Method for the production of levulinic acid and its derivatives

• US 6,054,611 A
• Filed: 05/13/1998
• Issued: 04/25/2000
• Est. Priority Date: 11/08/1996
• Status: Expired due to Term

• Current Assignee: Arkenol, Inc.
• Original Assignee: Arkenol, Inc.
• Inventors: Cuzens, John E., Farone, William A.
• Primary Examiner(s): DENTZ, BERNARD I
• Application Number:
  US09/076,941
• Time in Patent Office: 713 Days
• Field of Search: 562/515
• US Class Current: 562/515
• 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: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/716 Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• CPC Class Codes: C07D 307/06 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
• CPC Class Codes: C07D 307/50 Preparation from natural products

Abstract

A method of producing dehydration products from one more 5-carbon or 6-carbon sugars includes reacting said one or more sugars at 40-240° C. for 1 to 96 hours in the presence of 5-90% sulfuric acid, separating the reaction products, and recovering levulinic acid. The sugars are can be generated from strong acid hydrolysis of biomass, such as rice straw, paper, cotton and other cellulosic materials.

Claims

1. A method of producing levulinic acid comprising:

mixing biomass containing cellulose and hemicellulose with an acid to form an aqueous reaction solution which is 5-50% acid by weight while maintaining the temperature of the solution below about 60°

C., thereby at least partially decrystallizing the biomass;

heating said solution to about 80-200°

C. for 1 to 30 hours, thereby hydrolyzing the cellulose and hemicellulose materials to sugars which are reacted following hydrolysis;

separating the reaction products; and

recovering levulinic acid.

2. The method of claim 1, wherein the acid is sulfuric acid.

3. The method of claim 1, wherein the concentration of said biomass is about 20-40% by weight in the reaction solution.

4. The method of claim 1, wherein the concentration of said biomass is about 30% by weight in the reaction solution.

5. The method of claim 1, wherein the concentration of cellulose is about 12-39% by weight in the reaction solution.

6. The method of claim 1, wherein the concentration of cellulose is about 21-30% by weight in the reaction solution.

7. The method of claim 1, wherein said biomass comprises rice straw materials.

8. The method of claim 1, wherein said biomass comprises woody plant materials.

9. The method of claim 1, wherein said biomass comprises paper materials.

10. The method of claim 1, wherein said biomass comprises cotton material.

11. The method of claim 1, wherein said biomass comprise cellulosic materials.

12. The method of claim 1, wherein said biomass comprises corn stalks.

13. The method of claim 1, wherein said biomass comprises bagasse.

14. The method of claim 1, wherein the step of heating said solution is conducted at 110-160°

C.

15. The method of claim 1, wherein the concentration of the acid in the solution is about 10-30%.

16. The method of claim 1, wherein the step of heating the solution is conducted for 2 to 10 hours.

17. The method of claim 1, wherein the concentration of cellulose, the concentration of the acid and the temperature of the heating step are determined according to the equation:

space="preserve" listing-type="equation">A=0.4T+70-0.59(C-25.5);

wherein A is the percent sulfuric acid by weight in the reaction solution, T is the temperature in degrees Celsius, and C is the percent cellulose by weight in the reaction solution; and

wherein the conditions used deviate from those obtained from the equation by not more than 5% by weight in the reaction solution for the value obtained for A, not more than 5% by weight in the reaction solution for the value obtained for C, and not more than 10°

C. of the value obtained for T.

18. The method of claim 17, wherein the concentration of cellulose is 12-39% by weight in the reaction solution.

19. The method of claim 1, additionally comprising recovering a product selected from the group consisting of furfural, 5-HMF, succinic acid, maleic acid and fumaric acid.

20. The method of claim 1, wherein said product recovered is furfural.

21. The method of claim 1, wherein said products recovered is furfural and 5-HMF.

22. The method of claim 1, wherein the step of separating the products comprises chromatography.

23. The method of claim 1, wherein step of separating the products comprises chromatography using an ionic resin.

24. The method of claim 1, wherein step of separating the products comprises chromatography using an anionic resin.

25. The method of claim 1, wherein step of separating the products comprises chromatography using a multiple chromatographic columns.

26. The method of claim 1, additionally comprising:

hydrogenation of levulinic acid thus obtained in the presence of H₂ and a metal catalyst;

separating the reaction products; and

recovering methyltetrahydrofuran.

27. The method of claim 26, wherein ethanol is added during the hydrogenation step.

28. The method of claim 26, wherein the methyltetrahydrofuran is dried after the hydrogenation reaction, leaving a methyltetrahydrofuran product in a dry blend form.

29. The method of claim 26, wherein dry ethanol is added.

30. The method of claim 26, wherein the metal catalyst is Ni/Co catalyst.

31. The method of claim 1, additionally comprising dehydration of levulinic acid to yield a product comprising an angelica lactone.

32. The method of claim 1, additionally comprising filtering the reaction products prior to separation.

33. The method of claim 32, wherein the filter is washed with H₂ O.

34. The method of claim 32, wherein both the first filtrate and second filtrate following the H₂ O washed are combined before separation.

35. The method of claim 1, wherein levulinic acid is concentrated after separation and recovery.

36. The method of claim 1, additionally comprising:

adding an alcohol to the levulinic acid;

refluxing the resulting alcoholic solution for 1-10 hours;

separating the mixture;

recovering levulinate ester.

37. The method of claim 36, wherein the reaction mixture is refluxed for 2-8 hours.

38. The method of claim 36, wherein the reaction mixture is refluxed for 3-6 hours.