Catalytic process of making 1,3,3,3-tetrafluoropropene

• US 9,187,386 B2
• Filed: 05/13/2014
• Issued: 11/17/2015
• Est. Priority Date: 05/23/2013
• Status: Active Grant

• Current Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Original Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Inventors: Nappa, Mario Joseph, Sun, Xuehui
• Primary Examiner(s): Kumar, Shailendra
• Application Number:
  US14/275,934
• Publication Number:
  US 20140350310A1
• Time in Patent Office: 553 Days
• Field of Search: 570/155, 570/156, 570/157, 570/158
• US Class Current: 1/1
• CPC Class Codes: C07C 17/23 by dehalogenation
• CPC Class Codes: C07C 17/25 by splitting-off hydrogen halides from halogenated hydrocarbons
• CPC Class Codes: C07C 21/18 containing fluorine

Abstract

This disclosure relates to processes of making 1,3,3,3-tetrafluoropropene. The processes involve dehydrofluorinating 1,1,1,3,3-pentafluoropropane in vapor phase in the presence of a catalyst comprising a metal compound supported on alumina to produce a product mixture comprising 1,3,3,3-tetrafluoropropene, wherein said metal compound is selected from the group consisting of salts of sodium, potassium, zinc, magnesium, calcium, cobalt, copper, and chromium, and mixtures thereof.

Claims

1. A process for making 1,3,3,3-tetrafluoropropene, comprising dehydrofluorinating 1,1,1,3,3-pentafluoropropane in vapor phase in the presence of a catalyst comprising a metal compound supported on alumina to produce a product mixture comprising 1,3,3,3-tetrafluoropropene, wherein said metal compound is selected from the group consisting of salts of sodium, potassium, zinc, magnesium, calcium, cobalt, copper, and chromium, and mixtures thereof, wherein the selectivity for the production of 1,3,3,3-tetrafluoropropene is at least 99%.

2. The process of claim 1 wherein said metal compound is selected from the group consisting of halides, bicarbonates, carbonates, nitrates, oxides, and oxyfluorides of sodium, potassium, zinc, magnesium, calcium, cobalt, copper, and chromium, and mixtures thereof.

3. The process of claim 1 wherein said catalyst is pre-treated with a fluorinating agent.

4. The process of claim 3 wherein said fluorinating agent is HF.

5. The process of claim 1, 3 or 4, wherein said metal compound is selected from the group consisting of inorganic salts of potassium, zinc, and magnesium, and mixtures thereof.

6. The process of claim 5, wherein said metal compound is ZnCl₂.

7. The process of claim 6, wherein the process is conducted at a temperature of from about 250°

C. to about 350°

C.

8. The process of claim 5, wherein said metal compound is KHCO₃.

9. The process of claim 8, wherein the process is conducted at a temperature of from about 250°

C. to about 350°

C.

10. The process of claim 5, wherein said metal compound is MgCl₂.

11. The process of claim 1, wherein the process is conducted in the presence of a diluent.

12. The process of claim 1, wherein the process is conducted in the presence of oxygen or air.

13. The process of claim 1, wherein the selectivity to 1,3,3,3-tetrafluoropropene is at least about 99.5%.

14. The process of claim 1, further comprising recovering 1,3,3,3-tetrafluoropropene from the product mixture.