Low-pressure depolymerization of lignocellulosic biomass
Disclosed herein are systems and methods of depolymerizing a lignin component of a lignin-containing material. The method comprising contacting the lignin-containing material with a solvent and optionally a catalyst at a temperature in the range of 180-300° C. and at a maximum operating pressure of less than 10 barG during the depolymerization of the lignin component of the material and collecting at least one volatile stream comprising one or more depolymerized lignin products. In an embodiment, the step of contacting is carried out in a reactive distillation reactor, and the step of collecting comprises concurrently collecting at least one volatile stream via distillation apparatus connected to the reactive distillation reactor, at least one of the one or more depolymerized lignin products comprises a substituted phenol having the following general formula: (I) wherein R 1 is H, methyl, ethyl, n-propyl, propenyl, or allyl, and R 2 and R 3 are independently selected from H or methoxy group.
1. A method of depolymerizing a lignin component of a lignin-containing material comprising:
(i) contacting the lignin-containing material with a solvent and optionally a catalyst at a temperature in the range of 180-300° C. and at a maximum operating pressure of less than 10 barG during the depolymerization of the lignin component of the material, wherein the solvent has a boiling point higher than the reaction temperature; and
(ii) collecting at least one volatile stream comprising one or more depolymerized lignin products, wherein at least one of the one or more depolymerized lignin products comprises a substituted phenol having the following general formula:
wherein R 1 is H, methyl, ethyl, n-propyl, propenyl, or allyl, and R 2 and R 3 are independently selected from H or methoxy group, and
wherein the step of contacting the lignin-containing material with the solvent and optionally the catalyst is carried out in a reactive distillation reactor, and
wherein the step of collecting at least one volatile stream comprises concurrently collecting at least one volatile stream via a distillation apparatus connected to the reactive distillation reactor.
2. The method according to claim 1 , wherein the step of contacting the lignin-containing material with the solvent and optionally the catalyst comprises contacting in the presence of a hydrogenolysis catalyst.
3. The method according to claim 2 , wherein the catalyst comprises Ru, Ni, Raney Ni, Pd, NiPd, NiCu, NiCo, NiRu, RuPd, Fe, Co, Pt, Cu, or mixtures thereof.
4. The method according to claim 3 , wherein the catalyst is supported on a support selected from the group consisting of carbon, alumina, silica, and alumina-silica.
5. The method according to claim 2 , wherein a mass % of catalyst relative to the lignin component of the lignin-containing material is in a range of 0% to 200%.
6. The method according to claim 1 , wherein the solvent is a protic solvent selected from the group consisting of ethylene glycol, glycerin, erythritol, threitol, xylitol, arabitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, monosaccharides, and mixtures thereof.
7. The method according to claim 1 , wherein the step of contacting the lignin-containing material with the solvent and optionally the catalyst comprises contacting in the presence of nitrogen, air or argon, without added hydrogen.
8. The method according to claim 1 , wherein the step of contacting the lignin-containing material with the solvent and optionally the catalyst comprises contacting in the presence of hydrogen at a maximum operating pressure of less than 10 barG.
9. The method according to claim 1 , wherein the step of collecting at least one volatile stream further comprises extracting one or more depolymerized lignin products from at least one of the collected volatile streams by one of distillation, liquid-liquid extraction, chromatography, or extraction by a base followed by acidification.
10. The method according to claim 1 , wherein the volatile depolymerized lignin products comprise 2-methoxy-4-propylphenol, 2-methoxy-4-ethylphenol, 2-methoxyphenol, 2,6-dimethoxy-4-propylphenol, 2,6-dimethoxy-4-ethylphenol, 2,6-dimethoxyphenol, or mixtures thereof.
11. The method according to claim 1 , wherein at least one volatile stream comprises one or more non-phenolic compounds.
12. The method according to claim 11 , wherein the non-phenolic compounds comprise substituted furans, substituted methoxybenzenes, substituted cyclopentanones, substituted cyclopentenones, dioxalanes, solketal, and mixtures thereof.
13. The method according to claim 1 , wherein the lignin-containing material comprises untreated lignocellulosic biomass selected from woods, grasses, cereal crops and waste; partially treated lignocellulosic biomass, an isolated lignin, or mixtures thereof.
14. The method according to claim 1 , wherein the lignin-containing material comprises oak, alder, chestnut, ash, aspen, balsa, beech, birch, boxwood, walnut, laurel, camphor, chestnut, cherry, dogwood, elm, eucalyptus , pear, hickory, ironwood, maple, olive, poplar, sassafras , rosewood, coconut, locust, willow trees, miscanthus , switchgrass, bamboo, straw, barley, millet, wheat, corn stover, sugarcane bagasse, nutshells, olive seeds, tomato peels, brewers' spent grain (BSG), seeds, lignin-containing yard waste, lignin-containing municipal solid waste, lignin residue generated by cellulosic biorefinery and paper pulping industries, and mixtures thereof.
15. The method according to claim 1 , wherein the step of contacting the lignin-containing material with the solvent comprises contacting the lignin-containing material with the catalyst in the reactive distillation reactor, and
wherein the step of collecting at least one volatile stream comprises concurrently collecting at least one volatile stream via distillation apparatus connected to the reactive distillation reactor.
16. The method according to claim 1 , wherein the step of contacting the lignin-containing material with a solvent and optionally a catalyst is carried out in a closed cell reactor, and
wherein the subsequent step of collecting at least one volatile stream comprises collecting at least one volatile stream via distillation apparatus connected to the closed cell reactor, after the step of contacting the lignin-containing material with a solvent and optionally a catalyst.
17. The method of claim 1 comprising:
(i) providing a composition comprising one or more of the depolymerized lignin products collected at least one volatile stream, a solvent, and optionally one or more of the of partially depolymerized lignin, residual cellulose/hemicellulose and other non-lignin feedstock components, wherein the solvent has lower volatility than one or more of the depolymerized lignin products collected at least one volatile stream; and
(ii) distilling one or more depolymerized lignin products collected at least one volatile stream from the composition, wherein at least one of the one or more depolymerized lignin products collected at least one volatile stream comprises a substituted phenol having the following general formula:
wherein R 1 is H, methyl, ethyl, n-propyl, propenyl, allyl, or formyl, and R 2 and R 3 are independently selected from H or methoxy group.
18. The method of claim 17 , wherein the solvent is selected from the group consisting of ethylene glycol, glycerin, erythritol, threitol, xylitol, arabitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, monosaccharides, and mixtures thereof.