Renewable aromatics from lignocellulosic lignin
The present invention provides novel and improved processes for treating a lignocellulosic biomass or technical lignin using ionic liquids to obtain lignin breakdown products and polysaccharide biomass components. Recycling of ionic liquids can be included in the methods of the invention.
1. A method comprising:
(i) contacting a starting material containing lignin, cellulose, hemicellulose, or a mixture thereof with an ionic liquid to generate a solubilized material;
(ii) precipitating at least a fraction of the solubilized material with a precipitant to generate a supernatant and a precipitated fraction comprising the solubilized material wherein the precipitant is selected from the group consisting of octanol, hexanol, and mixtures thereof;
(iii) separating the precipitated fraction from the supernatant, wherein the separated supernatant comprises the precipitant and the ionic liquid;
(iv) adding a solvent directly to the separated supernatant comprising the ionic liquid and the precipitant, wherein the solvent promotes phase separation of the ionic liquid and the precipitant, thereby separating the supernatant into an ionic liquid phase and a precipitant phase; and
(v) isolating the ionic liquid from the ionic liquid phase of step (iv).
2. The method of claim 1 , further comprising isolating the precipitant from the precipitant phase of step (iv).
3. The method of claim 1 , further comprising reusing the ionic liquid, the precipitant, or the ionic liquid and the precipitant.
4. The method of claim 1 , wherein the ionic liquid is selected from the group consisting of [C 2 mim][OAc], EMIM Cl, EMIM HOSO 3 , EMIM MeOSO 3 , EMIM EtOSO 3 , EMIM MeSO 3 , EMIM AlCl 4 , EMIM SCN, BMIM Acetate, BMIM Cl, BMIM HOSO 3 , BMIM MeSO 3 , BMIM MeOSO 3 , BMIM AlCl 4 , BMIM SCN, EDIM EtOSO 3 , MTEOA MeOSO 3 , MIM Cl, MIM HOSO 3 , 1,2,4- trimethylpyrazolium methylsulfate, tributylmethylammonium methylsulfate, choline acetate, and choline salicylate.
5. The method of claim 1 , wherein the ionic liquid is [C 2 mim][OAc].
6. The method of claim 1 , wherein the solvent that promotes phase separation of the ionic liquid and the precipitant in step (iv) is selected from the group consisting of water, ethanol, acetone, and combinations thereof.
7. The method of claim 1 , further comprising extracting low molecular weight or monomeric non-polar aromatic lignin compounds from the supernatant with an extractant.
8. The method of claim 7 , wherein the aromatic lignin compounds are phenols, guaicols, syringols, eugenol, conyferols, catechols, or combinations thereof.
9. The method of claim 1 , wherein the precipitated fraction contains cellulose, hemicellulose, or mixtures thereof.
10. The method of claim 1 , wherein the starting material is selected from the group consisting of switchgrass, pine, eucalyptus, corn stover, corn fiber, hardwood, softwood, cereal straw, Miscanthus, rice hulls, corn fiber, wheat bran, pine wood, wood chips, poplar, bagasse, paper and pulp processing waste, technical lignin, and combinations thereof.
11. The method of claim 1 , wherein step (i) includes forming a mixture containing the ionic liquid and from about 5% to about 50% lignocellulosic biomass by weight.
12. The method of claim 1 , wherein from about 0.1 volumes to about 10 volumes of precipitant, with respect to the ionic liquid, are added to the mixture containing the solubilized material in step (ii).
13. The method of claim 1 , wherein the solvent that promotes phase separation of the ionic liquid and the precipitant in step (iv) is added to the supernatant in an amount of from about 1% (v/v) to about 50% (v/v).