Process for making HCFO-1233zd

Patent metadata

Field	Value
Publication number	US-9764998-B2
Application number	US-201615088599-A
Country	US
Kind code	B2
Filing date	Apr 1, 2016
Priority date	May 12, 2015
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

Disclosed is a process for the production of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) which includes reacting a propane feedstock comprising tetrachlorofluoropropanes, trichlorodifluoropropanes, dichlorotrifluoropropanes, or a mixture thereof, in the presence of a solid catalyst. The process generally comprises the following four steps: (i) providing a propane feedstock comprising trichlorodifluoropropanes and dichlorotrifluoropropanes, (ii) reacting the feedstock in a vapor phase reactor in the presence of HF and in the presence of a solid catalyst under conditions effective to form a product stream comprising HCFO-1233zd and unconverted starting materials, (iii) recovering or removing HCl and HF, and (iv) isolating HCFO-1233zd(E), HCFO-1233zd(Z), or both.

First claim

What is claimed is:

1. A process for the production of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) which comprises the steps of:
(i) providing only a partially fluorinated propane feedstock selected from the group consisting of tetrachlorofluoropropanes, trichlorodifluoropropanes, dichlorotrifluoro-propanes, and mixtures thereof;
(ii) reacting the propane feedstock in a vapor phase reactor in the presence of HF and in the presence of a solid catalyst under conditions effective to form a product stream comprising HCFO-1233zd isomers, HCl and unconverted starting materials,
(iii) recovering or removing HCl and HF, and
(iv) isolating the HCFO-1233zd E-isomer, the HCFO-1233zd Z-isomer, or both compounds.

2. The process of claim 1 , wherein the propane in the feedstock comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa).

3. The process of claim 1 , wherein the propane in the feedstock comprises 1,3,3-trichloro-1,1-difluoro-propane (HCFC-242fa).

4. The process of claim 1 , wherein the propane in the feedstock comprises 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb).

5. The process of claim 1 , wherein the propane in the feedstock comprises 1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa).

6. The process of claim 1 , wherein the propane in the feedstock comprises, 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb).

7. The process of claim 1 , wherein the solid catalyst comprises one or more halogenated metal oxides in bulk form or supported, metal halides in bulk form or supported, and carbon supported transition metals.

8. The process of claim 7 , wherein the catalyst comprises one or more halogenated metal oxides selected from the group consisting of fluorinated Cr 2 O 3 , fluorinated Al 2 O 3 , and fluorinated MgO.

9. The process of claim 7 , wherein the catalyst comprises one or more metal halides selected from the group consisting of CrF 3 , AlF 3 , AlCl 3 , FeCl 3 , and FeCl 3 /C.

10. The process of claim 7 , wherein the catalyst comprises one or more carbon supported zero oxidation state transition metals selected from the group consisting of Fe/C, Co/C, Ni/C, and Pd/C.

11. The process of claim 1 , wherein the feedstock comprises a mixture of HCFC-241, HCFC-242and HCFC-243, which is introduced into the reactor either in pure form, impure form, or together with an optional inert gas diluent.

12. The process of claim 11 , wherein the HCFC-241, HCFC-242 and HCFC-243 feedstock is pre-vaporized or preheated prior to entering the reactor.

13. The process of claim 11 , wherein the HCFC-241, HCFC-242 and HCFC-243 feedstock is vaporized inside the reactor.

14. The process of claim 11 , wherein the reactor temperature ranges from about 200° C. to about 600° C.

15. The process of claim 11 , wherein the reaction pressure is selected from the group consisting of atmospheric pressure, super-atmospheric pressure and under vacuum, wherein the vacuum pressure can be from about 5 Torr to about 760 Torr.

16. The process of claim 11 , wherein the reaction contact time of the HCFC-241, HCFC-242 and HCFC-243 feedstock with the catalyst ranges from about 0.5 seconds to about 120 seconds.

17. The process of claim 11 , wherein the HF is co-fed to the reactor together with the HCFC-241, HCFC-242 and HCFC-243 feedstock.

18. The process of claim 17 , wherein the HF is pre-vaporized or preheated prior to entering the reactor.

19. The process of claim 17 , wherein the HF is vaporized inside the reactor.

20. The process of claim 17 , wherein the molar ratio of HF to the HCFC-242 and HCFC-243 feedstock ranges from 0.01:1 to 10:1.

Assignees

• Honeywell Int Inc

Inventors

• Wang Haiyou
• Tung Hsueh Sung
• Cottrell Stephen A

Classifications

• C07C21/18

  containing fluorine · CPC title

• C07C19/10

  and chlorine · CPC title

• C07C17/42

  Use of additives, e.g. for stabilisation · CPC title

• C07C17/25 Primary

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