Process for the preparation of 2,3,3,3-tetrafluoropropene (1234yf)

Patent metadata

Field	Value
Publication number	US-10899686-B2
Application number	US-201615745505-A
Country	US
Kind code	B2
Filing date	Jul 14, 2016
Priority date	Jul 17, 2015
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

The present invention provides an integrated process for preparing 2,3,3, 3-tetrafluoropropene (1234yf), the process comprising: (a) vapour phase catalytic fluorination of a first composition comprising 3,3,3-trifluoro-2-chloro-prop-1-ene (CF3C—CNCH2, 1233xf) with hydrogen fluoride (HF) in a fluorination reactor to produce a fluorination product stream comprising 1,1,2,2-pentafluoropropane (245cb), HF and HCI; (b) vapour phase catalytic dehydrofluorination composition comprising 245cb in a dehydrofluorination reactor to produce a dehydrofluorination product stream comprising 1234yf and HF; wherein the fluorination product stream and the dehydrofluorination product stream are combined and subjected to (c) purification to produce a composition comprising 245cb and a 1234yf product stream.

First claim

The invention claimed is:

1. An integrated process for preparing 2,3,3,3-tetrafluoropropene (1234yf), the process comprising:
(a) vapour phase catalytic fluorination of a first composition comprising 3,3,3-trifluoro-2-chloro-prop-1-ene (CF 3 CCl=CH 2 , 1233xf) with hydrogen fluoride (HF) in a fluorination reactor to produce a fluorination product stream comprising 1,1,1,2,2-pentafluoropropane (245cb), HF and HCl;
(b) vapour phase catalytic dehydrofluorination of a second composition comprising 245cb in a dehydrofluorination reactor to produce a dehydrofluorination product stream comprising 1234yf and HF;
wherein the fluorination product stream and the dehydrofluorination product stream are combined and subjected to (c) purification to produce a composition comprising 245cb and a 1234yf product stream,
wherein the purification step (c) comprises a distillation step in which a lighter fraction comprising 245cb, 1234yf, any 1234ze(E) and some HF is distilled leaving a heavier fraction comprising the majority of the HF and unreacted 1233xf, and wherein the lighter fraction is removed from the distillation column and passed to a scrubbing train.

2. A process according to claim 1 , wherein the composition comprising 245cb and a 1234yf product stream is fed to the dehydrofluorination reactor as the second composition.

3. A process according to claim 1 , in which at least some of the 1234yf is removed from the composition comprising 245cb and a 1234yf product stream and the resulting composition is fed to the dehydrofluorination reactor as the second composition.

4. A process according to claim 3 , wherein after at least some of the 1234yf has been removed, the resulting composition is subjected to a purification step in which at least some of any 1234ze that may be present in the composition is removed before the composition with reduced 1234yf concentration is fed to the dehydrofluorination reactor as the second composition.

5. A process according to claim 1 , wherein the purification step (c) comprises one or more phase separation steps.

6. A process according to claim 1 , wherein the scrubbing train in the purification step (c) comprises in sequence a bulk acid removal step, a trace acid removal step and one or more drying steps.

7. A process according to claim 1 wherein HF is recovered from at least one distillation column and is optionally recycled for use in reaction (a).

8. A process according to claim 7 , wherein the HF is subjected to further purification prior to recycling.

9. A process according to claim 8 , wherein the HF is purified by phase separation.

10. A process according to claim 1 , wherein the process comprises a step of obtaining the 1233xf used in reaction (a) by the dehydrochlorination of 243db.

11. A process according to claim 10 , wherein the dehydrochlorination reaction takes place in the presence of HF and/or in the absence of air.

12. A process according to claim 10 , wherein the dehydrochlorination reaction takes place in the presence of a zinc/chromia catalyst.

13. A process according to claim 10 , wherein the dehydrochlorination reaction takes place in the presence of HF and at least part of the HF is recycled from step (c).

14. A process according to claim 1 , wherein reaction (a) takes place in the presence of air.

15. A process according to claim 14 , wherein the fluorination product stream is subjected to a purification step to remove at least some of the HCl and at least some of the air before this product stream is combined with the dehydrofluorination product stream.

16. A process according to claim 15 , wherein distillation is used to remove at least some of the HCl and at least some of the air.

17. A process according to claim 1 , wherein reaction (a) takes place in the presence of a zinc/chromia catalyst.

18. A process according to claim 1 , wherein reaction (b) takes place in the presence of a chrome on alumina or zinc/chromia catalyst.

19. A process according to claim 1 , wherein reaction (a) takes place at a temperature of from about 200 to about 300° C. and a pressure of from about 500 to about 1500 KPa.

20. A process according to claim 1 , wherein reaction (b) takes place at a temperature of from about 300 to about 500° C. and/or a pressure of from about 0 to 1500 kPa.

Assignees

• Mexichem Fluor Sa De Cv

Inventors

• Johnson Sheryl Louise
• Flaherty Stephen Andrew
• Murray James Henry
• Smith Fiona Louise
• Man Jonathan Junhay
• Giddis Clive Robert

Classifications

• C07C21/18

  containing fluorine · CPC title

• C07C17/21 Primary

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

• C07C17/38 Primary

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C17/25 Primary

  by splitting-off hydrogen halides from halogenated hydrocarbons · CPC title

• B01J38/46

  fluorine-containing · CPC title