Method for mitigating HFC-245cb formation during HCFO-1233xf hydrofluorination to HCFC-244bb

Patent metadata

Field	Value
Publication number	US-9399609-B2
Application number	US-201414203823-A
Country	US
Kind code	B2
Filing date	Mar 11, 2014
Priority date	Mar 12, 2013
Publication date	Jul 26, 2016
Grant date	Jul 26, 2016

Abstract

The present process relates to a method for minimizing the formation of 1,1,1,2,2-pentafluoropropane in a liquid phase reaction of 2-chloro-3,3,3-trifluoropropene and HF in the presence of a hydrofluorination catalyst comprising:
(a) reacting HF with sufficient amount of 2-chloro-3,3,3-trifluoropropene in the presence of a hydrofluorination catalyst under conditions effective to form 2-chloro-1,1,1,2-tetrafluoropropane, the hydrofluorination catalyst being present in sufficient amounts to catalyze said reaction and the 2-chloro-1,1,1,2-tetrafluoropropane being formed with both a conversion of greater than 80% and a 1,1,1,2,2-pentafluoropropane selectivity lower than 20%; and (b) maintaining the 2-chloro-1,1,1,2-tetrafluoropropane being formed with both a conversion of about 80% or more and a 1,1,1,2,2-pentafluoropropane selectivity of about 20% or less by adding said hydrofluorination catalyst to the reactor in small increments.

First claim

What is claimed is:

1. A method for minimizing the formation of 1,1,1,2,2-pentafluoropropane in a liquid phase reaction of 2-chloro-3,3,3-trifluoropropene and HF in the presence of a hydrofluorination catalyst in a reactor comprising:
(a) reacting HF with sufficient amount of 2-chloro-3,3,3-trifluoropropene in the presence of a hydrofluorination catalyst under conditions effective to form 2-chloro-1,1,1,2-tetrafluoropropane, the hydrofluorination catalyst being present in sufficient amounts to catalyze said reaction and 2-chloro-1,1,1,2-tetrafluoropropane being formed with both a conversion of about 80% or more and 1,1,1,2,2-pentafluoropropane selectivity of about 20% or less; and
(b) maintaining the 2-chloro-1,1,1,2-tetrafluoropropane being formed with both a conversion of about 80% or more and a 1,1,1,2,2-pentafluoropropane selectivity of about 20% or less by adding said hydrofluorination catalyst continuously or periodically to the reactor in small increments.

2. The method according to claim 1 wherein the hydrofluorination catalyst is added periodically in an amount ranging from about 0.5 wt % to about 10 wt % based on the total weight of the hydrofluorination catalyst and HF present in the reactor.

3. The method according to claim 1 wherein the initial catalyst concentration in step (a) ranges from about 2 wt % to about 50 wt %, based on the total weight of catalyst and HF in the reactor.

4. The method according to claim 1 wherein the initial catalyst concentration in step (a) ranges from about 10 wt % to about 40 wt %, based on the total weight of catalyst and HF in the reactor.

5. The method according to claim 1 wherein the initial catalyst concentration in step (a) ranges from about 15 wt % to about 25 wt %, based on the total weight of catalyst and HF in the reactor.

6. The method according to claim 2 wherein the catalyst is added periodically in an amount ranging from about 1 wt % to about 5 wt % or less, based on the total weight of HF and catalyst in the reactor.

7. The method according to claim 2 wherein the catalyst is added periodically in an amount ranging from about 2 wt % to about 3 wt %, based on the total weight of HF and catalyst in the reactor.

8. The method according to claim 1 wherein the hydrofluorination catalyst is antimony halide, a tin halide, a tantalum halide, a titanium halide, a niobium halide, and molybdenum halide, an iron halide, a fluorinated chrome halide, a fluorinated chrome oxide or combinations thereof.

9. The method according to claim 8 wherein the hydrofluorination catalyst is SbCl 5 , SbCl 3 , SbF 5 , SnCl 4 , TaCl 5 , TiCl 4 , NbCl 5 , MoCl 6 , FeCl 3 , a fluorinated species of SbCl 5 , a fluorinated species of SbCl 3 , a fluorinated species of SnCl 4 , a fluorinated species of TaCl 5 , a fluorinated species of TiCl 4 , a fluorinated species of NbCl 5 , a fluorinated species of MoCl 6 , a fluorinated species of FeCl 3 , or combination thereof.

10. The method according to claim 1 wherein the reaction is conducted at a temperature ranging from about 30° C. to about 200° C.

11. The method according to claim 1 wherein the reaction is conducted at a temperature ranging from about 50° C. to about 150° C.

12. The method according to claim 1 wherein the reaction is conducted at a temperature ranging from about 75° C. to about 125° C.

13. The method according to claim 1 wherein the mole ratio of HF to 2-chloro-3,3,3-trifluoropropene ranges from about 1:1 to about 50:1.

14. The method according to claim 1 wherein the mole ratio of HF to 2-chloro-3,3,3-trifluoropropene ranges from about 1:1 to about 30:1.

15. The method according to claim 1 wherein the mole ratio of HF to 2-chloro-3,3,3-trifluoropropene ranges from about 2:1 to about 15:1.

16. The method according to claim 1 wherein the hydrofluorination catalyst is antimony pentachloride.

17. A method for preparing 2,3,3,3-tetrafluoroprop-1-ene comprising:
(a) providing a starting composition comprising at least one compound having a structure selected from Formulas I, II and III:
CX 2 ═CCl—CH 2 X  Formula I

CX 3 —CCl═CH 2   Formula II

CX 3 —CHCl—CH 2 X  Formula III

wherein each X is independently F, Cl, Br or I, provided that at least one X is not fluorine:

(b) contacting said starting composition with a first hydrofluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene;
(c) reacting HF with sufficient amount of 2-chloro-3,3,3-trifluoropropene in the presence of a second hydrofluorination catalyst under conditions effective to form 2-chloro-1,1,1,2-tetrafluoropropane, the second hydrofluorination catalyst being present in sufficient amounts to catalyze said reaction and 2-chloro-1,1,1,2-tetrafluoropropane being formed with both a conversion of at least 80% and 1,1,1,2,2-pentafluoropropane selectivity of at most 20%; and
(d) maintaining the 2-chloro-1,1,1,2-tetrafluoropropane being formed with both a conversion of about 80% or more and a 1,1,1,2,2-pentafluoropropane selectivity of about 20% or less by adding said second hydrofluorination catalyst to the reactor periodically or continuously in small increments; and
(e) dehydrochlorinating 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoroprop-1-ene.

18. The method according to claim 17 wherein the second hydrofluorination catalyst is added periodically in an amount ranging from about 0.5 wt % to about 10 wt % based on the total weight of the hydrofluorination catalyst and HF present in the reactor.

19. The method according to claim 17 wherein the initial concentration of said second hydrofluorination catalyst in step (c) ranges from about 2 wt % to about 50 wt %, based on the total weight of catalyst and HF in the reactor.

20. The method according to claim 17 wherein the initial concentration of said second hydrofluorination catalyst in step (c) ranges from about 10 wt % to about 40 wt %, based on the total weight of catalyst and HF in the reactor.

21. The method according to claim 17 wherein the initial concentration of said second hydrofluorination catalyst in step (c) ranges from about 15 wt % to about 25 wt %, based on the total weight of catalyst and HF in the reactor.

22. The method according to claim 17 wherein said second hydrofluorination catalyst is added periodically in an amount ranging from about 1 wt % to about 5 wt % or less, based on the total weight of HF and catalyst in the reactor.

23. The method according to claim 17 wherein said second hydrofluorination catalyst is added periodically in an amount ranging from about 2 wt % to about 3 wt % or less, based on the total weight of HF and catalyst in the reactor.

24. The method according to the claim 1 wherein the hydrofluorination catalyst is added continuously at a rate of 0.03 wt % or less per hour based on the total weight of the catalyst and HF.

25. The method according to claim 24 where the hydrofluorination catalyst is added at a rate of about 0.01 wt % or less per hour, based on the total weight of the catalyst and HF.

26. The method according to claim 25 wherein the hydrofluorination catalyst is added at a rate of about 0.005 wt % or less per hour, based on the total weight of the catalyst and HF.

27. The method according to claim 16 wherein the hydrofluorination catalyst is added at a rate of about 0.03 wt % or less per hour, based on the t

Assignees

• Honeywell Int Inc

Inventors

• Wang Haiyou
• Merkel Daniel C
• Tung Hsueh Sung
• Kopkalli Haluk

Classifications

• C07C17/25 Primary

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

• C07C21/18

  containing fluorine · CPC title

• C07C17/087 Primary

  to unsaturated halogenated hydrocarbons · CPC title

• C07C17/23 Primary

  by dehalogenation · CPC title

• C07C19/10

  and chlorine · CPC title