Acid catalyzed synthesis of methyl acrylate from acrylic acid and methanol

Patent metadata

Field	Value
Publication number	US-12065403-B2
Application number	US-202017601094-A
Country	US
Kind code	B2
Filing date	Apr 2, 2020
Priority date	Apr 16, 2019
Publication date	Aug 20, 2024
Grant date	Aug 20, 2024

Abstract

A method for preparing methyl acrylate comprises heating in a reaction zone a mixture comprising acrylic acid, methanol, and an acid catalyst to react and form a reaction product comprising methyl acrylate which is vaporized with other light components and then fed to a distillation zone. A feed stream entering the reaction zone comprises methanol and acrylic acid in a molar ratio of greater than 1 and less than 2, and a residence time in the reaction zone ranges from 0.25 to 2 hours. A distillate from the distillation zone is condensed and phase-separated to form an organic phase comprising methyl acrylate and an aqueous phase. A portion of the organic phase is returned to the distillation zone as organic reflux. The remainder of the organic phase and the aqueous phase of the distillation zone is fed to an extraction column to form a methanol rich aqueous effluent and an organic effluent comprising methyl acrylate. The organic effluent from the extraction column is purified in a single finishing column, wherein a light ends stream is removed from the top of the finishing column, a bottoms stream is removed from the bottom of the finishing column, and methyl acrylate is removed from a side draw stream.

First claim

We claim:

1. A method for preparing methyl acrylate, comprising:
a) heating in a reaction zone a mixture comprising acrylic acid, methanol, and an acid catalyst to react and form a product comprising methyl acrylate, which is vaporized with other light components and then fed to a distillation zone, wherein a feed stream entering the reaction zone comprises methanol and acrylic acid in a molar ratio of greater than 1 and less than 2, and a residence time in the reaction zone ranges from 0.25 to 2 hours;
b) condensing and phase-separating a distillate from the distillation zone to form an organic phase comprising methyl acrylate and an aqueous phase;
c) returning a portion of the organic phase to the distillation zone as organic reflux;
d) feeding the remainder of the organic phase and the aqueous phase of the distillation zone to an extraction column to form a methanol rich aqueous effluent and an organic effluent comprising methyl acrylate; and
e) purifying the organic effluent from the extraction column in a single finishing column, wherein a light ends stream is removed from the top of the finishing column, a bottoms stream is removed from the bottom of the finishing column, and methyl acrylate is removed from a side draw stream.

2. The method according to claim 1 , wherein the acid catalyst is sulfuric acid or a sulfonic acid.

3. The method according to claim 1 , wherein acrylic acid entering the reaction zone as fresh feed comprises less than 2 wt. % impurities.

4. The method according to claim 1 , further comprising feeding the methanol rich aqueous effluent from the extraction column to an alcohol recovery column to form a distillate comprising methanol and a bottoms stream substantially free of organics more volatile than water.

5. The method according to claim 4 , wherein at least a portion of the distillate of the alcohol recovery column is recycled to a reactive zone.

6. The method according to claim 4 , wherein a portion of the bottoms stream of the alcohol recovery column is recycled to the extraction column.

7. The method according to claim 1 , wherein the finishing column is a distillation column with a side draw.

8. The method according to claim 1 , wherein the distillation column further comprises a dividing wall, wherein the organic effluent enters the dividing wall distillation column in a divided section on an opposing side of the dividing wall from the side draw.

9. The method according to claim 1 , wherein the bottoms stream from the finishing column is recycled to the reaction zone.

10. The method according to claim 1 , wherein a portion of the light ends stream from the finishing column is recycled to the extraction column.

11. The method according to claim 1 , wherein the reaction zone is operated at a temperature ranging from 60 to 150° C. and the acid catalyst comprises sulfuric acid in an amount ranging from 2 to 8 wt. % relative to the total weight of a bottoms stream exiting the reaction zone.

Assignees

• Rohm & Haas

Inventors

• Chakrabarti Reetam
• Ngo Minh N
• Elder James

Classifications

• C07C67/58

  by liquid-liquid treatment · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C07C67/54

  by distillation · CPC title

• B01D5/006

  with evaporation or distillation · CPC title

• B01D3/40

  Extractive distillation · CPC title