Catalytic fluorination process of making hydrohaloalkane
View Patent ↗The present disclosure provides a fluorination process which involves reacting a hydrohaloalkene of the formula R f C—Cl═CH 2 with HF in a reaction zone in the presence of a fluorination catalyst selected from the group consisting of TaF 5 and TiF 4 to produce a product mixture containing a hydrohaloalkane of the formula R f CFClCH 3 , wherein R f is a perfluorinated alkyl group.
1. A process comprising: reacting a hydrohaloalkene of the formula R f CCl═CH 2 with HF in a reaction zone in the presence of a fluorination catalyst selected from the group consisting of TaF 5 and TiF 4 to produce a product mixture comprising a hydrohaloalkane of the formula R f CFClCH 3 , wherein R f is a perfluorinated alkyl group, in an amount effective to form R f CFClCH 3 without substantially forming R f CF 2 CH 3 or R f CHClCH 2 F.
2. The process of claim 1 , further comprising: recovering said hydrohaloalkane of the formula R f CFClCH 3 from the product mixture.
3. The process of claim 1 , wherein R f is CF 3 .
4. The process of claim 3 , wherein the product selectivity to CF 3 CFClCH 3 is at least 90 mole %.
5. The process of claim 1 , wherein said fluorination catalyst is TaF 5 .
6. The process of claim 5 , wherein the temperature in the reaction zone is from about 90° C. to about 160° C.
7. The process of claim 5 wherein the amount of TaF 5 present ranges from about 1 mole % to about 30 mole % of the amount of the hydrohaloalkene.
8. The process of claim 7 where the amount of TaF 5 present ranges from about 10 mol % to about 20 mol % of hydrohaloalkene.
9. The process of claim 1 , wherein said fluorination catalyst is TiF 4 .
10. The process of claim 9 , wherein the temperature in the reaction zone is from about 90° C. to about 200° C.
11. The process of claim 9 wherein the amount of TiF 4 present ranges from about 1 mol % to about 30 mol % of the amount of hydrohaloalkene.
12. The process of claim 9 wherein the amount of TiF 4 ranges from about 10 mol % to about 30 mol % of hydrohaloalkene.
13. The process of claim 2 , further comprising: dehydrochlorinating the recovered hydrohaloalkane of the formula R f CFClCH 3 to produce a product mixture comprising a hydrofluoroalkene of the formula R f CF═CH 2 .
14. The process of claim 13 , wherein R f is CF 3 .
15. A liquid phase fluorination process for making CF 3 CFClCH 3 , comprising:
feeding HF and an organic feed mixture comprising about 18.2 mole % of CF 3 CCl═CH 2 , about 80 mole % of CF 3 CFClCH 3 , and about 1.6 mole % of CF 3 CF 2 CH 3 to a reaction zone containing TaF 5 and HF; and
reacting CF 3 CCl═CH 2 from the organic feed mixture with HF in the reaction zone to produce additional CF 3 CFClCH 3 ;
wherein the temperature in the reaction zone is from about 98° C. to about 114° C., and the pressure in the reaction zone is from about 130 psig to about 200 psig.
16. A liquid phase fluorination process for making CF 3 CFClCH 3 , comprising:
feeding HF and CF 3 CCl═CH 2 to a reaction zone containing TaF 5 and HF; and
reacting CF 3 CCl═CH 2 with HF in the reaction zone to produce CF 3 CFClCH 3 ;
wherein the temperature in the reaction zone is from about 98° C. to about 103° C., and the pressure in the reaction zone is from about 125 psig to about 145 psig.
17. A process for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising:
a. providing a starting composition comprising at least one compound having a structure selected from Formulas I, II and III:
CX 2 ═CCl—CH 2 X Formula I
CX 3 −CCl═CH 2 Formula II
CX 3 −CHCl═CH 2 X Formula III
wherein X is independently selected from F, Cl, Br and I, provided that at least one X is not fluorine:
b. contacting said starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene and a first chlorine-containing byproduct;
c. contacting said first intermediate composition with a second fluorinating agent in the presence of a fluorination catalyst selected from the group consisting of TaF 5 and TiF 4 to produce a product comprising 2-chloro-1,1,1,2-tetrafluoropropane without substantially forming 1,1,1,2,2-pentafluoropropane or 1,1,1,3-terafluoro-2-chloropropane and
d. dehydrochlorinating 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene.
18. The process according to claim 17 wherein the product selectivity to CF 3 CF 2 CH 3 is no more than 2 mole %.
19. The process according to claim 17 wherein said fluorinaton catalyst TaF 5 .
20. The process according to claim 19 wherein the amount of TaF 5 present ranges from about 1 mole % to about 30 mole % of the amount of 2-chloro-3,3,3-trifluoropropene and the temperature ranges from about 90° C. to about 160° C.
21. The process according to claim 17 wherein said fluorination catalyst is TiF 4 .
22. The process according to claim 21 wherein the amount of TiF 4 present ranges from about 1 mol % to about 30 mol % of 2-chloro-3,3,3-trifluoropropene and the temperature ranges from about 90° C. to about 200° C.