HIERARCHICAL ALUMINOPHOSPHATES AS CATALYSTS FOR THE BECKMANN REARRANGEMENT

• US 20160167030A1
• Filed: 11/30/2015
• Published: 06/16/2016
• Est. Priority Date: 12/16/2014
• Status: Abandoned Application

• Current Assignee: AdvanSix Resins & Chemicals, LLC (Advansix Inc.), University of Southampton
• Original Assignee: University of Southampton
• Inventors: Newland, Stephanie H., Levy, Alan B., Raja, Robert, Keenan, Scott R., Bare, Simon R.
• Application Number:
  US14/953,800
• Publication Number:
  US 20160167030A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 2229/183 in framework positions
• CPC Class Codes: B01J 29/041 Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
• CPC Class Codes: B01J 29/83 Aluminophosphates [APO compounds]
• CPC Class Codes: B01J 29/84 Aluminophosphates containing other elements, e.g. metals, boron
• CPC Class Codes: B01J 29/85 Silicoaluminophosphates [SAPO compounds]
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: B01J 35/643 less than 2 nm
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/69 bimodal
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: C01B 37/08 Silicoaluminophosphates [SAPO compounds] , e.g. CoSAPO
• CPC Class Codes: C01B 39/54 Phosphates, e.g. APO or SAPO compounds
• CPC Class Codes: C07D 223/10 attached in position 2
• CPC Class Codes: C07D 225/02 not condensed with other rings
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

Methods for producing lactams from oximes by performing a Beckmann rearrangement using a hierarchical porous aluminophosphate catalyst having interconnected microporous and mesoporous networks are provided. Exemplary catalysts include a plurality of weak Brønsted acid active sites, including silicon-containing aluminophosphates having the IZA framework code AFI, such as SAPO-5, CHA, such as SAPO-34, and FAU, such as SAPO-37.

Claims

1. A method of performing a Beckmann rearrangement reaction comprising the step of:

reacting an oxime in the presence of a catalyst to produce a lactam, said catalyst comprising a hierarchical porous aluminophosphate comprising a microporous framework and a mesoporous framework.

2. The method of claim 1, wherein the mesoporous framework has a pore diameter from 15 Å

to 50 Å

.

3. The method of claim 2, wherein the microporous framework has a pore diameter from 3 Å

to 10 Å

.

4. The method of claim 1, wherein the catalyst is a hierarchical porous aluminophosphate catalyst isomorphously substituted with one or two metals selected from the group consisting of:

manganese, iron, copper, magnesium, chromium, cobalt, copper, zinc, silicon, titanium, vanadium, and tin.

5. The method of claim 1, wherein the catalyst is a hierarchical porous aluminophosphate catalyst isomorphously substituted with one or two metals selected from the group consisting of:

cobalt, silicon, and titanium.

6. The method of claim 1, wherein the catalyst is a hierarchical porous silicoaluminophosphate catalyst selected from the group consisting of:

HP SAPO-5, HP SAPO-11, HP SAPO-18, HP SAPO-31, HP SAPO-34, HP SAPO-37, HP SAPO-41, and HP SAPO-44.

7. The method of claim 6, wherein the catalyst is selected from HP SAPO-5, HP SAPO-34, and HP SAPO-37.

8. The method of claim 1, wherein the catalyst is a hierarchical catalyst comprising a microporous structure having an IZA framework code selected from the group consisting of:

AFI, CHA, and FAU.

9. The method of claim 1, wherein the catalyst is a hierarchical porous aluminophosphate catalyst isomorphously substituted with one or two metals selected from the group consisting of:

cobalt and titanium.

10. The method of claim 9, wherein the catalyst is selected from the group consisting of HP Co AlPO-5, HP Ti AlPO-5, and HP Co Ti AlPO-5.

11. The method of claim 1, wherein the oxime is selected from cyclohexanone oxime, cyclooctanone oxime, and cyclododecanone oxime.

12. The method of claim 1, wherein said reacting is performed in the gas phase.

13. The method of claim 1, wherein said reacting is performed in the liquid phase.

14. A hierarchical porous catalyst comprising:

an aluminophosphate framework with an IZA framework code selected from the group consisting of AFI, CHA, and FAU;

a plurality of interconnected micropores, each micropore having a pore diameter from 3 to 10 Å

; and

a plurality of mesopores interconnected with the micropores, each mesopores having a pore diameter from 15 Å

to 50 Å

.

15. The hierarchical porous catalyst of claim 14, wherein the catalyst is a hierarchical porous aluminophosphate catalyst isomorphously substituted with one or two metals selected from the group consisting of:

cobalt, silicon, and titanium

16. The hierarchical porous catalyst of claim 14, wherein the catalyst is a hierarchical porous silicoaluminophosphate catalyst selected from the group consisting of:

HP SAPO-5, HP SAPO-34, and HP SAPO-37.

17. The hierarchical porous catalyst of claim 14, wherein the catalyst is a hierarchical porous aluminophosphate catalyst isomorphously substituted with one or two metals selected from the group consisting of:

cobalt and titanium.

18. The hierarchical porous catalyst of claim 17, wherein the catalyst is selected from the group consisting of HP Co AlPO-5, HP Ti AlPO-5, and HP Co Ti AlPO-5.

19. The hierarchical porous catalyst of claim 14, wherein the hierarchical porous catalyst is phase pure.

20. The hierarchical porous catalyst of claim 14, further comprising a plurality of weak Brø

nsted acid active sites.