Method for the dehydration of 3-hydroxypropanoic acid to form acrylic acid

Patent metadata

Field	Value
Publication number	US-9630900-B2
Application number	US-201414917983-A
Country	US
Kind code	B2
Filing date	Sep 2, 2014
Priority date	Sep 12, 2013
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

The invention relates to a process for dehydrating aqueous 3-hydroxypropionic acid to acrylic acid in the liquid phase, wherein aqueous acrylic acid is removed continuously from the liquid phase and the liquid phase comprises an inert organic solvent 1.

First claim

The invention claimed is:

1. A process for continuously dehydrating aqueous 3-hydroxypropionic acid to aqueous acrylic acid in a liquid phase, the liquid phase having a temperature of 120 to 250° C., comprising continuously supplying aqueous 3-hydroxypropionic acid to the liquid phase and continuously withdrawing the aqueous acrylic acid from the liquid phase, wherein the liquid phase comprises 5 to 95% by weight of an inert organic solvent 1 having a boiling point at 1013 mbar in the range from 200 to 350° C.

2. The process according to claim 1 , wherein the liquid phase has a temperature of 130 to 220° C.

3. The process according to claim 1 , wherein the liquid phase comprises 30 to 60% by weight of the inert organic solvent 1.

4. The process according to claim 1 , wherein the inert organic solvent 1 at a pressure of 1013 mbar has a boiling point of 280 to 300° C.

5. The process according to claim 1 , wherein the inert organic solvent 1 is selected from the group consisting of dimethyl phthalate, diethyl phthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate, diethyl terephthalate, nonanoic acid, decanoic acid, biphenyl, diphenyl ether, and mixtures thereof.

6. The process according to claim 1 , wherein the dehydration is base- or acid-catalyzed.

7. The process according to claim 1 , wherein the aqueous acrylic acid is removed by distillation from the liquid phase.

8. The process according to claim 7 , wherein distillation is effected with a rectification column.

9. The process according to claim 1 , wherein a space-time yield is from 10 to 150 kg/h of acrylic acid per m 3 of liquid phase.

10. The process according to claim 1 , wherein a ratio of oligomeric 3-hydroxypropionic acid to monomeric 3-hydroxypropionic acid in the aqueous 3-hydroxypropionic acid is at least 1:20 and/or the ratio of oligomeric 3-hydroxypropionic acid to monomeric 3-hydroxypropionic acid in the liquid phase is at least 1:1.

11. The process according to claim 1 , wherein a residence time in the liquid phase is at least 10 minutes.

12. The process according to claim 1 , wherein a polymerization inhibitor 1 is added to the liquid phase.

13. The process according to claim 12 , wherein the polymerization inhibitor 1 is selected from phenothiazine, hydroquinone, hydroquinone monomethyl ether, or a mixtures thereof.

14. The process according to claim 1 , wherein a polymerization inhibitor 2 is added to the aqueous acrylic acid.

15. The process according to claim 14 , wherein the polymerization inhibitor 2 is phenothiazine, hydroquinone, hydroquinone monomethyl ether, or a mixture thereof.

16. Aqueous acrylic acid comprising water and
20 to 80% by weight of acrylic acid,
0.001 to 1% by weight of formic acid,
0.001 to 1% by weight of acetic acid,
0.001 to 1% by weight of glycolic acid,
0.0001 to 0.05% by weight of formaldehyde,
0.0001 to 0.05% by weight of acetaldehyde,
0.0001 to 0.05% by weight of methanol,
0.0001 to 0.05% by weight of ethanol and
0.0001 to 0.1% by weight of an inert organic solvent 1 having a boiling point at 1013 mbar in the range of 200 to 350° C.

17. Aqueous acrylic acid according to claim 16 , wherein the inert organic solvent 1 is selected from the group consisting of dimethyl phthalate, diethyl phthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate, diethyl terephthalate, nonanoic acid, decanoic acid, biphenyl, diphenyl ether, and mixtures thereof.

Assignees

• Basf Se

Inventors

• Blaschke Tim
• Lang Ortmund
• Wörz Nicolai Tonio
• Raith Christian
• Hartmann Marco
• Zajaczkowski-Fischer Marta

Classifications

• C07C57/04

  Acrylic acid; Methacrylic acid · CPC title

• C07C51/50

  Use of additives, e.g. for stabilisation · CPC title

• C07C51/377 Primary

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• C07C51/44

  by distillation · CPC title