E-1-chloro-3,3,3-trifluoropropene production process from 1,1,3,3-tetrachloropropene

Patent metadata

Field	Value
Publication number	US-10532965-B2
Application number	US-201715809477-A
Country	US
Kind code	B2
Filing date	Nov 10, 2017
Priority date	Jan 13, 2014
Publication date	Jan 14, 2020
Grant date	Jan 14, 2020

Abstract

A production process for the production of E-1-chloro-3,3,3-trifluoropropene, the process including at least one stage during which 1,3,3,3-tetrachloropropene reacts with anhydrous hydrofluoric acid in the liquid phase, in the absence of a catalyst, with an HF/1,1,3,3-tetrachloropropene molar ratio between 3 and 20 inclusive, at a temperature between 50° C. and 150° C. inclusive and an absolute pressure of between 1 and 20 bar inclusive.

First claim

The invention claimed is:

1. A production process for the production of E-1-chloro-3,3,3-trifluoropropene, the process comprising:
at least one stage during which 1,1,3,3-tetrachloropropene reacts with anhydrous hydrofluoric acid in the liquid phase, in the absence of a catalyst, with an HF/1,1,3,3-tetrachloropropene molar ratio between 3 and 20 inclusive, at a temperature between 50° C. and 150° C. inclusive and an absolute pressure of between 1 and 20 bar inclusive,
wherein HF and recoverable organic compounds are collected in the reactor drain, treated by at least one of decantation and azeotropic distillation, and recycled back to the same reactor.

2. A production process for the production of E-1-chloro-3,3,3-trifluoropropene, the process comprising:
(i) at least one stage during which 1,1,3,3-tetrachloropropene reacts with anhydrous hydrofluoric acid in the liquid phase in an unstirred reactor equipped with a drain and an effluent outlet;
(ii) at least one stage for treating the effluent from the reactor in order to provide a flow A that comprises E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene and a flow B that comprises at least 50% HF in weight;
(iii) at least one stage for recovering the hydrochloric acid from flow A, the hydrochloric acid being in flow C and flow D that includes E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene, wherein the recovery of HCl in stage (iii) is obtained using a distillation column equipped with a reboiler at the bottom and a reflux system at the top and wherein the temperature at the bottom is between 20° C. and 110° C. and the temperature at the top is between −50 and 0° C.; and
(iv) at least one stage for purifying flow D from stage (iii) in order to purify the E-1233zd to a level higher than or equal to 98% in weight.

3. The production process of claim 2 , the process further comprising a drainage stage, wherein drainage collected in the reactor drain is, after treatment, recycled back to the reactor.

4. The production process of claim 2 , wherein before the purification stage (iv), the flow D from stage (iii) is subjected to at least one separation phase in order to provide a flow E that comprises at least 50% HF in weight that can be recycled to the reactor and a flow F that comprises E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene.

5. The production process of claim 2 , wherein the separation stage is by decantation, initiated at a temperature between −50° C. and 50° C.

6. The production process of claim 2 , wherein the treatment stage (ii) involves a reflux column, initiated at a temperature between 30° C. and 120° C. in order to provide the flow B which is recycled to the reactor.

7. The production process of claim 2 , wherein the purification stage (iv) comprises at least one distillation stage.

8. The production process of claim 2 , wherein, in the reactor, the HF/1,1,3,3-tetrachloropropene molar ratio is between 5 and 15.

9. The production process of claim 2 , wherein reaction temperature is between 80° C. and 120° C.

10. The production process of claim 2 , wherein the fluorination reaction is initiated at a pressure between 5 and 15 bar.

11. A production process for the production of E-1-chloro-3,3,3-trifluoropropene, the process comprising:
(i) at least one stage in an unstirred reactor during which 1,1,3,3-tetrachloropropene reacts with anhydrous hydrofluoric acid in the liquid phase in the absence of a catalyst with a HF/1,1,3,3-tetrachloropropene molar ratio between 3 and 20, at a temperature between 50° C. and 150° C. and an absolute pressure between 1 and 20 bar;
(ii) at least one stage for treating the effluent from the reactor in order to provide a flow A that includes the E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene and a flow B that comprises at least 50% HF in weight;
(iii) at least one stage for recovering the hydrochloric acid from flow A, the hydrochloric acid being in flow C and flow D that includes E-1-chloro-3,3,3-trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene, wherein the recovery of HCl in stage (iii) is obtained using a distillation column equipped with a reboiler at the bottom and a reflux system at the top and wherein the temperature at the bottom is between 20° C. and 110° C. and the temperature at the top is between −50 and 0° C.; and
(iv) at least one stage for purifying flow D from stage (iii) in order to purify the E-1233zd to a level higher than or equal to 98% in weight.

12. The production process of claim 11 , wherein before the purification stage (iv), the flow D from stage (iii) is subjected to at least one separation phase in order to provide a flow E that comprises at least 50% HF in weight that can be recycled to the reactor and a flow F that comprises E-1-chloro- 3 , 3 , 3 -trifluoropropene, HCl, HF and Z-1-chloro-3,3,3-trifluoropropene.

13. The production process of claim 11 , wherein the separation stage is by decantation, initiated at a temperature between −50° C. and 50° C.

14. The production process of claim 11 , wherein the treatment stage (ii) involves a reflux column, initiated at a temperature between 30° C. and 120° C. in order to provide the flow B which is recycled to the reactor.

15. The production process of claim 11 , wherein the purification stage (iv) comprises at least one distillation stage.

16. A production process for the production of E-1-chloro-3,3,3-trifluoropropene, the process comprising:
at least one stage in an unstirred reactor during which 1,1,3,3-tetrachloropropene reacts with anhydrous hydrofluoric acid in the liquid phase, in the absence of a catalyst, with an HF/1,1,3,3-tetrachloropropene molar ratio between 3 and 20 inclusive,
at a temperature between 50° C. and 150° C. inclusive and an absolute pressure of between 1 and 20 bar inclusive,
wherein the production process yields E-1-chloro-3,3,3-trifluoropropene with a purity greater than or equal to 98% in weight using a single reactor.

Assignees

• Arkema France

Inventors

• Pigamo Anne
• Wismer John
• Collier Bertrand
• Bonnet Philippe

Classifications

• C07B2200/09

  Geometrical isomers · CPC title

• C07C17/38

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

• C07C17/25

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

• C07C17/206 Primary

  the other compound being HX · CPC title

• C07C17/383

  by distillation · CPC title