Process for producing 1-chloro-3,3,3-trifluoropropene in an ionic liquid

Patent metadata

Field	Value
Publication number	US-2015105596-A1
Application number	US-201414507914-A
Country	US
Kind code	A1
Filing date	Oct 7, 2014
Priority date	Oct 15, 2013
Publication date	Apr 16, 2015
Grant date	—

Abstract

This invention relates to methods and systems for producing hydrochlorofluoro-olefins, particularly 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) by the fluorination of a starting material selected from the group consisting of 1,1,1,3,3-pentachloropropane (HCC-240fa), 1,1,3,3-tetrachloropropene, and 1,1,1,3-tetrachloropropene, alone or in combination, in an ionic liquid.

First claim

What is claimed is:

1 . A process for the formation of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) comprising reacting a starting material selected from the group consisting of 1,1,1,3,3-pentachloropropane (HCC-240fa), 1,1,3,3-tetrachloropropene, and 1,1,1,3-tetrachloropropene, alone or in combination, with hydrogen fluoride in a liquid phase reactor in the presence of an ionic liquid.

2 . The process of claim 1 , wherein the starting material comprises 1,1,1,3,3-pentachloropropane (HCC-240fa).

3 . The process of claim 1 , wherein the starting material comprises 1,1,3,3-tetrachloropropene.

4 . The process of claim 1 , wherein the starting material comprises 1,1,1,3-tetrachloropropene.

5 . The process of claim 1 , wherein the starting material comprises a mixture of two or three of the starting materials selected from the group consisting of 1,1,1,3,3-pentachloro-propane (HCC-240fa), 1,1,3,3-tetrachloropropene, and 1,1,1,3-tetrachloro-propene.

6 . The process of claim 1 , wherein the hydrogen fluoride is anhydrous.

7 . The process of claim 1 , wherein the ionic liquid comprises an anion selected from the group consisting of I − , Br − , Cl − , F − , (HF) n F − , wherein n=1.0-4.0, and combinations thereof.

8 . The process of claim 7 , wherein the anions in the ionic liquid are externally introduced into the process.

9 . The process of claim 7 , wherein the anions in the ionic liquid are in-situ generated.

10 . The process of claim 7 , wherein the anion (HF) n F − , wherein n=1.0-4.0, is formed by the interactions of an ionic liquid with Cl − as anion and HF in the reactor.

11 . The process of claim 1 , wherein the ionic liquid comprises a cation selected from the group consisting of ammonium, sulfonium, phosphonium, imidazolium, pyridinium, pyrrolidinium, thiazolium, triazolium, oxazolium, pyrazolium, and combinations thereof.

12 . The process of claim 1 , wherein the ionic liquid comprises an imidazolium cation selected from the group consisting of 1-methylimidazolium, 1-ethyl-imidazolium, 1-propylimidazolium, 1-butylimidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-n-butyl-3-methylimidazolium, 1-n-butyl-3-ethylimidazolium, 1,3-di-n-butylimidazolium, 1-methyl-3-octylimidazolium, 1-decyl-3-methylimidazolium, 3-butyl-1-methylimidazolium, 3-butyl-1-ethyl-imidazolium, 3-methyl-2-ethylimidazolium, 3-butyl-2-methylimidazolium, 3-butyl-2-ethyl-imidazolium, 3,4-dimethylimidazolium, 3-butyl-4-methylimidazolium, 1,2,3-trimethyl-imidazolium, 1-butyl-2,3-dimethylimidazolium, 1,3-dibutyl-2-methylimidazolium, 3-butyl-1,2-dimethylimidazolium, 1,3,4-trimethylimidazolium, 3-butyl-1,4-dimethyl-imidazolium, 2-ethyl-3,4-dimethylimidazolium, 3-butyl-2-ethyl-4-methylimidazolium, 1,3,4,5-tetramethylimidazolium, 3-butyl-1,4,5-trimethylimidazolium, and combinations thereof.

13 . The process of claim 1 , wherein the amount of ionic liquid used relative to the amount of starting material present is from about 0.001 to about 10 mol %.

14 . The process of claim 1 , further comprising a fluorination catalyst selected from Lewis acid catalysts.

15 . The process of claim 14 , wherein the Lewis acid catalyst is selected from the group consisting of TiCl 4 , SnCl 4 , SbCl 5 , TaCl 5 , AlCl 3 , FeCl 3 , and combinations thereof.

16 . The process of claim 1 , wherein the fluorination reaction is conducted without a catalyst

17 . The process of claim 1 , wherein the mole ratio of HF to starting material ranges from 3:1 to 30:1.

18 . The process of claim 1 , wherein the reaction temperature range is from 50° C. to 200° C.

19 . A process for the formation of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) comprising the following steps:
(a) fluorination of a starting material selected from the group consisting of 1,1,1,3,3-pentachloropropane (HCC-240fa), 1,1,3,3-tetrachloropropene, and 1,1,1,3-tetrachloropropene, alone or in combination, using HF in the presence of an ionic liquid, with simultaneous removal of by-product HCl and the product 1233zd(E+Z); (b) separation and purification of by-product HCl; (c) separation of excess HF back to step (a); and (d) purification of final product, 1233zd(E), 1233zd(Z), or a mixture of these two isomers.

Assignees

• Honeywell Int Inc

Inventors

• Wang Haiyou
• Tung Hsueh Sung

Classifications

• C07C17/206 Primary

  the other compound being HX · CPC title

• C07B2200/09

  Geometrical isomers · CPC title

• C07C17/25

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