Process for producing chlorotrifluoroethylene
The present invention relates, at least in part, to a process for making chlorotrifluoroethylene (CFO-1113) from 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a). In certain aspects, the process includes dehydrochlorinating 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the presence of a catalyst selected from the group consisting of (i) one or more metal halides; (ii) one or more halogenated metal oxides; (iii) one or more zero-valent metals or metal alloys; (iv) combinations thereof.
1. A process for producing chlorotrifluoroethylene (CFO-113) comprising:
dehydrochlorinating 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in the presence of a catalyst selected from the group consisting of (i) one or more metal halides; (ii) one or more halogenated metal oxides; (iii) one or more zero-valent metals or metal alloys; and (iv) combinations thereof to produce a reaction product comprising CFO-1113, wherein said catalyst comprises at least a catalyst (ii), wherein said catalyst (ii) comprises fluorinated MgO; and from about 5.0 wt. % to about 50 wt % based on the total weight of the catalyst of one or more of a fluorinated Cs 2 O, a fluorinated Li 2 O, a fluorinated Na 2 O, and/or a fluorinated K 2 O.
2. The process of claim 1 wherein the conversion of HCFC-123a is at least about 5 wt. %.
3. The process of claim 2 wherein a selectivity to chlorotrifluoroethylene is at least about 70 wt. %.
4. The process of claim 3 wherein said reaction product comprises less than about 10 wt. % of CFO-1112.
5. The process of claim 1 wherein the dehydrochlorinating step is conducted at a temperature greater than about 400° C.
6. The process of claim 1 wherein the dehydrochlorinating step is carried out at a temperature of from about 480° C. to about 550° C.
7. The process of claim 1 wherein said catalyst comprises a mono-valent metal halide, a bi-valent metal halide, a tri-valent metal halide, or a combination thereof.
8. The process of claim 1 wherein said catalyst comprises a mono-valent metal halide, a bi-valent metal halide or a combination thereof.
9. The process of claim 1 wherein the catalyst comprises at least one metal halide wherein the component metal is selected from the group consisting of Cr 3+ , Fe 3+ , Mg 2+ , Ca 2+ , Ni 2+ , Zn 2+ , Pd 2+ , Li + , Na + , K + , and Cs + , and the component halogen is selected from the group consisting of F − , Cl − , Br − , and I − .
10. The process of claim 1 wherein the catalyst comprises at least one optionally supported metal halide selected from the group consisting of LiF, NaF, KF, CsF, MgF 2 , CaF 2 , LiCl, NaCl, KCl, and CsCl.
11. The process of claim 1 wherein the catalyst comprises MgF 2 and one or more of CsCl, LiCl, NaCl, KCl, LiF, NaF, KF, and/or CsF.
12. The process of claim 11 wherein the CsCl, LiCl, NaCl, KCl, LiF, NaF, KF, and/or CsF is present in an amount of about 5.0 wt. % to about 50 wt % based on the total weight of the catalyst.
13. The process of claim 1 , wherein the catalyst further comprises a halogenated bi-valent metal oxide, a halogenated tri-valent metal oxide, or a combination thereof.
14. The process of claim 1 wherein the catalyst further comprises at least one halogenated metal oxide wherein the component metal is selected from the group consisting Cr 3+ , Fe 3+ , Ca 2+ , Ni 2+ , Zn 2+ , and Pd 2+ .
15. The process of claim 1 wherein the catalyst further comprises at least one fluorinated or chlorinated CaO, chlorinated Li 2 O, chlorinated Na 2 O, chlorinated K 2 O, and chlorinated Ca 2 O.
16. The process of claim 1 wherein the catalyst further comprises a zero valent metal, a zero valent metal alloy, or a combination thereof.
17. The process of claim 16 wherein the zero valent metal or zero valent metal alloy is optionally supported and comprises at least one metal selected from the group consisting of Pd, Pt, Rh, Ru, Ir, Os, Fe, Co, Ni, Cu, Mo, Cr, Mn, and combinations.
18. The process of claim 16 wherein the zero valent metal or zero valent metal alloy is supported by at least one support selected from the group consisting of MgO, fluorinated MgO, MgF 2 , carbon materials such as activated carbons and carbon molecular sieves, and α-Al 2 O 3 .
19. The process of claim 16 wherein the zero valent metal or zero valent metal alloy comprises one or more of Pd, Pt, Ru, Rh, and/or Ir supported on MgO.
20. The process of claim 19 wherein the Pd, Pr, Ru, Rh, and/or Ir is present in an amount of about 0.05 to about 5 wt % based on the total weight of the catalyst.
21. The process of claim 16 , wherein the zero valent metal alloy is present and is selected from the group consisting of alloys 304, 316, 316L, 400, 401, 404, 600, 617, 625, 718, B-2, C-4, C-22, C-276, 800, 825, and combinations thereof.
22. The process of claim 21 wherein the zero valent metal alloy comprises an 800, 825, alloy and combinations thereof.
23. The process of claim 21 wherein the zero valent metal alloy comprises 625 alloy.