Process for beta-lactone production

• US 9,493,391 B2
• Filed: 09/17/2015
• Issued: 11/15/2016
• Est. Priority Date: 04/08/2009
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Allen, Scott D., Valente, Ronald R., Lee, Han, Cherian, Anna E., Bunning, Donald L., Clinton, Nye A., Fruchey, Olan Stanley, Dombek, Bernard Duane
• Primary Examiner(s): Rozof, Timothy R
• Application Number:
  US14/857,313
• Publication Number:
  US 20160102040A1
• Time in Patent Office: 425 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 231/14 by formation of carboxamide groups together with reactions not involving the carboxamide groups
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 67/30 by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
• CPC Class Codes: C07C 67/317 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
• CPC Class Codes: C07D 305/12 Beta-lactones
• CPC Class Codes: C07D 307/60 Two oxygen atoms, e.g. succinic anhydride
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

The present application provides a method for producing an beta-lactone product. The method includes the steps of: reacting an epoxide, a solvent with a carbonylation catalyst and carbon monoxide to produce a reaction stream comprising a beta-lactone then separating a portion of the beta-lactone in the reaction stream from the solvent and carbonylation catalyst to produce: i) a beta-lactone stream with the beta-lactone, and ii) a catalyst recycling stream including the carbonylation catalyst and the high boiling solvent; and adding the catalyst recycling stream to the feed stream.

Claims

1. A continuous method of making poly(3-hydroxy propionic acid) from ethylene oxide, the method comprising steps of:

reacting the contents of a feed stream comprising ethylene oxide, a solvent, a carbonylation catalyst and carbon monoxide to produce a liquid reaction product stream comprising beta-propiolactone and a carbonylation catalyst;

separating at least a portion of the beta-propiolactone in the reaction product stream from the carbonylation catalyst to produce a liquid catalyst recycling stream comprising carbonylation catalyst;

polymerizing at least a portion of the separated beta-propiolactone to produce poly(3-hydroxy propionic acid); and

adding the liquid catalyst recycling stream to the feed stream.

3. The method of claim 1, further comprising treating the poly(3-hydroxy propionic acid) under conditions to convert the poly(3-hydroxy propionic acid) into a compound selected from the group consisting of acrylic acid, acrylates, acrylamide, and polyacrylates.

4. The method of claim 1, further comprising treating the poly(3-hydroxy propionic acid) under conditions to convert the poly(3-hydroxy propionic acid) into a compound selected from the group consisting of acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate.

5. The method of claim 1, further comprising treating the poly(3-hydroxy propionic acid) under conditions to convert the poly(3-hydroxy propionic acid) into acrylic acid.

6. The method of claim 1, wherein, upon reacting, the solvent has a boiling point that is higher than the boiling point of the beta-propiolactone when the solvent and beta-propiolactone are at the same pressure.

7. The method of claim 1, wherein the liquid catalyst recycling stream comprises beta-propiolactone.

8. The method of claim 1, wherein the liquid reaction product stream comprises ethylene oxide.

9. The method of claim 8, wherein the liquid reaction product stream comprises an amount of ethylene oxide sufficient to prevent anhydride formation.

10. The method of claim 9, wherein the liquid reaction product stream comprises at least about 0.1% ethylene oxide by weight.

11. The method of claim 1, further comprising treating the liquid catalyst recycling stream, prior to the adding step, by adding fresh carbonylation catalyst, removing spent carbonylation catalyst, adding solvent, adding ethylene oxide, adding a portion of the separated beta-propiolactone, or a combination thereof.

12. The method of claim 1, wherein the separating step comprises volatilizing at least a portion of the beta-propiolactone from the liquid reaction product stream to produce the separated beta-propiolactone.

13. The method of claim 1, wherein the separating step comprises exposing the liquid reaction product stream to reduced pressure.

14. The method of claim 13, wherein the reduced pressure is between about 5Torr and about 500 Torr.

15. The method of claim 13, wherein the reduced pressure is between about 10Torr and about 100 Torr.

16. The method of claim 13, wherein the reduced pressure is sufficient to reduce the boiling point of the beta-propiolactone by about 20 to about 100 °

C. below its boiling point at atmospheric pressure.

17. The method of claim 1, wherein the separating step comprises exposing the liquid reaction product stream to elevated temperature.

18. The method of claim 17, wherein the elevated temperature is greater than the boiling point of the beta-propiolactone but less than the boiling point of the solvent.

19. The method of claim 1, wherein the separating step comprises exposing the liquid reaction product stream to reduced pressure and elevated temperature.

20. The method of claim 12, further comprising a step of condensing beta-propiolactone from the separated beta-propiolactone.

21. The method of claim 1, further comprising adding beta-propiolactone to the feed stream.

22. The method of claim 21, wherein the beta-propiolactone added to the feed stream is taken from the separated beta-propiolactone.

23. The method of claim 22, wherein the beta-propiolactone is added to the feed stream until the weight percent of beta-propiolactone in the liquid reaction product stream is in the range of about 10% to about 90%, and the method then comprises withdrawing beta-propiolactone from the liquid reaction product stream while maintaining the weight percent of beta-propiolactone in the liquid reaction product stream in the range of about 10% to about 90%.

24. The method of claim 1, wherein the boiling point of the solvent is at least 20°

C. higher than the boiling point of the beta-propiolactone.

25. The method of claim 1, wherein the solvent has a boiling point of at least 172°

C. at atmospheric pressure.

26. The method of claim 1, wherein the carbonylation catalyst comprises a metal carbonyl compound.

27. The method of claim 26, wherein the metal carbonyl compound has the general formula [QM_y(CO)_w]^x,

where:

Q is any ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number that provides a metal carbonyl compound that is stable; and

x is an integer from −

3 to +3 inclusive.

28. The method of claim 27, wherein M is selected from the group consisting of Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga and In.

29. The method of claim 27, wherein M is Co.

30. The method of claim 27, wherein M is Co, y is 1, and w is 4.

31. The method of claim 27, wherein the metal carbonyl compound comprises a carbonyl cobaltate and the carbonylation catalyst further comprises a Lewis acidic co-catalyst which comprises a metal-centered cationic Lewis acid.

32. The method of claim 31, wherein the metal-centered cationic Lewis acid comprises an aluminum cation.

33. The method of claim 1, wherein the liquid reaction product stream comprises carbon monoxide and ethylene oxide and the separating step comprises:

separating the liquid reaction product stream into i) a gaseous stream comprising carbon monoxide and ethylene oxide, and ii) a liquid stream comprising beta-propiolactone and carbonylation catalyst; and

separating the liquid stream comprising beta-propiolactone and carbonylation catalyst into i) the separated beta-propiolactone; and

ii) the liquid catalyst recycling stream comprising carbonylation catalyst.

34. The method of claim 33, wherein the solvent has a boiling point higher than the boiling point of the beta-propiolactone and the catalyst recycling stream further comprises solvent.

35. The method of claim 33, further comprising the step of returning the gaseous stream comprising carbon monoxide and ethylene oxide to the feed stream.

36. The method of claim 33, wherein the solvent has a boiling point lower than the boiling point of the beta-propiolactone and the gaseous stream comprising carbon monoxide and ethylene oxide further comprises solvent.

38. The method of claim 1, wherein the separated beta-propiolactone is gaseous.

2. A continuous method of making poly(3-hydroxy propionic acid) from ethylene oxide, the method comprising steps of:

reacting the contents of a feed stream comprising ethylene oxide, a solvent, a carbonylation catalyst and carbon monoxide to produce a liquid reaction product stream comprising beta-propiolactone and a carbonylation catalyst;

returning the liquid reaction product stream to the feed stream until the weight percent of beta-propiolactone in the liquid reaction product stream is in the range of about 10% to about 90%; and

then separating at least a portion of the beta-propiolactone in the reaction product stream from the carbonylation catalyst to produce a liquid catalyst recycling stream comprising carbonylation catalyst;

polymerizing at least a portion of the separated beta-propiolactone to produce poly(3-hydroxy propionic acid); and

adding the liquid catalyst recycling stream to the feed stream.

37. The method of claim 2, wherein the liquid reaction product stream is returned to the feed stream until the weight percent of beta-propiolactone in the liquid reaction product stream is in the range of about 43% to about 53%, and the method then comprises withdrawing beta-propiolactone from the liquid reaction product stream while maintaining the weight percent of beta-propiolactone in the liquid reaction product stream in the range of about 43% to about 53%.

39. The method of claim 2, wherein the separated beta-propiolactone is gaseous.