Process for preparing acrylic acid from ethylene oxide and carbon monoxide

• US 9,115,070 B2
• Filed: 07/16/2013
• Issued: 08/25/2015
• Est. Priority Date: 07/16/2012
• Status: Expired due to Fees

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Pazicky, Marek, Raith, Christian, Paciello, Rocco, Brand, Raphael Heinrich, Hartmann, Marco, Mueller-Engel, Klaus Joachim, Zurowski, Peter, Fischer, Wolfgang
• Primary Examiner(s): Valenrod, Yevegeny
• Assistant Examiner(s): Doletski, Blaine G
• Application Number:
  US13/943,068
• Publication Number:
  US 20140018570A1
• Time in Patent Office: 770 Days
• Field of Search: 562/517
• US Class Current: 1/1
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/12 on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C08G 63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C08G 63/81 using solvents C08G63/79 takes precedence
• CPC Class Codes: C08G 63/826 Metals not provided for in groups C08G63/83 - C08G63/86 C08G63/823 takes precedence
• CPC Class Codes: C08G 63/90 Purification; Drying

Abstract

A process for preparing acrylic acid from ethylene oxide and carbon monoxide, in which ethylene oxide is carbonylated in an aprotic solvent with carbon monoxide in the presence of a cobalt catalyst system to give poly-3-hydroxypropionate, the cobalt content in the poly-3-hydroxypropionate formed is reduced with the aid of water and/or an aqueous solution as a precipitation and/or wash liquid, and the poly-3-hydroxypropionate is subsequently split by thermolysis to give acrylic acid.

Claims

1. A process for preparing acrylic acid from ethylene oxide and carbon monoxide, the process comprising:

converting by carbonylating ethylene oxide dissolved in an aprotic solvent with carbon monoxide at elevated pressure and elevated temperature in the presence of a catalyst system comprising a cobalt source in a reaction zone A to obtain a product mixture A comprising poly-3-hydroxypropionate,

removing poly-3-hydroxypropionate from the product mixture A in a separation zone A, and

thermolyzing poly-3-hydroxypropionate removed in separation zone A in a thermolysis zone A to form acrylic acid,

wherein the removing comprises at least one of;

adding water, an aqueous solution, or both, as an aqueous precipitation liquid to a portion of product mixture A, to a total amount of product mixture A, or both, in order to precipitate poly-3-hydroxypropionate presently dissolved in the portion of product mixture A or in the total amount of product mixture A;

or

washing poly-3-hydroxypropionate removed from product mixture A in separation zone A with water, with an aqueous solution, or both, as an aqueous wash liquid.

2. The process according to claim 1, wherein the aprotic solvent comprises or is at least one solvent selected from the group consisting of saturated hydrocarbon, aromatic hydrocarbon, halogenated saturated hydrocarbon, halogenated aromatic hydrocarbon, an ester of organic acids, a ketone, a nitrile, a diakylamide, a carbonic ester, a sulfoxide, a sulfone, an N-alkylpyrrolidone, a cyclic ether and an acyclic ether.

3. The process according to claim 1, wherein the aprotic solvent comprises or is at least one solvent selected from the group consisting of n-hexane, n-heptane, petroleum ether, cyclohexane, benzene, toluene, dichloromethane, n-butyl propionate, phenyl acetate, glyceryl acetate, acetic acid ethyl acetate, acetone, ethyl methyl ketone, methyl isobutyl ketone, benzophenone, acetonitrile, propionitrile, n-butyronitrile, benzonitrile, dimethylformamide, dimethylacdetamide, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, ethylene oxide, diethyl ether, anisole, tetahydrofuran, 1,4-dioxane, diphenyl ether, alkylene glycol diakyl ether, and polyalkylene glycol dialkyl ether.

4. The process according to claim 1, wherein the aprotic solvent is an aprotic solvent only to an extent of at least 90% of its weight.

5. The process according to claim 1, wherein the poly-3-hydroxypropionate removed from product mixture A has a relative weight-average molecular weight of from 1000 to 20,000.

6. The process according to claim 1, wherein the catalyst system comprises the cobalt source in such an amount that it comprises, based on a molar amount of ethylene oxide for carbonylating conversion, of from 0.005 to 20 mol % of Co.

7. The process according to claim 1, wherein the cobalt source is a salt of cobalt.

8. The process according to claim 1, wherein the cobalt source is dicobalt octacarbonyl.

9. The process according to claim 1, wherein the catalyst system comprises a Brø

nsted acid as cocatalyst A, a Brø

nsted base as cocatalyst B, or a Brø

nsted acid as cocatalyst A and a Brø

nsted base as cocatalyst B.

10. The process according to claim 1, wherein the catalyst system comprises a compound as a cocatalyst C which has both a nucleophilic Brø

nsted-basic functionality like a cocatalyst B and a Brø

nsted-acidic functionality like a cocatalyst A.

11. The process according to claim 10, wherein the cocatalyst C is at least one compound selected from the group consisting of 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 3,4-dihydroxypyridine, 3-hydroxyquinoline, 4-hydroxy-2-methylpyridine, 3-hydroxy-4-methylpyridine, 2,6-dihydroxypyridine, 2-hydroxyquinoline, 1-hydroxyisoquinoline, 3-hydroxyquinoline, 2,3-dihydroxyquinoxaline, 8-hydroxyquinoline, 2-pyridylmethanol, 3-pyridylmethanol, 2-(2-pyridyl)ethanol and nicotinic acid.

12. The process according to claim 10, wherein the aprotic solvent comprises diglyme, the cobalt source comprises dicobalt octacarbonyl, and the catalyst system additionally comprises 3-hydroxypyridine as cocatalyst C.

13. The process according to claim 1, wherein the converting of ethylene oxide is ≧

90 mol %.

14. The process according to claim 1, wherein a pH of the aqueous precipitation liquid, based on a temperature of 25°

C. and a pressure of 1.0133·

10⁵ Pa, is ≦

7.5.

15. The process according to claim 1, wherein a pH of the aqueous precipitation liquid, based on a temperature of 25°

C. and a pressure of 1.0133·

10⁵ Pa, is ≧

0.

16. The process according to claim 1, wherein a pH of product mixture A or of a portion of product mixture A on completion of the adding of an aqueous precipitation liquid, based on a temperature of 25°

C. and a pressure of 1.0133·

10⁵ Pa, is ≦

7.5.

17. The process according to claim 1, wherein a pH of product mixture A or of a portion of product mixture A on completion of the adding of an aqueous precipitation liquid, based on a temperature of 25°

C. and a pressure of 1.0133·

10⁵ Pa, is ≧

0.

18. The process according to claim 1, wherein the aqueous precipitation liquid is the aqueous solution of an inorganic acid, of an organic acid, or both.

19. The process according to claim 1, wherein the aqueous precipitation liquid is an aqueous acetic acid solution.

20. The process according to claim 1, wherein the adding of the aqueous precipitation liquid is undertaken in the presence of an oxidizing agent for Co in oxidation states <

+2.

21. The process according to claim 20, wherein the adding of the aqueous precipitation liquid is undertaken in the presence of air or in the presence of a molecular oxygen-comprising gas other than air.

22. The process according to claim 1, wherein a pH of the aqueous wash liquid, based on a temperature of 25°

C. and a pressure of 1.0133·

10⁵ Pa, is ≦

7.5.

23. The process according to claim 1, wherein a pH of the aqueous wash liquid, based on a temperature of 25°

C. and a pressure of 1.0133·

10⁵ Pa, is ≧

0.

24. The process according to claim 1, wherein the aqueous wash liquid is the aqueous solution of an inorganic acid, of an organic acid, or both.

25. The process according to claim 1, wherein the aqueous wash liquid is an aqueous acetic acid solution.

26. The process according to claim 1, wherein the washing of poly-3-hydroxypropionate removed from product mixture A is effected in the presence of an oxidizing agent for Co in oxidation states <

+2.

27. The process according to claim 1, wherein the washing of the poly-3-hydroxypropionate removed from product mixture A is undertaken in the presence of air, a molecular oxygen-comprising gas other than air, or both.

28. The process according to claim 1, wherein the thermolyzing of the poly-3-hydroxypropionate removed in a separation zone A is effected from a solid substance thereof, from a melt thereof, from a solution thereof in a solvent, from a suspension thereof in a dispersant, or from an emulsion thereof in a dispersant.

29. The process according to claim 1, wherein 7 a splitting catalyst which catalyzes the thermolyzing is added to the poly-3-hydroxypropionate removed in a separation zone A.

30. The process according to claim 28, wherein a splitting catalyst which catalyzes the thermolyzing is added to the solid substance, to the melt, to the solution, to the suspension, or to the emulsion.

31. The process according to claim 29, wherein the splitting catalyst is a molecular organic active compound consisting of carbon atoms, hydrogen atoms, at least one nitrogen atom and optionally at least one oxygen atom in covalently bonded form, and the nitrogen atom is a tertiary nitrogen atom.

32. The process according to claim 31, wherein the molecular organic active compound has a tertiary nitrogen atom which has a covalent bond to three different carbon atoms.

33. The process according to claim 31, wherein the molecular organic active compound has at least two tertiary nitrogen atoms or at least three tertiary nitrogen atoms which each have a covalent bond to three different carbon atoms.

34. The process according to claim 31, wherein a molar mass of the molecular organic active compound is ≧

59.1 g/mol and ≦

600 g/mol.

35. The process according to claim 1, wherein the process for preparing acrylic acid is followed by a process comprising free-radical polymerizing the acrylic acid to form a polymer, optionally with other one or more monounsaturated compounds, polyunsaturated compounds, or both.

36. The process according to claim 1, wherein a cobalt content of the poly-3-hydroxypropionate removed in a separation zone A in the thermolyzing is from 0 to 1% by weight.

37. The process according to claim 1, wherein a cobalt content of the poly-3-hydroxypropionate in the thermolyzing is from 10⁻

6 to 1% by weight.

38. The process according to claim 36, wherein the cobalt contents are the total contents in the poly-3-hydroxypropionate of Co⁺².

39. The process according to claim 36, wherein the cobalt contents are the total contents in the poly-3-hydroxypropionate of Co⁺¹.

40. The process according to claim 36, wherein the cobalt contents are the total contents in the poly-3-hydroxypropionate of Co⁰.

41. The process according to claim 36, wherein the cobalt contents are the total contents in the poly-3-hydroxypropionate of Co⁻

1.

42. The process according to claim 1, wherein the aqueous precipitation liquid comprises an organic solvent other than an inorganic acid, an organic acid, or both.

43. The process according to claim 1, wherein the aqueous wash liquid comprises an organic solvent other than an inorganic acid, an organic acid, or both.