Process for eliminating interfering by-products in the direct oxidative esterification of methacrolein

Patent metadata

Field	Value
Publication number	US-12017987-B2
Application number	US-202218054109-A
Country	US
Kind code	B2
Filing date	Nov 9, 2022
Priority date	Nov 12, 2021
Publication date	Jun 25, 2024
Grant date	Jun 25, 2024

Abstract

A process can be used for preparing methyl methacrylate (MMA), by direct oxidative esterification of methacrolein. The MMA and polymers produced therefrom feature a very low yellowness index. A workup of the reactor output from the oxidative esterification of methacrolein allows for particularly discolouring by-products to be removed or degraded without significant MMA losses.

First claim

The invention claimed is:

1. A process for preparing alkyl methacrylates, comprising:
a) preparing methacrolein in a reactor I,
b) oxidatively esterifying the methacrolein in the presence of an alcohol, oxygen, and a heterogeneous noble metal-containing catalyst in at least one reactor II,
c) distilling a reactor output from the at least one reactor II in a distillation column I for separation of the methacrolein and portions of the methanol,
d) optionally, pretreating a bottom output from c), comprising
i) adding an acid to change a pH of the bottom output,
ii) adding water to obtain a biphasic mixture, and
iii) reactively treating at least a portion of the biphasic mixture from ii), and

e) extracting the bottom output from distillation column I from c) or an organic phase of the bottom output from distillation column I from d), in an extraction I,
wherein an amount of the methacrolein in the organic phase from extraction I is greater than that in the bottom output from distillation column I, and
wherein there is produced an alkyl methacrylate composition comprising methacrolein dimethyl acetal (DMIB), and which has a DMIB content of less than 90 ppm.

2. The process according to claim 1 , wherein e) is an extraction of the bottom output from distillation column I from the extraction I, wherein extraction I and optionally distillation column I are acid-resistant,
wherein an organic and/or a mineral acid is mixed with the reactor output from the at least one reactor II, and is passed into the distillation column I and/or the extraction I,
wherein the reactor output has an average residence time in distillation column I of between 1 and 30 min at a temperature of between 30 and 100° C., and
wherein in extraction I, the bottom output transferred from distillation column I with additionally transferred acid resides in the extraction I at a temperature of between 10 and 100° C. for 1 to 20 min.

3. The process according to claim 1 , wherein a reaction in the at least one reactor II is effected at a water content of between 0.1% and 10% by weight and a pH of between 5 and 8.

4. The process according to claim 1 , wherein a) in reactor I involves a reaction of propanal with formaldehyde in the presence of at least one acid and optionally an amine, and
wherein the alcohol in b) is methanol and the alkyl methacrylate is methyl methacrylate (MMA).

5. The process according to claim 1 , wherein in c), methacrolein dimethyl acetal is cleaved with water into methacrolein and methanol, which in distillation column I together with remaining reactants of b), are largely removed overhead or in a side stream of the distillation column I and are recycled into the at least one reactor II.

6. The process according to claim 1 , wherein in c), sulfuric acid is passed into the distillation column I and optionally, additionally in e) into the extraction I.

7. The process according to claim 1 , wherein additional water is introduced into the bottom output of distillation column I, and wherein the distillation is effected at a bottom temperature of between 50 and 100° C.

8. The process according to claim 1 , wherein the extraction I involves a mixer-settler, and wherein an extractant used is water, aqueous sulfuric acid, or a bottom stream from an additional distillation column IV.

9. The process according to claim 1 , wherein the acid is added to the bottom output departing from the bottom of distillation column I.

10. The process according to claim 1 , wherein e) is followed by isolation and purification stages, which comprise at least one optional phase separator, at least one high boiler column, and at least one low boiler column.

11. The process according to claim 10 , wherein d) is present and wherein in d) in the extraction I, the bottom output from distillation column I is separated into the organic phase containing MMA and a polar phase containing the acid and salts thereof, and
wherein the organic phase is subsequently passed into a distillation column II.

12. The process according to claim 11 , wherein the distillation column II is of acid-resistant design, and wherein a further acid is introduced into a bottom and/or a feed of distillation column 11 .

13. The process according to claim 11 , wherein the distillation column II is a distillation column for separating low-boiling constituents from the organic phase, into a bottom and/or a feed of which a further acid is introduced, and
wherein bottoms of distillation column II are passed into an acid-resistant distillation column III for separating high-boiling constituents from an MMA phase.

14. The process according to claim 1 , wherein the acid added has a pKa value which is 1 less than that of methacrylic acid.

15. The process according to claim 11 , wherein the distillation column II is a distillation column for separating high-boiling constituents from the organic phase.

16. The process according to claim 12 , wherein the further acid is sulfuric acid.

17. The process according to claim 13 , wherein the further acid is sulfuric acid.

18. The process according to claim 1 , wherein the composition comprises methyl isobutyrate, and has a methyl isobutyrate content of less than 240 ppm.

19. The process according to claim 1 , wherein d) is present.

Assignees

• Roehm Gmbh

Inventors

• Krill Steffen

Classifications

• C07C47/22

  Acryaldehyde; Methacryaldehyde · CPC title

• C07C45/515 Primary

  the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group (cyclic acetals or ketals C07C45/59, C07C45/60) · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C07C67/54

  by distillation · CPC title

• C07C67/39 Primary

  by oxidation of groups which are precursors for the acid moiety of the ester · CPC title