Production of 1,6-hexanediol from adipic acid

Patent metadata

Field	Value
Publication number	US-10150719-B2
Application number	US-201414913730-A
Country	US
Kind code	B2
Filing date	Aug 22, 2014
Priority date	Aug 23, 2013
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

Processes are disclosed for the conversion of adipic acid to 1,6-hexanediol employing a chemocatalytic reaction in which an adipic acid substrate is reacted with hydrogen in the presence of particular heterogeneous catalysts including a first metal and a second metal on a support. The adipic acid substrate includes adipic acid, mono-esters of adipic acid, di-esters of adipic acid, and salts thereof. The first metal is selected form the group of Pt, Rh and mixtures thereof and the second metal is selected from the group of Mo, W, Re and mixtures thereof.

First claim

We claim:

1. A process for preparing 1,6-hexanediol, the process comprising:
reacting an adipic acid substrate and hydrogen in the presence of a heterogeneous catalyst comprising a first metal selected from the group consisting of Pt, Rh, and mixtures thereof and a second metal selected from the group consisting of Mo, W, and mixtures thereof to convert at least a portion of the adipic acid substrate to 1,6-hexanediol, wherein the adipic acid substrate is a compound of formula I:

wherein each R 1 and R 2 is independently hydroxyl or OR a
each R a is independently selected from the group consisting of alkyl and a salt-forming ion;
the reaction is carried out at a temperature in the range of from 40° C. to 200° C.; and
wherein the molar ratio of the first metal to the second metal (M1:M2) is in the range of from 10:1 to 2:1.

2. The process of claim 1 , wherein reacting the adipic acid substrate with hydrogen in the presence of the heterogeneous catalyst comprises any one of the following:
a) combining the adipic acid substrate, heterogeneous catalyst, and a solvent and contacting the combined adipic acid substrate, heterogeneous catalyst, and solvent with hydrogen; or
b) combining the adipic acid substrate and a solvent and contacting the combined adipic acid substrate and solvent with a heterogeneous catalyst and hydrogen; or
c) contacting the heterogeneous catalyst with hydrogen and adding the adipic acid substrate and a solvent to the heterogeneous catalyst contacted with hydrogen.

3. The process of claim 1 , wherein reacting the adipic acid substrate with hydrogen in the presence of the heterogeneous catalyst comprises any one of the following:
a) combining the adipic acid substrate, heterogeneous catalyst, and a solvent at a temperature in the range of from about 20° C. to about 200° C. and contacting with hydrogen the combined adipic acid substrate, heterogeneous catalyst, and solvent; or
b) contacting the heterogeneous catalyst with a solvent at a temperature in the range of from about 20° C. to about 200° C. and contacting the heterogeneous catalyst and solvent with the adipic acid substrate and hydrogen.

4. The process of claim 2 wherein the solvent is selected from the group of water, ethers, alcohols which do not react with the adipic acid substrate, and mixtures thereof.

5. The process of claim 1 , wherein reacting the adipic acid substrate with hydrogen in the presence of the heterogeneous catalyst and solvent comprises:
a) contacting the adipic acid substrate with water; and,
b) contacting the adipic acid substrate and water with a solvent, hydrogen, and catalyst.

6. The process of claim 1 , wherein, each R a is independently selected from the group consisting of C 1 -C 18 alkyl and salt-forming ion.

7. The process of claim 1 , wherein the salt-forming ion is selected from the group consisting of ammonium ions, alkali metal ions, and alkaline earth metal ions.

8. The process of claim 1 , wherein the reaction is carried out at a temperature in the range of from about 70° C. to about 180° C.

9. The process of claim 1 , wherein the reaction is carried out at a pressure in the range of from about 650 psig (4583 kPa) to about 1250 psig (8720 kPa) and a temperature in the range of from about 70° C. to about 180° C.

10. The process of claim 1 , wherein the reaction is carried out at a partial pressure of hydrogen in the range of from about 650 psi (4482 kPa) to about 1250 psi (8,618 kPa) and a temperature in the range of from about 70° C. to about 180° C.

11. The process of claim 1 , wherein the yield of 1,6-hexanediol is at least about 60%.

12. The process of claim 1 , wherein the mass ratio of adipic acid substrate to the first metal (M1) is at least about 1:1.

13. The process of claim 1 , wherein the mass ratio of adipic acid substrate to the first metal (M1) is in the range of from about 1:1 to about 1000:1.

14. The process of claim 1 , wherein the mass ratio of adipic acid substrate to the second metal (M2) is at least about 5:1.

15. The process of claim 1 , wherein mass ratio of adipic acid substrate to the second metal (M2) is in the range of from about 5:1 to about 2000:1.

16. The process of claim 1 , wherein the mass ratio of adipic acid substrate to the total mass of the first and second metals (M1+M2) is at least about 1:1.

17. The process of claim 1 , wherein the mass ratio of adipic acid substrate to the total mass of the first and second metals (M1+M2) is in the range from about 1:1 to about 1500:1.

18. The process of claim 1 , wherein the adipic acid substrate and hydrogen are reacted in the presence of a heterogeneous catalyst in a fixed bed reactor.

19. The process of claim 1 , wherein the first metal comprises Rh and the second metal comprises Mo.

20. The process of claim 1 , wherein the first metal comprises Rh and the second metal comprises W.

21. A process for preparing 1,6-hexanediol, the process comprising:
reacting an adipic acid substrate and hydrogen in the presence of a heterogeneous catalyst comprising a first metal comprising Pt and a second metal comprising Mo to convert at least a portion of the adipic acid substrate to 1,6-hexanediol, wherein the adipic acid substrate is a compound of formula I:

wherein each R 1 and R 2 is independently hydroxyl or OR a
each R a is independently selected from the group consisting of alkyl and a salt-forming ion;
the reaction is carried out at a temperature in the range of from 40° C. to 200° C.; and
wherein the molar ratio of the first metal to the second metal (M1:M2) is in the range of from about 10:1 to about 2:1.

22. A process for preparing 1,6-hexanediol, the process comprising:
reacting an adipic acid substrate and hydrogen in the presence of a heterogeneous catalyst comprising a first metal comprising Pt and a second metal comprising W to convert at least a portion of the adipic acid substrate to 1,6-hexanediol, wherein the adipic acid substrate is a compound of formula I:

wherein each R 1 and R 2 is independently hydroxyl or OR a
each R a is independently selected from the group consisting of alkyl and a salt-forming ion;
the reaction is carried out at a temperature in the range of from 40° C. to 200° C.; and
wherein the molar ratio of the first metal to the second metal (M1:M2) is in the range of from about 10:1 to about 2:1.

Assignees

• Archer Daniels Midland Co

Inventors

• Murphy Vincent J
• Dias Eric L
• Shoemaker James A W

Classifications

• B01J23/6567

  Rhenium · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J23/6525

  Molybdenum · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title

• B01J23/6527

  Tungsten · CPC title