Process for producing 2-chloro-3,3,3-trifluoropropene and 2,3,3,3-tetrafluoropropene

Patent metadata

Field	Value
Publication number	US-9540295-B2
Application number	US-201214348819-A
Country	US
Kind code	B2
Filing date	Sep 29, 2012
Priority date	Sep 30, 2011
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

The present invention relates, in part, to the discovery that high temperatures during the fluorination of 1,1,2,3-tetrachloropropene (HCO-1230xa) to 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) results in catalyst instability, reduced selectivity of the conversion, and/or the formation of one or more undesirable by-products. By controlling the reaction temperature, it is shown that the catalyst life may be extended and the selectivity of the reaction improved. Such control similarly results in an overall improvement in the production of certain hydrofluoroolefins, particularly 2,3,3,3-tetrafluoropropene (HFO-1234yf).

First claim

What is claimed is:

1. 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 each X is independently F, Cl, Br, or I, provided that at least one X is not fluorine;
contacting said starting composition with a fluorinating agent in the presence of a fluorinating catalyst to produce a final composition comprising 2-chloro-3,3,3-trifluoropropene; and
conducting the contacting step at a temperature ranging from about 180° C. to about 300° C. in the presence of said fluorinating catalyst, controlling the temperature of the contacting step such that it does not exceed about 300° C., and
when the fluorinating catalyst is deactivating, increasing the temperature of the contacting step in small increments ranging from about 0.5° C. to about 20° C., but not to exceed about 300° C.;

wherein the process is conducted in the vapor phase.

2. The process of claim 1 , wherein the temperature of the reaction does not exceed 275° C.

3. The process of claim 1 , wherein the temperature of the reaction ranges from about 180° C. to about 300° C.

4. The process of claim 1 , wherein the small increments range from about 1° C. to about 10° C.

5. The process according to claim 1 wherein the small increments range from about 3° C. to about 8° C.

6. The process of claim 1 , wherein the product collection rate ranges from about 0.1 lbs/hr to about 1.0 lbs/hr per lb of organic feed provided to the reaction.

7. The process according to claim 6 wherein the product collection rate ranges from about 0.3 lbs/hour to about 0.8 lbs/hour of organic feed provided to the reaction.

8. The process of claim 1 , wherein at least one compound of formula I is a compound comprising at least one X is a chlorine.

9. The process of claim 1 , wherein at least one compound of formula I is a compound where all Xs are chlorine.

10. The process of claim 1 , wherein the at least one compound of formula I is 1,1,2,3-tetrachloropropene.

11. The process of claim 1 , wherein the fluorination 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.

12. The process of claim 1 , wherein the catalyst comprises a chromium oxide.

13. A process for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising:
a. providing a starting composition comprising a compound of formula I
CX 2 ═CCl—CH 2 X  (I)

 wherein each X is independently F, Cl, Br, or I, provided that at least one X is not fluorine;
b. contacting said starting composition with a first fluorinating agent in a vapor phase to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene in the presence of a fluorination catalyst at a temperature ranging from about 180° C. to about 300° C. and, when the fluorinating catalyst is deactivating, increasing the temperature in small increments ranging from about 0.5° C. about 20° C. and controlling the temperature during the contacting step such that it does not exceed about 300° C.
c. 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
d. 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.

14. The process of claim 13 , wherein the pressure of the reaction ranges from about 50 psig to about 125 psig.

15. The process of claim 13 , wherein the temperature during the contacting step (b) does not exceed 275° C.

16. The process of claim 13 , wherein the small increments range from about 1° C. to about 10° C.

17. The process according to claim 13 wherein the small increments range from about 3° C. to about 8° C.

18. The process of claim 13 , wherein the product collection rate ranges from about 0.1 lbs/hr to about 1.0 lbs/hr per lb of organic feed provided to the reaction.

19. The process according to claim 18 wherein the product collection rate ranges from about 0.3 lbs/hour to about 0.8 lbs/hour of organic feed provided to the reaction.

Assignees

• Honeywell Int Inc

Inventors

• Bektesevic Selma
• Tung Hsueh Sung
• Wang Haiyou

Classifications

• C07C17/21 Primary

  with simultaneous increase of the number of halogen atoms · CPC title

• C07C17/25

  by splitting-off hydrogen halides from halogenated hydrocarbons · CPC title

• C07C17/206

  the other compound being HX · CPC title

• C07C17/087 Primary

  to unsaturated halogenated hydrocarbons · CPC title

• C07C17/20

  of halogen atoms by other halogen atoms · CPC title