Method and apparatus for production of levulinic acid via reactive extrusion

• US 5,859,263 A
• Filed: 08/14/1996
• Issued: 01/12/1999
• Est. Priority Date: 05/22/1996
• Status: Expired due to Term

• Current Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Board of Regents of the University of Nebraska
• Inventors: Ghorpade, Viswas M., Hanna, Milford A.
• Primary Examiner(s): OWENS, AMELIA A
• Application Number:
  US08/696,764
• Time in Patent Office: 881 Days
• Field of Search: 562/515, 585/603, 585/604, 568/853, 549/326
• US Class Current: 549/326
• CPC Class Codes: C07C 51/00 Preparation of carboxylic acids or their salts, halides or anhydrides of acids by hydrolysis of oils, fats or waxes C11C
• CPC Class Codes: C07C 59/185 Saturated compounds having only one carboxyl group and containing keto groups
• CPC Class Codes: C07D 315/00 Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00

Abstract

The present invention relates to a continuous process for preparing levulinic acid from starch in a reactive extrusion process. In a preferred embodiment, the extrusion takes place in a twin-screw extruder having a plurality of temperature zones wherein the starch slurry is preconditioned, extruded, filter pressed, reboiled, vacuum distilled, condensed, centrifuged, whereby the waste effluent from the centrifugation is reprocessed upstream to the preconditioning stage.

Claims

1. A process for preparing levulinic acid from starch, comprising the steps of mixing starch, water, and a mineral acid so as to form a slurry;

extruding said slurry with an extruder to form an extrudate containing levulinic acid.

2. The process according to claim 1 wherein said starch has an amylose content of from about 20% to about 30%.

3. The process according to claim 1 wherein said starch is selected from the group consisting of corn starch, wheat starch, rice starch, tapioca starch, and mixtures thereof.

4. The process according to claim 1 wherein said mineral acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, and sulfuric acid.

5. The process according to claim 1 wherein said mineral acid is sulfuric acid and wherein said starch is corn starch.

6. The process according to claim 1 wherein said extruder is a twin-screw extruder.

7. The process according to claim 1 further comprising the step of heating said slurry in the extruder to temperatures ranging between about 80°

C. and about 150°

C.

8. The process according to claim 1 further comprising the step of mixing and heating said slurry to precondition the slurry before it is fed to the extruder.

9. The process according to claim 1, comprising the steps of mixing starch, water, and a mineral acid so as to form a slurry;

extruding said slurry with an extruder to form an extrudate containing levulinic acid; and

separating levulinic acid from the extrudate.

10. The process according to claim 9 wherein said starch has an amylose content of from about 20-30%.

11. The process according to claim 10 wherein said starch has an amylose content of about 25%.

12. The process according to claim 9 wherein said starch is selected from the group consisting of corn starch, wheat starch, rice starch, tapioca starch, and mixtures thereof.

13. The process according to claim 12 wherein said starch is corn starch.

14. The process according to claim 9 wherein said mineral acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, and sulfuric acid.

15. The process according to claim 14 wherein said mineral acid is sulfuric acid.

16. The process according to claim 9 further comprising the step of heating said slurry in the extruder to temperatures ranging between about 80°

C. and about 150°

C.

17. The process according to claim 16 wherein said extruder is a twin-screw extruder.

18. The process according to claim 17 wherein the barrel of the extruder has a plurality of temperature zones having different temperatures.

19. The process according to claim 9 wherein said extruder is a twin-screw extruder.

20. The process according to claim 9 further comprising the step of mixing and heating said slurry to precondition the slurry before it is fed to the extruder.

21. The process according to claim 9 wherein gases are vented from said extruder during the extrusion step.

22. The process according to claim 9 wherein separating levulinic acid from the extrudate comprises one or more steps selected from the group consisting of partial neutralization, filtration, and solvent extraction of the extrudate.

23. The process according to claim 22 comprising the step of separating levulinic acid from the extrudate by filtering the extrudate to produce a filtrate, and further comprising the step of distilling said filtrate.

24. The process according to claim 23 wherein said distillation step is performed under a vacuum.

25. The process according to claim 24 wherein said distillation step is performed in the presence of steam.

26. The process according to claim 9 wherein the step of separating levulinic acid from the extrudate comprises filter pressing the discharge product of the extruder and vacuum distilling the discharge product of the filter press.

27. The process according to claim 26 wherein the step of separating levulinic acid from the extrudate comprises filter pressing the discharge product of the extruder, vacuum distilling the discharge product of the filter press, condensing the discharge product of the vacuum distiller so as to produce a mixture containing levulinic acid, and centrifuging said mixture containing levulinic acid.

28. The process according to claim 27 wherein at least a portion of the liquor discharged from said centrifuge is recycled by mixing with said water to be mixed with said starch and mineral acid to be utilized in continuation of said process.

29. The process according to claim 26 wherein said starch has an amylose content of from about 20-30%.

30. The process according to claim 26 wherein said starch has an amylose content of from about 23-25%.

31. The process according to claim 26 wherein said starch is selected from the group consisting of corn starch, wheat starch, rice starch, tapioca starch, and mixtures thereof.

32. The process according to claim 31 wherein said starch is corn starch.

33. The process according to claim 26 wherein said mineral acid is selected from the group consisting of hydrochloric acid, hydrobromic acid, and sulfuric acid.

34. The process according to claim 33 wherein said mineral acid is sulfuric acid.

35. The process according to claim 26 wherein said extruder is a twin-screw extruder.

36. The process according to claim 35 further comprising the step of heating said slurry in the extruder to temperatures ranging between about 80°

C. and about 150°

C.

37. The process according to claim 36 wherein the barrel of the extruder has a plurality of temperature zones.

38. The process according to claim 27 further comprising the step of mixing and heating said slurry to precondition the slurry before it is fed to the extruder.

39. The process according to claim 27 wherein gases are vented from said extruder.

40. The process according to claim 27 wherein humin is a byproduct of the filter press.

41. The process according to claim 27 wherein a reboiler is utilized to reheat the discharge material from said filter press during the vacuum distillation step.

42. The process according to claim 27 wherein tar is discharged as a reaction byproduct during said vacuum distillation.

43. The process according to claim 1, comprising the steps of:

mixing starch, water, and a mineral acid so as to form a slurry;

extruding said slurry in an extruder at a temperature of from about 80°

C. to about 150°

C.;

filter pressing the discharge product of the extruder

vacuum distilling the discharge product of the filter press;

condensing the discharge product of the vacuum distiller so as to produce a mixture containing levulinic acid; and

centrifuging said mixture containing levulinic acid;

wherein said starch is selected from the group consisting of corn starch, wheat starch, rice starch, tapioca starch, and mixtures thereof;

wherein said slurry is preconditioned by heating and mixing prior to extruding said slurry;

wherein at least a portion of the liquor discharged from said centrifuge is recycled by mixing with said water to be mixed with said starch and mineral acid to be utilized in continuation of said process.

44. Levulinic acid prepared by the process of claim 1.

45. A process for preparing valeric γ

-lactone comprising the steps of mixing starch, water, and a mineral acid so as to form a slurry;

extruding said slurry with an extruder to form an extrudate containing levulinic acid;

separating levulinic acid from the extrudate; and

hydrogenating said levulinic acid to obtain valeric γ

-lactone.

46. A process for preparing 1,3-pentadiene comprising the steps of mixing starch, water, and a mineral acid so as to form a slurry;

extruding said slurry with an extruder to form an extrudate containing levulinic acid;

separating levulinic acid from the extrudate;

reducing the ketone and carboxy moieties of said levulinic acid to obtain 1,4-pentandiol; and

dehydrating said 1,4-pentandiol to yield 1,3-pentadiene.

47. A process for preparing 1,4-pentanediol comprising the steps of mixing starch, water, and a mineral acid so as to form a slurry;

extruding said slurry with an extruder to form an extrudate containing levulinic acid;

separating levulinic acid from the extrudate; and

reducing the ketone and carboxy moieties of said levulinic acid to obtain 1,4-pentandiol.