Catalysts for hydrodeoxygenation of oxygenated hydrocarbons

Patent metadata

Field	Value
Publication number	US-9314778-B2
Application number	US-201414585852-A
Country	US
Kind code	B2
Filing date	Dec 30, 2014
Priority date	Aug 15, 2012
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

The present invention provides catalysts, methods, and reactor systems for converting oxygenated hydrocarbons to oxygenated compounds. The invention includes methods for producing cyclic ethers, monooxygenates, dioxygenates, ketones, aldehydes, carboxylic acids, and alcohols from oxygenated hydrocarbons, such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like, using catalysts containing palladium, molybdenum, tin, and tungsten. The oxygenated compounds produced are useful in the production of liquid fuels, chemicals, and other products.

First claim

The invention claimed is:

1. A heterogeneous catalyst, the heterogeneous catalyst comprising (i) a Group VIII metal, (ii) a member selected from the group consisting of molybdenum, tungsten, tin, and combinations thereof, and (iii) a metal oxide support,
wherein the heterogeneous catalyst is configured to produce a monooxygenated cyclic ether and/or a monooxygenated cyclic ketone when an aqueous oxygenated hydrocarbon feedstock solution, the aqueous feedstock solution comprising water and an oxygenated hydrocarbon selected from the group consisting of a starch, a sugar, a sugar alcohol, a polysaccharide, an oligosaccharide, a trisaccharide, a disaccharide, a monosaccharide, and combinations thereof, and hydrogen are contacted with the heterogeneous catalyst.

2. The heterogeneous catalyst of claim 1 , wherein the Group VIII metal is palladium.

3. The heterogeneous catalyst of claim 1 , wherein the heterogeneous catalyst comprises between 0.05 and 5.0 wt % palladium.

4. The heterogeneous catalyst of claim 1 , wherein the heterogeneous catalyst comprises between 0.05 and 10.0 wt % molybdenum, between 0.0125 to 5.0 wt % tin, between 0.1 and 20.0 wt % tungsten, or combinations thereof.

5. The heterogeneous catalyst of claim 1 , wherein the metal oxide support is an acidic support.

6. The heterogeneous catalyst of claim 1 , wherein the metal oxide support is stable in the aqueous oxygenated hydrocarbon feedstock solution.

7. The heterogeneous catalyst of claim 1 , wherein the metal oxide support is selected from the group consisting of alumina, zirconia, titania, vanadia, ceria, heteropolyacid, kieselguhr, zinc oxide, chromia, acidic alumina, silica-alumina, iron aluminate, theta alumina, niobia, and mixtures thereof.

8. The heterogeneous catalyst of claim 1 , wherein the metal oxide support is modified with a modifier selected from the group consisting of tungsten, titania, sulfate, phosphate, and silica.

9. The heterogeneous catalyst of claim 1 , wherein the metal oxide support is selected from the group consisting of tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, and mixtures thereof.

10. A method for converting oxygenated hydrocarbons to cyclic ethers or cyclic ketones, the method comprising:
contacting an aqueous oxygenated hydrocarbon feedstock and hydrogen with the heterogeneous catalyst of claim 1 to produce a reaction product comprising a monooxygenated cyclic ether and/or a monooxygenated cyclic ketone in an amount greater than 1 wt % of the oxygenated hydrocarbon feedstock.

11. The method of claim 10 , wherein the aqueous oxygenated hydrocarbon feedstock comprises water and one or more oxygenated hydrocarbons selected from the group consisting of a starch, a sugar, a sugar alcohol, a polysaccharide, an oligosaccharide, a trisaccharide, a disaccharide, a monosaccharide, and combinations thereof.

12. The method of claim 10 , wherein the aqueous oxygenated hydrocarbon feedstock further comprises one or more oxygenated hydrocarbons selected from the group consisting of a polyhydric alcohol, a sugar degradation product, lignin, phenolics, methoxy-substituted phenolics, ash components, extractives, and combinations thereof.

13. The method of claim 10 , wherein the reaction product comprises monooxygenated cyclic ethers and monooxygenated cyclic ketones.

14. The method of claim 10 , wherein the reaction product further comprises one or more oxygenates selected from the group consisting of a polyol, a ketone, an aldehyde, a carboxylic acid, an alcohol, and combinations thereof.

15. The method of claim 10 , wherein the oxygenated hydrocarbon feedstock is contacted with the heterogeneous catalyst at a reaction temperature between 100° C. and 300° C.

16. The method of claim 10 , wherein the oxygenated hydrocarbon feedstock is contacted with the heterogeneous catalyst at the reaction pressure between 70 psig and 2000 psig.

17. The method of claim 10 , wherein the oxygenated hydrocarbon feedstock is contacted with the heterogeneous catalyst at a weight hour space velocity of 0.01 to 10.0 grams of soluble oxygenated hydrocarbon per gram of heterogeneous catalyst per hour.

18. The method of claim 10 , the method further comprising catalytically reacting a portion of the reaction product with a condensation catalyst to produce C 4+ compounds selected from the group consisting of a C 4+ alcohol, a C 4+ ketone, a C 4+ alkane, a C 4+ alkene, a C 5+ cycloalkane, a C 5+ cycloalkene, an aryl, and a fused aryl.

19. The method of claim 18 , wherein the C 4+ compounds comprise an aryl selected from the group consisting of toluene, orthoxylene, metaxylene, paraxylene, ethylbenzene, and combinations thereof.

20. The method of claim 18 , the method further comprising distilling the C 4+ compounds to provide a composition selected from the group consisting of an aromatic fraction, a gasoline fraction, a kerosene fraction, and a diesel fraction.

Assignees

• Virent Inc

Inventors

• Blank Brian
• Cortright Randy
• Beck Taylor
• Woods Elizabeth
• Jehring Mike

Classifications

• C07C27/04

  by reduction of oxygen-containing compounds (C07C29/14 takes precedence) · CPC title

• B01J37/0201

  Impregnation · CPC title

• B01J23/6527

  Tungsten · CPC title

• C07D307/33

  in position 2, the oxygen atom being in its keto or unsubstituted enol form · CPC title

• C07D309/04

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title