Gas-phase catalytic fluorination with chromium catalysts

Patent metadata

Field	Value
Publication number	US-10577294-B2
Application number	US-201616060037-A
Country	US
Kind code	B2
Filing date	Dec 7, 2016
Priority date	Dec 14, 2015
Publication date	Mar 3, 2020
Grant date	Mar 3, 2020

Abstract

The present invention relates to a method for fluorinating a chlorinated compound including the steps of (a) placing said chlorinated compound in contact with gaseous hydrogen fluoride within a reactor and in the presence of a fluorination catalyst to produce a fluorinated compound, and (b) regenerating the fluorination catalyst used in step a), the step of regenerating the fluorination catalyst including (c) treating said fluorination catalyst with an oxidizing agent to form an oxidized fluorination catalyst, and (d) treating the oxidized fluorination catalyst obtained in step (c) with a gas mixture including a reducing agent.

First claim

The invention claimed is:

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.

Assignees

• Arkema France

Inventors

• Andre David
• Deur-Bert Dominique
• Garrait Dominique
• Pigamo Anne
• Wendlinger Laurent

Classifications

• C07C17/21

  with simultaneous increase of the number of halogen atoms · CPC title

• B01J27/132

  with chromium, molybdenum, tungsten or polonium · CPC title

• B01J38/04

  Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst · CPC title

• B01J23/26

  Chromium · CPC title

• B01J38/42

  using halogen-containing material · CPC title