Catalytic gas phase fluorination

Patent metadata

Field	Value
Publication number	US-10011544-B2
Application number	US-201715453986-A
Country	US
Kind code	B2
Filing date	Mar 9, 2017
Priority date	Jan 21, 2011
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

The present invention relates to a fluorination process, comprising:
an activation stage comprising contacting a fluorination catalyst with an oxidizing agent-containing gas flow for at least one hour; and at least one reaction stage comprising reacting a chlorinated compound with hydrogen fluoride in gas phase in the presence of the fluorination catalyst, so as to produce a fluorinated compound.

First claim

The invention claimed is:

1. A fluorination process, comprising:
an activation stage comprising the following steps, in succession:
i. reacting a chlorinated compound selected from the group consisting of hydrochlorocarbons, hydrochlorofluorocarbons and hydrochlorofluoroolefins with hydrogen fluoride in gas phase in the presence of a chromium-based fluorination catalyst, and
ii. contacting the chromium-based fluorination catalyst with a first oxidizing agent-containing gas flow comprising an oxidizing agent and hydrogen fluoride, wherein the proportion of oxidizing agent in the first oxidizing agent-containing gas flow is from 2 to 98 mol %, relative to the total amount oxidizing agent and hydrogen fluoride;

at least one reaction stage comprising reacting the chlorinated compound with hydrogen fluoride in gas phase in the presence of the fluorination catalyst, so as to produce a fluorinated compound; and
at least one regeneration stage comprising contacting the fluorination catalyst with a second oxidizing agent-containing gas flow.

2. The process of claim 1 , wherein the first and/or second oxidizing agent-containing gas flows comprise an oxygen-containing gas flow.

3. The process of claim 1 , wherein the activation stage and/or the at least one regeneration stage comprise contacting the fluorination catalyst with the first and/or second oxidizing agent-containing gas flows for at least 2 hours.

4. The process of claim 1 , wherein the second oxidizing agent-containing gas flow contains hydrogen fluoride in addition to the oxidizing agent, and wherein the proportion of oxidizing agent in the second oxidizing agent-containing gas flow is from 2 to 98 mol %, relative to the total amount oxidizing agent and hydrogen fluoride.

5. The process of claim 1 , wherein the second oxidizing agent-containing gas flow does not contain hydrogen fluoride.

6. The process of claim 1 , wherein the first and/or second oxidizing agent-containing gas flow comprise air.

7. The process of claim 1 , wherein the activation stage and/or the at least one regeneration stage comprise contacting the fluorination catalyst with a hydrogen fluoride gas flow, either:
before contacting the fluorination catalyst with the oxidizing agent-containing gas flow; or
after contacting the fluorination catalyst with the oxidizing agent-containing gas flow.

8. The process of claim 1 , wherein the first and/or second oxidizing agent-containing gas flow is/are contacted with the fluorination catalyst at a temperature of from 250 to 500° C.

9. The process of claim 1 , wherein the fluorinated compound is a fluoroolefin.

10. The process of claim 1 , wherein the fluorination catalyst is a supported catalyst.

11. The process of claim 1 , wherein the fluorination catalyst is an unsupported catalyst.

12. The process of claim 1 , wherein the fluorination catalyst further comprises a co-catalyst selected from the group consisting of Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Ni and mixtures thereof.

13. The process of claim 12 , wherein the co-catalyst is present in an amount from about 1-10 wt % of said fluorination catalyst.

14. The process of claim 1 , wherein the fluorination catalyst is a mixed chromium/nickel catalyst.

15. The process of claim 1 , wherein the chlorinated compound is 2-chloro-3,3,3-trifluoro-1-propene.

16. The process of claim 1 , wherein the at least one reaction stage is carried out at a pressure of from 1 to 20 bars.

17. The process of claim 1 , wherein the at least one reaction stage is carried out at a temperature of from 200 to 450° C.

18. The process of claim 1 , wherein the contact time between hydrogen fluoride and the chlorinated compound during the at least one reaction stage is from 6 to 100 s.

19. The process of claim 1 , wherein the at least one reaction stage is carried out in the presence of an oxidizing agent.

Assignees

• Arkema France

Inventors

• Pigamo Anne
• Doucet Nicolas
• Wendlinger Laurent

Classifications

• B01J38/12

  Treating with free oxygen-containing gas · CPC title

• B01J23/866

  Nickel and chromium · CPC title

• C07C17/206 Primary

  the other compound being HX · CPC title

• B01J27/125

  with scandium, yttrium, aluminium, gallium, indium or thallium · CPC title

• B01J37/26

  Fluorinating · CPC title