Catalytic gas phase fluorination

Patent metadata

Field	Value
Publication number	US-9969663-B2
Application number	US-201715644973-A
Country	US
Kind code	B2
Filing date	Jul 10, 2017
Priority date	Jan 21, 2011
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

The invention relates to a fluorination process, alternately comprising reaction stages and regeneration stages, wherein the reaction stages comprise reacting a chlorinated compound with hydrogen fluoride in gas phase in the presence of a fluorination catalyst to produce a fluorinated compound, and the regeneration stages comprise contacting the fluorination catalyst with an oxidizing agent-containing gas flow.

First claim

The invention claimed is:

1. A process for producing 2,3,3,3-tetrafluoropropene or 2-chloro-3,3,3-trifluoropropene, comprising:
drying a fluorination catalyst;
activating the fluorination catalyst by:
i) contacting the fluorination catalyst with hydrogen fluoride and with 2-chloro-3,3,3-trifluoro-1-propene, 1,1,1,2,3-pentachloropropane, 1,1,2,3-tetrachloropropene, or 2,3,3,3-tetrachloropropene; and
ii) optionally contacting the fluorination catalyst with an oxidizing agent-containing gas flow;

reacting 1,1,1,2,3-pentachloropropane with hydrogen fluoride in the gas phase in the presence of the activated fluorination catalyst so as to produce 2-chloro-3,3,3-trifluoro-1-propene or reacting 1,1,2,3-tetrachloropropene or 2,3,3,3-tetrachloropropene with hydrogen fluoride in the gas phase in the presence of the activated fluorination catalyst so as to produce 2-chloro-3,3,3-trifluoro-1-propene or 2,3,3,3-tetrafluoropropene; and
regenerating the fluorination catalyst by contacting it with an oxidizing agent-containing gas flow.

2. The process of claim 1 , wherein the activation stage and the reaction stage take place in a single reactor.

3. The process of claim 1 , wherein the oxidizing agent-containing gas flow of the regeneration stage is an oxygen-containing gas flow.

4. The process of claim 1 , wherein the regeneration stage comprises contacting the fluorination catalyst with the oxidizing agent-containing gas flow for at least 2 hours.

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

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

7. The process of claim 6 , wherein the oxidizing agent-containing gas flow of the regeneration stage is air.

8. The process of claim 1 , wherein the regeneration stage comprises 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.

9. The process of claim 1 , wherein the oxidizing agent-containing gas flow is contacted with the fluorination catalyst during the regeneration stage at a temperature of from 250 to 500° C.

10. The process of claim 1 , wherein the fluorination catalyst is supported on a support comprising fluorinated alumina, fluorinated chromia, fluorinated activated carbon or graphite carbon.

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 comprising Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Ni or mixtures thereof, and wherein said co-catalyst is present in an amount from about 1-10 wt % of said fluorination catalyst.

13. The process of claim 1 , wherein the fluorination catalyst is a mixed chromium/nickel catalyst, the atomic ratio of nickel to chromium being from 0.5 to 2.

14. The process of claim 1 , wherein the reaction stages are carried out at a pressure of from 1 to 20 bars.

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

16. The process of claim 1 , wherein the contact time between hydrogen fluoride and the chlorinated compound during the reaction stages is from 6 to 100 s.

17. The process of claim 1 , wherein the reaction stages are carried out in the presence of oxygen as the oxidizing agent, the ratio of oxygen being from 0.05 to 15 mole %, with respect to the total amount of 1,1,1,2,3-pentachloropropane, 1,1,2,3-tetrachloropropene, or 2,3,3,3-tetrachloropropene and oxygen.

Assignees

• Arkema France

Inventors

• Pigamo Anne
• Wendlinger Laurent
• Doucet Nicolas

Classifications

• B01J38/12

  Treating with free oxygen-containing gas · CPC title

• B01J23/94

  of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper · CPC title

• B01J37/14

  with gases containing free oxygen · CPC title

• B01J37/26

  Fluorinating · CPC title

• C07C17/206 Primary

  the other compound being HX · CPC title