HF at 0 ° C; from 5 to 70% HF at 25 ° C; and from 5 to 60% HF at 40 ° C.

Exemple 2 - Composition quaternaire HF / HCFO-1233zdZ / HFO-1234zeE / HFC-245fa

Azeotropic and hetero-azeotropic behavior was observed for the quaternary mixture HF / HCFO-1233zdZ / HFO-1234zeE / HFC

2 illustrates the azeotropic behavior for the isotherm at 25 ° C, for various proportions HCFO-1233zdZ / HFO-1234zeE / HFC-245fa, namely:

- A: 5% HCFO-1233zdZ, 90% HFO-1234zeE and 5% HFC-245fa (relative to the total of the three);

- B: 40% HCFO-1233zdZ, 30% HFO-1234zeE and 30% HFC-245fa (relative to the total of the three);

- C: 5% HCFO-1233zdZ, 5% of HFO-1234zeE and 90% HFC-245fa (relative to the total of the three);

- D : 90 % de HCFO-1233zdZ, 5 % de HFO-1234zeE et 5 % de

HFC-245fa (relative to the total of the three).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 8.6 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdZ, HFO-1234zeE and HFC-245fa are: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 70% HF at 40 ° C.

Exemple 3 - Composition quaternaire HF / HCFO-1233zdZ / HFO-1234zeZ / HFC-245fa

An azeotropic and hetero-azeotropic behavior was observed for the quaternary mixture HF / HCFO-1233zdZ / HFO-1234zeZ / HFC-245fa.

3 illustrates the azeotropic behavior for the isotherm at 25 ° C, for various proportions HCFO-1233zdZ / HFO-1234zeZ / HFC-245fa, namely:

- A: 5% HCFO-1233zdZ, 90% HFO-1234zeZ and 5% HFC-245fa (relative to the total of the three);

- B: 5% HCFO-1233zdZ, 5% of HFO-1234zeZ and 90% HFC-245fa (relative to the total of the three);

- C: 40% HCFO-1233zdZ, 30% HFO-1234zeZ and 30% HFC-245fa (relative to the total of the three);

- D: 90% of HCFO-1233zdZ, 5% of HFO-1234zeZ and 5% HFC-245fa (relative to the total of the three).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 4.8 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdZ, HFO-1234zeZ and

HFC-245fa: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 75% HF at 40 ° C.

Example 4 - quaternary composition HF / HCFO-1233zdE / HCFO-1233zdZ / HFC-245fa

Azeotropic and hetero-azeotropic behavior was observed for the quaternary mixture HF / HCFO-1233zdE / HCFO-1233zdZ / HFC-245fa.

4 illustrates the azeotropic behavior for the isotherm at 25 ° C, for various proportions HCFO-1233zdE / HCFO-1233zdZ / HFC-245fa, namely:

- A: 5% HCFO-1233zdE, 5% HCFO-1233zdZ and 90% HFC-245fa (relative to the total of the three);

- B: 90% of HCFO-1233zdE, 5% HCFO-1233zdZ and 5% HFC-245fa (relative to the total of the three);

- C: 40% HCFO-1233zdE, 30% HCFO-1233zdZ and 30% HFC-245fa (relative to the total of the three);

- D: 5% HCFO-1233zdE, 90% of HCFO-1233zdZ and 5% HFC-245fa (relative to the total of the three).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 4.4 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdE of HCFO-1233zdZ and HFC-245fa are: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 75% HF at 40 ° C.

Exemple 5 - Composition quinquénaire HF / HCFO-1233zdZ / HFO-1234zeE / HFO-1234zeZ / HFC-245fa

An azeotropic and hetero-azeotropic behavior was observed for the mixture quinquénaire HF / HCFO-1233zdZ / HFO-1234zeE / HFO-1234zeZ / HFC-245fa.

5 illustrates the azeotropic behavior for the isotherm at 25 ° C, for various proportions HCFO-1233zdZ / HFO-1234zeE / HFO-1234zeZ / HFC-245fa, namely:

- A: 1% HCFO-1233zdZ, 97% HFO-1234zeE, 1% HFO 1234zeZ and 1% of HFC-245fa (relative to the total of four); - B: 25% HCFO-1233zdZ, 25% of HFO-1234zeE, 25% of HFO-1234zeZ and 25% of HFC-245fa (relative to the total of four);

- C: 1% HCFO-1233zdZ, 1% HFO-1234zeE, 97% of HFO 1234zeZ and 1% of HFC-245fa (relative to the total of four);

- D: 1% HCFO-1233zdZ, 1% HFO-1234zeE, 1% HFO 1234zeZ and 97% HFC-245fa (relative to the total of four);

- E: 97% of HCFO-1233zdZ, 1% HFO-1234zeE, 1% HFO 1234zeZ and 1% of HFC-245fa (relative to the total of four). It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 8.9 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ and HFC-245fa are: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 65% HF at 40 ° C.

Exemple 6 - Composition quinquénaire HF / HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeE / HFC-245fa

An azeotropic and hetero-azeotropic behavior was observed for the mixture quinquénaire HF / HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeE / HFC-245fa.

6 illustrates the azeotropic behavior for the isotherm at 25 ° C, for various proportions HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeE / HFC-245fa, namely:

- A: 1% de HCFO-1233zdE, 1% de HCFO-1233zdZ, 97% de

HFO-1234zeE and 1% of HFC-245fa (relative to the total of four);

- B: 25% HCFO-1233zdE, 25% HCFO-1233zdZ, 25% of HFO-1234zeE and 25% of HFC-245fa (relative to the total of four);

- C: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO 1234zeE and 97% HFC-245fa (relative to the total of four);

- D: 97% of HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeE and 1% of HFC-245fa (relative to the total of four);

- E: 1% HCFO-1233zdE, 97% of HCFO-1233zdZ, 1% HFO-1234zeE and 1% of HFC-245fa (relative to the total of four).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 8.9 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdE of HCFO-1233zdZ, HFO-1234zeE and HFC-245fa are: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 65% HF at 40 ° C.

Exemple 7 - Composition quinquénaire HF / HCFO-1233zdE / HCFO- 1233zdZ / HFO-1234zeZ / HFC-245fa

Azeotropic and hetero-azeotropic behavior was observed for quinquénaire mixture HF / HCFO-1233zdE / HCFO-1233zdZ / 1234zeZ HFO / HFC-245fa.

7 illustrates the azeotropic behavior for isotherm

25 ° C, for various proportions HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeZ / HFC-245fa, namely:

- A: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 97% HFO-1234zeZ and 1% of HFC-245fa (relative to the total of four);

- B: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO 1234zeZ and 97% of HFC-245fa (relative to the total of four);

- C: 25% HCFO-1233zdE, 25% HCFO-1233zdZ, 25% of HFO-1234zeZ and 25% of HFC-245fa (relative to the total of four);

- D: 97% of HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeZ and 1% of HFC-245fa (relative to the total of four);

- E: 1% HCFO-1233zdE, 97% of HCFO-1233zdZ, 1% HFO-1234zeZ and 1% of HFC-245fa (relative to the total of four).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 4.8 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdE of HCFO-1233zdZ, HFO-1234zeZ and HFC-245fa are: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 70% HF at 40 ° C.

Exemple 8 - Composition sénaire HF / HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeE / HFO-1234zeZ / HFC-245fa

Azeotropic and hetero-azeotropic behavior was observed for senaire mixture HF / HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeE / HFO-1234zeZ / HFC-245fa.

8 illustrates the azeotropic behavior for the isotherm at 25 ° C, for various proportions HCFO-1233zdE / HCFO-1233zdZ / HFO-1234zeE / HFO-1234zeZ / HFC-245fa, namely:

- A : 1 % de HCFO-1233zdE, 1 % de HCFO-1233zdZ, 96 % de HFO-1234zeE, 1 % de HFO-1234zeZ et 1 % de HFC-245fa (par rapport au total des cinq) ;

- B: 20% de HCFO-1233zdE, 20% de HCFO-1233zdZ, 20% de

HFO-1234zeE, 20% HFO-1234zeZ and 20% HFC-245fa (based on the total of five);

- C : 1 % de HCFO-1233zdE, 1 % de HCFO-1233zdZ, 1 % de HFO- 1234zeE, 96 % de HFO-1234zeZ et 1 % de HFC-245fa (par rapport au total des cinq) ;

- D: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO 1234zeE, 1% HFO-1234zeZ and 96% HFC-245fa (based on the total of five);

- E : 96 % de HCFO-1233zdE, 1 % de HCFO-1233zdZ, 1 % de HFO-1234zeE, 1 % de HFO-1234zeZ et 1 % de HFC-245fa (par rapport au total des cinq) ;

- F : 1 % de HCFO-1233zdE, 96 % de HCFO-1233zdZ, 1 % de HFO-1234zeE, 1 % de HFO-1234zeZ et 1 % de HFC-245fa (par rapport au total des cinq).

It is noted that the composition has a boiling point of 0 to 40 ° C at a pressure of 0.6 bar absolute to about 8.8 bar absolute.

Settling ranges for a mixture comprising equal proportions by weight of HCFO-1233zdE of HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ and HFC-245fa are: 5 to 80% HF at 0 ° C; from 5 to 75% HF at 25 ° C; and from 5 to 65% HF at 40 ° C.

CLAIMS

azeotropic composition or quasi-azeotropic comprising hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène and one or more compounds (hydro) halocarbon having 1 to 3 carbon atoms.

The composition of claim 1, wherein the compound (hydro) halocarbon contain 3 carbon atoms, and are preferably chosen from propane and propene partially or fully substituted by halogens.

The composition of claim 1 or 2, wherein the compound (hydro) halocarbon are selected from tétrachlorofluoropropanes, the trichlorodifluoropropanes, the dichlorotrifluoropropanes, the chlorotétrafluoropropanes, the pentafluoropropanes, the dichlorodifluoropropènes, the richiorofluoropropénes, the chlorotrifluoropropènes and tetrafluoropropenes.

Composition according to one of claims 1 to 3, comprising hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-3,3,3-trifluoro-1 and one or -chloropropène more other compounds (hydro) halocarbon having 1 to 3 carbon atoms.

Composition according to one of claims 1 to 4, comprising hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, E-1, 3,3,3-tetrafluoropropene and one or more other compounds (hydro) halocarbon comprising from 1 to 3 carbon atoms.

Composition according to one of claims 1 to 5, comprising hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, Z-1, 3,3,3-tetrafluoropropene and one or more other compounds (hydro) halocarbon comprising from 1 to 3 carbon atoms.

Composition according to one of claims 1 to 6, comprising hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène, 1, 1, 1, 3,3-pentafluoropropane and one or more other compounds (hydro) halocarbon comprising from 1 to 3 carbon atoms.

Composition according to one of claims 1 to 7 which is a ternary mixture, and preferably is a mixture of hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène and E-3, 3 , 3-trifluoro-1 -chloropropène.

Composition according to one of claims 1 to 7 which is a quaternary mixture, and preferably is a mixture of:

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, E-3, 3, 3-trifluoro-1 -chloropropène and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, E-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, Z-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane.

Composition according to one of claims 1 to 7 which is a quinquénaire mixture, and preferably is a mixture of:

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, E-3, 3, 3-trifluoro-1 -chloropropène, Z-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, E-3, 3, 3-trifluoro-1 -chloropropène, E-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane; or

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, Z-1, 3,3,3-tetrafluoropropene, E-

1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane.

Composition according to one of claims 1 to 7 which is a senaire mixture, and preferably is a mixture of:

- Hydrogen fluoride, Z-3,3,3-trifluoro-1 - chloropropene, E-3,3,3-trifluoro-1 -chloropropène, Z- 1, 3,3,3-tetrafluoropropene, E-1, 3,3,3-tetrafluoropropene and 1, 1, 1, 3,3-pentafluoropropane.

Composition according to one of claims 1 to 1 1, which is hetero-azeotropic or near-azeotropic hetero.

13. Composition according to one of claims 1 to 12 which comprises from 1 to 85% by weight, preferably 1 to 80% by weight, more preferably 5 to 80% by weight and very particularly preferably 5 to 75% by weight of hydrogen fluoride; and / or 15 to 99% by weight, preferably 20 to 99% by weight, more preferably from 20 to 95% by weight and most preferably from 25 to 95% by weight of compounds (hydro ) halocarbon having 1 to 3 carbon atoms.

14. Composition according to one of Claims 1 to 13, having a boiling point of 0 to 40 ° C at a pressure of 0.5 to 9 bar absolute.

15. A method for producing a compound (hydro) halocarbon principal, comprising:

- Forming a mixture of compounds including hydrogen fluoride, Z-3,3,3-trifluoro-1 -chloropropène and one or more other compounds (hydro) halocarbon;

- Distillation of this mixture, to collect on the one hand an azeotropic composition according to one of claims 1 to 14, and secondly at least one of the compounds of the mixture.

The method of claim 15, wherein the distillation is used to collect on the one hand an azeotropic composition according to one of claims 1 to 14, and secondly hydrogen fluoride; or firstly an azeotropic composition according to one of claims 1 to 14, and secondly the E- 3,3,3-trifluoro-1 -chloropropène.

A method according to claim 15 or 16 which is a process for producing 3,3,3-trifluoro-1 -chloropropène, and preferably S-3,3,3-trifluoro-1 -chloropropène.

Method according to one of claims 15 to 17, wherein the mixture of compounds is obtained as a result of a fluorination step, comprising the reaction of a chlorinated compound with hydrogen fluoride.

Method according to one of claims 15 to 18, wherein the collected azeotropic composition is separated, preferably by settling into two immiscible liquid fractions, namely a fraction rich in hydrogen fluoride and a fraction low in fluoride hydrogen, the fraction rich in hydrogen fluoride containing a higher proportion of hydrogen fluoride that the fraction low in hydrogen fluoride; and the fraction rich in hydrogen fluoride is optionally recycled to the fluorination step.

20. A method according to one of claims 15 to 19 wherein the chlorinated compound is 1, 1, 1, 3,3-pentachloropropane or 1, 1, 3,3-tetrachloropropene.