# US 2013/0158286 A1 · Process to produce alkenoic acid esters from lactones

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- Number: US 2013/0158286 A1
- Document ID: US20130158286A1
- Status: Published application
- Kind: A1
- Application number: 13/722,241
- Filed: 2012-12-20
- Published: 2013-06-20
- Earliest claimed: 2011-12-20
- Assignees: Dsm IP Assets B.V.
- Inventors: Anna Maria Cornelia Francisca CASTELIJNS
- Web page: https://patentgrep.com/patent/US20130158286A1

## CPC

- C07C 67/03: by reacting an ester group with a hydroxy group
- B01J 21/20: Regeneration or reactivation
- B01J 29/90: Regeneration or reactivation
- B01J 38/60: using acids
- B01J 38/62: organic
- C07C 51/09: from carboxylic acid esters or lactones
- C07C 67/36: by reaction with carbon monoxide or formates (C07C67/02, C07C67/03, C07C67/10 take precedence)
- C07C 67/38: by addition to an unsaturated carbon-to-carbon bond
- B01J 21/12: Silica and alumina
- B01J 29/7007: {Zeolite Beta}
- B01J 2229/37: Acid treatment
- Y02P 20/584: Recycling of catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

This invention relates to a process for the preparation of alkenoic acid esters comprising contacting a lactone with an alcohol and an acidic heterogeneous catalyst, characterised in that the process is carried out in the presence of at least 20 ppm of an acid having a pKa of 5 or less, relative to the amount of the lactone. The presence of at least 20 ppm of an acid having a pKa of 5 or less may stabilise the catalyst during the reaction and may also be used for reactivating an acidic heterogeneous catalyst. The improved yield advantageously allows energy conservation.

## Claims

### Claim 1

Process for the preparation of alkenoic acid ester comprising:
(a) contacting a lactone with an alcohol and an acidic heterogeneous catalyst, wherein the process is carried out in the presence of at least 20 ppm of an acid having a pKa of 5 or less, relative to the amount of the lactone.

### Claim 2 (depends on 1)

Process according to claim 1 wherein the acidic heterogeneous catalyst comprises a zeolite or an amorphous silica-alumina catalyst.

### Claim 3 (depends on 1)

Process according to claim 1 wherein the acidic heterogeneous catalyst comprises a beta zeolite.

### Claim 4 (depends on 1)

Process according to claim 1 wherein the acid is methanesulphonic acid or p-toluenesulphonic acid.

### Claim 5 (depends on 1)

Process according to claim 1 further comprising adding the acid.

### Claim 6 (depends on 1)

Process according to claim 1 wherein the process is carried out in the presence of from 0.26% to 10% wt water relative to the amount of the lactone.

### Claim 7 (depends on 1)

Process according to claim 1 wherein the alcohol is an alkanol, optionally methanol.

### Claim 8 (depends on 1)

Process according to claim 1 wherein the lactone comprises 5-methylbutyrolactone.

### Claim 9 (depends on 1)

Process according to claim 1 wherein the alcohol is methanol and wherein the lactone is 5-methylbutyrolactone, thereby forming pentenoic acid methyl ester.

### Claim 10 (depends on 1)

Process according to claim 1 which is a continuous process.

### Claim 11 (depends on 1)

Process according to claim 1 which is a repetitive batch process, wherein the process further comprises:
(b) recovering the acidic heterogeneous catalyst from the alkenoic acid esters in the presence of said acid having a pKa of 5 or less, wherein the amount of said acid having a pKa of 5 or less in the recovered acidic heterogeneous catalyst is at least 20 ppm relative to the amount of lactone; and
(c) repeating (a) wherein at least part of the acidic heterogeneous catalyst in (a) is the recovered acidic heterogeneous catalyst obtained in (b).

### Claim 12 (depends on 8)

Process according to claim 8 wherein the 5-methylbutyrolactone is produced by converting levulinic acid to 5-methylbutyrolactone in a hydrogenation reaction.

### Claim 13 (depends on 12)

Process according to claim 12 wherein the levulinic acid is prepared by converting a C6 carbohydrate to levulinic acid in an acid-catalysed reaction.

### Claim 14 (depends on 9)

Process to produce adipic acid dimethyl ester comprising converting pentenoic acid methyl ester produced in the process according to claim 9 to adipic acid dimethyl ester in a carbonylation reaction in the presence of CO and methanol.

### Claim 15 (depends on 14)

Process to produce adipic acid comprising converting adipic acid dimethyl ester produced in the process of claim 14 in a hydrolysis reaction.

### Claim 16

Process for reactivation of an at least partially inactivated acidic heterogeneous catalyst comprising:
recovering said at least partially inactivated acidic heterogeneous catalyst from a process for the preparation of alkenoic acid esters from a lactone in the presence of an alcohol; and
contacting said acidic heterogeneous catalyst with an acid having a pKa of 5 or less.