Method for producing liquid hydrocarbon fuels directly from lignocellulosic biomass

Patent metadata

Field	Value
Publication number	US-9487712-B2
Application number	US-201113883755-A
Country	US
Kind code	B2
Filing date	Nov 8, 2011
Priority date	Nov 8, 2010
Publication date	Nov 8, 2016
Grant date	Nov 8, 2016

Abstract

A process that directly converts carbohydrates, particularly biomass derived carbohydrates and more specifically biomass (e.g., lignocellulosic biomass), to furfural-/HMF-ketone adducts for liquid hydrocarbon production under mild conditions.

First claim

The invention claimed is:

1. A method for making a hydrocarbon fuel which comprises the steps of:
(a) converting a feedstock containing monosaccharides, oligosaccharides, polysaccharides or a mixture thereof with one or more ketones in the presence of a bromide or chloride salt, mineral acid or formic acid and water to furfural-ketone adducts, hydroxymethylfurfural (HMF)-ketone adducts or both in a single step by reacting the feedstock with one or more ketones in the presence of a bromide or chloride salt, mineral acid or formic acid and water; and
(b) at least partially hydrogenating and dehydrating the ketone adducts to form hydrocarbons or oxygenated hydrocarbons, wherein the bromide or chloride salt is selected from the group consisting of CaBr 2 , NaBr, LiBr, LiCl, CaCl 2 , MgCl 2 , ZnBr 2 , ZnCl 2 and FeBr 3 .

2. The method of claim 1 wherein the one or more ketones is acetone.

3. The method of claim 1 wherein the bromide or chloride salt is lithium bromide or lithium chloride.

4. The method of claim 1 wherein-step (a) is conducted at a temperature from 85 to 160° C.

5. The method of claim 1 wherein the volume ratio of ketone to water ranges from 20:1 to 5:1.

6. The method of claim 1 wherein the weight ratio of salt to feedstock ranges from 1:1 to 4:1.

7. The method of claim 1 wherein the weight % of acid added to the reaction mixture based on total weight of ketone and water ranges from 0.25 to 2 wt %.

8. The method of claim 1 wherein feedstock loading ranges from about 1% wt/volume to about 50% wt/volume ketone and water.

9. The method of claim 1 wherein the feedstock is biomass.

10. The method of claim 1 wherein the feedstock contains lignin.

11. The method of claim 10 wherein at least a portion of the lignin is solubilized in the ketone.

12. The method of claim 11 further comprising the step(s) of:
(c) separating the lignin portion solubilized in the ketone from ketone adducts; or
(d) separating the lignin portion solubilized in the ketone from unreacted; biomass; or
(e) both steps (c) and step (d).

13. The method of claim 1 further comprising the step of hydrogenating the ketone adducts, such that the resulting product contains less than 5% by weight oxygen.

14. The method of claim 1 further comprising a step of partially hydrogenating and dehydrating the ketone adducts, such that the resulting product contains from 30-20% by weight oxygen.

15. The method of claim 1 wherein the bromide or chloride salt is LiBr and the ketone is acetone.

16. The method of claim 14 wherein the ketone adducts are hydrogenated and dehydrated in the presence of Pt or Pd supported on SiO 2 —Al 2 O 3 .

17. A method for depolymerizing lignin which comprises the step of contacting biomass containing lignin with one or more ketones in the presence of a bromide or chloride salt, mineral acid or formic acid and water at a temperature ranging from 85 to 160° C., wherein the bromide or chloride salt is selected from the group consisting of CaBr 2 , NaBr, LiBr, LiCl, CaCl 2 , MgCl 2 , ZnBr 2 , ZnCl 2 and FeBr 3 .

18. The method of claim 17 wherein the bromide or chloride salt is LiBr and the ketone is acetone.

19. A method for solubilizing at least a portion of the lignin in biomass in a ketone which comprises the step of contacting the biomass containing lignin with one or more ketones in the presence of a bromide or chloride salt, mineral acid or formic acid and water at a temperature ranging from 85 to 160° C., wherein the bromide or chloride salt is selected from the group consisting of CaBr 2 , NaBr, LiBr, LiCl, CaCl 2 , MgCl 2 , ZnBr 2 , ZnCl 2 and FeBr 3 .

20. The method of claim 19 wherein the bromide or chloride salt is LiBr and the ketone is acetone.

21. The method of claim 1 wherein the bromide or chloride salt is selected from CaBr 2 , NaBr, LiBr, or LiCl.

22. The method of claim 1 wherein the ketone and added water form one phase.

23. The method of claim 1 wherein the ketone is water-miscible at reaction temperature.

24. A method for making a hydrocarbon fuel of claim 1 consisting of the steps of:
(a) converting a feedstock containing monosaccharides, oligosaccharides, polysaccharides or a mixture thereof with one or more ketones in the presence of a bromide or chloride salt, mineral acid or formic acid and water to furfural-ketone adducts, hydroxymethylfurfural (HMF)-ketone adducts or both by reacting the feedstock with one or more ketones in the presence of a bromide or chloride salt, mineral acid or formic acid and water; and
(b) at least partially hydrogenating and dehydrating the ketone adducts to form hydrocarbons or oxygenated hydrocarbons, wherein the bromide or chloride salt is selected from the group consisting of CaBr 2 , NaBr, LiBr, LiCl, CaCl 2 , MgCl 2 , ZnBr 2 , ZnCl 2 and FeBr 3 .

Assignees

• Shuai Li
• Pan Xuejun
• Wisconsin Alumni Res Found

Inventors

• Shuai Li
• Pan Xuejun

Classifications

• C10G3/47

  containing platinum group metals or compounds thereof · CPC title

• C10L1/04

  essentially based on blends of hydrocarbons · CPC title

• C10G2300/44

  Solvents · CPC title

• C10G3/50 Primary

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• Y02P30/20

  using bio-feedstock · CPC title