Process for producing 2,3,3,3-tetrafluoropropene
View Patent ↗The present invention relates, in part, to the discovery that the presence of impurities in 1,1,2,3-tetrachloropropene (1230xa) results in catalyst instability during the fluorination of 1230xa to 2-chloro-3,3,3-trifluoropropene. By substantially removing the impurities, it is shown that the catalyst life is extended and results in improved operation efficiency of the fluorination reaction. Such steps similarly result in an overall improvement in the production of certain hydrofluoroolefins, particularly 2,3,3,3-tetrafluoropropene (1234yf).
1. A feed stock for use in preparing a fluoroolefin comprising a composition comprising 1,1,2,3-tetrachlopropene that is substantially free of impurities, wherein said impurities comprise one or more materials selected from ionic metal, hexachloroethane, tetrachloropropane, pentachloropropane, dichloropropene, trichloropropane, hexachlorohexadiene, trichloropropene, pentachloropropene, dichlorobutene, and combinations thereof.
2. The feed stock of claim 1 wherein less that 1% impurity is present as measured by GC (FID) area.
3. The feed stock of claim 1 , wherein the impurity is an ionic metal, wherein the ionic metal is present in the composition in an amount less than about 100 ppm.
4. The feed stock of claim 1 , wherein the impurities comprise one or more organic compounds selected from the group consisting of hexachloroethane, tetrachloropropane, pentachloropropane, dichloropropene, trichloropropane, hexachlorohexadiene, trichloropropene, pentachloropropene, dichlorobutene, and combinations thereof.
5. The feed stock of claim 4 , wherein any one of the organic compounds is present in the composition in an amount less than 1000 ppm.
6. The feed stock of claim 4 , wherein the one or more organic compounds are provided at less than 0.5% (w/w) of the composition.
7. A process for preparing 2-chloro-3,3,3-trifluoropropene comprising:
providing a starting composition comprising at least one compound of formula I
CX 2 ═CCl—CH 2 X (I)
wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine and wherein the starting composition is substantially free of impurities, wherein said impurities comprise one or more materials selected from ionic metal, hexachloroethane, tetrachloropropane, pentachloropropane, di chloropropene, trichloropropane, hexachlorohexadiene, trichloropropene, pentachloropropene, dichlorobutene, and combinations thereof; and
contacting said starting composition with a fluorinating agent to produce a final composition comprising 2-chloro-3,3,3-trifluoropropene.
8. The process of claim 7 , wherein at least one compound of formula I is a compound comprising at least one X is a chlorine.
9. The process of claim 7 , wherein at least one compound of formula I is a compound where all Xs are chlorine.
10. The process of claim 7 , wherein the at least one compound of formula I comprises 1,1,2,3-tetrachloropropene.
11. The process of claim 7 , wherein the contacting of said starting composition with a fluorinating agent occurs in a vapor phase.
12. The process of claim 7 , wherein the contacting occurs in the presence of a catalyst.
13. The process of claim 12 , wherein the catalyst is a vapor phase catalyst.
14. The process of claim 13 , wherein the vapor phase catalyst is selected from the group consisting of a chromium oxide, a chromium hydroxide, a chromium halide, a chromium oxyhalide, an aluminum oxide, an aluminum hydroxide, an aluminum halide, an aluminum oxyhalide, a cobalt oxide, a cobalt hydroxide, a cobalt halide, a cobalt oxyhalide, a manganese oxide, a manganese hydroxide, a manganese halide, a manganese oxyhalide, a nickel oxide, a nickel hydroxide, a nickel halide, a nickel oxyhalide, an iron oxide, an iron hydroxide, an iron halide, an iron oxyhalide, inorganic salts thereof, fluorinated derivatives thereof and combinations thereof.
15. The process of claim 14 wherein the catalyst comprises a chromium oxide.
16. The process of claim 7 wherein less than 1% impurity is present as measured by GC area.
17. The process of claim 7 , wherein the impurity is an ionic metal, wherein the ionic metal is present in the composition in an amount less than about 100 ppm.
18. The process of claim 7 , wherein the impurities comprise one or more organic compounds selected from the group consisting of hexachloroethane, tetrachloropropane, pentachloropropane, dichloropropene, trichloropropene, trichloropropane, hexachlorohexadiene, pentachloropropene, dichlorobutene, and combinations thereof.
19. The process of claim 18 , wherein any one of the organic compounds is present in the composition in an amount less than 1000 ppm.
20. The process of claim 18 , wherein the one or more organic compounds are collectively present in a concentration of less than 0.5% (w/w) of the composition.
21. The process of claim 7 wherein contacting the composition with hydrogen fluoride is conducted in the absence of supplied oxygen and/or in the absence of a polymerization inhibitor.
22. The process of claim 7 wherein contacting the composition with hydrogen is conducted in the presence of supplied oxygen and/or in the presence of a polymerization inhibitor.
23. The process of claim 15 where the catalyst has a surface area ranging from about 60 m 2 /g to about 300 m 2 /g.
24. The process of claim 7 wherein contacting the starting composition with hydrogen fluoride is conducted at a temperature ranging from about 180° C. to about 400° C.
25. The process of claim 7 wherein contacting the starting composition with hydrogen fluoride is conducted at a pressure ranging from about 5 psia to about 100 psia.
26. A process for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising:
providing a starting composition comprising a compound of formula I
CX 2 ═CCl—CH 2 X (I)
wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine and the starting composition is substantially free of impurities, wherein said impurities comprise one or more materials selected from ionic metal, hexachloroethane, tetrachloropropane, pentachloropropane, dichloropropene, trichloropropane, hexachlorohexadiene, trichloropropene, pentachloropropene, dichlorobutene, and combinations thereof;
contacting said starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene;
contacting said first intermediate composition with a second fluorinating agent to produce a second intermediate composition comprising 2-chloro-1,1,1,2-tetrafluoropropane; and
dehydrochlorinating at least a portion of said 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene.
27. A feed stock for use in preparing a fluoroolefin according to claim 1 comprising a composition comprising 1,1,2,3-tetrachloropropene that is substantially free of impurities, wherein said impurities comprise one or more materials selected from ionic metal, hexachloroethane, tetrachloropropane, pentachloropropane, trichloropropane, and combinations thereof.
28. The process according to claim 7 wherein the starting composition is substantially is substantially free of impurities, wherein the impurities comprise one or more materials selected from ionic metal, hexachloroethane, tetrachloropropane, pentachloropropane, trichloropropane, and combinations thereof.
29. The process according to claim 26 wherein the starting is substantially free of impurities wherein said impurities comprise one or more materials selected from ionic metal, hexachloroethane, tetrachloropropane, pentachloropropane, trichloropropane, and combinations thereof.