Process for producing organic carbonates

• US 20070093672A1
• Filed: 10/21/2005
• Published: 04/26/2007
• Est. Priority Date: 10/21/2005
• Status: Active Grant

• Current Assignee: Catalytic Distillation Technologies (Lummus Technology LLC)
• Original Assignee: Catalytic Distillation Technologies (Lummus Technology LLC)
• Inventors: Ryu, J.
• Granted Patent: US 7,378,540 B2
• Time in Patent Office: Days
• US Class Current: 558/270
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 23/20 Vanadium, niobium or tantalum
• CPC Class Codes: B01J 23/92 of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 37/0209 involving a reaction between the support and a fluid
• CPC Class Codes: B01J 38/52 oxygen-containing
• CPC Class Codes: C07C 68/06 from organic carbonates
• CPC Class Codes: C07C 69/96 Esters of carbonic or haloformic acids
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

A process for producing various organic carbonates by performing transesterification and disproportionation reactions in dual vapor/liquid phase mode preferably in the presence of solid catalyst composition selected from the group consisting of oxides, hydroxides, oxyhydroxides or alkoxides of two to four elements from Group IV, V and VI of the Periodic Table supported on porous material which has surface hydroxyl groups and the method of reactivating catalyst deactivated by polymer deposition by contacting the deactivated catalyst with a solution of hydroxy containing compound in a solvent such as benzene or THF.

Claims

1. A process of the production of diaryl carbonate comprising:

(a) a plurality of reaction zones comprising a primary and a secondary reaction zone;

(b) supplying to said primary reaction zone a dialkyl carbonate and an aromatic hydroxy compound;

(c) maintaining the primary reaction zone under dual phase and reaction conditions conducive for the formation of alkyl aryl carbonate;

(d) transesterifing the dialkyl carbonate with the aromatic hydroxy compound in the presence of a solid catalyst selected from the group consisting of two to four elements from Group IV, V and VI of the Periodic Table supported on porous material which have surface hydroxyl groups;

(e) recovering a dual phase product stream from the primary reaction zone;

(f) separating the dual phase product stream from (e) to recover vaporous alkyl alcohol and liquid alkyl aryl carbonate;

(g) maintaining the secondary reaction zone under dual phase and reaction conditions conducive for the disproportionation of alkyl aryl carbonate to dialkyl carbonate;

(h) disproportionating the alkyl aryl carbonate in the presence of a solid catalyst selected from the group consisting of two to four elements from Group IV, V and VI of the Periodic Table on porous material which have surface hydroxyl groups;

(i) recovering a dual phase product stream from the secondary reaction zone; and

(j) separating the dual phase product stream from (i) to recover a vaporous component comprising aryl alkyl carbonate and liquid product comprising diaryl carbonate.

2. The process according to claim 1 wherein the dialkyl carbonate is DEC, the aromatic hydroxy compound is phenol, the alkyl aryl carbonate is EPC and dialkyl carbonate is DPC.

3. The process according to claim 2 wherein the alkyl carbonate is DEC, the alkyl aryl carbonate is EPC and the aromatic hydroxy compound is phenol.

4. The process according to claim 3 wherein in (h) the mole ratio of phenol to DPC is in the range of 0.05 to 10.

5. The process according to claim 1 wherein in the solid catalyst of (d) is oxides, hydroxides, oxyhydroxides, alkoxides or mixtures thereof of elements from Groups IV, V and VI.

6. The process according to claim 5 wherein in the support comprises treated silica.

7. The process according to claim 5 wherein in the solid catalyst of (h) is oxides, hydroxides, oxyhydroxides, alkoxides or mixtures thereof of elements from Groups IV, V and VI.

8. The process according to claim 6 wherein in the solid catalyst of (d)is selected from the group consisting of a metal alkoxide and mixed metal alkoxides of Group IV and V.

9. The process according to claim 5 wherein in the solid catalyst of (d) is TiO₂/Nb₂O₅ supported on treated silica, said treated silica having less than 0.05 wt. % Na.

10. The process according to claim 1 wherein in the solid catalyst of (h) is oxides, hydroxides, oxyhydroxides, alkoxides or mixtures thereof of elements from Groups IV, V and VI.

11. The process according to claim 10 wherein in the support comprises treated silica.

12. The process according to claim 11 wherein in the solid catalyst of (h) is oxides, hydroxides, oxyhydroxides, alkoxides or mixtures thereof of elements from Groups IV, V and VI.

13. The process according to claim 12 wherein in the solid catalyst of (h) is selected from the group consisting of a metal alkoxide and mixed metal alkoxides of Group IV and V.

14. The process according to claim 10 wherein in the solid catalyst of (h) is TiO₂/Nb₂O₅ supported on treated silica, said treated silica having less than 0.05 wt. % Na.

15. The process according to claim 1 wherein (h) is carried out in the presence of an aromatic hydroxy compound in a mole ratio of aromatic hydroxy compound to DPC in the range of 0.05:

1 to 10;

1.

16. The process according to claim 15 wherein (h) is carried out in the presence of a trace amount of water in an amount of up to 0.3 wt %.

17. The process according to claim 1 wherein (d) is carried out in the presence of an aromatic hydroxy compound in a mole ratio of aromatic hydroxy compound to DEC is above 0.2.

20. The method according to claim 1 wherein said support have had the surface hydroxyl groups increased by treatment with a base solution to obtain the maximum number of hydroxyl groups without degrading the physical integrity and strength of the support.

18. The method of reactivating a solid catalyst composition selected from the group consisting of oxides, hydroxides, oxyhydroxides or alkoxides of two to four elements from Group IV, V and VI of the Periodic Table supported on porous material which have surface hydroxyl groups, which has been deactivated by polymer deposited thereon comprising contacting the deactivated catalyst with a fluid comprising a hydroxy containing compound in a solvent selected from the group consisting of benzene, toluene, xylenes, pentane, hexane, octane, decane, THF and mixtures thereof at a temperature in the range of 250°

to 600°

F.

19. The method according to claim 18 wherein the hydroxy containing compound is selected from the group selected from water, alcohol, phenol and mixtures thereof.

21. A solid catalyst composition selected from the group consisting of oxides, hydroxides, oxyhydroxides and alkoxides of two to four elements from Group IV, V and VI of the Periodic Table supported on porous material which have surface hydroxyl groups.

22. The solid catalyst composition according to claim 21 wherein said support has been subjected to a treatment to increase the number of hydroxyl groups thereon.

23. The solid catalyst composition according to claim 22 wherein said treatment comprises contacting said support with a basic solution.

24. The solid catalyst composition according to claim 23 wherein said support comprises silica.