Gas-phase catalytic fluorination with chromium catalysts

1. A process for the fluorination of a chlorinated C3 alkane or alkene compound having at least one chlorine atom into a fluorinated C3 alkane or alkene compound having at least one fluorine atom comprising:

(a) contacting, in a reactor, the chlorinated compound with hydrogen fluoride in gas phase in the presence of a fluorination catalyst to produce a fluorinated compound,

(b) regenerating the fluorination catalyst used in step a), wherein regenerating the fluorination catalyst comprises:

(c) treating said fluorination catalyst with an oxidizing agent-containing gas flow to form an oxidized fluorination catalyst, and

(d) treating the oxidized fluorination catalyst obtained in step (c) with a gaseous mixture comprising a reducing agent, an inert gas and HF, wherein the reducing agent is selected from the group consisting of hydrogen, carbon monoxide, nitrogen monoxide, formaldehyde, C 1 -C 6 alkanes and C 1 -C 10 hydrohalocarbons; and

(e) reusing the catalyst regenerated in step b) in step a).

2. The process according to claim 1 , wherein the reducing agent is selected from the group consisting of hydrogen and C 1 -C 10 hydrohalocarbons.

3. The process according to claim 1 , wherein the inert gas comprises nitrogen, helium, argon, or mixtures thereof.

4. The process according to claim 1 , wherein the gaseous mixture of step (d) comprises from 1 to 10% by volume of reducing agent based on the total volume of the gaseous mixture.

5. The process according to claim 1 , wherein the gaseous mixture from step (d) comprises hydrogen and nitrogen or argon, or the gaseous mixture from step (d) comprises a C 2 -C 6 hydrohalocarbon, nitrogen or argon, and HF.

6. The process according to claim 1 , wherein step d) is carried out at a temperature ranging from 100° C. to 450° C., with a contact time of from 1 to 100 s, for a time greater than 1 hour.

7. The process according to claim 1 , wherein the chlorinated compound comprises 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf), 1,1,1,2,3-pentachloropropane (HCC-240db), 1,1,2,2,3-pentachloropropane (HCC-240aa), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,2,3-tetrachloro-1-propene (HCO-1230xa), 2,3,3,3-tetrachloro-1-propene (HCO-1230xf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 1,1,1,3,3-pentachloropropane (HCC-240fa), 1,1,3,3-tetrachloropropene (HCO-1230za), 1,3,3,3-tetrachloropropene (HCO-1230zd), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 1,1,1,3-tetrachloropropane (HCC-250fb), 1,1,3-trichloropropene (HCO-1240za), 3,3,3-trichloropropene (HCO-1240zf); more preferably the chlorinated compound is selected from the group consisting of 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf), 1,1,1,2,3-pentachloropropane (HCC-240db), 1,1,2,2,3-pentachloropropane (HCC-240aa), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,2,3-tetrachloro-1-propene (HCO-1230xa), 2,3,3,3-tetrachloro-1-propene (HCO-1230xf) or 2-chloro-1,1,1,2-tetrafluorocarbons (HCFC-244bb).

8. The process according to claim 1 , wherein the fluorinated compound comprises 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3-tetrafluoro-3-chloropropane (HCFC-244fa), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf) or 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf).

9. The process according to claim 1 , wherein the fluorination of the chlorinated compound into a fluorinated compound comprises:

2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);

1,1,1,2,3-pentachloropropane (HCC-240db) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);

1,1,2,2,3-pentachloropropane (HCC-240aa) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);

2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);

1,1,2,3-tetrachloro-1-propene (HCO-1230xa) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);

2,3,3,3-tetrachloro-1-propene (HCO-1230xf) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);

1,1,1,2,3-pentachloropropane (HCC-240db) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);

1,1,2,2,3-pentachloropropane (HCC-240aa) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);

2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);

1,1,2,3-tetrachloro-1-propene (HCO-1230xa) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);

2,3,3,3-tetrachloro-1-propene (HCO-1230xf) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);

2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf) to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb);

1,1,1,2,3-pentachloropropane (HCC-240db) to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb);

1,1,2,2,3-pentachloropropane (HCC-240aa) to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb);

2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb);

1,1,2,3-tetrachloro-1-propene (HCO-1230xa) to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb);

2,3,3,3-tetrachloro-1-propene (HCO-1230xf) to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb);

1,1,1,2,3-pentachloropropane (HCC-240db) to 1,1,1,2,2-pentafluoropropane (HFC-245cb);

1,1,2,2,3-pentachloropropane (HCC-240aa) to 1,1,1,2,2-pentafluoropropane (HFC-245cb);

2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 1,1,1,2,2-pentafluoropropane (HFC-245cb);

1,1,2,3-tetrachloro-1-propene (HCO-1230xa) to 1,1,1,2,2-pentafluoropropane (HFC-245cb); or

2,3,3,3-tetrachloro-1-propene (HCO-1230xf) to 1,1,1,2,2-pentafluoropropane (HFC-245cb).

10. The process according to claim 1 , wherein the fluorination catalyst comprises chromium oxyfluoride, chromium oxides, chromium halides or mixtures thereof.

11. The process according to claim 1 , wherein the fluorination catalyst contains one or more co-catalysts comprising a salt of a transition metal selected from the group consisting of Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, Ni; and a phosphorous salt.

12. The process according to claim 1 , further comprising an activation step carried out before step (a) which comprises a first step of contacting the fluorination catalyst with a gas flow containing an oxidizing agent comprising oxygen, air, chlorine or a mixture of oxygen and nitrogen.

13. The process according to the claim 12 , further comprising a second activation step, subsequent to the first step, the second step comprising treating the fluorination catalyst obtained after the first step with a gaseous mixture containing a reducing agent and an inert gas, said reducing agent comprising hydrogen or a C 2 -C 6 hydrohalocarbon.

14. The process according to claim 1 , wherein steps (a) and (b) are carried out alternately.

15. The process according to claim 1 , further comprising purging the reactor before and/or after step (b), the purge comprising introducing a stream of nitrogen in the reactor or maintaining the reactor under vacuum.