Process for the preparation of 3,3,3-trifluoropropene

Patent metadata

Field	Value
Publication number	US-10689316-B2
Application number	US-201615745460-A
Country	US
Kind code	B2
Filing date	Jul 14, 2016
Priority date	Jul 17, 2015
Publication date	Jun 23, 2020
Grant date	Jun 23, 2020

Abstract

The present invention provides a process for preparing 3,3,3-trifluoropropene (1243zf), the process comprising: (a)fluorinating CCl 3 CH 2 CH 2 CI (250fb) to produce a reaction product comprising CF 3 CH 2 CH 2 CI (253fb) in the liquid phase in a first reactor, using HF as the fluorinating agent; and (b)(i) dehydrohalogenating 253fb to produce 1243zf in the vapour phase in the presence of a catalyst in a second reactor; or (b)(ii) dehydrohalogenating 253fb to produce 1243zf in a second reactor, wherein the reaction product comprising 253fb produced in step (a) has subjected to one or more purification steps before step (b). The present invention also provides an azeotropic or near-azeotropic composition comprising HF and 253fb.

First claim

The invention claimed is:

1. A process for preparing 3,3,3-trifluoropropene (1243zf), the process comprising:
(a) fluorinating CCl 3 CH 2 CH 2 Cl (250fb) to produce a reaction product comprising CF 3 CH 2 CH 2 Cl (253fb) in the liquid phase conducted at a temperature from 20° C. to 100° C., in a first reactor, using HF as the fluorinating agent; and
(b) dehydrohalogenating 253fb to produce 1243zf in the vapour phase, conducted at a temperature from 250° C. to 350° C., in the presence of a catalyst in a second reactor.

2. A process according to claim 1 , wherein the catalyst used in step (b) comprises activated carbon, alumina and/or chromia or zinc/chromia.

3. A process according to claim 1 , wherein the catalyst used in step (b) is activated carbon, Pd/carbon, Pt/carbon, Au/carbon, Pd/alumina, Ni/alumina, Pt/alumina, Cr/alumina or Zn/chromia.

4. A process according to claim 1 , wherein the catalyst used in step (b) is pre-fluorinated.

5. A process according to claim 1 , wherein the process in step (b) is continuous.

6. A process according to claim 1 , wherein step (b) is conducted at a temperature of from about 250° C. to about 300° C.

7. A process according to claim 2 , wherein the catalyst used in step (b) comprises activated carbon and the process of step (b) is conducted at a temperature from about 250° C. to about 300° C.

8. A process according to claim 4 , wherein the catalyst used in step (b) is a pre-fluorinated Zn/chromia catalyst and the process of step (b) is conducted at a temperature from about 250° C. to about 350° C.

9. A process according to claim 1 , wherein in step (b) HF is co-fed with 253fb.

10. A process according to claim 1 , wherein the reaction product comprising 253fb produced in step (a) is subjected to one or more purification steps before step (b).

11. A process for preparing 3,3,3-trifluoropropene (1243zf), the process comprising:
(a) fluorinating CCl 3 CH 2 CH 2 Cl (250fb) to produce a reaction product comprising CF 3 Cl 2 CH 2 Cl (253fb) in the liquid phase in a first reactor, using HF as the fluorinating agent; and
(b) dehydrohalogenating 253fb to produce 1243zf in a second reactor;
wherein the reaction product comprising 253fb produced in step (a) is subjected to one or more purification steps before step (b).

12. A process according to claim 9 , wherein the purification steps comprise subjecting product stream from step (a) to distillation to remove or reduce the concentration of HCl and then phase separation to separate HF from the product stream comprising 253fb and optionally passing the stream comprising 253fb through a H 2 SO 4 scrubber.

13. A process according to claim 11 , wherein HF is recycled to step (a).

14. A process according to claim 1 , wherein the first reactor is connected to a rectifying column.

15. A process according to claim 14 , wherein at least part of the HF is introduced into the first reactor via the top of the rectifying column.

16. A process according to claim 11 , wherein unused HF is separated from the reaction product produced in step (a) and recycled to the first reactor.

17. A process according to claim 1 , wherein step (a) is conducted at a temperature of from about 40 to about 70° C.

18. A process according to claim 1 , wherein step (a) is conducted at a pressure of from about 200 kPa to about 700 kPa.

19. A process according to claim 1 , wherein step (a) is conducted in the presence of a polymerisation inhibitor and/or retarder.

20. A process according to claim 19 , wherein the polymerisation inhibitor and/or retarder is selected from cyclic ketone or quinone-based aromatic compounds, nitro- or nitrogen-containing compounds, and sulphur-containing compounds.

21. A process according to claim 20 , wherein the cyclic ketone is cyclobutanone or cyclohexanone or a mixture thereof.

22. A process according to claim 1 , wherein step (a) is conducted in the presence of a Lewis acid catalyst.

23. A process according to claim 22 , wherein the catalyst is SnCl 4 .

24. A process according to claim 1 , wherein step (a) is a semi-continuous reaction.

Assignees

• Mexichem Fluor Sa De Cv
• Mexican Fluor S A De C V

Inventors

• Hodgson Emma Jayne
• Mcguinness Claire Elizabeth
• Giddis Clive Robert
• Murray James Henry
• Skae Clare Mary
• Lloyd Gary

Classifications

• C09K2205/126

  Unsaturated fluorinated hydrocarbons · CPC title

• C09K2205/122

  Halogenated hydrocarbons · CPC title

• C09K5/045

  containing only fluorine as halogen · CPC title

• C07C21/18

  containing fluorine · CPC title

• C07C19/10

  and chlorine · CPC title