Processes for the production of fluoropropanes and halopropenes and azeotropic compositions of 2-chloro-3,3,3-trifluoro-1-propene with HF and of 1,1,1,2,2-pentafluoropropane with HF
View Patent ↗A process is disclosed for making CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and/or CF 3 CCl═CH 2 . The process involves reacting at least one starting material selected from the group consisting of halopropanes of the formula CX 3 CHClCH 2 X, halopropenes of the formula CClX 2 CCl═CH 2 and halopropenes of the formula CX 2 ═CClCH 2 X, wherein each X is independently F or Cl, with HF in a reaction zone to produce a product mixture comprising HF, HCl, CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and CF 3 CCl═CH 2 ; and recovering the CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and/or CF 3 CCl═CH 2 from the product mixture.
1. A vapor-phase process for making at least one product compound selected from the group consisting of CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and CF 3 CCl═CH 2 , comprising:
reacting a halopropane of the formula CX 3 CHClCH 2 X wherein each X is independently selected from the group consisting of F and Cl, with HF in a reaction zone, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising HF, HCl, CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and CF 3 CCI═CH 2 , wherein the molar ratio of HF to total amount of starting material fed to the reaction zone is from about 10:1 to about 30:1; and
recovering said at least one product compound from the product mixture.
2. The process of claim 1 wherein CF 3 CF═CH 2 is recovered.
3. The process of claim 2 wherein CF 3 CF 2 CH 3 from the product mixture is dehydrofluorinated to produce additional CF 3 CF═CH 2 .
4. The process of claim 1 wherein CF 3 CCI═CH 2 from the product mixture is fluorinated to produce at least one of CF 3 CF═CH 2 and CF 3 CF 2 CH 3 .
5. The process of claim 1 wherein the product mixture further comprises CF 3 CH 2 CHF 2 ; and wherein CF 3 CH 2 CHF 2 from the product mixture is dehydrofluorinated to produce CF 3 CH═CHF.
6. The process of claim 1 wherein the product mixture further comprises CF 3 CH═CHF; and wherein a mixture of CF 3 CF 2 CH 3 and CF 3 CH═CHF is recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a mixture comprising CF 3 CH═CHF and CF 3 CF═CH 2 .
7. The process of claim 1 wherein the product mixture further comprises CF 3 CH 2 CHF 2 and CF 3 CH═CHCl, and wherein the CF 3 CCl═CH 2 , CF 3 CH 2 CHF 2 and CF 3 CH═CHCl from the product mixture are further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 .
8. The process of claim 1 wherein the starting material is reacted in the presence of a fluorination catalyst.
9. The process of claim 8 wherein the fluorination catalyst comprises at least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms, and crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms which has been treated with a fluorinating agent.
10. The process of claim 1 wherein the product mixture further comprises CF 3 CH═CHF; and wherein a mixture of CF 3 CF 2 CH 3 and CF 3 CH═CHF is recovered and further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 .
11. The process of claim 1 wherein CF 3 CF 2 CH 3 , CF 3 CF═CH 2 , and CF 3 CCl═CH 2 from the product mixture together with CF 3 CH 2 CHF 2 , CF 3 CH═CHF, and CF 3 CH═CHCl from the product mixture, if present, are further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 .
12. The process of claim 11 wherein CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 from the mixture is dehydrofluorinated to produce both CF 3 CH═CHF and CF 3 CF═CH 2 ; and wherein both CF 3 CH═CHF and CF 3 CF═CH 2 are recovered.
13. The process of claim 1 wherein the reaction zone temperature is from about 150° C. to about 275° C. and wherein CF 3 CCl═CH 2 is the major product.
14. The process of claim 1 wherein the halopropane is CF 3 CHClCH 2 Cl, the reaction zone temperature is from about 275° C. to about 400° C., and the total yield of CF 3 CF═CH 2 and CF 3 CCl═CH 2 is at least about 54.2% 50%.
15. A liquid-phase process for making at least one product compound selected from the group consisting of CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and CF 3 CCl═CH 2 , comprising:
reacting a halopropane of the formula CX 3 CHClCH 2 X wherein each X is independently selected from the group consisting of F and Cl, with HF in a reaction zone, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising HF, HCl, CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and CF 3 CCl═CH 2 , wherein the molar ratio of HF to total amount of starting material fed to the reaction zone is from about 8:1 to about 50:1; and
recovering said at least one product compound from the product mixture.
16. The process of claim 15 wherein CF 3 CF═CH 2 is recovered.
17. The process of claim 16 wherein CF 3 CF 2 CH 3 from the product mixture is dehydrofluorinated to produce additional CF 3 CF═CH 2 .
18. The process of claim 15 wherein CF 3 CCl═CH 2 from the product mixture is fluorinated to produce at least one of CF 3 CF═CH 2 and CF 3 CF 2 CH 3 .
19. The process of claim 15 wherein the product mixture further comprises CF 3 CH 2 CHF 2 ; and wherein CF 3 CH 2 CHF 2 from the product mixture is dehydrofluorinated to produce CF 3 CH═CHF.
20. The process of claim 15 wherein the product mixture further comprises CF 3 CH═CHF; and wherein a mixture of CF 3 CF 2 CH 3 and CF 3 CH═CHF is recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a mixture comprising CF 3 CH═CHF and CF 3 CF═CH 2 .
21. The process of claim 15 wherein the product mixture further comprises CF 3 CH 2 CHF 2 and CF 3 CH═CHCl, and wherein the CF 3 CCl═CH 2 , CF 3 CH 2 CHF 2 and CF 3 CH═CHCl from the product mixture are further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 .
22. The process of claim 15 wherein the starting material is reacted in the presence of a fluorination catalyst.
23. The process of claim 15 wherein the product mixture further comprises CF 3 CH═CHF; and wherein a mixture of CF 3 CF 2 CH 3 and CF 3 CH═CHF is recovered and further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 .
24. The process of claim 15 wherein CF 3 CF 2 CH 3 , CF 3 CF═CH 2 , and CF 3 CCl═CH 2 from the product mixture together with CF 3 CH 2 CHF 2 , CF 3 CH═CHF, and CF 3 CH═CHCl from the product mixture, if present, are further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 .
25. The process of claim 24 wherein CF 3 CH 2 CHF 2 and CF 3 CF 2 CH 3 from the mixture is dehydrofluorinated to produce both CF 3 CH═CHF and CF 3 CF═CH 2 ; and wherein both CF 3 CH═CHF and CF 3 CF═CH 2 are recovered.