Process for the reduction of RfC=CX impurities in fluoroolefins

Patent metadata

Field	Value
Publication number	US-12180134-B2
Application number	US-202318528224-A
Country	US
Kind code	B2
Filing date	Dec 4, 2023
Priority date	Mar 15, 2013
Publication date	Dec 31, 2024
Grant date	Dec 31, 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;
b) contacting a mixture having at least one R 71 C≡CX 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 pressure of between 10 kPa and 3000 kPa;
c)reducing said level of said impurity to a second level lower than said first level with said activated zeolite which consists essentially of at least one zeolite having at least one of a pore opening of at least 4 Angstroms and no more than about 5 Angstroms and a pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, excluding zeolite 4A; 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═CHF, 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 C≡CX 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═CHF, 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═CFCl 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 C≡CX 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 C≡CX 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 C≡CX 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 C≡CX 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 C≡CX impurity is CF 3 C≡CH.

12. The process of claim 1 , wherein said at least one zeolite has a said pore opening of at least about 5 Angstroms and said Sanderson electronegativity of no more than about 2.6, excluding zeolite 4A.

13. The process of claim 1 , wherein said at least one zeolite is selected from zeolite 5A, zeolite 13X, zeolite LSX, zeolite AW-300, zeolite AW-500, and mixtures thereof.

14. The process of claim 1 , wherein said at least one zeolite is zeolite 5A, zeolite 13X, or mixtures thereof.

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

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

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

18. The process of claim 1 , wherein said activated zeolite is activated by contacting one of a (1) zeolite having a pore opening of at least 4 Angstroms and no more than about 5 Angstroms and (2) a pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, excluding zeolite 4A with heated air.

Assignees

• Chemours Co Fc Llc

Inventors

• Nappa Mario Joseph
• Sun Xuehui
• Corbin David Richard

Classifications

• 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

• C07C17/389 Primary

  by adsorption on solids · CPC title