Methods for producing fuels, gasoline additives, and lubricants using amine catalysts

Patent metadata

Field	Value
Publication number	US-2017334823-A1
Application number	US-201515522269-A
Country	US
Kind code	A1
Filing date	Oct 28, 2015
Priority date	Oct 29, 2014
Publication date	Nov 23, 2017
Grant date	—

Abstract

Provided herein are methods for producing ketone(s) from the condensation of methyl ketone(s) and alcohol(s) in the presence of an amine catalyst and a metal catalyst. Such amine catalysts may be supported, for example, on a silica-alumina support. Such ketones may be suitable for use in producing fuels, gasoline additives, and/or lubricants, or precursors thereof. The methyl ketone(s) and/or alcohol(s) may be obtained from renewable sources, such as by fermentation of biomass.

First claim

1 . A method of producing a ketone mixture, comprising contacting a methyl ketone and at least one alcohol with an amine catalyst and a metal catalyst to produce a ketone mixture from the condensation of the methyl ketone and the at least one alcohol, wherein:
the methyl ketone has the structure of Formula (A):

wherein:
R 1 is H, alkyl, carbocyclyl, or heterocyclyl;
wherein the alkyl, carbocyclyl, or heterocyclyl is unsubstituted or substituted with one or more substituents independently selected from the group consisting of hydroxyl, nitro, and halo; and

x is an integer greater than or equal to 1.

2 . The method of claim 1 , the methyl ketone and the at least one alcohol are contacted with the amine catalyst and the metal catalyst in the presence of water.

3 . The method of claim 1 , further comprising contacting a composition comprising biomass or sugars with a fermentation host to produce a fermentation product mixture, wherein the fermentation product mixture comprises at least a portion of the methyl ketone and the at least one alcohol.

4 . A method of producing a ketone mixture, comprising:
contacting a composition comprising biomass or sugars with a fermentation host to produce a fermentation product mixture, wherein the fermentation product mixture comprises acetone, butanol and ethanol; and contacting the acetone, butanol and ethanol with an amine catalyst and a metal catalyst to produce a ketone mixture.

5 . The method of claim 4 , wherein at least a portion of the ketone mixture produced is by double alkylation of the acetone.

6 . The method of claim 1 , wherein at least 15% of the ketone mixture produced is C 7+ hydrocarbon ketones.

7 . The method of claim 1 , wherein at least 25% of the ketone mixture produced is C 5+ hydrocarbon ketones.

8 . The method of claim 1 , wherein the amine catalyst comprises an amine moiety having the structure:

wherein R a and R b at each occurrence are independently H, alkyl, carbocyclyl, heterocyclyl, or ether, or any combinations thereof;
wherein the alkyl, carbocyclyl, heterocyclyl, or ether is independently unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, hydroxyl, amine, oxo, carboxyl, imine, carbocyclyl, heterocyclyl, halo, ether, and thioether;

or R a and R b are taken together with the nitrogen atom to which they are both attached to form a heterocycle,
wherein the heterocycle is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, hydroxyl, amine, oxo, carboxyl, imine, carbocyclyl, heterocyclyl, halo, ether, and thioether.

9 . The method of claim 1 , wherein the amine catalyst comprises an amine moiety, wherein the amine moiety comprises a heterocycle containing at least one nitrogen atom, wherein the heterocycle is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, carbocyclyl, heterocyclyl, carboxyl, hydroxyl, halo, ether, and thioether.

10 . The method of claim 1 , wherein the amine catalyst further comprises a solid support and a linker, wherein the linker attaches the amine moiety to the solid support.

11 . The method of claim 10 , wherein the solid support comprises silica, alumina, silica-alumina, TiO 2 , ZrO 2 , or Nb 2 O 5 , or any combinations thereof.

12 . The method of claim 10 , wherein the solid support is porous.

13 . The method of claim 10 , wherein the solid support comprises a plurality of pores, wherein at least a portion of the pores have a pore diameter between 2 nm and 50 nm.

14 . The method of claim 10 , wherein the solid support comprises an acid moiety.

15 . The method of claim 10 , wherein the linker comprises:
-alkyl-, -aliphatic-, -aryl-, -carbocycle-, -heterocycle-, -sulfone-, or -ether-, or any combinations thereof; wherein the -alkyl-, -aliphatic-, -aryl-, -carbocycle-, -heterocycle-, -sulfone-, -ether- are unsubstituted or substituted with one or more substituents independently selected from the group consisting of alkyl, hydroxyl, amine, oxo, carboxyl, imine, carbocyclyl, and heterocyclyl.

16 . The method of claim 10 , wherein the linker comprises at least three linear chain atoms.

17 . The method of claim 1 , wherein the amine catalyst comprises a secondary amine.

18 . The method of claim 1 , wherein the metal catalyst is palladium on alumina.

19 . A ketone mixture produced according to the method of claim 1 .

20 . A composition, comprising:
a methyl ketone of Formula (A):

wherein:
R 1 is H, alkyl, carbocyclyl, or heterocyclyl;
wherein the alkyl, carbocyclyl, or heterocyclyl is unsubstituted or substituted with one or more substituents independently selected from the group consisting of hydroxyl, nitro, and halo; and

x is an integer greater than or equal to 1;

at least one alcohol;
an amine catalyst; and
a metal catalyst.

21 . The composition of claim 20 , further comprising water.

22 . The composition of claim 20 , wherein the amine catalyst comprises an amine moiety having the structure:

wherein R a and R b at each occurrence are independently H, alkyl, carbocyclyl, heterocyclyl, or ether, or any combinations thereof;
wherein the alkyl, carbocyclyl, heterocyclyl, or ether is independently unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, hydroxyl, amine, oxo, carboxyl, imine, carbocyclyl, heterocyclyl, halo, ether, and thioether;

or R a and R b are taken together with the nitrogen atom to which they are both attached to form a heterocycle,
wherein the heterocycle is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, hydroxyl, amine, oxo, carboxyl, imine, carbocyclyl, heterocyclyl, halo, ether, and thioether.

23 . The composition of claim 20 , wherein the amine catalyst comprises an amine moiety, wherein the amine moiety comprises a heterocycle containing at least one nitrogen atom, wherein the heterocycle is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl, carbocyclyl, heterocyclyl, carboxyl, hydroxyl, halo, ether, and thioether.

24 . A composition, comprising:
a fermentation product mixture comprising a methyl ketone, at least one alcohol; an amine catalyst, a metal catalyst; and water.

25 . A method, comprising:
producing a ketone mixture according to the method of claim 1 ; and hydrodeoxygenating at least a portion of the ketone mixture to produce an alkane or a mixture of alkanes.

26 . A method, comprising:
producing a ketone mixture according to the method of claim 1 ; and reducing at least a portion of the ketone mixture to produce an alcohol or a mixture of alcohols.

27 . A fuel or a lubricant, comprising:
at least one alkane produced according

Assignees

• Univ California
• Bp Corp North America Inc

Inventors

• Sankaranarayanapillai Shylesh
• Sreekumar Sanil
• Toste F Dean
• Bell Alexis T
• Gokhale Amit A
• Grippo Adam

Classifications

• B01J31/0237 Primary

  Amines · CPC title

• C07C49/04

  Saturated compounds containing keto groups bound to acyclic carbon atoms · CPC title

• C10L1/04

  essentially based on blends of hydrocarbons · CPC title

• C07C45/71 Primary

  being hydroxy groups · CPC title

• B01J31/0244

  with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine · CPC title