Reduction of HMF ethers with metal catalyst

Patent metadata

Field	Value
Publication number	US-9416119-B2
Application number	US-201414215264-A
Country	US
Kind code	B2
Filing date	Mar 17, 2014
Priority date	Oct 30, 2008
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

Methods of making reduced derivatives of hydroxymethyl furfural using metal catalysts are described. The derivatives may have tetrahydrofuran or furan nucleus with alkoxymethyl ether or ester moieties on the 5′ carbon and methanol on the 2′ carbon. Suitable metal catalyst include Raney nickel, a nickel catalyst with a zirconium promoter, a chromite catalyst with a barium, a palladium catalyst, such as palladium on carbon, or a ruthenium catalyst. Also provided are a new class of compounds, which are n-alkoxy hexane diols (i.e., 1,2 or 1,5 hexane diol ethers) and methods of making the same by reduction of furan or tetrahydrofuran derivatives.

First claim

The invention claimed is:

1. A composition comprising an n-alkoxy-hexanediol compound of the structure

wherein R is an alkyl group of 1 to 5 carbons.

2. A method of making the compound of claim 1 comprising,
selecting a compound from the group consisting of:

and combinations of any thereof,
wherein R is an alkyl group of 1 to 5 carbons;
contacting the selected compound with hydrogen and at least one catalyst selected from the group consisting of a Ni catalyst and a Ru catalyst, at a pressure of at least 1000 psi and a temperature of at least 170° C. for a time sufficient to form at least one n-alkoxy-hexanediol compound of claim 1 .

3. The method of claim 2 , wherein the metal catalyst comprises a support material selected from the group consisting of silicic acid, silica gel, siliceous earth, diatomaceous earth, kieselguhr and combinations thereof.

4. The method of claim 2 , wherein the Ni catalyst comprises nickel with a zirconium promoter on an inert substrate.

5. The method of claim 4 , wherein the catalyst is G-69B nickel on kieselguhr with zirconium.

6. The method of claim 2 , wherein the Ru catalyst comprises activated carbon as the support.

7. The method of claim 2 , wherein the selected compound is used without purification.

8. The method of claim 2 , wherein the selected compound is subjected to purification.

9. A bio-based replacement for a petroleum based solvent comprising compound of claim 1 .

10. A method of replacing a petroleum based solvent with a bio-based solvent of claim 7 , comprising;
selecting a target product that includes a petroleum based solvent having a bio-based content of less than 37.5% according to ASTM International Radioisotope Standard Method D 6866;
selecting a substitute solvent from the group consisting of:

and combinations thereof,
wherein said substitute solvent has a bio-based content of at least 37.5% according to ASTM International Radioisotope Standard Method D 6866;
formulating the target product with the selected substitute solvent,
thus reducing or eliminating the petroleum based solvent in the product.

11. The method of claim 10 , wherein the target product is a surfactant and the petroleum based solvent is an ether, and the surfactant is formulated with an alkoxy-hexanediol compound to substitute for the ether.

12. A surfactant formulated by the method of claim 10 .

13. A polymer formulated by the method of claim 10 .

14. A solvent system comprising an n-alkoxy-hexanediol compound according to claim 1 .

15. The solvent system of claim 14 further including a pigment.

Assignees

• Archer Daniels Midland Co
• Archer Daniels Wudland Company

Inventors

• Bloom Paul
• Sanborn Alexandra

Classifications

• C09K3/00

  Materials not provided for elsewhere · CPC title

• C07D307/44

  Furfuryl alcohol · CPC title

• C07C41/26

  by introduction of hydroxy or O-metal groups · CPC title

• C07D307/54 Primary

  Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title

• C07C43/13

  containing hydroxy or O-metal groups (C07C43/11 takes precedence) · CPC title