Process for producing 2,3,3,3-tetrafluoropropene
View Patent ↗The present invention relates, in part, to the discovery that, during the fluorination of certain fluoroolefin starting reagents, oligomerization/polymerization of such reagents reduces the conversion process and leads to increased catalyst deactivation. The present invention also illustrates that vaporizing such starting reagents in the presence of one or more organic co-feed reduces such oligomerization/polymerization and improves catalytic stability.
1. A process for reducing polymerization of a starting composition comprising:
providing a liquid phase composition comprising an organic compound of formulas I, II, and/or III
CX 2 ═CClCH 2 X (Formula I)
CX 3 —CCl═CH 2 (Formula II)
CX 3 —CHCl—CH 2 X (Formula III)
and one or more organic co-feed compounds, other than the compound of formulas I, II, and/or III, the one or more organic co-feed compounds being present in an effective amount to reduce polymerization of the compound of Formula I, II and/or III, said effective amount ranging from about 3 to about 50 wt % based on the total weight of the organic compound Formulas I, II, and/or III and the one or more organic co-feed compounds, and optionally hydrogen fluoride, wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine; and
heating said starting composition to form a vapor phase composition.
2. The process of claim 1 , wherein the organic co-feed compound is a halocarbon or haloolefin.
3. The process of claim 1 , wherein the organic co-feed compound is selected from the group consisting of trichlorofluoropropene (1231), 2,3-dichloro-3,3-difluoropropene (1232xf), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 1,1,1,2,2-pentafluoropropane (HFC-245cb), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), trifluoroethane (HFC-143), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and combinations thereof.
4. The process of claim 1 , wherein the effective amount of organic co-feed compound is between about 5 to about 15 wt %.
5. The process of claim 1 wherein the effective amount of organic co-feed is between about 3 to about 30 wt %.
6. The process of claim 1 wherein the organic co-feed compound has a boiling point lower than the boiling point of the organic compound of formulas I, II, or III.
7. A process for preparing 2-chloro-3,3,3-trifluoropropene comprising:
providing, in a liquid phase, a starting composition comprising at least one organic compound of formulas I, II, and/or 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;
vaporizing said starting composition with an effective amount of one or more organic co-feed compounds, other than the compound of formula I, II, and/or III to form a vapor phase composition, wherein said one or more organic co-feed compounds are present in an effective amount to reduce polymerization of the compound of Formula I, II and/or III, said effective amount ranging from about 3 to about 50 wt % based on the total weight of the organic compound of Formulas I, II and/or III and the organic co-feed; and
contacting said vaporized starting composition with a fluorinating agent to produce a final composition comprising 2-chloro-3,3,3trifluoropropene.
8. The process of claim 7 , wherein the organic co-feed compound is a halocarbon or haloolefin.
9. The process of claim 7 , wherein the organic co-feed compound is selected from the group consisting of trichlorofluoropropene (1231), 2,3-dichloro-3,3-difluoropropene (1232xf), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), 2-chloro-3,3,3-trifluoropropene (1233xf), 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 1,1,1,2,2-pentafluoropropane (HFC-245cb), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), trifluoroethane (HFC-143), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and combinations thereof.
10. The process of claim 7 , wherein the effective amount of organic co-feed compound is between about 5 to about 15 wt %.
11. The process of claim 7 , wherein at least one compound of formula I, II, or III is a compound comprising at least one X is chlorine.
12. The process of claim 7 , wherein at least one compound of formula I, II, or III is a compound where all Xs are chlorine.
13. The process of claim 7 , wherein the at least one compound is 1,1,2,3-tetrachloropropene, 2,3,3,3-tetrachloropropene or 1,1,1,2,3-pentachloropropane.
14. The process of claim 7 , wherein the contacting of said starting composition with a fluorinating agent occurs in a vapor phase.
15. The process of claim 14 , wherein the contacting step occurs in the presence of a vapor phase catalyst.
16. The process of claim 15 , 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.
17. The process of claim 16 wherein the catalyst comprises a chromium oxide.
18. The process of claim 7 wherein the effective amount of organic co-feed is between about 3 to about 30 wt %.
19. The process of claim 7 wherein the organic co-feed compound has a boiling point lower than the boiling point of the organic compound of formulas I, II, or III.