Process for producing 2,3,3,3-tetrafluoropropene

Patent metadata

Field	Value
Publication number	US-9328043-B2
Application number	US-201314382082-A
Country	US
Kind code	B2
Filing date	Feb 25, 2013
Priority date	Feb 29, 2012
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

The present invention relates, in part, an improved process for the production of certain hydrofluoroolefins, particularly 2,3,3,3-tetrafluoropropene (1234yf). In certain non-limiting embodiments, the invention relates to methods for improving process efficiency during the fluorination of 1,1,2,3-tetrachloropropene, 2,3,3,3-tetrachloropropene, and/or 1,1,1,2,3-pentachloropropane to 2-chloro-3,3,3-trifluoropropene by separating and recycling unreacted HF, unreacted starting materials, and/or certain process intermediates from the 2-chloro-3,3,3-trifluoropropene product stream.

First claim

What is claimed is:

1. A process for preparing 2-chloro-3,3,3-trifluoropropene comprising:
providing a composition comprising at least one starting compound of formula I, II and/or formula III
CX 2 ═CCl—CH 2 X  (I)

CX 3 —CCl═CH 2   (II)

CX 3 —CHCl—CH 2 X  (III)

wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine;
(a) contacting said starting composition with a fluorinating agent to produce a final composition comprising 2-chloro-3,3,3-trifluoropropene, HCl, unreacted HF, optional unreacted starting compound, and one or more by-products selected from the group consisting of trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 1,1,1,2,2-pentafluoropropane (245cb), dichlorotrifluoropropane (243), trichlorodifluorpropane (242), C 6 H 3 F 6 Cl, C 6 H 3 F 7 Cl 2 , C 6 F 6 Cl 2 , C 6 H 8 Cl 2 , C 6 F 5 Cl 3 , C 6 H 3 F 2 Cl 5 , and combinations thereof, wherein at least one by-product is recyclable to the contacting step;
(b) separating the final composition into a first stream comprising 2-chloro-3,3,3-trifluoropropene and HCl and a second stream comprising the optional unreacted starting compound, the one or more by-products, and unreacted HF;
(c) separating the 2-chloro-3,3,3-trifluoropropene of the first stream from the HCl;
(d) separating the unreacted HF of the second stream from the optional unreacted starting compound and one or more by-products; and
(e) separating and recycling recyclable by-product(s) to contacting step (a).

2. The process of claim 1 , wherein the separating step (b) comprises distillation wherein at least the 2-chloro-3,3,3-trifluoropropene and HCl is recovered in a first stream and at least the optional unreacted starting compound, one or more by-products, and a portion of the unreacted HF are recovered in a second stream.

3. The process of claim 1 , wherein the 2-chloro-3,3,3-trifluoropropene of the first stream is separated from the HCl in step (c) by distillation.

4. The process of claim 1 , wherein in step (d) the unreacted HF is separated from the optional unreacted starting compound and one or more by-products by phase separation, wherein a first layer comprises unreacted HF and a second layer comprises the optional unreacted starting compound and one or more by-products.

5. The process of claim 4 , wherein the first layer is extracted and optionally purified.

6. The process of claim 5 , wherein the moisture present in the first layer is removed.

7. The process of claim 6 , wherein the first layer is recycled.

8. The process of claim 4 , wherein the second layer is extracted.

9. The process of claim 8 , wherein the optional unreacted starting compound is isolated.

10. The process of claim 8 , wherein the optional unreacted starting compound is recycled.

11. The process of claim 8 , wherein the recyclable by-product is isolated.

12. The process of claim 8 , wherein the recyclable by-product is recycled.

13. A process for preparing 2-chloro-3,3,3-trifluoropropene comprising:
providing a composition comprising at least one starting compound of formula I, II and/or formula III
CX 2 ═CCl—CH 2 X  (I)

CX 3 —CCl═CH 2   (II)

CX 3 —CHCl—CH 2 X  (III)

wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine;
(a) contacting said starting composition with a fluorinating agent to produce a final composition comprising 2-chloro-3,3,3-trifluoropropene, HCl, unreacted HF, optional unreacted starting compound, trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), at least one first by-product selected from the group consisting of 1,1,1,2-tetrafluoropropane (244bb), 1,1,1,2,2-pentafluoropropane (245cb), and combinations thereof, at least one second by-product selected from the group consisting of dichlorotrifluoropropane (243), trichlorodifluoropropane (242) and combinations thereof, and a least one third by-product selected from the group consisting of C 6 H 3 F 6 Cl, C 6 H 3 F 7 Cl 2 , C 6 F 6 Cl 2 , C 6 H 8 Cl 2 , C 6 F 5 Cl 3 , C 6 H 3 F 2 Cl 5 , and combinations thereof;
(b) separating a first stream comprising at least the 2-chloro-3,3,3-trifluoropropene, first by-product(s), and HCl, from a second stream comprising a portion of the unreacted HF and the remainder of the final composition;
(c) separating the 2-chloro-3,3,3-trifluoropropene of the first stream from the HCl and first by-product(s); and
(d) separating the unreacted HF of the second stream from the optional unreacted starting compound, trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), the second by-product(s), and the third by-product(s); and
(e) separating the optional unreacted starting compound, trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), and second by-product(s) from the third by-product(s).

14. The process of claim 13 , wherein the separating step (b) comprises distillation wherein at least the 2-chloro-3,3,3-trifluoropropene, first by product(s), and HCl is recovered in a first stream and at least the optional unreacted starting compound, second by-products, third by-products, and a portion of the unreacted HF are recovered in a second stream.

15. The process of claim 13 , wherein the 2-chloro-3,3,3-trifluoropropene of the first stream is separated from the HCl and the first by product(s) in step (c) by distillation.

16. The process of claim 13 , wherein in step (d) the unreacted HF of the second stream is separated from the optional unreacted starting compound, trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), second by-products(s), and third by-products by phase separation, wherein a first layer comprises unreacted HF and a second layer comprises the unreacted starting compound, trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), second by-products(s), and third by-products.

17. The process of claim 16 , wherein the first layer is extracted and purified.

18. The process of claim 17 , wherein the moisture present in the first layer is removed.

19. The process of claim 17 , wherein the first layer is recycled.

20. The process of claim 15 , wherein the second layer is extracted.

21. The process of claim 16 , wherein at least the optional unreacted starting compound, trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), and second by-product separated in step (e) are recycled.

22. A separation process comprising:
a) providing a composition to a phase separator, said composition comprising
i) 2-chloro-3,3,3-trifluoropropene (1233xf),
ii) HF,
iii) one or more organics selected from the group consisting of trichlorofluoropropene (1231) isomers, 2,3-dichloro-3,3-difluoropropene (1232xf), 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 1,1,1,2,2-pentafluoropropane (245cb), dichlorotrifluoropropane (243), trichlorodifluorpropane (242), and
iv) one or more dimers selected from the group consisting of C 6 H 3 F 6 Cl, C 6 H 3 F 7 Cl 2 , C 6 F 6 Cl 2 , C 6 H 8 Cl 2 , C 6 F 5 Cl 3 , C 6 H 3 F 2 Cl 5 ;
b) separating the composition into a top layer and a bottom layer in said phase separator, said top layer being comprised of substantially all of the HF and 1233xf from said composition, and said second layer being comprised of substantially all of the organics and the dimers of the composition.

Assignees

• Honeywell Int Inc

Inventors

• Wang Haiyou
• Bektesevic Selma
• Tung Hsueh S
• Kopkalli Haluk
• Chiu Yuon

Classifications

• C07C17/38

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

• C07C17/206 Primary

  the other compound being HX · CPC title

• C07C17/35 Primary

  by reactions not affecting the number of carbon or of halogen atoms in the reaction · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C21/18

  containing fluorine · CPC title