Processes for the production of fluoropropanes and halopropenes

Abstract

A process is disclosed for making CF3CF2CH3, CF3CF═CH2 and/or CF3CCl═CH2. The process involves reacting at least one starting material selected from the group consisting of halopropanes of the formula CX3CH2CH2X, halopropenes of the formula CX3CH═CH2 and halopropenes of the formula CX2═CHCH2X, wherein each X is independently F or Cl, with HF and Cl2 in a reaction zone to produce a product mixture comprising HF, HCl, CF3CF2CH3, CF3CF═CH2, and CF3CCl═CH2; and recovering the CF3CF2CH3, CF3CF═CH2 and/or CF3CCl═CH2 from the product mixture. Also disclosed is a process for making CF3CH2CHF2, CF3CH═CHF, and/or CF3CH═CHCl. This process involves reacting at least one starting material selected from the group consisting of halopropenes of the formula CX3CH═CH2 and halopropenes of the formula CX2═CHCH2X, wherein each X is independently F or Cl, with HF and Cl2 in a reaction zone to produce a product mixture comprising HF, HCl, CF3CH2CHF2, CF3CH═CHF and CF3CH═CHCl; and recovering the CF3CH2CHF2, CF3CH═CHF, and/or CF3CH═CHCl from the product mixture. The molar ratio of HF to the total amount of starting materials fed to the reaction zone for both of these processes is at least stoichiometric, and the molar ratio of Cl2 to total amount of starting material fed to the reaction zone for both of these processes is 2:1 or less.

The invention claimed is: 
     
       1. A process for making at least one product compound selected from the group consisting of CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2  (1233xf), comprising:
 reacting at least one starting material selected from the group consisting of halopropanes of the formula CX 3 CH 2 CH 2 X, halopropenes of the formula CX 3 CH═CH 2  and halopropenes of the formula CX 2 ═CHCH 2 X, wherein each X is independently selected from the group consisting of F and Cl, with HF and Cl 2  in a reaction zone, optionally in the presence of a chlorofluorination catalyst, to produce a product mixture comprising at least one product compound selected from the group consisting of CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2  (1233xf), 
 wherein the molar ratio of HF to total amount of starting material fed to the reaction zone is at least stoichiometric and wherein the molar ratio of Cl 2  to total amount of starting material fed to the reaction zone is 2:1 or less; and 
 recovering said at least one product compound from the product mixture. 
 
     
     
       2. The process of  claim 1  wherein CF 3 CF═CH 2  (1234yf) is recovered. 
     
     
       3. The process of  claim 2  wherein CF 3 CF 2 CH 3  (245cb) from the product mixture is dehydrofluorinated to produce additional CF 3 CF═CH 2  (1234yf). 
     
     
       4. The process of  claim 1  wherein CF 3 CCl═CH 2  from the product mixture is fluorinated to produce at least one of CF 3 CF═CH 2  (1234yf) and CF 3 CF 2 CH 3  (245cb). 
     
     
       5. The process of  claim 1  wherein the product mixture further comprises CF 3 CH═CHF (1234ze); and wherein CF 3 CH═CHF from the product mixture is recovered. 
     
     
       6. The process of  claim 1  wherein the product mixture further comprises CF 3 CH═CHCl (1233zd); and wherein CF 3 CH═CHCl (1233zd) from the product mixture is fluorinated to produce at least one of CF 3 CH═CHF (1234ze) and CF 3 CH 2 CHF 2  (245fa). 
     
     
       7. The process of  claim 1  wherein the product mixture further comprises CF 3 CH 2 CHF 2  (245fa); and wherein CF 3 CH 2 CHF 2  (245fa) from the product mixture is recovered. 
     
     
       8. The process of  claim 1  wherein the product mixture further comprises CF 3 CH 2 CHF 2  (245fa); and wherein CF 3 CH 2 CHF 2  (245fa) from the product mixture is dehydrofluorinated to produce CF 3 CH═CHF (1234ze). 
     
     
       9. The process of  claim 1  wherein the product mixture further comprises CF 3 CH═CHF (1234ze); and wherein a mixture of CF 3 CF 2 CH 3  (245cb) and CF 3 CH═CHF (1234ze) is recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a mixture comprising CF 3 CH═CHF (1234ze) and CF 3 CF═CH 2  (1234yf). 
     
     
       10. The process of  claim 1  wherein the product mixture further comprises CF 3 CH 2 CHF 2  (245fa) and CF 3 CH═CHCl (1233zd); and wherein the CF 3 CCl═CH 2  (1233xf), CF 3 CH 2 CHF 2  (245fa) and CF 3 CH═CHCl (1233zd) from the product mixture are further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a mixture comprising CF 3 CH 2 CHF 2  (245fa) and CF 3 CF 2 CH 3  (245cb). 
     
     
       11. The process of  claim 1  wherein the starting material is reacted in the vapor phase in the presence of a chlorofluorination catalyst. 
     
     
       12. The process of  claim 11  wherein the chlorofluorination catalyst comprises at least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms, and crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms which has been treated with a fluorinating agent. 
     
     
       13. A process for making at least one product compound selected from the group consisting of CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2 , (1233xf) comprising:
 reacting at least one starting material selected from the group consisting of halopropanes of the formula CX 3 CH 2 CH 2 X, halopropenes of the formula CX 3 CH═CH 2  and halopropenes of the formula CX 2 ═CHCH 2 X, wherein each X is independently selected from the group consisting of F and Cl, with HF and Cl 2  in a reaction zone, in the presence of a chlorofluorination catalyst, to produce a product mixture comprising HF, HCl, CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2  (1233xf), wherein the molar ratio of HF to total amount of starting material fed to the reaction zone is at least stoichiometric and wherein the molar ratio of Cl 2  to total amount of starting material fed to the reaction zone is 2:1 or less; and 
 recovering said at least one product compound from the product mixture. 
 
     
     
       14. The process of  claim 13  wherein said at least one starting material is halopropenes of the formula CX 3 CH═CH 2  (1243zf). 
     
     
       15. The process of  claim 14  wherein said at least one starting material is CF 3 CH═CH 2  (1243zf). 
     
     
       16. A process for making at least one product compound selected from the group consisting of CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf), CF 3 CCl═CH 2  (1233xf), CF 3 CH 2 CHF 2  (245fa), CF 3 CH═CHF (1234ze) and CF 3 CH═CHCl (1233zd), comprising:
 reacting at least one starting material selected from the group consisting of halopropanes of the formula CX 3 CH 2 CH 2 X, halopropenes of the formula CX 3 CH═CH 2  and halopropenes of the formula CX 2 ═CHCH 2 X, wherein each X is independently selected from the group consisting of F and Cl, with HF and Cl 2  in a reaction zone, in the presence of a chlorofluorination catalyst, to produce a product mixture comprising CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf), CF 3 CCl═CH 2  (1233xf), CF 3 CH 2 CHF 2  (245fa), CF 3 CH═CHF (1234ze) and CF 3 CH═CHCl (1233zd), wherein the molar ratio of HF to total amount of starting material fed to the reaction zone is at least stoichiometric and wherein the molar ratio of Cl 2  to total amount of starting material fed to the reaction zone is 2:1 or less; and 
 recovering said at least one product compound from the product mixture. 
 
     
     
       17. A process for preparing 1,1,1-trifluoro-2,3-dichloropropane (243db), comprising contacting 3,3,3-trifluoropropene (1243zf) with HF and Cl 2  in a reaction zone, optionally in the presence of a chlorofluorination catalyst, to produce a product mixture comprising 1,1,1-trifluoro-2,3-dichloropropane (243db) and optionally at least one product compound selected from the group consisting of CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2  (1233xf), wherein the molar ratio of HF to total amount of starting material fed to the reaction zone is at least stoichiometric and wherein the molar ratio of Cl 2  to total amount of starting material fed to the reaction zone is 2:1 or less; and recovering said at least one product compound from the product mixture. 
     
     
       18. The process of claim 17, wherein the process is conducted in the liquid phase and the catalyst is selected from carbon, AlF 3 , BF 3 , FeCl 3-a F a , where a=0 to 3, FeX 3  supported on carbon where X is Cl or F, SbCl 3-a F a , AsF 3 , MCl 5-b F b , where b=0 to 5, and M is Sb, Nb, Ta, or Mo, and M′Cl 4-c F c , where c=0 to 4, and M′ is Sn, Ti, Zr, or Hf. 
     
     
       19. The process of claim 1, wherein the product mixture comprises at least two of CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2  (1233xf). 
     
     
       20. The process of claim 19, wherein the product mixture comprises CF 3 CF 2 CH 3  (245cb) and CF 3 CF═CH 2  (1234yf). 
     
     
       21. The process of claim 19, wherein the product mixture comprises CF 3 CF 2 CH 3  (245cb) and CF 3 CCl═CH 2  (1233xf). 
     
     
       22. The process of claim 1, wherein the product mixture comprises CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) and CF 3 CCl═CH 2  (1233xf). 
     
     
       23. The process of claim 15, wherein the CF 3 CH═CH 2  (1243zf) starting material is formed by fluorinating CCl 3 CH 2 CH 2 Cl (250fb). 
     
     
       24. The process of claim 1, wherein the starting material comprises the halopropane comprising CCl 3 CH 2 CH 2 Cl (250fb), and the process further comprises contacting CCl 3 CH 2 CH 2 Cl (250fb), HF and Cl 2  in a pre-reactor at a temperature of between 80° C. to about 250° C. prior to reaction in the reaction zone of a vapor-phase reactor. 
     
     
       25. The process of claim 24, wherein the pre-reactor contains a packing material inert to HCl and HF. 
     
     
       26. The process of claim 24 wherein the Cl 2 :starting material ratio is between about 0.5:1 to about 2:1. 
     
     
       27. The process of claim 24 wherein a mixture containing predominantly CF 3 CH═CH 2  (1243zf) and CF 3 CHClCHCl (243db) is formed in the pre-reactor. 
     
     
       28. The process of claim 25 wherein a mixture containing predominantly CF 3 CH═CH 2  (1243zf) and CF 3 CHClCHCl (243db) is formed in the pre-reactor. 
     
     
       29. The process of claim 26 wherein a mixture containing predominantly CF 3 CH═CH 2  (1243zf) and CF 3 CHClCHCl (243db) is formed in the pre-reactor. 
     
     
       30. The process of claim 15, further comprising forming CF 3 CH═CH 2  (1243zf) by passing CCl 3 CH 2 CH 2 Cl (250fb), HF and Cl 2  through a pre-reactor to form a vaporized mixture. 
     
     
       31. The process of claim 30, wherein the CCl 3 CH 2 CH 2 Cl (250fb) is vaporized at temperature of between 80° C. to about 250° C. prior to reaction in the reaction zone of a vapor-phase reactor. 
     
     
       32. The process of claim 16, wherein the starting material comprises a halopropane of the formula CX 3 CH 2 CH 2 X, where X=Cl, and the process further comprises contacting CCl 3 CH 2 CH 2 Cl (250fb), HF and Cl 2  at a temperature of between 80° C. to about 250° C. to form CF 3 CH═CH 2  (1243zf). 
     
     
       33. The process of claim 16, further comprising using one or more distillation columns to recover at least one of HF, CF 3 CF 2 CH 3  (245cb), CF 3 CH═CHF (1234ze), CF 3 CCl═CH 2  (1233xf), CF 3 CH═CHCl (1233zd), CF 3 CH 2 CHF 2  (245fa), CF 3 CHClCH 2 Cl (243db) and CF 3 CHClCH 2 F (244db). 
     
     
       34. The process of claim 1 further comprising separating HCl and Cl 2  from the product mixture. 
     
     
       35. The process of claim 11 wherein the vapor phase reaction is conducted at temperature of between 250° C. to 375° C. 
     
     
       36. The process of claim 16 wherein the vapor phase reaction is conducted at temperature of between 300° C. to 375° C. 
     
     
       37. The process of claim 11 wherein the chlorofluorination catalyst comprises chromium-containing catalysts. 
     
     
       38. The process of claim 11 wherein the chlorofluorination catalyst comprises Cr 2 O 3  substituted with cobalt. 
     
     
       39. The process of claim 11 wherein the chlorofluorination catalyst comprises crystalline alpha-chromium oxide comprising 2 to <6 atom % cobalt. 
     
     
       40. The process of claim 11 wherein the chlorofluorination catalyst comprises one of Cr98%/Co2%, Cr95%/Co5% and Cr90%/Co10%. 
     
     
       41. The process of claim 11 wherein the catalyst, optionally supported on one of alumina, aluminum fluoride, fluorided alumina, or carbon, further includes chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, and zinc. 
     
     
       42. The process of claim of claim 13 wherein CF 3 CCl═CH 2  (1233xf) is separated and fluorinated to produce at least one of CF 3 CF 2 CH 3  (245cb) and CF 3 CF═CH 2  (1234yf). 
     
     
       43. The process of claim of claim 13 wherein CF 3 CF 2 CH 3  (245cb) is separated and dehydrofluorinated to produce CF 3 CF═CH 2  (1234yf). 
     
     
       44. A mixture comprising CF 3 CCl═CH 2  (1233xf), CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf), CF 3 CH═CHF (1234ze), E/Z-CF 3 CH═CHCl (1233zd), CF 3 CCl═CHCl (HCFC-1223xd) and CF 3 CH 2 CHF 2  (245fa). 
     
     
       45. The mixture of claim 44 further comprising at least one of CF 3 CHClCH 2 Cl (243db) and CF 3 CHClCH 2 F (244db). 
     
     
       46. A mixture comprising CF 3 CCl═CH 2  (1233xf), CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) CF 3 CH═CHF (1234ze), E/Z-CF 3 CH═CHCl (1233zd), CF 3 CH 2 CHF 2  (245fa) and further comprising at least one of C 3 HCl 3 F 4 , C 3 HCl 2 F 5 , C 3 HClF 6 , C 3 Cl 3 F 5 , and C 3 Cl 2 F 6 . 
     
     
       47. A mixture comprising C 3 CCl═CH 2  (1233xf), CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf) CF 3 CH═CHF (1234ze), E/Z-CF 3 CH═CHCl (1233zd), CF 3 CH 2 CHF 2  (245fa) and further comprising CF 3 CClFCHF 2  (226ba). 
     
     
       48. A mixture consisting essentially of CF 3 CCl═CH 2  (1233xf), CF 3 CF 2 CH 3  (245cb), CF 3 CF═CH 2  (1234yf), CF 3 CH═CHF (1234ze), E/Z-CF 3 CH═CHCl (1233zd) and CF 3 CH 2 CHF 2  (245fa).