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

Patent metadata

Field	Value
Publication number	US-2017327448-A1
Application number	US-201515522251-A
Country	US
Kind code	A1
Filing date	Oct 28, 2015
Priority date	Oct 29, 2014
Publication date	Nov 16, 2017
Grant date	—

Abstract

Provided herein are methods for producing α,β-unsaturated ketones from the condensation of methyl ketones in the presence of an amine catalyst. Such amine catalysts may be supported, for example, on a silica-alumina support. Such amine catalysts may be used in the presence of an additional acid. The α,β-unsaturated ketones may be produced by dimerization and/or timerization of the methyl ketones. Such α,β-unsaturated ketones may be suitable for use in producing fuels, gasoline additives, and/or lubricants, or precursors thereof. The methyl ketones may be obtained from renewable sources, such as by the fermentation of biomass.

First claim

1 . A method of producing an α,β-unsaturated ketone, comprising:
contacting a methyl ketone of Formula (A) with an amine catalyst; and
producing an α,β-unsaturated ketone from at least a portion of the methyl ketone by a condensation reaction, wherein:
the methyl ketone of Formula (A) is:

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 , wherein the α,β-unsaturated ketone is a compound of Formula (L):

or any isomers thereof, wherein R 1 and x are as defined for Formula (A).

3 . The method of claim 2 , wherein the methyl ketone is contacted with the amine catalyst in the presence of water.

4 . The method of claim 2 , wherein the α,β-unsaturated ketone of Formula (L), or any isomers thereof, is produced with a yield of at least 10% at a weight hourly space velocity of about 0.2 grams of ketone of Formula (A) per gram of catalyst per hour.

5 . 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 the methyl ketone of Formula (A).

6 . 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.

7 . 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.

8 . 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.

9 . The method of claim 8 , wherein the solid support comprises silica, alumina, silica-alumina, TiO 2 , ZrO 2 , or Nb 2 O 5 , or any combinations thereof.

10 . The method of claim 8 , wherein the solid support is porous.

11 . The method of claim 8 , 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.

12 . The method of claim 8 , wherein the solid support comprises an acid moiety.

13 . The method of claim 8 , 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.

14 . The method of claim 8 , wherein the linker comprises at least three linear chain atoms.

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

16 . The method of claim 1 , wherein the methyl ketone is contacted with the amine catalyst in the presence of an acid.

17 . The method of claim 16 , wherein the acid is supported or unsupported.

18 . The method of claim 1 , wherein the methyl ketone of Formula (A) is provided in a fermentation product mixture.

19 . An α,β-unsaturated ketone 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 selected from the group consisting of hydroxyl, and halo; and

x is an integer greater than or equal to 1; and

an amine catalyst.

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

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

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 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 . The composition of claim 20 , further comprising an acid.

25 . A composition, comprising:
a fermentation product mixture comprising a methyl ketone; an amine catalyst; and water.

26 . A method, comprising:
producing an α,β-unsaturated ketone according to the method of claim 1 ; and hydrodeoxygenating the α,β-unsaturated ketone to produce an alkane.

27 . A method, comprising:
producing an α,β-unsaturated ketone according to the method of claim 1 ; and reducing the α,β-unsaturated ketone to produce an alcohol.

28 . A fuel or a lubricant, comprising:
at least one alkane produced according to the method of claim 26 .

Assignees

• Univ California
• Bp Corp North America Inc

Inventors

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

Classifications

• C10M105/12

  monohydroxy · CPC title

• B01J31/0238

  with a primary amino group · CPC title

• B01J31/0251

  Guanidides (R2N-C(=NR)-NR2) · CPC title

• C10M105/20

  Aldehydes; Ketones · CPC title

• C10M2207/0215

  used as base material · CPC title