Process for 1-chloro-3,3,3-trifluoropropene from trifluoropropene
View Patent ↗The present invention provides routes for making 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from commercially available raw materials. More specifically, this invention provides several routes for forming HCFO-1233zd from 3,3,3-trifluoropropene (FC-1234zf).
1. A method for the formation of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from 3,3,3-trifluoropropene (FC-1234zf) comprising the direct conversion of 3,3,3-trifluoropropene into CF 3 CH═CHCl by reaction with oxygen and hydrogen chloride.
2. The method of claim 1 , wherein the reaction is run in a continuous manner.
3. A method for the formation of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from 3,3,3-trifluoropropene (FC-1234zf), selected from the group of reactions consisting of:
(a) the reaction of 3,3,3-trifluoropropene with XCl, whereby XCl is added across the double to afford CF 3 CHXCH 2 Cl which is then converted to CF 3 CH═CHCl by an HX elimination reaction;
(b) the reaction of 3,3,3-trifluoropropene with hydrogen to afford CF 3 CH 2 CH 3 , which is then chlorinated and dehydrochlorinated to give 1-chloro-3,3,3-trifluoropropene; and
(c) combinations of these reactions.
4. The method of claim 3 , wherein the oxychlorination reaction comprises the reaction of oxygen and hydrogen chloride with the propene, in the vapor phase over a supported catalyst.
5. The method of claim 4 where oxygen to hydrogen chloride ratio is 0.5 to 1.
6. The method of claim 4 , wherein the supported catalyst is selected from the group consisting of copper chloride salts, rare earth salts, and equivalents thereof.
7. The method of claim 5 , wherein the catalyst comprises CuCl 2 .
8. The method of claim 5 , wherein the catalyst comprises CuCO 3 /CeO 2 .
9. The method of claim 4 , wherein the support of the catalyst is selected from the group consisting of carbon, alumina, and equivalents thereof.
10. The method of claim 4 , wherein the reaction temperature of the oxychlorination reaction ranges from 400° to 550° C.
11. The method of claim 3 , wherein X in XCl is selected from the group consisting of Br, I, and OR, wherein R is a C 1 to C 6 carbon group.
12. The method of claim 11 , wherein R is selected from methyl, ethyl, propyl, butyl, heptyl, and hexyl.
13. The method of claim 11 , wherein XCl comprises BrCl.
14. The method of claim 11 , wherein XCl comprises ICl.
15. The method of claim 11 , wherein XCl comprises ROCl.
16. The method of claim 11 , wherein CF 3 CHXCH 2 Cl comprises CF 3 CHICH 2 Cl.
17. The method of claim 3 , wherein the chlorination reaction of CF 3 CH 2 CH 3 generates a product intermediate comprising CF 3 CH 2 CHCl 2 .
18. The method of claim 17 , wherein dehydrochlorination reaction of CF 3 CH 2 CHCl 2 is conducted in the vapor phase at about 400° C. to yield HCFO-1233zd.
19. The method of claim 18 , wherein the ratio of trans to cis HCFO-1233zd is 90:10.
20. A process for producing 1-chloro-3,3,3-trilfuoroproene (HCFO-1233zd) from 3,3,3-tri-fluoropropene (FC-1234zf) comprising the steps of:
(a) addition of XCl to 3,3,3-trifluorpropene to form CF 3 CHXCH 2 Cl; and
(b) elimination of HX from CF 3 CHXCH 2 Cl to form HCFO-1233zd.
21. A process for producing 1-chloro-3,3,3-trilfuoroproene (HCFO-1233zd) from 3,3,3-trifluoropropene (FC-1234zf) comprising the steps of:
(a) hydrogenation of 3,3,3-trifluorpropene to form CF 3 CH 2 CH 3 ;
(b) chlorination of CF 3 CH 2 CH 3 to form CF 3 CH 2 CHCl 2 and
(c) dehydrochlorination of CF 3 CH 2 CHCl 2 to form HCFO-1233zd.