Gas and liquid phase catalytic Beckmann rearrangement of oximes to produce lactams
View Patent ↗Methods for producing lactams from oximes by performing a Beckmann rearrangement using a silicoaluminophosphate catalyst are provided. These catalysts may be used in gas phase or liquid phase reactions to convert oximes into lactams. High conversion of oxime and high selectivity for the desired lactams are produced using the disclosed methods, including high conversion and selectivity for ε-caprolactam produced from cyclohexanone oxime and high conversion and selectivity for ω-laurolactam produced from cyclododecanone oxime.
1. A method of performing a Beckmann rearrangement reaction comprising the step of:
reacting an oxime in a liquid phase in the presence of a catalyst to produce a lactam, said catalyst comprising a silicon-containing aluminophosphate with the IZA framework code FAU;
wherein the oxime is selected from cyclohexanone oxime and cyclododecanone oxime and the lactam is selected from ε-caprolactam and ω-laurolactam.
2. The method of claim 1 , wherein the catalyst is a SAPO-37 catalyst.
3. The method of claim 2 , wherein the catalyst is prepared from a composition having a gel loading ratio of moles of SiO 2 to moles H 3 PO 4 of from 0.1:1 to 0.8:1.
4. The method of claim 3 , wherein the catalyst has a silica weight percentage of from 1 wt. % to 12 wt. % of the total weight of the catalyst.
5. The method of claim 2 , wherein the catalyst comprises well-isolated, discrete Brønsted acid sites.
6. The method of claim 5 , wherein the catalyst comprises an aluminophosphate framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework.
7. The method of claim 1 , wherein said reacting step is performed in the presence of a solvent comprising at least one solvent selected from the group consisting of:
an organic nitrile of the formula R 1 —CN;
an aromatic solvent of the formula R 2 —Ar; and
an alcohol of the formula R 3 —OH;
wherein:
R 1 is C 1 -C 8 -alkyl, C 1 -C 8 -alkenyl, C 1 -C 8 -alkynyl, C 3 -C 8 -cycloalkyl; or C 3 -C 8 -aralkyl;
Ar is an aromatic ring and R 2 is H, F, Cl, Br; and
R 3 is H, C 1 -C 8 -alkyl, C 1 -C 8 -alkenyl, C 1 -C 8 -alkynyl, C 3 -C 8 -cycloalkyl; C 3 -C 8 -aralkyl.
8. The method of claim 1 , wherein said reacting step is performed at a temperature from 100° C. to 220° C.
9. The method of claim 1 wherein said reacting step further comprises a conversion of the oxime of from 90% to 100% and a selectivity of the lactam of from 70% to 100%.
10. A method of performing a Beckmann rearrangement reaction comprising the step of:
reacting an oxime in a gas phase in the presence of a catalyst to produce a lactam, said catalyst comprising a silicon-containing aluminophosphates with the IZA framework code FAU;
wherein said reacting step further comprises the combination of conversion of oxime and selectivity of the lactam is selected from the group consisting of:
the conversion of the oxime is at least 50% and the selectivity of the lactam is at least 90%; and
the conversion of the oxime is at least 90% and the selectivity of the lactam is at least 80%;
wherein the oxime is selected from cyclohexanone oxime and cyclododecanone oxime and the lactam is selected from ε-caprolactam and ω-laurolactam.
11. The method of claim 10 , wherein said reacting step further comprises a conversion of the oxime of from 90% to 100% and a selectivity of the lactam of from 90% to 100%.
12. The method of claim 10 , wherein said reacting step is performed in the absence of water.
13. The method of claim 10 , wherein the catalyst is a SAPO-37 catalyst.
14. The method of claim 13 , wherein said reacting step further comprises said SAPO-37 catalyst being prepared from a composition having a gel loading ratio of moles of SiO 2 to moles H 3 PO 4 of from 0.1:1 to 0.8:1.
15. The method of claim 13 , wherein said reacting step further comprises said SAPO-37 having a silica weight percentage of from 2 wt. % to 9.1 wt. % of the weight of total weight of the catalyst.
16. The method of claim 13 , wherein the catalyst comprises well isolated, discrete Brønsted acid sites.
17. The method of claim 16 , wherein the catalyst comprises an aluminophosphate framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework.
18. The method of claim 10 , wherein said reacting step is performed in the presence of a solvent comprising at least one solvent selected from the group consisting of:
an organic nitrile of the formula R 1 —CN;
an aromatic solvent of the formula R 2 —Ar; and
an alcohol of the formula R 3 —OH;
wherein
R 1 is C 1 -C 8 -alkyl, C 1 -C 8 -alkenyl, C 1 -C 8 -alkynyl, C 3 -C 8 -cycloalkyl; or C 3 -C 8 aralkyl;
Ar is an aromatic ring and R 2 is H, F, Cl, Br; and
R 3 is H, C 1 -C 8 -alkyl, C 1 -C 8 -alkenyl, C 1 -C 8 -alkynyl, C 3 -C 8 -cycloalkyl; C 3 -C 8 -aralkyl.
19. The method of claim 1 , wherein the oxime is cyclohexanone oxime and the lactam is ε-caprolactam.
20. The method of claim 1 , wherein the oxime is cyclododecanone oxime and the lactam is ω-laurolactam.
21. The method of claim 10 , wherein the oxime is cyclohexanone oxime and the lactam is ε-caprolactam.
22. The method of claim 10 , wherein the oxime is cyclododecanone oxime and the lactam is ω-laurolactam.