Process for oxidative esterification of aldehydes to carboxylic acid esters

Patent metadata

Field	Value
Publication number	US-11124471-B2
Application number	US-201816611546-A
Country	US
Kind code	B2
Filing date	Apr 23, 2018
Priority date	May 9, 2017
Publication date	Sep 21, 2021
Grant date	Sep 21, 2021

Abstract

The present invention relates to a novel process for performing a heterogeneously catalyzed reaction for oxidative esterification of aldehydes to give carboxylic esters. Against this background, it has been possible by the present process according to the invention to perform such processes for longer periods without disruption, with constant or even increased activities and selectivities. This gives rise to the possibility of performing such processes in a very simple, economically viable and environmentally benign manner.

First claim

The invention claimed is:

1. A process, comprising: continuously performing a reaction for oxidative esterification of methacrolein with an alkyl alcohol and oxygen to produce an alkyl methacrylate in the presence of a gold catalyst in a reactor system comprising a reactor, the reactor comprising a gas feed and offgas outlet, wherein
a molar ratio of the alkyl alcohol at a steady-state concentration to the methacrolein at a steady-state concentration in the reactor is less than 10:1,
an oxygen concentration in a gas phase at the offgas outlet in the reactor is less than 4.5% by volume,
a steady-state molar ratio of the alkyl alcohol to the methacrolein in the reactor to a steady-state molar ratio of the alkyl alcohol to the methacrolein in the gas feed is between 1.5 and 15, and
a steady-state concentration of the methacrolein in the reactor is less than 21% by weight.

2. The process according to claim 1 , wherein
the molar ratio of the alkyl alcohol at a steady-state concentration to the methacrolein at a steady-state concentration in the reactor is between 4:1 and less than 10:1,
the steady-state molar ratio of the alkyl alcohol to the methacrolein in the reactor to the steady-state molar ratio of the alkyl alcohol to the methacrolein in the gas feed is between 1.8 and 15, and
the steady-state concentration of the methacrolein in the reactor is less than 15% by weight.

3. The process according to claim 1 , wherein
the molar ratio of the alkyl alcohol at a steady-state concentration to the methacrolein at a steady-state concentration in the reactor is between 5:1 and less than 9.5:1,
the steady-state molar ratio of the alkyl alcohol to the methacrolein in the reactor to the steady-state molar ratio of the alkyl alcohol to the methacrolein in the gas feed is between 2 and 13, and
the steady-state concentration of the methacrolein in the reactor is less than 12% by weight.

4. The process according to claim 1 , wherein the catalyst is in the form of catalyst particles comprising oxygen, silicon, aluminium, at least basic element, gold and optionally one of nickel, cobalt, iron and zinc,
wherein the at least one basic element is an alkali metal, an alkaline earth metal, a rare earth metal or mixtures of these metals.

5. The process according to claim 1 , wherein a reaction temperature is between 60 and 100° C. and an internal reactor pressure is between 1 and 20 bar.

6. The process according to claim 5 , wherein the reaction temperature is between 70 and 95° C. and the internal reactor pressure is between 2 and 10 bar.

7. The process according to claim 1 , wherein a partial oxygen pressure at the offgas outlet in the reactor is between 0.01 and 0.8 bar, and a partial oxygen pressure in a gas mixture fed to the reactor is less than 10 bar.

8. The process according to claim 1 , wherein the steady-state concentration of the methacrolein in the reactor is 3% or more and less than 21% by weight.

9. The process according to claim 8 , wherein the steady-state concentration of the methacrolein in the reactor is between 5% and 20% by weight.

10. The process according to claim 1 , wherein the alkyl alcohol is methanol and the alkyl methacrylate is methyl methacrylate.

11. The process according to claim 1 , wherein a ratio of a mass of the catalyst to a liquid reaction mixing volume in the reactor is between 0.01 and 0.3 kg/l.

12. The process according to claim 1 , wherein the reactor is a slurry reactor.

13. The process according to claim 1 , wherein a reaction mixture is discharged continuously from the reactor and the catalyst, after being separated off, remains in the reactor.

14. The process according to claim 1 , wherein a reaction mixture, after being withdrawn continuously from the reactor, is worked up in at least one distillation column, and the alkyl alcohol and methacrolein are separated off as distillate and returned to the reactor.

15. The process according to claim 1 , wherein the oxygen concentration in the gas phase at the offgas outlet in the reactor is less than 3.0% by volume.

16. The process according to claim 3 , wherein the steady-state molar ratio of the alkyl alcohol to the methacrolein in the reactor to the steady-state molar ratio of the alkyl alcohol to the methacrolein in the gas feed is between 1.5 and 3.5.

Assignees

• Roehm Gmbh

Inventors

• Lygin Alexander
• Krill Steffen
• Ait Aissa Belaid
• Zschunke Florian

Classifications

• B01J2219/00033

  Continuous processes · CPC title

• C07C67/39 Primary

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

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C07C67/54

  by distillation · CPC title

• B01J23/52

  Gold · CPC title