# US 8,772,476 B2 · Gas and liquid phase catalytic Beckmann rearrangement of oximes to produce lactams

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- Number: US 8,772,476 B2
- Document ID: US8772476B2
- Status: Granted
- Kind: B2
- Application number: 13/658,495
- Filed: 2012-10-23
- Published: 2013-05-02
- Granted: 2014-07-08
- Earliest claimed: 2011-10-28
- Assignees: Honeywell International Inc.
- Applicants: Honeywell International Inc.; University of Southampton
- Inventors: Alan B. Levy; Robert Raja; Matthew E. Potter
- Web page: https://patentgrep.com/patent/US8772476B2

## CPC

- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- C01B 37/08: Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO}
- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- C07D 201/04: from or via oximes by Beckmann rearrangement
- C07D 223/10: attached in position 2
- C07D 225/02: not condensed with other rings
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2235/05: Nuclear magnetic resonance [NMR]
- B01J 2235/10: Infrared [IR]
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

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.

## Claims

### Claim 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.

### Claim 2 (depends on 1)

The method of claim 1, wherein the catalyst is a SAPO-37 catalyst.

### Claim 3 (depends on 2)

The method of claim 2, wherein the catalyst is prepared from a composition having a gel loading ratio of moles of SiO2 to moles H3PO4 of from 0.1:1 to 0.8:1.

### Claim 4 (depends on 3)

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.

### Claim 5 (depends on 2)

The method of claim 2, wherein the catalyst comprises well-isolated, discrete Brønsted acid sites.

### Claim 6 (depends on 5)

The method of claim 5, wherein the catalyst comprises an aluminophosphate framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework.

### Claim 7 (depends on 1)

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 R1—CN;
an aromatic solvent of the formula R2—Ar; and
an alcohol of the formula R3—OH;
wherein:
R1 is C1-C8-alkyl, C1-C8-alkenyl, C1-C8-alkynyl, C3-C8-cycloalkyl; or C3-C8-aralkyl;
Ar is an aromatic ring and R2 is H, F, Cl, Br; and
R3 is H, C1-C8-alkyl, C1-C8-alkenyl, C1-C8-alkynyl, C3-C8-cycloalkyl; C3-C8-aralkyl.

### Claim 8 (depends on 1)

The method of claim 1, wherein said reacting step is performed at a temperature from 100° C. to 220° C.

### Claim 9 (depends on 1)

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%.

### Claim 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.

### Claim 11 (depends on 10)

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%.

### Claim 12 (depends on 10)

The method of claim 10, wherein said reacting step is performed in the absence of water.

### Claim 13 (depends on 10)

The method of claim 10, wherein the catalyst is a SAPO-37 catalyst.

### Claim 14 (depends on 13)

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 SiO2 to moles H3PO4 of from 0.1:1 to 0.8:1.

### Claim 15 (depends on 13)

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.

### Claim 16 (depends on 13)

The method of claim 13, wherein the catalyst comprises well isolated, discrete Brønsted acid sites.

### Claim 17 (depends on 16)

The method of claim 16, wherein the catalyst comprises an aluminophosphate framework, the acid sites comprising silicon isomorphously substituted for phosphorous in the framework.

### Claim 18 (depends on 10)

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 R1—CN;
an aromatic solvent of the formula R2—Ar; and
an alcohol of the formula R3—OH;
wherein
R1 is C1-C8-alkyl, C1-C8-alkenyl, C1-C8-alkynyl, C3-C8-cycloalkyl; or C3-C8 aralkyl;
Ar is an aromatic ring and R2 is H, F, Cl, Br; and
R3 is H, C1-C8-alkyl, C1-C8-alkenyl, C1-C8-alkynyl, C3-C8-cycloalkyl; C3-C8-aralkyl.

### Claim 19 (depends on 1)

The method of claim 1, wherein the oxime is cyclohexanone oxime and the lactam is ε-caprolactam.

### Claim 20 (depends on 1)

The method of claim 1, wherein the oxime is cyclododecanone oxime and the lactam is ω-laurolactam.

### Claim 21 (depends on 10)

The method of claim 10, wherein the oxime is cyclohexanone oxime and the lactam is ε-caprolactam.

### Claim 22 (depends on 10)

The method of claim 10, wherein the oxime is cyclododecanone oxime and the lactam is ω-laurolactam.