PROCESSES FOR THE PRODUCTION OF FLUOROPROPANES AND HALOPROPENES
A process is disclosed for making CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and/or CF 3 CCl═CH 2 . The process involves 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 F or Cl, with HF and Cl 2 in a reaction zone to produce a product mixture comprising HF, HCl, CF 3 CF 2 CH 3 , CF 3 CF═CH 2 , and CF 3 CCl═CH 2 ; and recovering the CF 3 CF 2 CH 3 , CF 3 CF═CH 2 and/or CF 3 CCl═CH 2 from the product mixture. Also disclosed is a process for making CF 3 CH 2 CHF 2 , CF 3 CH═CHF, and/or CF 3 CH═CHCl. This process involves reacting at least one starting material selected from the group consisting of halopropenes of the formula CX 3 CH═CH 2 and halopropenes of the formula CX 2 ═CHCH 2 X, wherein each X is independently F or Cl, with HF and Cl 2 in a reaction zone to produce a product mixture comprising HF, HCl, CF 3 CH 2 CHF 2 , CF 3 CH═CHF and CF 3 CH═CHCl; and recovering the CF 3 CH 2 CHF 2 , CF 3 CH═CHF, and/or CF 3 CH═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 Cl 2 to total amount of starting material fed to the reaction zone for both of these processes is 2:1 or less.
1 . A process for preparing 3,3,3-trifluoro-2-chloroprop-1-ene (1233xf) comprising:
a. contacting 3,3,3-trifluoropropene (1243zf) with Cl 2 in a reaction zone, optionally in the presence of a chlorofluorination catalyst, to produce an intermediate product, wherein the molar ratio of Cl 2 to total amount of 1243zf fed to the reaction zone is 2:1 or less; and
b. converting the intermediate product to 3,3,3-trifluoro-2-chloroprop-1-ene (1233xf).
2 . The process of claim 1 , wherein the molar ratio of Cl 2 to total amount of 1243zf is from about 0.5:1 to about 2:1.
3 . The process of claim 1 , wherein the catalyst comprises at least one of carbon, alumina, and a metal oxide, wherein the metal is selected from chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, titanium, zirconium, and hafnium, copper, silver, gold, and zinc.
4 . The process of claim 3 , wherein the catalyst comprises chromium (III) oxide.
5 . The process of claim 1 , wherein step (a) comprises contacting 1243zf with Cl 2 and HF in the reaction zone.
6 . The process of claim 1 , further comprising (c) fluorinating the 1233xf.
7 . The process of claim 6 , wherein step (c) comprising reacting the 1233xf with HF optionally in the presence of a fluorination catalyst.
8 . The process of claim 6 , wherein step (c) comprises reacting 1233xf with HF in the liquid phase, optionally in the presence of a fluorination catalyst.
9 . The process of claim 7 , wherein the molar ratio of HF to 1233xf is 1:1 to 2:1.
10 . The process of claim 7 , wherein the molar ratio of HF to 1233xf is 1:1 to 100:1.
11 . The process of claim 7 , wherein the molar ratio of HF to 1233xf is 8:1 to 50:1.
12 . The process of claim 7 , wherein step (c) is performed at about 50 to about 150° C.
13 . The process of claim 6 , further comprising (d) converting the product of step (c) to CF 3 CF═CH 2 (1234yf).
14 . The process of claim 6 , wherein the fluorination in step (c) produces CF 3 CF 2 CH 3 (245cb).
15 . The process of claim 14 , further comprising (d) converting the product of step (c) to CF 3 CF═CH 2 (1234yf).
16 . A process comprising:
a. converting CCl 3 CH 2 CH 2 Cl (250fb) to 3,3,3-trifluoropropene (1243zf); and
b. contacting 3,3,3-trifluoropropene (1243zf) with Cl 2 in a reaction zone, optionally in the presence of a chlorofluorination catalyst, to produce an intermediate product, wherein the molar ratio of Cl 2 to total amount of 1243zf fed to the reaction zone is 2:1 or less.
17 . The process of claim 16 , wherein 250fb is formed by reacting ethylene with carbon tetrachloride.
18 . The process of claim 16 , wherein step (a) comprises reacting 250fb with HF.
19 . The process of claim 18 , wherein the reaction in step (a) is performed in the vapor phase.
20 . The process of claim 16 , wherein the molar ratio of Cl 2 to total amount of 1243zf is from about 0.5:1 to about 2:1.
21 . The process of claim 16 , wherein the catalyst comprises at least one of carbon, alumina, and a metal oxide, wherein the metal is selected from chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, titanium, zirconium, and hafnium, copper, silver, gold, and zinc.
22 . The process of claim 21 , wherein the catalyst comprises chromium (III) oxide.
23 . The process of claim 16 , wherein step (a) comprises contacting 1243zf with Cl 2 and HF in the reaction zone.
24 . The process of claim 16 further comprising (c) converting the intermediate product to 3,3,3-trifluoro-2-chloroprop-1-ene (1233xf).
25 . The process of claim 24 , further comprising (d) fluorinating the 1233xf.
26 . The process of claim 25 , wherein step (d) comprising reacting the 1233xf with HF optionally in the presence of a fluorination catalyst.
27 . The process of claim 25 , wherein step (d) comprises reacting 1233xf with HF in the liquid phase, optionally in the presence of a fluorination catalyst.
28 . The process of claim 26 , wherein the molar ratio of HF to 1233xf is 1:1 to 2:1.
29 . The process of claim 26 , wherein the molar ratio of HF to 1233xf is 1:1 to 100:1.
30 . The process of claim 26 , wherein the molar ratio of HF to 1233xf is 8:1 to 50:1.
31 . The process of claim 26 , wherein step (d) is performed at about 50 to about 150° C.
32 . The process of claim 25 , further comprising (e) converting the product of step (d) to CF 3 CF═CH 2 (1234yf).
33 . The process of claim 25 , wherein the fluorination in step (d) produces CF 3 CF 2 CH 3 (245cb).
34 . The process of claim 33 , further comprising (e) converting the product of step (d) to CF 3 CF═CH 2 (1234yf).
35 . A mixture comprising CF 3 CH═CHF (1234yf), CF 3 CH 2 CHF 2 (245cb), and CF 3 CH═CHCl (1233xf).
36 . The mixture of claim 35 , further comprising CF 3 CH 2 CHF 2 (245fa).
37 . The mixture of claim 35 , wherein the mixture further comprises: at least one of CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), and CHCl═CHCF 3 (1233zd).
38 . The mixture of claim 35 , wherein the mixture further comprises: at least one of CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), CF 3 CCl═CHCl (1223xd) and CHCl═CHCF 3 (1233zd).
39 . The mixture of claim 35 , wherein the mixture further comprises CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), and CHCl═CHCF 3 (1233zd).
40 . A mixture comprising CF 3 CH═CHF (1234yf), CF 3 CH 2 CHF 2 (245cb), CF 3 CH═CHCl (1233xf), and CHF═CHCF 3 (1234ze).
41 . A mixture comprising CF 3 CH═CHF (1234yf), CF 3 CH 2 CHF 2 (245cb), CF 3 CH═CHCl (1233xf), CHF═CHCF 3 (1234ze), and CHCl═CHCF 3 (1233zd).
42 . A mixture comprising CF 3 CH═CHF (1234yf) and CHF═CHCF 3 (1234ze).
43 . A mixture comprising: CF 3 CH═CHCl (1233xf) and CF 3 CH═CHF (1234yf), and optionally at least one of CF 3 CH 2 CHF 2 (245fa) CHF═CHCF 3 (1234ze), CF 3 CH 2 CHF 2 (245fa), CF 3 CCl═CHCl (1223xd) and CHCl═CHCF 3 (1233zd).
44 . A mixture comprising: CF 3 CH═CHCl (1233xf) and CF 3 CH 2 CHF 2 (245cb), and optionally at least one of CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), CF 3 CH 2 CHF 2 (245fa), (1223xd and CHCl═CHCF 3 (1233zd).
45 . The mixture according to claim 44 , further comprising CF 3 CH═CHF (1234yf).
46 . A mixture comprising: CF 3 CH═CHCl (1233xf), CF 3 CH 2 CHF 2 (245cb), and CF 3 CH═CHF (1234yf), and optionally at least one of CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), CF 3 CH 2 CHF 2 (245fa), and CHCl═CHCF 3 (1233zd).
47 . A mixture comprising: CF 3 CH 2 CHF 2 (245cb) and CF 3 CH═CHCl (1233xf) and optionally at least one of CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), CF 3 CH 2 CHF 2 (245fa), (1223xd and CHCl═CHCF 3 (1233zd).
48 . The mixture according to claim 47 , further comprising CF 3 CH═CHF (1234yf).
49 . A mixture comprising: CF 3 CHClCH 2 F (244db), CF 3 CH═CHCl (1233xf), CF 3 CH═CHF (1234yf), and optionally at least one of CF 3 CH 2 CHF 2 (245fa), CHF═CHCF 3 (1234ze), CF 3 CH 2 CHF 2 (245fa), and CHCl═CHCF 3 (1233zd).