Oxidation catalysts

• US 9,770,705 B2
• Filed: 12/13/2010
• Issued: 09/26/2017
• Est. Priority Date: 06/11/2010
• Status: Active Grant

• Current Assignee: Archer Daniels Midland Company
• Original Assignee: Rennovia Inc.
• Inventors: Murphy, Vincent J., Shoemaker, James, Zhu, Guang, Archer, Raymond, Salem, George Frederick, Dias, Eric L.
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): Corno, James
• Application Number:
  US12/966,702
• Publication Number:
  US 20110306790A1
• Time in Patent Office: 2,479 Days
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/066 Zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/52 Gold
• CPC Class Codes: B01J 29/06 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 37/0211 using a colloidal suspension
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/0248 Coatings comprising impregnated particles
• CPC Class Codes: B01J 37/18 with gases containing free hydrogen
• CPC Class Codes: C07B 2200/07 Optical isomers
• CPC Class Codes: C07C 209/00 Preparation of compounds containing amino groups bound to a carbon skeleton
• CPC Class Codes: C07C 211/12 1,6-Diaminohexanes
• CPC Class Codes: C07C 253/00 Preparation of carboxylic acid nitriles of cyanogen or compounds thereof C01C3/00
• CPC Class Codes: C07C 255/04 containing two cyano groups bound to the carbon skeleton
• CPC Class Codes: C07C 51/235 of —CHO groups or primary alcohol groups
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 51/412 by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
• CPC Class Codes: C07C 55/14 : Adipic acid
• CPC Class Codes: C07C 59/285 : Polyhydroxy dicarboxylic acids having five or more carbon atoms, e.g. saccharic acids
• CPC Class Codes: C07D 201/08 : from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
• CPC Class Codes: C07D 223/10 : attached in position 2
• CPC Class Codes: C07D 309/30 : Oxygen atoms, e.g. delta-lactones
• CPC Class Codes: C08G 63/16 : Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 69/14 : Lactams
• CPC Class Codes: C08G 69/26 : derived from polyamines and polycarboxylic acids
• CPC Class Codes: C08G 69/36 : derived from amino acids, polyamines and polycarboxylic acids
• CPC Class Codes: Y02P 20/582 : Recycling of unreacted starting or intermediate materials

Abstract

Disclosed are catalysts comprised of platinum and gold. The catalysts are generally useful for the selective oxidation of compositions comprised of a primary alcohol group and at least one secondary alcohol group wherein at least the primary alcohol group is converted to a carboxyl group. More particularly, the catalysts are supported catalysts including particles comprising gold and particles comprising platinum, wherein the molar ratio of platinum to gold is in the range of about 100:1 to about 1:4, the platinum is essentially present as Pt(0) and the platinum-containing particles are of a size in the range of about 2 to about 50 nm. Also disclosed are methods for the oxidative chemocatalytic conversion of carbohydrates to carboxylic acids or derivatives thereof. Additionally, methods are disclosed for the selective oxidation of glucose to glucaric acid or derivatives thereof using catalysts comprising platinum and gold. Further, methods are disclosed for the production of such catalysts.

Claims

1. A catalyst composition comprising particles of gold-platinum alloy and particles consisting essentially of platinum (0) on a support comprising titania wherein (a) the molar ratio of platinum to gold of the catalyst is from about 4:

1 to 1;

1, (b) the particle sizes of the platinum (0) particles are substantially in the range of from about 2 to about 50 nanometers, (c) the total gold and platinum metal loading of the catalyst is from about 2 to about 8 wt %, and (d) the gold-platinum alloy is formed at a temperature between about 200°

C. and about 350°

C. and wherein the catalyst has the ability to catalyze conversion of glucose to glucaric acid at a yield in excess of 60%.

2. The catalyst composition of claim 1 wherein the total gold and platinum metal loading of the catalyst is from about 2 to about 4 wt %.

3. The catalyst composition of claim 2 wherein the molar ratio of platinum to gold of the catalyst is from about 3:

1 to 1;

1.

4. The catalyst composition of claim 2 wherein the molar ratio of platinum to gold of the catalyst is from about 2:

1 to 1;

1.

5. The catalyst composition of claim 1 wherein the particles sizes of the particles consisting essentially of platinum (0) are substantially in the range of from about 5 to about 20 nanometers.

6. The catalyst composition of claim 1 wherein the particle sizes of the gold-platinum alloy particles are substantially in the range of from about 2 to about 20 nanometers.

7. The catalyst composition of claim 6 wherein at least about 50% of the gold-platinum alloy particles have a size from about 5 to about 12 nanometers.

8. The catalyst composition of claim 6 wherein the total gold and platinum metal loading of the catalyst is from about 2 to about 4 wt %.

9. The catalyst composition of claim 8 wherein the molar ratio of platinum to gold of the catalyst is from about 3:

1 to 1;

1.

10. The catalyst composition of claim 8 wherein the molar ratio of platinum to gold of the catalyst is from about 2:

1 to 1;

1.

11. The catalyst composition of claim 1 wherein at least about 50% of the particles consisting essentially of platinum (0) have a size from about 8 to about 12 nanometers.

12. The catalyst composition of claim 1 wherein the molar ratio of platinum to gold of the catalyst is from about 3:

1 to 1;

1.

13. The catalyst composition of claim 1 wherein the molar ratio of platinum to gold of the catalyst is from about 2:

1 to 1;

1.

14. The catalyst composition of claim 1 further comprising metal selected from Group 6 metals.

15. The catalyst composition of claim 1 further comprising a Group 10 metal in addition to platinum.

16. A process for preparing glucaric acid or derivatives thereof comprising reacting glucose with a source of oxygen in the presence of the catalyst of claim 1.

17. The process of claim 16 wherein the particle sizes of the gold-platinum alloy particles are substantially in the range of from about 2 to about 20 nanometers.

18. The process of claim 17 wherein the total gold and platinum metal loading of the catalyst is from about 2 to about 4 wt %.

19. The process of claim 16 wherein the total gold and platinum metal loading of the catalyst is from about2 to about 4 wt %.

20. The process of claim 16 wherein the catalyst further comprises a metal selected from Group 6 metals.

21. The process of claim 16 wherein the catalyst further comprises a Group 10 metal in addition to platinum.

22. The process of claim 16 wherein the catalyst further comprises wherein the molar ratio of platinum to gold of the catalyst is from about 2:

1 to 1;

1.