Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase

• US 10,301,236 B2
• Filed: 05/20/2016
• Issued: 05/28/2019
• Est. Priority Date: 05/21/2015
• Status: Active Grant

• Current Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Original Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Inventors: Sun, Xuehui, Nappa, Mario Joseph, Krause, Karl
• Primary Examiner(s): Bahta, Medhanit W
• Application Number:
  US15/575,526
• Publication Number:
  US 20180127338A1
• Time in Patent Office: 1,103 Days
• CPC Class Codes: B01J 23/16 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 23/18 Arsenic, antimony or bismuth
• CPC Class Codes: B01J 27/08 Halides
• CPC Class Codes: C07C 17/08 to unsaturated hydrocarbons
• CPC Class Codes: C07C 17/087 to unsaturated halogenated hydrocarbons
• CPC Class Codes: C07C 17/206 the other compound being HX
• CPC Class Codes: C07C 17/25 by splitting-off hydrogen halides from halogenated hydrocarbons
• CPC Class Codes: C07C 19/08 containing fluorine
• CPC Class Codes: C07C 19/10 and chlorine
• CPC Class Codes: C07C 21/18 containing fluorine
• CPC Class Codes: C07C 2527/12 Fluorides
• CPC Class Codes: C07C 2527/133 Compounds comprising a halogen and vanadium, niobium, tantalium, antimonium or bismuth

Abstract

The disclosure relates to a method for hydrofluorination of an olefin of the formula: RCX=CYZ to produce a hydrofluoroalkane of formula RCXFCHYZ or RCHXCFYZ, wherein X, Y, and Z are independently the same or different and are selected from the group consisting of H, F, Cl, Br, and C₁-C₆ alkyl which is partially or fully substituted with chloro or fluoro or bromo; and R is a C₁-C₆ alkyl which is unsubstituted or substituted with chloro or fluoro or bromo, comprising reacting the olefin with HF in the liquid-phase, in the presence of SbF₅, at a temperature ranging from about −30° C. to about 65° C.

Claims

1. A method for preparing a hydrofluoroalkane of formula RCXFCHYZ comprising reacting HF with an olefin comprising at least one member selected from the group consisting of 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluooropropene, chlorotetrafluoropropenes, 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, and 3,3,3-trifluoropropene in the liquid phase in the presence of a catalyst at a temperature ranging from about −

30°

C. to about 25°

C. to produce the hydrofluoroalkane, wherein X, Y and Z are independently the same or different and are H, F, or Cl, and R is trifluoromethyl, and wherein the catalyst is SbF₅.

2. The method of claim 1, wherein the mole ratio of HF to the olefin is in the range of from about 1 to about 10.

3. The method of claim 2, wherein the mole ratio of HF to the olefin is in the range of from about 1 to about 5.

4. The method of claim 1, wherein the catalyst is present in an amount from about 1% to about 50% by weight of a mixture comprising said olefin, catalyst and HF.

5. The method of claim 4, wherein the catalyst is present in an amount from about 2% to about 30% by weight of the mixture.

6. The method of claim 5, wherein the catalyst is present in an amount from about 3% to about 15% by weight of the mixture.

7. The method of claim 1, wherein the temperature is from about 5°

C. to about 25°

C.

8. The method of claim 1, wherein the hydrofluoroalkane is 2-chloro-1,1,1,2-tetrafluoropropane.

9. The method of claim 1 wherein the olefin is 2-chloro-3,3,3-trifluoropropene and the hydrofluoroalkane is 2-chloro-1,1,1,2-tetrafluoropropane.

10. The method of claim 9, wherein the 2-chloro-1,1,1,2-tetrafluoropropane is dehydrochlorinated to form 2,3,3,3-tetrafluoro-1-propene.

11. The method of claim 1 wherein the olefin is (Z)- or (E)-1-chloro-3,3,3-trifluooropropene, and the hydrofluoroalkane is 3-chloro-1,1,1,3-tetrafluoropropane.

12. The method of claim 1 wherein the olefin is 1-chloro-2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,2,2-pentafluoro-3-chloropropane or 1,1,1,2,3-pentafluoro-3-chloropropane.

13. The method of claim 1 where the olefin is 2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,2,2-pentafluoropropane.

14. The method of claim 1 wherein the olefin is 1,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,3,3-pentafluoropropane.

15. A method for preparing 2,3,3,3-tetrafluoro-1-propene comprising reacting 2-chloro-1,1,1-trifluoropropene with HF in a liquid phase reactor charged with a hydrofluorination catalyst at a reaction temperature above 65°

C. to produce a mixture of 2-chloro-1,1,1-trifluoropropene and 2-chloro-1,1,1,2-tetrafluoropropane;

reacting HF with said mixture in the liquid phase in the presence of SbF₅ at a temperature ranging from about −

30°

C. to about 65°

C. to further react the unconverted 2-chloro-1,1,1-trifluoropropene to form additional 2-chloro-1,1,1,2-tetrafluoropropane and dehydrohalogenating 2-chloro-1,1,1,2-tetrafluoropropane in a vapor phase reactor with or without a catalyst to form 2,3,3,3-tetrafluoro-1-propene.

16. The method according to claim 15 wherein the temperature for reacting the unconverted 2-chloro-1,1,1-1,1,1-trifluoropropne with HF in the presence of SbF₅ ranges from about −

30°

C. to about 25°

C.

17. A method for preparing 3-chloro-1,1,1,3-tetrafluoropropane comprises reacting HF with an olefin selected from the group consisting of (Z) and (E) 1-chloro-3,3,3-trifluoropropene in the liquid phase in the presence of SbF₅ at a temperature ranging from about −

30°

C. to about 65°

C.

18. A method for preparing a hydrofluoroalkane selected from the group consisting of 1,1,1,2,2-pentafluoro-3-chloropropane and 1,1,1,2,3-pentafluoro-3-chloropropane comprising reacting HF with 1-chloro-2,3,3,3-tetrafluoropropene in the liquid phase in the presence of SbF₅ at a temperature ranging from about −

30°

C. to about 65°

C. to produce the hydrofluoroalkane.