Integrated process for the production of Z-1,1,1,4,4,4-hexafluoro-2-butene

Patent metadata

Field	Value
Publication number	US-10654777-B2
Application number	US-201916262834-A
Country	US
Kind code	B2
Filing date	Jan 30, 2019
Priority date	Feb 7, 2014
Publication date	May 19, 2020
Grant date	May 19, 2020

Abstract

Disclosed is a process for the preparation of cis-1,1,1,4,4,4-hexafluoro-2-butene comprising contacting 1,1,1-trifluorotrichloroethane with hydrogen in the presence of a catalyst comprising ruthenium to produce a product mixture comprising 1316mxx, recovering said 1316mxx as a mixture of Z- and E-isomers, contacting said 1316mxx with hydrogen, in the presence of a catalyst selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon and copper and palladium on carbon, to produce a second product mixture, comprising E- or Z—CFC-1326mxz, and subjecting said second product mixture to a separation step to provide E- or Z-1326mxz. The E- or Z-1326mxz can be dehydrochlorinated in an aqueous basic solution with an alkali metal hydroxide in the presence of a phase transfer catalyst to produce hexafluoro-2-butyne, which can then be selectively hydrogenated to produce Z-1,1,1,4,4,4-hexafluoro-2-butene using either Lindlar's catalyst, or a palladium catalyst further comprising a lanthanide element or silver.

First claim

What is claimed is:

1. A process for the preparation of fluorine-containing olefins comprising contacting a chlorofluoroalkene having the formula E- and Z—CF 3 CCl=CClCF 3 with hydrogen in the presence of a catalyst comprising copper and palladium on a support, wherein the catalyst comprises 0.1 to 1.0 weight percent palladium and 0.1 to 20 weight percent copper, at a temperature of from about 150° C. to 250° C., to produce a product mixture comprising a fluorine-containing olefin having the formula E- or Z—CF 3 CH═CClCF 3 , or a mixture thereof.

2. The process of claim 1 , wherein said support is carbon.

3. The process of claim 1 , wherein the process is conducted at a temperature of from 175° C. to 250° C.

4. The process of claim 1 , wherein the ratio of hydrogen to E- or Z—CF 3 CCl═CClCF 3 1:1 to 8:1.

5. The process of claim 1 , wherein the ratio of hydrogen to E- or Z—CF 3 CCl═CClCF 3 1:1 to 2:1.

6. The process of claim 1 wherein the catalyst comprises 0.6 to 5.0 weight percent copper.

7. The process of claim 1 wherein the reactivity of the Z-isomer to the E-isomer is less than 2.5:1.

8. The process of claim 1 wherein the ratio of reactivity of the Z-isomer to the E-isomer is less than 2.0:1.

9. The process of claim 1 wherein the ratio of reactivity of the Z-isomer to the E-isomer is less than 1.5:1.

10. The process of claim 1 wherein the product mixture further comprises one or more of E- and/or Z-1,1,1,4,4,4-hexafluoro-2-butene (HFC-1336mzz), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), pentafluorobutane (HFC-1345, different isomers), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HFC-346mdf), and 1,1,1,4,4,4-hexafluoro-2-butyne (HFB).

11. A process for the preparation of Z-HFO-1336mzz comprising: dimerizing CFC-113a in the presence of a ruthenium catalyst to produce a product mixture comprising Z- and E-CFC-1316mxx and HCl; scrubbing HCl from the product mixture; hydrogenating Z- and E-CFC-1316mxx in the presence of a catalyst comprising copper and palladium on a support, wherein the catalyst comprises 0.1 to 1.0 weight percent palladium and 0.1 to 20 weight percent copper, at a temperature of from about 150° C. to 250° C., to produce a product mixture comprising a fluorine-containing olefin having the formula E- or Z—CF 3 CH═CClCF 3 or a mixture thereof; dehydrochlorinating HCFO-1326mxz to produce hexafluoro-2-butyne, and then hydrogenating the hexafluoro-2-butyne to produce Z-HFO-1336mzz.

Assignees

• Chemours Co Fc Llc

Inventors

• Baldychev Ivan Sergeyevich
• Brandstadter Stephan M
• Cheung Patricia
• Nappa Mario Joseph

Classifications

• B01J23/462

  Ruthenium · CPC title

• C07C17/281

  of only one compound · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C17/354

  by hydrogenation · CPC title

• C07C17/25

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