Method for producing levulinic acid ester

Patent metadata

Field	Value
Publication number	US-10150726-B2
Application number	US-201615525108-A
Country	US
Kind code	B2
Filing date	Feb 1, 2016
Priority date	Feb 13, 2015
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

Provided is a method for efficiently producing a levulinic acid ester from a cellulose-containing raw material or a carbohydrate-containing raw material in an alcohol solvent using an inexpensive, easily available catalytic system. In a method for producing a levulinic acid ester by reacting at least one of a cellulose-containing raw material and a carbohydrate-containing raw material in the presence of an alcohol and a catalyst, use is made of, as a catalyst, a combination of: at least one metal compound (exclusive of gallium acetylacetonate and indium acetylacetonate) selected from the group consisting of hydroxide salts, sulfates, nitrates, carboxylates, alkoxides, acetylacetonates, and oxides of at least one metal selected from the group consisting of metals belonging to Group XIII and Group XIV of the Periodic Table; and an organic sulfonic acid.

First claim

The invention claimed is:

1. A method for producing a levulinic acid ester by reacting a carbohydrate-containing raw material in the presence of an alcohol and a catalyst, the method using, as a catalyst, a combination of: at least one metal compound (exclusive of gallium acetylacetonate and indium acetylacetonate) selected from the group consisting of hydroxide salts, sulfates, nitrates, carboxylates, alkoxides, acetylacetonates, and oxides of at least one metal selected from the group consisting of metals belonging to Group XIII and Group XIV of the Periodic Table; and an organic sulfonic acid; wherein
the carbohydrate-containing raw material is contained in at least one raw material selected from the group consisting of cedar powder, eucalyptus powder, alkali-cooked cedar pulp, alkali-oxygen-cooked cedar pulp, alkali-oxygen-cooked eucalyptus pulp, soda-AQ cedar pulp, and soda-AQ eucalyptus pulp.

2. The method for producing a levulinic acid ester according to claim 1 , wherein the metal is at least one selected from the group consisting of boron, aluminum, gallium, indium, germanium, tin, and lead.

3. The method for producing a levulinic acid ester according to claim 1 , wherein the organic sulfonic acid is at least one selected from the group consisting of alkyl sulfonic acids with 1 to 6 carbon atoms and aryl sulfonic acids with 6 to 24 carbon atoms.

4. The method for producing a levulinic acid ester according to claim 1 , wherein the organic sulfonic acid is at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, hexanesulfonic acid, camphorsulfonic acid, methanedisulfonic acid, ethanedisulfonic acid, propanedisulfonic acid, butanedisulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, anthracenesulfonic acid, anthracenedisulfonic acid, pyrenesulfonic acid, and pyrenedisulfonic acid.

5. The method for producing a levulinic acid ester according to claim 1 , wherein an amount of the metal compound used is 0.1% to 20% by mole relative to sugar constituting part of the carbohydrate-containing raw material.

6. The method for producing a levulinic acid ester according to claim 1 , wherein an amount of the organic sulfonic acid used is 1% to 30% by mole relative to sugar constituting part of the carbohydrate-containing raw material.

7. The method for producing a levulinic acid ester according to claim 1 , wherein an amount of the alcohol present is 10 to 400 equivalents relative to sugar constituting part of carbohydrate-containing raw material.

8. The method for producing a levulinic acid according to claim 1 , wherein a reaction temperature is 160° C. to 230° C.

9. The method for producing a levulinic acid ester according to claim 1 , wherein the catalyst is Al(acac) 3 and the organic sulfonic acid is p-toluenesulfonic acid.

Assignees

• Ube Industries
• Aist

Inventors

• Nemoto Koji
• Tominaga Kenichi
• Sato Kazuhiko
• Yamada Atsushi
• Yamamoto Yasushi

Classifications

• C07C67/08 Primary

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C69/716

  Esters of keto-carboxylic acids {or aldehydo-carboxylic acids} · CPC title

• C07B61/00

  Other general methods · CPC title

• C07C67/00 Primary

  Preparation of carboxylic acid esters · CPC title