Process for the reduction of RƒC≡CX impurities in fluoroolefins

Patent metadata

Field	Value
Publication number	US-11905226-B2
Application number	US-202217815608-A
Country	US
Kind code	B2
Filing date	Jul 28, 2022
Priority date	Mar 15, 2013
Publication date	Feb 20, 2024
Grant date	Feb 20, 2024

Abstract

This disclosure relates to processes which involve: contacting a mixture comprising at least one fluoroolefin and at least one impurity with at least one zeolite to reduce the concentration of the at least one impurity in the mixture; and the at least one zeolite is selected from the group consisting of zeolites having pore opening of at least 4 Angstroms and no more than about 5 Angstroms, zeolites having pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, and mixtures thereof; provided that the at least one zeolite is not zeolite 4A. This disclosure also relates to processes for making at least one hydrotetrafluoropropene product selected from the group consisting of CF 3 CF═CH 2 , CF 3 CH═CHF, and mixtures thereof; and relates to processes for making at least one hydrochlorotrifluoropropene product selected from the group consisting of CF 3 CCl═CH 2 , CF 3 CH═CHCl, and mixtures thereof.

First claim

What is claimed is:

1. A process comprising:
a) providing an activated zeolite comprising at least one zeolite selected from zeolite 5A, zeolite 13X, zeolite LSX, zeolite AW-300, and mixtures thereof;
b) contacting a mixture having at least one R f ≡CCX impurity at a first level, wherein R f is a straight-chain perfluorinated alkyl group, and X is H, F, Cl, Br, or I, with said activated zeolite at a temperature of between −20° C. to about 200° C.;
c) reducing said first level of said at least one R f ≡CCX impurity to a second level lower than said first level with said activated zeolite; and
d) optionally, recovering a purified mixture having an impurity level lower than said first level.

2. The process of claim 1 , wherein the mixture comprises at least one of a hydrochlorofluoroolefin and a hydrofluoroolefin.

3. The process of claim 2 , wherein said at least one of a hydrochlorofluoroolefin and a hydrofluoroolefin is selected from CF 3 CF═CH 2 , CF 3 CH═C H F, CF 3 CH═CH 2 , CF 3 CCl═CH 2 , CF 3 CH═CHCl, CF 3 CH═CFCl, CF 3 CH═CF 2 , CF 3 CCl═CHF, CF 3 CF═CHF, CF 3 CF═CHCl, CF 3 CH═CCl 2 , CF 3 CCl═CHCl, and mixtures thereof, and wherein said at least one R f ≡CCX impurity is selected from CF 3 C≡CH, CF 3 C≡CCl, and CF 3 C≡CF.

4. The process of claim 1 , wherein said mixture includes at least one of CF 3 CF═CH 2 , CF 3 CH═CHF, CF 3 CH═CH 2 , CF 3 CCl═CH 2 , CF 3 CH═CHCl, and CF 3 CF═CHCl, and said impurity is selected from CF 3 C≡CH, CF 3 C≡CCl, and CF 3 C≡CF.

5. The process of claim 1 , wherein said mixture comprises at least one hydrofluoroolefin selected from CF 3 CF═CH 2 , CF 3 CH═C H F, CF 3 CH═CH 2 , CF 3 CH═CF 2 , and CF 3 CF═CHF.

6. The process of claim 1 , wherein said mixture comprises at least one chlorofluoroolefin selected from CF 3 CCl═CH 2 , CF 3 CH═CHCl, CF 3 CH F Cl CF 3 CF═CHCl, CF 3 CH═CCl 2 , and CF 3 CCl═CHCl.

7. The process of claim 3 , wherein said at least one R f ≡CCX impurity is selected from CF 3 C≡CH and CF 3 C≡CCl.

8. The process of claim 5 , wherein said at least one hydrofluoroolefin is CF 3 CF═CH 2 , and wherein said at least one R f CCX impurity is CF 3 C≡CH.

9. The process of claim 5 , wherein said at least one hydrofluoroolefin is CF 3 CH═CHF, and wherein said at least one R f CCX impurity is CF 3 C≡CH.

10. The process of claim 5 , wherein said at least one hydrofluoroolefin is a mixture of CF 3 CF═CH 2 and CF 3 CH═CHF, and wherein said at least one R f ≡CCX impurity is CF 3 C≡CH.

11. The process of claim 4 , wherein said at least one chlorofluoroolefin is CF 3 CH═CHCl, and wherein said at least one R f CCX impurity is CF 3 C≡CH.

12. The process of claim 1 , wherein said at least one zeolite is selected from zeolite 5A, zeolite 13X, and mixtures thereof.

13. The process of claim 1 , wherein said second level of said at least one R f ≡CCX impurity is 300 ppm or less.

14. The process of claim 1 , wherein said first level of said at least one R f ≡CCX impurity is reduced at least about 20%.

15. The process of claim 1 further comprising recovering said purified mixture.

16. The process of claim 3 , wherein said temperature of is from about 10° C. to about 60° C.

17. The process of claim 16 , wherein said temperature of is from about room temperature.

18. The process of claim 1 , wherein said activated zeolite is activated by contacting said at least one zeolite with heated air.

19. A process comprising:
a) contacting a mixture comprising CF 3 CF═CH 2 , CF 3 CH═CHF, and at least one impurity defined by the formula R f ≡CCX wherein R f is a straight-chain perfluorinated alkyl group, and X is H, F, or Cl with an activated zeolite comprising at least one zeolite selected from zeolite 5A, zeolite 13X, zeolite LSX, zeolite AW-300, and mixtures thereof, and
b) reducing said impurity from an initial level to a lower level as a result of contacting said mixture with said activated zeolite at a temperature of between 0° C. and 100° C.

20. The process of claim 19 , wherein said at least one zeolite is selected from zeolite 5A, zeolite 13X, and mixtures thereof.

21. A process comprising:
a) contacting a (chloro)fluoroolefin mixture comprising at least CF 3 CF═CH 2 and at least one impurity defined by the formula R f ≡CCX wherein R f is a straight-chain perfluorinated alkyl group, and X is H, F, or Cl with an activated zeolite comprising at least one zeolite selected from zeolite 5A, zeolite 13X, zeolite LSX, zeolite AW-300, and mixtures thereof at a temperature of between 20° C. and 60° C., and
b) recovering a purified (chloro)fluoroolefin mixture comprising at least CF 3 CF═CH 2 with reduced levels of said at least one impurity.

22. The process of claim 21 , wherein said at least one zeolite is selected from zeolite 5A, zeolite 13X, and mixtures thereof.

Assignees

• Chemours Co Fc Llc

Inventors

• Nappa Mario Joseph
• Sun Xuehui
• Corbin David Richard

Classifications

• C07C17/389 Primary

  by adsorption on solids · CPC title

• C07C17/087

  to unsaturated halogenated hydrocarbons · CPC title

• C07C17/25

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

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title