Process for the dimerisation of levulinic acid, dimers obtainable by such process and esters of such dimers

• US 20060135793A1
• Filed: 11/21/2005
• Published: 06/22/2006
• Est. Priority Date: 11/26/2004
• Status: Abandoned Application

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Petrus, Leonardus, Blessing, Robert Wiegbertus
• Application Number:
  US11/283,985
• Publication Number:
  US 20060135793A1
• Time in Patent Office: Days
• US Class Current: 549/318
• CPC Class Codes: C07C 51/36 by hydrogenation of carbon-to-carbon unsaturated bonds
• 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 59/347 containing keto groups
• CPC Class Codes: C07C 69/716 Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• CPC Class Codes: C07D 307/33 in position 2, the oxygen atom being in its keto or unsubstituted enol form
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10L 1/19 Esters ester radical containing compounds; ester ethers; carbonic acid esters C10L1/1802, C10L1/1805, C10L1/1808, C10L1/1811, C10L1/1814, C10L1/1817 take precedence
• CPC Class Codes: C10L 1/1905 of di- or polycarboxylic acids
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

The present invention provides a process for dimerisation of levulinic acid, wherein an organic phase comprising levulinic acid is contacted, in the presence of hydrogen, with a strong acidic heterogeneous catalyst comprising a hydrogenating metal, at a temperature in the range of from 60 to 170° C. and a pressure in the range of from 1 to 200 bar (absolute). The invention further relates to dimers of levulinic acid and their esters, to a mixture comprising levulinic acid and its dimers obtainable by such process and to an ester mixture obtainable by esterifying such mixture of levulinic acid and its dimers.

Claims

1. A process for dimerisation of levulinic acid, wherein an organic phase comprising levulinic acid is contacted, in the presence of hydrogen, with a strong acidic heterogeneous catalyst comprising a hydrogenating metal, at a temperature in the range of from 60 to 170°

C. and a pressure in the range of from 1 to 200 bar (absolute).

2. A process according to claim 1, wherein the hydrogenating metal is a Group VIII metal.

3. A process according to claim 1, wherein the catalyst further comprises a strong acidic ion-exchange resin.

4. A process according to claim 1, wherein the organic phase is contacted with the catalyst at a temperature in the range of from 80 to 160°

C.

5. A process according to claim 1, wherein the pressure is in the range of from 2 to 100 bar (absolute).

6. A process according to claim 1, wherein the organic phase comprises levulinic acid and one or more ketones or aldehydes.

7. A process according to claim 6, wherein the organic phase comprises levulinic acid and one or more aldehydes selected from the group consisting of formaldehyde, acetaldehyde, and butanal.

8. A process according to claim 6, wherein the organic phase comprises levulinic acid and one or more ketones selected from the group consisting of acetone, methyl ethyl ketone, and methyl isobutyl ketone.

9. A process according to claim 6, wherein the organic phase comprises at least 20 wt % of levulinic acid.

10. A process according to claim 1, wherein the organic phase is substantially pure levulinic acid.

16. A mixed dimer obtainable by a process according to claim 6, wherein the mixed dimer is formed from one molecule of levulinic acid and one molecule of a ketone selected from the group consisting of acetone, methyl ethyl ketone, and methyl isobutyl ketone, or the mixed dimer is formed from one molecule of levulinic acid and one molecule of an aldehyde selected from the group consisting of formaldehyde, acetaldehyde, and butanal.

11. A di-carboxylic acid having the molecular structure according to formula

17. A mixture comprising levulinic acid and the di-carboxylic acid according to claim 11.

21. A mixture comprising an ester of levulinic acid and a di-ester of the di-carboxylic acid according to claim 11, obtainable by reacting a mixture comprising the levulinic acid and the di-carboxylic acid with an alcohol under esterifying conditions wherein the alcohol comprises an alkyl alcohol comprising 1 to 10 carbon atoms.

12. A di-carboxylic acid having the molecular structure according to formula

13. A C₁₀ compound with a carboxylic group and a lactone group having the molecular structure according to formula

14. A C₁₀ compound with two lactone groups having the molecular structure according to formula

15. A C₁₀ compound with a carboxylic group and a lactone group having the molecular structure according to formula

18. A di-ester having the general molecular structure according to formula

wherein R₁ and R₂ are, independently, an organic radical which is covalently connected to the oxygen atom by a carbon atom.

19. A di-ester according to claim 18, wherein R₁ and R₂ are, independently, a straight or branched alkyl group having up to 22 carbon atoms.

20. An ester obtainable by reacting a C₁₀ compound comprising a carboxyl group and a lactone group, or by reacting a mixed dimer, with an alcohol under esterifying conditions.