Method for producing hydrofluoroolefin

Patent metadata

Field	Value
Publication number	US-10189758-B2
Application number	US-201715611310-A
Country	US
Kind code	B2
Filing date	Jun 1, 2017
Priority date	Dec 5, 2014
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

Abstract

To provide a method for producing a hydrofluoroolefin, wherein formation of an over-reduced product having hydrogen added to an aimed hydrofluorolefin and an over-reduced product having some of fluorine atoms in the aimed product replaced with hydrogen atoms, as by-products, is suppressed.
A method for producing a hydrofluoroolefin, which comprises reacting a specific chlorofluoroolefin with hydrogen in the presence of a catalyst supported on a carrier, to obtain a specific hydrofluoroolefin, wherein the catalyst is a catalyst composed of particles of an alloy containing at least one platinum group metal selected from the group consisting of palladium and platinum, and gold, and the proportion of the gold at the surface of the alloy particles is from 5 to 30 mass % per 100 mass % in total of the platinum group metal and the gold at the surface of the alloy particles.

First claim

What is claimed is:

1. A method for producing 2,3,3,3-tetrafluoropropene, the method comprising:
reacting 1,1-dichloro-2,3,3,3-tetrafluoropropene with hydrogen in the presence of a catalyst supported on a carrier, to obtain 2,3,3,3-tetrafluoropropene,
wherein the catalyst comprises alloy particles comprising at least one platinum group metal selected from the group consisting of palladium and platinum, and gold,
the proportion of the gold at the surface of the alloy particles is from 8.6 to 19.4 mass % per 100 mass % in total of the platinum group metal and the gold at the surface of the alloy particles,
the 1,1-dichloro-2,3,3,3-tetrafluoropropene and the hydrogen are introduced to a catalyst layer packed with the carrier supporting the catalyst, and
the temperature of the region at the highest temperature in the catalyst layer is from 99.7° C. to 166.4° C.

2. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the proportion of the gold at the surface of the alloy particles is from 8.6 to 15 mass % per 100 mass % in total of the platinum group metal and the gold at the surface of the alloy particles.

3. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the catalyst comprises alloy particles of a palladium-gold alloy.

4. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the carrier is at least one member selected from the group consisting of activated carbon, carbon black and carbon fibers.

5. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the carrier is activated carbon.

6. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the carrier is at least one member selected from the group consisting of alumina, silica, titania and zirconia.

7. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the amount of the alloy particles supported is from 0.1 to 10 parts by mass based on 100 parts by mass of the carrier.

8. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the 1,1-dichloro-2,3,3,3-tetrafluoropropene and hydrogen are reacted in a gaseous phase.

9. The method for producing 2,3,3,3-tetrafluoropropene according to claim 8 , wherein the 1,1-dichloro-2,3,3,3-tetrafluoropropene and hydrogen are introduced to a gas introduction part of the catalyst layer, and, at the same time, hydrogen is introduced from at least one point between the gas introduction part and a gas discharge part of the catalyst layer.

10. The method for producing 2,3,3,3-tetrafluoropropene according to claim 1 , wherein the 1,1-dichloro-2,3,3,3-tetrafluoropropene and hydrogen are reacted in a liquid phase in the presence of the carrier supporting the catalyst.

11. A method for producing a hydrofluoroolefin, the method comprising:
reacting a chlorofluoroolefin of formula (1) with hydrogen in the presence of a catalyst supported on a carrier, to obtain a hydrofluoroolefin of formula (2),
wherein the catalyst comprises alloy particles comprising at least one platinum group metal selected from the group consisting of palladium and platinum, and gold,
the proportion of the gold at the surface of the alloy particles is from 8.6 to 19.4 mass % per 100 mass % in total of the platinum group metal and the gold at the surface of the alloy particles, and
the reacting of the chlorofluoroolefin is conducted by at least one method selected from the group consisting of: a method of dividedly introducing hydrogen to a catalyst layer which is packed with the carrier supporting the catalyst; a method of flowing an inert gas together with the chlorofluoroolefin and hydrogen in the catalyst layer; and a method of setting the temperature of a heat medium to at least 10° C. higher than and at most 80° C. higher than the dew point of the chlorofluoroolefin, and
the temperature of the region at the highest temperature in the catalyst layer is from 99.7° C. to 166.4° C.:
CZX═CClY  (1)

wherein X is a fluorine atom or a chlorine atom, Y is a fluorine atom, a chlorine atom or a hydrogen atom, and Z is a fluorine atom or CF 3 ;
CZX′═CHY′  (2)

wherein X′ is a fluorine atom when X is a fluorine atom, or X′ is a hydrogen atom when X is a chlorine atom, Y′ is a fluorine atom when Y is a fluorine atom, or Y′ is a hydrogen atom when Y is a chlorine atom or a hydrogen atom, and Z is the same as Z in the formula (1).

12. The method for producing a hydrofluoroolefin according to claim 11 , wherein the reacting of the chlorofluoroolefin is conducted by at least one method selected from the group consisting of: a method of dividedly introducing hydrogen to the catalyst layer; and a method of setting the temperature of the heat medium to at least 10° C. higher than and at most 80° C. higher than the dew point of the chlorofluoroolefin.

13. The method for producing a hydrofluoroolefin according to claim 11 , wherein the proportion of the gold at the surface of the alloy particles is from 8.6 to 15 mass % per 100 mass % in total of the platinum group metal and the gold at the surface of the alloy particles.

14. The method for producing a hydrofluoroolefin according to claim 11 , wherein the catalyst comprises alloy particles of a palladium-gold alloy.

15. The method for producing a hydrofluoroolefin according to claim 11 , wherein the carrier is activated carbon.

16. The method for producing a hydrofluoroolefin according to claim 11 , wherein the carrier is at least one member selected from the group consisting of alumina, silica, titania and zirconia.

17. The method for producing a hydrofluoroolefin according to claim 11 , wherein the amount of the alloy particles supported is from 0.1 to 10 parts by mass based on 100 parts by mass of the carrier.

18. The method for producing a hydrofluoroolefin according to claim 11 , wherein the chlorofluoroolefin and hydrogen are introduced to a gas introduction part of the catalyst layer, and, at the same time, hydrogen is introduced from at least one point between the gas introduction part and a gas discharge part of the catalyst layer.

19. The method for producing a hydrofluoroolefin according to claim 11 , wherein the ratio (H 2 /Cl) of the number of moles of hydrogen to the number of moles of chlorine atoms in the chlorofluoroolefin is from 0.1 to 0.7.

20. The method for producing a hydrofluoroolefin according to claim 11 , wherein the chlorofluoroolefin is 1,1-dichloro-2,3,3,3-tetrafluoropropene, and the hydrofluoroolefin is 2,3,3,3-tetrafluoropropene.

Assignees

• Agc Inc

Inventors

• Wang Xu
• Terazono Shinji
• Hayasaka Yuki
• Suzuki Toshio
• Kawaguchi Satoshi
• Kasagawa Mitsugu

Classifications

• C07C17/23 Primary

  by dehalogenation · CPC title

• B01J23/52

  Gold · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J23/44

  Palladium · CPC title

• B01J21/18

  Carbon · CPC title