Process for the manufacture of fluorinated olefins

Patent metadata

Field	Value
Publication number	US-10364201-B2
Application number	US-201615076191-A
Country	US
Kind code	B2
Filing date	Mar 21, 2016
Priority date	Mar 14, 2013
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

In certain aspects, the present invention relates to methods for increasing the cost efficiency and safety of the hydrogenation of a fluorinated olefin by controlling the reaction conditions and parameters. In further aspects, the hydrogenation reaction is provided in a two stage reaction wherein the reactant amounts, temperature and other parameters are controlled such that the conversion percentage, selectivity, and reaction parameters are all within commercially acceptable levels.

First claim

What is claimed is:

1. A method for producing at least one fluorinated alkane comprising:
a. providing a starting material stream comprising at least one alkene according to Formula (I)
(CX n Y 3−n )(CR 1 a R 2 b ) z CX═CH m X 2−m   (I)

and at least one alkane according to Formula (II)
(CX n Y 3−n )(CR 1 a R 2 b ) z CHXCH m+1 X 2−m   (II)

wherein:
each X is independently Cl, F, I or Br, provided that at least two Xs are F;
each Y is independently H, Cl, F, I or Br;
each R 1 is independently H, Cl, F, I, Br or unsubstituted or halogen substituted methyl or ethyl radical;
each R 2 is independently H, Cl, F, I, Br or unsubstituted or halogen substituted methyl or ethyl radical;
n is 1, 2 or 3;
a and b are each 0, 1 or 2, provided that a+b=2;
m is 0, 1 or 2; and
z is 0, 1, 2 or 3,
b. hydrogenating the starting material stream in a liquid phase reaction in a first reactor to produce an intermediate material stream by contacting said starting material stream with a reducing agent such that at least a portion of the fluorinated alkene of Formula I is converted to the fluorinated alkane of Formula II, wherein the selectivity of the conversion to said fluorinated alkane of Formula II is at least about 80 wt %;
c. separating a portion of the intermediate product stream into at least a first intermediate product stream comprising the fluorinated alkene of Formula I and the fluorinated alkane of Formula II and a second intermediate product stream comprising the fluorinated alkene of Formula I and the fluorinated alkane of Formula II;
d. adding the fluorinated alkene to the first intermediate product stream and recycling the first intermediate product stream to step b; and
e. hydrogenating the second intermediate product stream in a second reactor to produce a final product stream.

2. The method of claim 1 wherein said reducing agent is H 2 .

3. The method of claim 1 wherein step b results in a percent conversion of the fluorinated alkene in the starting material feed stream of between about 25 wt. % and about 75 wt. %.

4. The method of claim 1 wherein step b results in a percent conversion of the fluorinated alkene in the starting material feed stream of between about 45 wt. % and about 55 wt. %.

5. The method of claim 1 wherein the final product steam comprises less than 20 ppm of the fluorinated alkene of formula I.

6. The method of claim 1 wherein the final product steam comprises less than 200 ppm of the fluorinated alkene of formula I.

7. The method of claim 1 wherein said fluorinated alkene of formula I comprises hexafluoropropylene or 1,2,3,3,3-pentafluoropropene.

8. The method of claim 1 wherein said fluorinated alkane of formula II comprises 1,1,1,2,3,3-hexafluoropropane or 1,1,1,2,3-pentafluoropropane.

9. The method of claim 1 , further comprising dehydrohalogenating said final product stream to produce a second fluorinated olefin of formula I.

10. The method of claim 9 , wherein the second fluorinated olefin of formula I has one less fluorine atom that the fluorinated olefin of step a.

11. The method of claim 1 , wherein the hydrogenating step (b) occurs in the presence of a I catalyst selected from the group consisting of Pd on carbon, Pd/α-Al 2 O 3 , Ni/C, and Ni/Al 2 O 3 .

12. The method of claim 1 , wherein the hydrogenating step (e) occurs in a liquid phase reaction.

13. The method of claim 12 , wherein the hydrogenating step (e) occurs in the presence of a catalyst selected from the group consisting of Pd on carbon, Pd/α-Al 2 O 3 , Ni/C, and Ni/Al 2 O 3 .

14. A method for producing a fluorinated alkane comprising:
a. providing a starting material stream comprising hexafluoropropene and 1,1,1,2,3,3-hexafluoropropane;
b. hydrogenating the starting material stream with a reducing agent in a liquid phase reaction in a first reactor such that at least a portion of said hexafluoropropene is converted to 1,1,1,2,3,3-hexafluoropropane and to produce an intermediate stream comprising hexafluoropropene and 1,1,1,2,3,3-hexafluoropropane, wherein the selectivity of the conversion to said 1,1,1,2,3,3-hexafluoropropane is at least about 80 wt %;
c. separating a portion of the intermediate product stream into at least a first intermediate product stream comprising hexafluoropropene and 1,1,1,2,3,3-hexafluoropropane and a second intermediate product stream comprising hexafluoropropene and 1,1,1,2,3,3-hexafluoropropane;
d. adding hexafluoropropene to the first intermediate product stream and recycling the first intermediate product stream to step b; and
e. hydrogenating the second intermediate product stream in a second reactor to produce a final product stream.

15. A method for producing a fluorinated alkane comprising:
a. providing a starting material stream comprising 1,2,3,3,3-pentafluoropropene and 1,1,1,2,3-pentafluoropropane;
b. hydrogenating the starting material stream with a reducing agent in a liquid phase reaction in a first reactor such that at least a portion of said 1,2,3,3,3-pentafluoropropene is converted to 1,1,1,2,3-pentafluoropropane and to produce an intermediate stream comprising 1,2,3,3,3-pentafluoropropene and 1,1,1,2,3-pentafluoropropane wherein the selectivity of the conversion to said 1,1,1,2,3-pentafluoropropane is at least about 80 wt %;
c. separating a portion of the intermediate product stream into at least a first intermediate product stream comprising 1,2,3,3,3-pentafluoropropene and 1,1,1,2,3-pentafluoropropane and a second intermediate product stream comprising 1,2,3,3,3-pentafluoropropene and 1,1,1,2,3-pentafluoropropane;
d. adding 1,2,3,3,3-pentafluoropropene to the first intermediate product stream and recycling the first intermediate product stream to step b; and
e. hydrogenating the second intermediate product stream in a second reactor to produce a final product stream.

Assignees

• Honeywell Int Inc

Inventors

• Cottrell Stephen A
• Senetar John J
• Tung Hsueh S
• Merkel Daniel C
• Chiu Yuon
• Kopkalli Haluk

Classifications

• C07C19/08

  containing fluorine · CPC title

• C07C17/38

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

• C07C17/354 Primary

  by hydrogenation · CPC title

• C07C17/383

  by distillation · CPC title

• C07C17/25

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