Method for producing terpene aldehydes and terpene ketones

Patent metadata

Field	Value
Publication number	US-11028033-B2
Application number	US-201716642188-A
Country	US
Kind code	B2
Filing date	Aug 26, 2017
Priority date	Aug 26, 2017
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

The invention relates to a method for producing terpene aldehydes and terpene ketones by oxidatively dehydrogenating the corresponding terpene alcohols, comprising or consisting of the following steps: (a) providing terpene alcohols or terpene-alcohol-containing reactants; (b) bringing the starting substances from step (a) in contact with a heterogeneous ruthenium catalyst; (c) heating the mixture from step (b) to at least 150° C. in the presence of oxygen; optionally (d) separating the terpene aldehydes or terpene ketones from the obtained reaction mixture.

First claim

The invention claimed is:

1. A method for producing terpene ketones by oxidative dehydrogenation of the corresponding terpene alcohols, the method comprising:
bringing starting materials comprising terpene alcohols or terpene alcohol-containing reactants into contact with a heterogeneous ruthenium catalyst to form a mixture;
heating the mixture at a temperature of about 180 to about 320° in the presence of oxygen to form a reaction mixture; and optionally
separating the terpene ketones from the resulting reaction mixture,
wherein a reaction to form the reaction mixture is carried out in a reactor through which a gas stream flows continuously, said gas stream comprising at least one terpene alcohol and an oxygen-containing gas and optionally an inert gas when entering the reactor.

2. The method as claimed in claim 1 , wherein the starting materials comprise menthol.

3. The method as claimed in claim 1 , wherein the heterogeneous ruthenium catalyst comprises one or more metal oxides.

4. The method as claimed in claim 3 , wherein the one or more metal oxides are selected from the group comprising cerium oxides, copper oxides, iron oxides, manganese oxides, cobalt oxides, molybdenum oxides, silver oxides, and mixtures thereof.

5. The method as claimed in claim 3 wherein the one or more metal oxides are selected from the group comprising CeO 2 , CuO, Cu 2 O, Fe 2 O 3 , Fe 3 O 4 , MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4 , Co 3 O 4 , CoO, MoO 3 , AgO, Ag 2 O, and mixtures thereof.

6. The method as claimed in claim 1 , wherein the heterogeneous ruthenium catalyst comprises catalytically active species that are applied to a support material.

7. The method as claimed in claim 6 wherein the support material is also catalytically active.

8. The method as claimed in claim 6 , wherein the support material is an oxidic support material.

9. The method as claimed in claim 6 , wherein the support material is selected from the group comprising cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon oxide, silica, iron oxide, manganese oxide, niobium oxide, aluminosilicate, hydrotalcite, hydroxyapatite, and mixtures thereof.

10. The method as claimed in claim 6 , wherein the support material comprises activated carbon.

11. The method as claimed in claim 6 , wherein a concentration of ruthenium on the support material is between approximately 0.1 and approximately 10% by weight.

12. The method as claimed in claim 1 , wherein the oxygen-containing gas comprises at least 0.1% by volume oxygen, based on the total volume of the oxygen-containing gas, determined at 20° C. and 1013.25 hPa.

13. The method as claimed in claim 1 , wherein
(i) the flow rate of the gas stream based on the volume of the heterogeneous catalyst (gas hourly space velocity GHSV) is about 100 h-1 to about 5000 h-1, and/or
(ii) the concentration of terpene alcohol in the gas stream entering the reactor is about 1 mol % to about 15 mol %.

14. The method as claimed in claim 13 , wherein
(i) the flow rate of the gas stream based on the volume of the heterogeneous catalyst (gas hourly space velocity GHSV) is about 200 h-1 to about 1000 h-1, and/or
(ii) the concentration of terpene alcohol in the gas stream entering the reactor is about 3 mol % to about 10 mol %.

15. The method as claimed in claim 6 , wherein a concentration of ruthenium on the support material is between approximately 0.5 and approximately 5% by weight.

16. The method as claimed in claim 1 , wherein a reaction to form the reaction mixture is carried out at a temperature in the range of approximately 250 to approximately 300° C.

17. A method for producing terpene aldehydes and terpene ketones by oxidative dehydrogenation of the corresponding terpene alcohols, the method comprising:
bringing starting materials comprising terpene alcohols or terpene alcohol-containing reactants into contact with a heterogeneous ruthenium catalyst of type RuMnCe/CeO 2 ;
heating the mixture to at least 150° C. in the presence of oxygen to form a reaction mixture; and optionally
separating the terpene aldehydes or terpene ketones from the resulting reaction mixture.

18. A method for producing terpene aldehydes and terpene ketones by oxidative dehydrogenation of the corresponding terpene alcohols, the method comprising:
bringing starting materials comprising menthol or a menthol-containing reactant into contact with a heterogeneous ruthenium catalyst to form a mixture;
heating the mixture to at least 150° C. in the presence of oxygen to form a reaction mixture; and optionally
separating the menthone from the resulting reaction mixture.

Assignees

• Symrise Ag

Inventors

• Kulik Anna
• Eckelt Reinhard
• Köckritz Angela
• Neubauer Katja

Classifications

• C07C45/29 Primary

  of hydroxy groups · CPC title

• C07C45/39 Primary

  being a secondary hydroxyl group · CPC title