Process for production of acrylates from epoxides

• US 9,096,510 B2
• Filed: 10/25/2012
• Issued: 08/04/2015
• Est. Priority Date: 10/26/2011
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Porcelli, Richard V., Farmer, Jay J., Lapointe, Robert E.
• Primary Examiner(s): BOYKIN, TERRESSA M
• Application Number:
  US14/353,532
• Publication Number:
  US 20140309399A1
• Time in Patent Office: 1,013 Days
• Field of Search: 549/263, 549/328, 562/599, 562/600
• 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: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/36 by reaction with carbon monoxide or formates C07C67/02, C07C67/03, C07C67/10 take precedence
• CPC Class Codes: C07C 67/475 by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C07D 301/08 in the gaseous phase
• CPC Class Codes: C07D 305/12 Beta-lactones
• CPC Class Codes: C08G 63/06 derived from hydroxycarboxylic acids
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/81 using solvents C08G63/79 takes precedence
• CPC Class Codes: C08G 63/82 characterised by the catalyst used
• CPC Class Codes: C08G 63/823 for the preparation of polylactones or polylactides
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

The methods of the present invention comprise the steps of: providing a feedstock stream comprising an epoxide and carbon monoxide; contacting the feedstock stream with a metal carbonyl in a first reaction zone to effect conversion of at least a portion of the provided epoxide to a beta lactone; directing the effluent from the first reaction zone to a second reaction zone where the beta lactone is subjected to conditions that convert it to a compound selected from the group consisting of: an alpha beta unsaturated acid, an alpha beta unsaturated ester, an alpha beta unsaturated amide, and an optionally substituted polypropiolactone polymer; and isolating a final product comprising the alpha-beta unsaturated carboxylic acid, the alpha-beta unsaturated ester, the alpha-beta unsaturated amide or the polypropiolactone.

Claims

1. A method for the synthesis of acrylic acid comprising the steps of:

providing a gaseous feedstock stream comprising ethylene oxide and carbon monoxide;

directing the feedstock stream to a first reaction zone where it is contacted with a metal carbonyl compound and where at least a portion of the ethylene oxide is converted to a carbonylation product stream comprising beta propiolactone;

directing the carbonylation product stream to a second reaction zone where it is contacted with a catalyst, which catalyzes the conversion of beta propiolactone to acrylic acid, wherein the conversion of beta propiolactone to acrylic acid is performed in a continuous flow format;

withdrawing an acrylic acid product stream from the second reaction zone; and

isolating acrylic acid from the product stream.

2. The method of claim 1, further comprising the step of adding water to the carbonylation product stream before it enters the second reaction zone.

3. The method of claim 1, wherein the conversion of ethylene oxide to beta propiolactone is a gas phase reaction.

4. The method of claim 1, wherein the metal carbonyl compound has a formula [QM_y(CO)_w]^x, where:

Q is any ligand or more than one ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number such as to provide the stable metal carbonyl; and

x is an integer from −

3 to +3 inclusive.

5. The method of claim 1, wherein the metal carbonyl compound comprises an anionic metal carbonyl.

6. The method of claim 5, wherein the anionic metal carbonyl compound comprises a moiety selected from the group consisting of:

[Co(CO)₄]⁻

, [Ti(CO)₆]²⁻

, [V(CO)₆]⁻

, [Rh(CO)₄]⁻

, [Fe(CO)₄]²⁻

, [Ru(CO)₄]²⁻

, [Os(CO)₄]²⁻

, [Cr₂(CO)₁₀]²⁻

, [Fe₂(CO)₈]²⁻

, [Tc(CO)₅]⁻

, [Re(CO)₅]⁻

, and [Mn(CO)₅]⁻

.

7. The method of claim 5, wherein the anionic metal carbonyl compound comprises [Co(CO)₄]⁻

.

8. The method of claim 5, wherein the anionic metal carbonyl compound comprises [Rh(CO)₄]⁻

.

9. The method of claim 1, wherein the metal carbonyl compound comprises a neutral metal carbonyl compound.

10. The method of claim 9, wherein the neutral metal carbonyl compound is selected from the group consisting of:

Ti(CO)₇;

V₂(CO)₁₂;

Cr(CO)₆;

Mo(CO)₆;

W(CO)₆ Mn₂(CO)₁₀, Tc₂(CO)₁₀, Re₂(CO)₁₀ Fe(CO)₅, Ru(CO)₅ Os(CO)₅ Ru₃(CO)₁₂, Os₃(CO)₁₂ Fe₃(CO)₁₂ Fe₂(CO)₉ Co₄(CO)₁₂, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Ir₄(CO)₁₂, Co₂(CO)₈, and Ni(CO)₄.

11. The method of claim 9, wherein the neutral metal carbonyl compound comprises Co₂(CO)₈.

12. The method of claim 1, wherein the metal carbonyl compound comprises a solid.

13. The method of claim 1, wherein the metal carbonyl compound is supported on a solid.

14. The method of claim 13, wherein the solid support is selected from the group consisting of inorganic solids and polymer supports.

15. The method of claim 13, wherein the solid support is selected from the group consisting of:

silica, glass, alumina, zirconia, diatomaceous earth, metal oxides, metal salts, ceramics, clays, molecular sieves, kieselgur, and titanium dioxide.

16. The method of claim 13, herein the solid support is selected from the group consisting of silica gel, alumina, and glass.

17. The method of claim 1, wherein the ratio of carbon monoxide to ethylene oxide in the feedstock stream is between about 1:

1 and about 100;

1.

18. The method of claim 1, wherein the ratio of carbon monoxide to ethylene oxide in the feedstock stream is greater than about 10:

1.

19. The method of claim 1, wherein the feedstock stream is provided to the first reaction zone at a pressure between about 20 and about 200 atmospheres.

20. The method of claim 1, wherein the feedstock stream is provided to the first reaction zone at a temperature between about 50 and about 200°

C.

21. The method of claim 1, where the catalyst in the second reaction zone comprises an acid.

22. The method of claim 21, wherein the acid comprises phosphoric acid.

23. The method of claim 21, wherein the acid comprises a solid acid catalyst.

24. The method of claim 1, wherein the carbonylation product stream is provided to the second reaction zone as a gaseous stream.

25. The method of claim 24, wherein the carbonylation product stream comprises a mixture of beta propiolactone and carbon monoxide.

26. The method of claim 24, wherein the carbonylation product stream is essentially free of unreacted ethylene oxide.

27. The method of claim 1, wherein the step of isolating the acrylic acid comprises condensing the acrylic acid.

28. The method of claim 1, further comprising the step of oxidizing ethylene gas to provide the ethylene oxide feedstock stream.

29. The method of claim 28, wherein the step of oxidizing ethylene gas comprises contacting ethylene with oxygen in an ethylene oxidation reactor in the presence of a suitable catalyst to convert at least a portion of the ethylene to ethylene oxide, withdrawing a gaseous ethylene oxide stream from the ethylene oxidation reactor;

and combining the gaseous ethylene oxide stream with carbon monoxide to provide the feedstock stream.

30. A method for the synthesis of acrylate esters comprising the steps of:

providing a gaseous feedstock stream comprising ethylene oxide and carbon monoxide;

directing the feedstock stream to a first reaction zone where it is contacted with a metal carbonyl compound and where at least a portion of the ethylene oxide is converted to a carbonylation product stream comprising beta propiolactone;

adding a C_1-8 alcohol to the carbonylation product stream comprising beta propiolactone;

directing the carbonylation product stream comprising beta propiolactone and the C_1-8 alcohol to a second reaction zone where it is contacted with a catalyst which catalyzes the conversion of beta propiolactone and the C_1-8 alcohol to the corresponding acrylic acid ester, wherein the conversion to acrylic acid ester is performed in a continuous flow format;

withdrawing an acrylic acid ester product stream from the second reaction zone; and

isolating an acrylate ester from the acrylic acid ester product stream.

31. The method of claim 30, wherein the C_1-8 alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, hexanol, and 2-ethyl hexanol.

32. The method of claim 30, wherein the C_1-8 alcohol comprises methanol.

33. The method of claim 30, wherein the C_1-8 alcohol comprises butanol.

34. The method of claim 30, wherein the metal carbonyl compound comprises a solid.

35. The method of claim 30, wherein the metal carbonyl compound is supported on a solid.

36. The method of claim 30, wherein the solid support is selected from the group consisting of inorganic solids and polymer supports.

37. The method of claim 30, wherein the solid support is selected from the group consisting of:

silica, glass, alumina, zirconia, diatomaceous earth, metal oxides, metal salts, ceramics, clays, molecular sieves, kieselgur, and titanium dioxide.

38. A method for the synthesis of acrylic acid comprising the steps of:

providing an ethylene stream;

contacting the ethylene stream with oxygen in the presence of a catalyst to provide an ethylene oxide stream;

adding carbon monoxide to the ethylene oxide stream to provide a feedstock stream;

directing the feedstock stream to a first reaction zone where it is contacted with a metal carbonyl compound and where at least a portion of the ethylene oxide is converted to a carbonylation product stream comprising beta propiolactone;

directing the carbonylation product stream to a second reaction zone where it is contacted with a catalyst, which catalyzes the conversion of beta propiolactone to acrylic acid, wherein the conversion of beta propiolactone to acrylic acid is performed in a continuous flow format;

withdrawing an acrylic acid product stream from the second reaction zone; and

isolating acrylic acid from the product stream.

39. The method of claim 38, wherein the ethylene oxide remains substantially in the gas phase between the oxidation step and the first reaction zone.