# US 9,434,709 B2 · Production of adipic acid and derivatives from carbohydrate-containing materials

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- Number: US 9,434,709 B2
- Document ID: US9434709B2
- Status: Granted
- Kind: B2
- Application number: 14/854,780
- Filed: 2015-09-15
- Published: 2016-03-17
- Granted: 2016-09-06
- Earliest claimed: 2009-06-13
- Assignees: Rennovia Inc.
- Applicants: Rennovia Inc.
- Inventors: Thomas R. Boussie; Eric L. Dias; Zachary M. Fresco; Vincent J. Murphy; James Shoemaker; Raymond Archer; Hong Jiang
- Web page: https://patentgrep.com/patent/US9434709B2

## CPC

- C07C 51/377: by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)}
- B01J 23/40: of the platinum group metals
- B01J 23/44: Palladium
- B01J 23/462: {Ruthenium}
- B01J 23/464: {Rhodium}
- B01J 23/468: {Iridium}
- B01J 23/52: Gold
- B01J 23/6525: {Molybdenum}
- B01J 23/6562: {Manganese}
- B01J 23/6567: {Rhenium}
- B01J 23/8906: {Iron and noble metals}
- B01J 23/8913: {Cobalt and noble metals}
- B01J 23/8926: {Copper and noble metals}
- B01J 37/0205: {in several steps}
- C07C 51/235: of —CHO groups or primary alcohol groups
- C07C 51/31: of cyclic compounds with ring-splitting
- C07C 51/412: {by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part}
- C07C 201/08: by substitution of hydrogen atoms by nitro groups
- C07C 209/00: Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C 253/00: Preparation of carboxylic acid nitriles (of cyanogen or compounds thereof C01C3/00)
- C07D 201/08: from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
- C07D 223/10: attached in position 2
- C07D 309/30: Oxygen atoms, e.g. delta-lactones
- C08G 63/16: Dicarboxylic acids and dihydroxy compounds
- C08G 69/14: Lactams
- C08G 69/26: derived from polyamines and polycarboxylic acids
- C08G 69/36: derived from amino acids, polyamines and polycarboxylic acids
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 21/08: Silica
- B01J 21/16: Clays or other mineral silicates
- B01J 21/18: Carbon
- C07B 2200/07: Optical isomers
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention generally relates to processes for the chemocatalytic conversion of a glucose source to an adipic acid product. The present invention includes processes for the conversion of glucose to an adipic acid product via glucaric acid or derivatives thereof. The present invention also includes processes comprising catalytic oxidation of glucose to glucaric acid or derivative thereof and processes comprising the catalytic hydrodeoxygenation of glucaric acid or derivatives thereof to an adipic acid product. The present invention also includes products produced from adipic acid product and processes for the production thereof from such adipic acid product.

## Claims

### Claim 1

A process for preparing glucaric acid or lactone thereof, the process comprising:
reacting glucose with oxygen in the presence of a heterogeneous oxidation catalyst comprising a metal selected from the group consisting of Pd, Pt, and a combination thereof to convert at least a portion of the glucose to glucaric acid or lactone thereof, wherein the pH of the reaction mixture is less than 7 and the reaction is conducted in the substantial absence of added base, and wherein at least about 50% of the glucose is converted to glucaric acid or lactone thereof.

### Claim 2 (depends on 1)

The process as set forth in claim 1 wherein at least about 60% of the glucose is converted to glucaric acid or lactone thereof.

### Claim 3 (depends on 1)

The process as set forth in claim 1 wherein at least about 50% of the glucose is converted to glucaric acid.

### Claim 4 (depends on 1)

The process as set forth in claim 1 wherein at least a portion of the glucose is converted to a glucarolactone.

### Claim 5 (depends on 1)

The process as set forth in claim 1 wherein at least a portion of the glucose is solubilized with a weak carboxylic acid.

### Claim 6 (depends on 5)

The process as set forth in claim 5 wherein the weak carboxylic acid is acetic acid.

### Claim 7 (depends on 1)

The process as set forth in claim 1 wherein the heterogeneous oxidation catalyst comprises Pt.

### Claim 8 (depends on 7)

The process as set forth in claim 7 wherein the heterogeneous oxidation catalyst further comprises Au.

### Claim 9 (depends on 1)

The process as set forth in claim 1 wherein the heterogeneous oxidation catalyst comprises a catalyst support selected from the group consisting of carbon, alumina, silica, titania, zirconia, and zeolite.

### Claim 10 (depends on 9)

The process as set forth in claim 9 wherein the catalyst support comprises carbon.

### Claim 11 (depends on 10)

The process as set forth in claim 10 wherein the catalyst support comprises carbon black.

### Claim 12 (depends on 1)

The process as set forth in claim 1 wherein the reaction mixture is maintained at a temperature of at least about 60° C.

### Claim 13 (depends on 1)

The process as set forth in claim 1 wherein the reaction mixture is maintained at a temperature from about 60° C. to about 150° C.

### Claim 14 (depends on 1)

The process as set forth in claim 1 wherein the reaction is conducted under a partial pressure of oxygen that is at least about 60 psia (414 kPa).

### Claim 15 (depends on 1)

The process as set forth in claim 1 wherein the reaction is conducted under a partial pressure of oxygen in the range of from about 15 psia (104 kPa) to about 2000 psia (13790 kPa).

### Claim 16 (depends on 1)

The process as set forth in claim 1 wherein the glucose is obtained from a carbohydrate source.

### Claim 17 (depends on 1)

The process as set forth in claim 1 wherein the oxygen is supplied to the reaction as air, oxygen-enriched air, oxygen alone, or oxygen with one or more other constituents substantially inert to the reaction.

### Claim 18 (depends on 1)

The process as set forth in claim 1 wherein the reaction mixture is essentially free of nitrogen as an active reaction constituent.

### Claim 19 (depends on 1)

The process as set forth in claim 1 wherein the metal selected from the group consisting of Pd, Pt, and a combination thereof constitutes from about 1% to about 8% of the total weight of the heterogeneous oxidation catalyst.

### Claim 20 (depends on 1)

A process for preparing adipic acid, the process comprising:
preparing glucaric acid or lactone thereof according to the process as set forth in claim 1; and
reacting, in the presence of a hydrodeoxygenation catalyst, a halogen source and hydrogen, at least a portion of the glucaric acid or lactone thereof, to convert at least a portion of the glucaric acid or lactone thereof to adipic acid.

### Claim 21 (depends on 7)

The process as set forth in claim 7 wherein the heterogeneous oxidation catalyst comprises a catalyst support selected from the group consisting of carbon, alumina, silica, titania, zirconia, and zeolite.

### Claim 22 (depends on 21)

The process as set forth in claim 21 wherein the catalyst support comprises carbon.

### Claim 23 (depends on 22)

The process as set forth in claim 22 wherein the catalyst support comprises carbon black.

### Claim 24 (depends on 1)

The process as set forth in claim 1 wherein the heterogeneous oxidation catalyst further comprises a second metal besides Pd and/or Pt.

### Claim 25 (depends on 24)

The process as set forth in claim 24 wherein the molar ratio of the Pd and/or Pt to the second metal is from about 10:1 to about 1:1.

### Claim 26 (depends on 7)

The process as set forth in claim 7 wherein at least about a portion of the glucose is converted to glucaric acid, the reaction mixture is maintained at a temperature from about 80° C. to about 120° C., and the reaction is conducted under a partial pressure of oxygen in the range of from about 15 psia (104 kPa) to about 2000 psia (13790 kPa).

### Claim 27 (depends on 26)

The process as set forth in claim 26 wherein the heterogeneous oxidation catalyst comprises a catalyst support selected from the group consisting of carbon, alumina, silica, titania, zirconia, and zeolite.

### Claim 28 (depends on 27)

The process as set forth in claim 27 wherein the catalyst support comprises carbon.

### Claim 29 (depends on 28)

The process as set forth in claim 28 wherein the catalyst support comprises carbon black.

### Claim 30 (depends on 27)

The process as set forth in claim 27 wherein the heterogeneous oxidation catalyst further comprises a second metal besides Pd and/or Pt and the molar ratio of Pt to the second metal is from about 10:1 to about 1:1.

### Claim 31 (depends on 7)

The process as set forth in claim 7 wherein at least about 60% of the glucose is converted to glucaric acid or lactone thereof.

### Claim 32 (depends on 7)

The process as set forth in claim 7 wherein at least about 50% of the glucose is converted to glucaric acid.

### Claim 33 (depends on 8)

The process as set forth in claim 8 wherein at least about 60% of the glucose is converted to glucaric acid or lactone thereof.

### Claim 34 (depends on 8)

The process as set forth in claim 8 wherein at least about 50% of the glucose is converted to glucaric acid.

### Claim 35 (depends on 1)

The process as set forth in claim 1 wherein the heterogeneous oxidation catalyst comprises Pd.

### Claim 36 (depends on 35)

The process as set forth in claim 35 wherein at least about 60% of the glucose is converted to glucaric acid or lactone thereof.

### Claim 37 (depends on 35)

The process as set forth in claim 35 wherein at least about 50% of the glucose is converted to glucaric acid.

### Claim 38 (depends on 7)

The process as set forth in claim 7 wherein the pH of the reaction mixture is less than 6.

### Claim 39 (depends on 8)

The process as set forth in claim 8 wherein the pH of the reaction mixture is less than 6.