Process for producing hydroquinone and derivates

Patent metadata

Field	Value
Publication number	US-9630899-B1
Application number	US-201514922358-A
Country	US
Kind code	B1
Filing date	Oct 26, 2015
Priority date	Oct 26, 2015
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

The present disclosure relates to an improved, environmentally friendly, process for producing compounds such as hydroquinone (benzene-1,4-diol) and its derivatives. The process can be carried out at ambient temperature and pressure using a recyclable copper catalyst and recyclable intermediate materials. The process generally entails reacting an aromatic compound such as benzene with hydrogen peroxide in the present of a pure elemental copper catalyst or a copper (I) salt catalyst to form oxidation product such as benzoquinone, and reducing the compound to hydroquinone or a hydroquinone derivative.

First claim

The invention claimed is:

1. A process for producing hydroquinone comprising reacting benzene with hydrogen peroxide in the presence of elemental copper catalyst or a copper(I) salt catalyst to form oxidation product comprising benzoquinone and phenol, and converting the oxidation product to hydroquinone by reduction, provided that the selectivity for hydroquinone from benzene is greater than 60%.

2. The process according to claim 1 , wherein the catalyst is a copper(I) salt catalyst and the copper (I) salt catalyst is a tetrakis(acetonitrile)copper(I) salt having the following formula:
Cu(CH 3 CN) 4 -A,
wherein A is an anion.

3. The process of claim 2 , wherein the anion is selected from the group consisting of ClO 4 − , NO 3 − , BF 4 − , PF 6 − , and CF 3 SO 3 − .

4. The process of claim 1 carried out at a temperature of from 10° C. to 80° C.

5. The process of claim 1 , wherein the reaction of benzene with hydrogen peroxide is carried out in a solvent.

6. The process of claim 5 , wherein the solvent is selected from the group consisting of nitrile, a C 3 -C 7 ketone, a C 5 -C 10 ether, a C 2 -C 7 ester, and a C 5 -C 10 hydrocarbon.

7. The process of claim 6 , wherein the nitrile is selected from the group consisting of acetonitrile, propionitrile, butanenitrile, and benzonitrile.

8. A process for producing hydroquinone comprising:
(a) reacting benzene with hydrogen peroxide in the presence of elemental copper catalyst or a copper(I) salt catalyst dissolved in acetonitrile at a temperature of between 10° C. to 80° C.;
(b) separating a water phase from an oil phase generated in (a);
(c) adding additional benzene and acetonitrile to the water phase and using azeotropic distillation at a temperature of between 65° C. to 90° C. to remove the water and acetonitrile;
(d) regenerating the used catalyst in (a);
(e) separating the mixture of benzoquinone and phenol from the unreacted benzene and acetonitrile;
(f) recycling the unreacted benzene and acetonitrile of (e) and using it as the additional benzene and acetonitrile added to the water phase in (c); and
(g) converting the mixture of benzoquinone and phenol to hydroquinone by reduction.

9. The process of claim 8 , wherein a selectivity ratio for hydroquinone is greater than about 2.

10. The process according to claim 1 , wherein the catalyst is an elemental copper catalyst.

11. The process according to claim 5 , wherein the solvent comprises acetonitrile.

12. A process for producing hydroquinone comprising:
reacting benzene with hydrogen peroxide in solvent in the presence of elemental copper catalyst or a copper(I) salt catalyst to form oxidation product comprising benzoquinone and phenol;
removing water generated by the reaction of benzene with hydrogen peroxide; and
converting the oxidation product to hydroquinone by reduction, provided that the selectivity percent for hydroquinone from benzene is greater than 60%.

13. The process according to claim 12 , wherein the catalyst is a copper(I) salt catalyst.

14. The process according to claim 12 , wherein the copper (I) salt catalyst is a tetrakis(acetonitrile)copper(I) salt having the following formula:
Cu(CH 3 CN) 4 -A,
wherein A is an anion.

15. The process according to claim 12 , wherein the catalyst is an elemental copper catalyst.

16. The process according to claim 12 carried out at a temperature of from 10° C. to 80° C.

17. The process according to claim 12 , wherein the solvent is a nitrile.

18. The process according to claim 12 , wherein the nitrile is acetonitrile.

19. The process according to claim 12 , further comprising regenerating the catalyst.

20. The process according to claim 12 , further comprising recycling unreacted benzene and solvent.

Assignees

• Chang Chun Plastics Co Ltd

Inventors

• Huang Chien Fu
• Chou Yi Hung

Classifications

• C07C46/06 Primary

  of at least one hydroxy group on a six-membered aromatic ring · CPC title

• C07C45/28

  of CHx-moieties · CPC title

• C07C37/60 Primary

  by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen · CPC title

• C07C37/07

  with simultaneous reduction of C=O group in that ring · CPC title

• C07C46/04 Primary

  of unsubstituted ring carbon atoms in six-membered aromatic rings · CPC title