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WO2012075053A2 - Oxydation de la lignine et produits dérivés - Google Patents

Oxydation de la lignine et produits dérivés Download PDF

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Publication number
WO2012075053A2
WO2012075053A2 PCT/US2011/062477 US2011062477W WO2012075053A2 WO 2012075053 A2 WO2012075053 A2 WO 2012075053A2 US 2011062477 W US2011062477 W US 2011062477W WO 2012075053 A2 WO2012075053 A2 WO 2012075053A2
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Prior art keywords
lignin
trihydroxybenzene
acid
subjecting
conditions sufficient
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WO2012075053A3 (fr
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Kim Albizati
Cara Tracewell
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Strategic Enzyme Applications Inc
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Strategic Enzyme Applications Inc
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    • C07—ORGANIC CHEMISTRY
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    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
    • C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
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    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
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    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/51—Phenylenediamines
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    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
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    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/008—Preparation of nitrogen-containing organic compounds containing a N-O bond, e.g. nitro (-NO2), nitroso (-NO)
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    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
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    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/66—Preparation of oxygen-containing organic compounds containing the quinoid structure
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    • C12Y—ENZYMES
    • C12Y110/00—Oxidoreductases acting on diphenols and related substances as donors (1.10)
    • C12Y110/03—Oxidoreductases acting on diphenols and related substances as donors (1.10) with an oxygen as acceptor (1.10.3)
    • C12Y110/03002—Laccase (1.10.3.2)
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    • C12Y114/00—Oxidoreductases acting on paired donors, with incorporation or reduction of molecular oxygen (1.14)
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    • C07C2601/14—The ring being saturated
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    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Biomass means biological material that is used for industrial production (e.g., to generate chemical compounds).
  • Sources of biomass include, but are not limited to, trees, shrubs, grasses, wheat, wheat straw, sugar cane bagasse, corn, corn husks, corn kernel including fiber from kernels, and products and by-products from milling of grains.
  • Lignin comprises about 15% to about 30% the weight of dry wood.
  • compositions and methods for converting lignin e.g., purified or native lignin
  • the single phenyl moiety product is then optionally converted via at least one oxidation step into further desired products, including 2-methoxyphenol, catechol, phenol, muconic acid, adipic acid, butadiene, acrylic acid, methanol, 2-aminophenol, aniline, cyclohexyl carboxylic acid, caprolactam, ortho-phenylenediamine, hydroquinone, 4-aminophenol, para- phenylenediamine, p-terephthalic acid, t-butylhydroquinone, butylated hydro xyanisole, ⁇ - acetylacrylic acid, ⁇ -aminolevulinic acid, and levulinate esters.
  • the aforementioned desired products that are prepared from lignin (e.g., purified or native lignin) into small molecule products having a single phenyl mo
  • a method of obtaining 1,2,4- trihydroxybenzene from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene.
  • the lignin is isolated from biomass. In certain embodiments, the lignin is not isolated from biomass.
  • the oxidative conditions comprise contacting lignin with a ligninase. In certain embodiments, the oxidative conditions comprise contacting lignin with an oxidase, a peroxidase, or both. In some embodiments, the oxidative conditions comprise contacting lignin with an oxidizing agent. In certain embodiments, the oxidative conditions comprise contacting lignin with molecular oxygen; hydrogen peroxide; or both. In some
  • the oxidative conditions comprise contacting lignin with (a) an oxidizing agent; and (b) a metal catalyst.
  • the oxidative conditions comprise contacting lignin with (a) an oxidizing agent; and (b) a metal catalyst selected from a Group VII transition metal; a Group VA metal, or both.
  • the oxidative conditions comprise contacting lignin with (a) an oxidizing agent; and (b) Co, Rh, Ir, MeReC , or combinations thereof.
  • the oxidative conditions comprise contacting lignin with (a) hydrogen peroxide; and (b) MeRe0 3 .
  • provided herein is 1,2,4-trihydroxybenzene obtained according to any method described herein.
  • Also provided herein is a method of obtaining hydroquinone, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce hydroquinone; and hydroquinone obtained thereby.
  • Also provided herein is a method of obtaining 4-aminophenol, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce 4-aminophenol; and 4-aminophenol obtained thereby.
  • Also provided herein is a method of obtaining p-phenylenediamine, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce p- phenylenediamine; and p-phenylenediamine obtained thereby.
  • Also provided herein is a method of obtaining p-terephthalic acid, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce p-terephthalic acid; and p-terephthalic acid obtained thereby.
  • Also provided herein is a method of obtaining t-butylhydroquinone, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce t- butylhydroquinone; and t-butylhydroquinone obtained thereby.
  • Also provided herein is a method of obtaining butylated hydro xyanisole, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4- trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce butylated hydroxyanisole; and butylated hydro xyanisole obtained thereby.
  • Also provided herein is a method of obtaining ⁇ -acetylacrylic acid, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to produce ⁇ -acetylacrylic acid; and ⁇ -acetylacrylic acid obtained thereby.
  • ⁇ -aminolevulinic acid comprising:
  • Also provided herein is a method of obtaining levulinate esters, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene; and
  • the step of subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene comprises (1) contacting lignin with a catalytic amount of nitroarene catalyst to oxidize lignin and provide an inactive nitroarene byproduct; and (2) recycling the nitroarene byproduct to regenerate the nitroarene catalyst.
  • recycling the nitroarene byproduct to regenerate the nitroarene catalyst comprises contacting the nitroarene byproduct with molecular oxygen and a metal catalyst.
  • recycling the nitroarene byproduct to regenerate the nitroarene catalyst comprises contacting the nitroarene byproduct with molecular oxygen and an N-oxygenase.
  • the N- oxygenase is AurF from Streptomyces thioluteus.
  • a compound selected from the group of hydroquinone, 4-aminophenol, terephthalic acid, p-phenylenediamine, butylated
  • hydro xyanisole t-butylhydroquinone
  • ⁇ -acetylacrylic acid levulinate esters
  • ⁇ - aminolevulinic acid wherein the 14 C/C ratio of the compound is greater than 10 ⁇ 15 .
  • a compound selected from the group of 2- methoxyphenol, catechol, phenol, muconic acid, adipic acid, butadiene, 2-aminophenol, aniline, OPDA, caprolactam, wherein the 14 C/C ratio of the compound is greater than 10 ⁇ 15 .
  • Figure 1 illustrates nitroarene byproducts produced by oxidative deconvolution of lignin with nitroarenes.
  • Figure 2 illustrates the depolymerization of lignin and one embodiment of the recycling of catalytic nitroarene from nitroarene byproducts produced by the oxidative depolymerization of lignin with nitroarenes.
  • Figure 3 illustrates recycling of catalytic nitroarene from nitroarene byproducts pro prised by the reduction o f nitro arenes .
  • Figure 4 illustrates the depolymerization of lignin and one embodiment of the recycling of catalytic nitroarene from nitroarene byproducts produced by the oxidative depolymerization of lignin with nitroarenes.
  • Figure 5 illustrates oxidative, reductive and thermal deconvolution to 1,2,4- trihydroxybenzene and downstream processing.
  • Figure 6 illustrates the laccase catalytic cycle without a mediator molecule.
  • Figure 7 illustrates the laccase catalytic cycle with a mediator molecule.
  • Figure 8 illustrates one optional oxidative, reductive, and thermal deconvolution process for the preparation of 1,2,4-trihydroxybenzene.
  • Figure 9 illustrates one optional oxidative and thermal deconvolution process for the preparation of vanillic acid.
  • Figure 10 illustrates various lignin deconvolution processes and downstream processing.
  • Figure 11 illustrates one optional aqueous and catalytic deconvolution process for the preparation of catechol.
  • purified refers to lignin which is at least 50% pure, at least 55% pure, at least 60%> pure, at least 65%> pure, at least 70%> pure, at least 75% pure, at least 80%> pure, at least 85% pure, at least 88% pure, at least 90% pure, at least 93% pure, at least 95% pure, at least 96% pure, at least 97% pure, at least 98% pure, or at least 99% or greater pure.
  • biomass means biological material that is used for industrial production (e.g., to generate chemical compounds).
  • biomass is virgin biomass, non-virgin biomass (e.g., agricultural biomass, commercial organics, and yard waste); or blended biomass.
  • Biomass includes, but is not limited to, trees, shrubs, grasses, wheat, wheat straw, sugar cane bagasse, corn, corn husks, corn stover, corn kernel including fiber from kernels, products and by-products from milling of grains such as corn (including wet milling and dry milling).
  • biomass is used as collected from the field.
  • biomass is processed, for example by milling, grinding, shredding, etc.
  • biomass is treated by chemical or physical means prior to use, for example by treating with acid, treating with base, heating, drying, freezing, or by ensiling (storing for period of time at high moisture content).
  • agricultural biomass includes branches, bushes, canes, corn and corn husks, energy crops, forests, fruits, flowers, grains, grasses, herbaceous crops, leaves, bark, needles, logs, roots, saplings, short rotation woody crops, shrubs, switch grasses, trees, vegetables, vines, and hard and soft woods (not including woods with deleterious materials).
  • the substrate is of high lignocellulose content, including corn stover, corn fiber, Distiller's dried grains, rice straw, hay, sugarcane bagasse, wheat, oats, barley malt and other agricultural biomass, switchgrass, forestry wastes, poplar wood chips, pine wood chips, sawdust, yard waste, wood residues (e.g., sawmill and paper mill discards), paper waste and the like, including any combination of substrate.
  • high lignocellulose content including corn stover, corn fiber, Distiller's dried grains, rice straw, hay, sugarcane bagasse, wheat, oats, barley malt and other agricultural biomass, switchgrass, forestry wastes, poplar wood chips, pine wood chips, sawdust, yard waste, wood residues (e.g., sawmill and paper mill discards), paper waste and the like, including any combination of substrate.
  • solid biomass means any mixture or blend of virgin and non- virgin biomass, preferably having about 5-95% by weight non-virgin biomass.
  • lignin means a water-insoluble macromolecule comprised of three monolignol monomers: p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol.
  • lignin further comprises additional monomeric units. In certain instances, lignin comprises about 15% to about 30% the weight of dry wood. In some embodiments, lignin is isolated from a lignin source (i.e., any source of lignin; e.g., unprocessed biomass and processed biomass). In some embodiments, lignin is not isolated from a lignin source.
  • a lignin source i.e., any source of lignin; e.g., unprocessed biomass and processed biomass. In some embodiments, lignin is not isolated from a lignin source.
  • cellulose means a polysaccharide consisting of a linear chain of about 7,000 to about 15,000 ⁇ (1 ⁇ 4) linked D-glucose units. In certain instances, cellulose comprises about 30%> to about 50%> the weight of dry wood.
  • hemicellulose means a heteropolymer consisting of a branched chain of about 500 to about 3000 sugar (e.g., glucose, xylose, mannose, galactose, rhamnose, and arabinose) units. In certain instances, hemicellulose comprises about 10% to about 35%) the weight of dry wood.
  • sugar e.g., glucose, xylose, mannose, galactose, rhamnose, and arabinose
  • ligninase or "lignin-modifying enzymes” are interchangeable. As used herein, the terms mean an enzyme that catalyzes the breakdown of lignin. In various instances, the enzymes may be oxidative enzymes. In certain instances, the enzymes may be extracellular fungal enzymes, fungal enzymes, bacterial enzymes, or the like. Ligninase includes, but is not limited to, peroxidases (e.g., Lignin peroxidase, Manganese peroxidase and Versatile peroxidase), and phenol-oxidases of Laccase type.
  • peroxidases e.g., Lignin peroxidase, Manganese peroxidase and Versatile peroxidase
  • Fungi that produce ligninase include, but are not limited to, Phanerochaete chrysosporium, Ceriporiopsis subvermispora, Trametes versicolor, Phlebia radiata, Pleurotus ostreatus, Pleurotus eryngii, and Agaricus bisporus.
  • Bacteria that produce ligninase include, but are not limited to, Streptomyces viridosporus T7A, Streptomyces lavendulae REN-7 and Clostridium stercorarium. In some embodiments, the ligninase has been post-translationally modified.
  • a ligninase is produced by fermentation methods and/or recombinant methods. In some embodiments, the ligninase is immobilized.
  • carboxy-lyase and “decarboxylase” are used interchangeably. As used herein, the terms mean a carbon-carbon lyase that adds or removes a carboxyl group from organic compounds.
  • a decarboxylase is produced by fermentation methods and/or recombinant methods. In some embodiments, a decarboxylase is derived from Streptomyces sp., Bacillus megaterium (CAS 68038-67-5), or a combination thereof.
  • the decarboxylases are modified forms of known or naturally- occurring decarboxylases and/or have been selected from a library of naturally-occurring and/or modified decarboxylases. In some embodiments, the decarboxylase has been "post- translationally modified.” In some embodiments, the decarboxylase is immobilized.
  • catechol dioxygenase means a metalloprotein enzyme that catalyzes the oxidative cleavage of catechols.
  • Catechol dioxygenases have several different substrate specificities, including catechol 1 ,2-dioxygenase (EC 1.13.11.1), catechol 2,3-dioxygenase (EC 1.13.11.2), and protocatechuate 3,4-dioxygenase (EC 1.13.11.3).
  • the catechol dioxygenase is an isolated catechol dioxygenase.
  • catechol dioxygenase is selected from a catechol dioxygenase of
  • Pseudomonas putida Escherichia coli
  • Pseudomonas arvill e.g., ATCC 23974
  • the catechol dioxygenase is a naturally occurring enzyme. In some embodiments, the catechol dioxygenase has been isolated from cell culture in which it has been produced by fermentation. In further or alternative embodiments, the catechol dioxygenase has been produced in a recombinant host cell. In further or alternative embodiments, the catechol dioxygenase is a modified form of a naturally occurring enzyme. In some embodiments, the catechol dioxygenase has been "post-translationally modified.” In some embodiments, the catechol dioxygenase is immobilized.
  • post-translationally modified means any modification of an amino acid which occurs after such an amino acid has been translationally incorporated into a polypeptide chain. Such modifications include, but are not limited to, co-translational in vivo modifications, co-translational in vitro modifications (such as in a cell- free translation system), post-translational in vivo modifications, and post-translational in vitro
  • an “alkyl” group refers to an aliphatic hydrocarbon group.
  • the alkyl moiety may be a "saturated alkyl” group, which means that it does not contain any alkene or alkyne moieties.
  • the alkyl moiety may also be an "unsaturated alkyl” moiety, which means that it contains at least one alkene or alkyne moiety.
  • alkene refers to a group consisting of at least two carbon atoms and at least one carbon-carbon double bond
  • an "alkyne” moiety refers to a group consisting of at least two carbon atoms and at least one carbon-carbon triple bond.
  • the alkyl moiety, whether saturated or unsaturated may be branched, straight chain, or cyclic. Furthermore, the alkyl moiety, whether saturated or unsaturated, may comprise branched, straight chain, and/or cyclic portions.
  • an alkyl group can be a monoradical or a diradical (i.e., an alkylene group).
  • a “heteroalkyl” group is as described for “alkyl” with at least one of the C atoms thereof substituted with an N, S, or O atom.
  • the “heteroalkyl” group may comprise linear, branched, and/or cyclic portions.
  • a “lower alkyl” is an alkyl group with 1-6 carbon atoms (i.e., a Ci-C 6 alkyl group). In specific instances, the "lower alkyl” may be straight chained or branched.
  • aryl refers to an aromatic ring wherein each of the atoms forming the ring is a carbon atom.
  • Aryl rings can be formed by five, six, seven, eight, nine, or more than nine carbon atoms.
  • Aryl groups can be optionally substituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, anthracenyl, fluorenyl, and indenyl.
  • an aryl group can be a monoradical or a diradical (i.e., an arylene group).
  • cycloalkyl refers to a monocyclic or polycyclic non-aromatic radical, wherein each of the atoms forming the ring (i.e. skeletal atoms) is a carbon atom.
  • Cycloalkyls may be saturated, or partially unsaturated. Cycloalkyl groups include groups having from 3 to 10 ring atoms. Illustrative examples of cycloalkyl groups include the following moieties:
  • heteroaryl or, alternatively, “hetero aromatic” refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • An N-containing “heteroaromatic” or “heteroaryl” moiety refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • the polycyclic heteroaryl group may be fused or non-fused.
  • Illustrative examples of heteroaryl groups include the following moieties:
  • a heteroaryl group can be a monoradical or a diradical (i.e., a heteroarylene group).
  • heterocycloalkyfgroup refers to a cycloalkyl group that includes at least one ring atom that is not a carbon, i.e. at least one ring atom is a heteroatom selected from nitrogen, oxygen and sulfur.
  • the heterocycloalkyl radicals may be fused with an aryl or heteroaryl.
  • Illustrative examples of heterocycloalkyl groups, also referred to as non- aromatic heterocycles, include:
  • heteroalicyclic also includes all ring forms of the carbohydrates, including but not limited to the monosaccharides, the disaccharides and the oligosaccharides.
  • Heterocycloalkyls have from 2 to 10 carbons in the ring.
  • a "lower heterocycloalkyl” has 2 to 8 ring carbon atoms. It is understood that when referring to the number of carbon atoms in a heterocycloalkyl, the number of carbon atoms in the heterocycloalkyl is not the same at the total number of atoms (including the heteroatoms) that make up the heterocycloalkyl (i.e skeletal atoms of the heterocycloalkyl ring).
  • modulate refers to having some effect on (e.g., increasing, enhancing or maintaining a certain level).
  • the term "optionally substituted” or “substituted” means that the referenced group may be substituted with one or more additional group(s) individually and independently selected from Ci-Cealkyl, Cs-Cscycloalkyl, aryl, heteroaryl, C2-C 6 heteroalicyclic, hydroxy, Ci-Cealkoxy, aryloxy, Ci-Cealkylthio, arylthio, Ci-Cealkylsulfoxide, arylsulfoxide, Ci- Cealkylsulfone, arylsulfone, cyano, halo, C 2 -C 8 acyl, C 2 -Csacyloxy, nitro, Ci-Cehaloalkyl, Ci-Cefluoroalkyl, and amino, including Ci-Cealkylamino, and the protected derivatives thereof.
  • the protecting groups that may form the protective derivatives of the above substituents are known to those of skill in the art and may be found in references such as Greene and Wuts, above.
  • alkyl groups described herein are optionally substituted with an O that is connected to two adjacent carbon atoms (i.e., forming an epoxide).
  • the lignin is obtained from any suitable source. In some embodiments, the lignin is obtained from biomass. In other embodiments, the lignin is not obtained from biomass. In some embodiments, lignin is obtained from biomass comprising a lignin-carbohydrate complex. In some embodiments, the lignin is obtained from lignocellulose.
  • the lignin is obtained from biomass that has been treated by a pretreatment process of the paper, pulp or biofuel industries (e.g., Kraft process, acid hydrolysis, steam explosion, ammonia fiber explosion, ammonia recycle percolation, soaking in aqueous ammonia, lime (with or without oxygen) treatment, alkaline wet oxidation and ozonolysis).
  • a pretreatment process of the paper, pulp or biofuel industries e.g., Kraft process, acid hydrolysis, steam explosion, ammonia fiber explosion, ammonia recycle percolation, soaking in aqueous ammonia, lime (with or without oxygen) treatment, alkaline wet oxidation and ozonolysis.
  • the lignin is purified lignin.
  • the lignin is substantially intact lignin.
  • the lignin utilized in any of the methods described herein is substantially intact.
  • substantially intact means that the lignin comprises coumarylalcohol, coniferylalcohol and sinapylalcohol condensation moieties that have not been substantially or significantly modified by a process described herein (e.g., the coumarylalcohol, coniferylalcohol and sinapylalcohol condensation moieties of the lignin are substantially in their natural state).
  • the lignin utilized in a method described herein is
  • 1,2,4-trihydroxybenzene obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining 1,2,4- trihydroxybenzene from lignin. It is to be understood that provided in various embodiments herein are both (1) 1,2,4-trihydroxybenzene prepared according to any of the processes described herein for preparing 1,2,4-trihydroxybenzene from a lignin source; and (2) any process described herein for preparing 1,2,4-trihydroxybenzene from a lignin source.
  • a method of obtaining 1,2,4- trihydroxybenzene from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein.
  • the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non-limiting example, heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 475° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • a method of obtaining 1,2,4- trihydroxybenzene from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene.
  • the method comprises contacting lignin with a ligninase.
  • the enzymatic reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the ligninase is an oxidative ligninase.
  • the ligninase is a peroxidase, an oxidase, or combinations thereof.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • heating a lignin containing combination includes, by way of non-limiting example, heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 475° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • the peroxidase is an isolated peroxidase. In some embodiments, the peroxidase is an isolated peroxidase.
  • the peroxidase is produced by fermentation methods and/or recombinant methods.
  • the peroxidase is a naturally-occurring peroxidase.
  • the peroxidase is a modified form of a known or naturally-occurring peroxidase and/or has been selected from a library of naturally-occurring and/or modified peroxidases.
  • the oxidase is an isolated oxidase. In some embodiments, the oxidase is produced by fermentation methods and/or recombinant methods. In some embodiments, the oxidase is a modified form of a known or naturally-occurring oxidase and/or has been selected from a library of naturally-occurring and/or modified oxidases.
  • a method of obtaining 1,2,4- trihydroxybenzene from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene.
  • the method comprises contacting lignin with an oxidizing agent.
  • the oxidizing agent is hydrogen peroxide (H 2 0 2 ).
  • the oxidizing agent is molecular oxygen (i.e., 0 2 ).
  • the oxidizing agent is a nitroarene, such as nitrobenzene (e.g., catalytic nitrobenzene) or substituted nitrobenzene.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass. In some embodiments, the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non- limiting example, heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 475° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • the oxidizing agent is a nitroarene.
  • the use of non- catalytic amounts of nitroarene in oxidizing lignin can be commercially cost prohibitive.
  • the oxidizing agent is catalytic nitroarene (e.g., catalytic nitrobenzene and/or substituted nitrobenzene). Oxidation of lignin produces inactive (i.e., reduced) nitroarene byproducts.
  • Figure 1 illustrates one embodiment wherein the reduction of nitrobenzene and various byproducts results from use of such oxidants.
  • a method described herein further comprises recycling these inactive nitroarene byproducts, e.g., by re-oxidizing the reduced nitroarene byproducts to an active oxidizing agent, e.g., a catalytic nitroarene.
  • an active oxidizing agent e.g., a catalytic nitroarene.
  • the nitroarene oxidizes lignin and is recycled in a single pot.
  • the nitroarene byproducts are removed from the lignin oxidation system, re-oxidized, and returned to the lignin oxidation system.
  • nitroarene oxidation of lignin is performed at ambient or low pressure (e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm).
  • nitroarene oxidation of lignin is performed at ambient or low temperature (e.g., less than 80 °C, less than 75 °C, less than 70 °C, less than 65 °C, less than 60 °C, less than 55 °C, less than 50 °C, less than 45 °C, less than 40 °C, less than 35 °C, less than 30 °C, or less than 25 °C).
  • an additional additive is added to the lignin/nitroarene combination.
  • the additive is an additive for improving aldehyde yields (e.g., an anthraquinone).
  • the nitroarene byproducts are re-oxidized utilizing any suitable system.
  • the nitroarene byproducts are re-oxidized utilizing an oxidizing agent (e.g., molecular oxygen) and a metal catalyst (e.g., a molybdenum catalyst, a rhenium catalyst, a tungsten catalyst, a cobalt (e.g., Co 2+ ) catalyst, or the like).
  • Figure 2 illustrates oxidation of lignin and recycling of nitroarene catalysts according to one embodiment of a process described herein. Specifically, Figure 2 illustrates an electron transport from lignin to, eventually, molecular oxygen.
  • the metal catalyst is utilized in an amount of less than 5 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In more specific embodiments, the metal catalyst is utilized in an amount of less than 1 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In some embodiments, the metal catalyst is utilized in an amount of less than 0.5 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In some embodiments, the metal catalyst is utilized in an amount of less than 0.1 mol % (e.g., compared to the amount of nitroarene catalyst utilized).
  • the metal catalyst is utilized in an amount of less than 0.05 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In some embodiments, the metal catalyst is utilized in an amount of less than 0.01 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In other specific embodiments, the metal catalyst is utilized in an amount of 0.01 mol % to about 1 mol % (e.g., compared to the amount of nitroarene catalyst utilized).
  • re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low pressure (e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm). In some embodiments, re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low temperature (e.g., less than 80 °C, less than 75 °C, less than 70 °C, less than 65 °C, less than 60 °C, less than 55 °C, less than 50 °C, less than 45 °C, less than 40 °C, less than 35 °C, less than 30 °C, or less than 25 °C). In certain embodiments, provided herein is a composition comprising lignin, nitroarene, and a metal catalyst. In some embodiments, the composition further comprises any compound of Formula I:
  • R a is CHO, COOH, CH 2 OH, COCH 3 , or CHOHCH 3 ; and R b is H, OCH 3 , or COOH.
  • the nitroarene catalytic byproducts are re-oxidized by contacting the nitroarene byproducts with an N-oxygenase (e.g., the N-oxygenase AurF, such as from Streptomyces thioluteus).
  • an oxidizing agent such as molecular oxygen (e.g., air) is utilized in combination with the N-oxygenase, e.g., as a terminal oxidant of the catalytic nitroarene recycling process.
  • Figure 3 illustrates recycling of nitroarene catalytic byproducts with AurF according to one embodiment of a process described herein.
  • Figure 4 illustrates oxidation of lignin and recycling of nitroarene catalysts according to one embodiment of a process described herein. Specifically, Figure 4 illustrates an electron transport from lignin to, eventually, molecular oxygen. In certain embodiments, re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low pressure (e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm).
  • ambient or low pressure e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm.
  • re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low temperature (e.g., less than 80 °C, less than 75 °C, less than 70 °C, less than 65 °C, less than 60 °C, less than 55 °C, less than 50 °C, less than 45 °C, less than 40 °C, less than 35 °C, less than 30 °C, or less than 25 °C).
  • ambient or low temperature e.g., less than 80 °C, less than 75 °C, less than 70 °C, less than 65 °C, less than 60 °C, less than 55 °C, less than 50 °C, less than 45 °C, less than 40 °C, less than 35 °C, less than 30 °C, or less than 25 °C.
  • a composition comprising lignin, nitroarene, and an N-oxygenase (e.g., AurF).
  • a nitroarene group described herein is a compound of Formula II:
  • R is 0-4 substituents, each of which independently are, by way of non-limiting example, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
  • Q is, by way of non-limiting example, H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, cyano, nitro, hydroxy, thiol, arylthio, Ci-Cealkylsulfoxide, arylsulfoxide, Ci-Cealkylsulfone, arylsulfone, cyano, halo, C 2 -Csacyl, C 2 -Csacyloxy, Ci-C 6 haloalkyl, Ci-Cefiuoroalkyl, and amino, including Ci-Cealkylamino, or L q R q , wherein each L q is independently selected from a bond, -0-
  • R q is independently selected from H, (Ci-C 4 alkyl), (Cs-Cscycloalkyl), heteroaryl, aryl, or Ci-Ceheteroalkyl.
  • Q is a hydrogen bond donor group.
  • R is an electron withdrawing group. In other embodiments, R is an electron releasing group.
  • any method described herein for obtaining 1 ,2,4- trihydroxybenzene from lignin further comprises contacting lignin with a metal catalyst.
  • the metal catalyst is a transition metal.
  • the metal catalyst is a Group VII transition metal.
  • the metal catalyst is Co, Rh, Ir, or combinations thereof.
  • the catalyst is a Cobalt catalyst (e.g., a Co(II) catalyst).
  • the metal catalyst is a Group VA metal.
  • the metal catalyst is Bi.
  • the metal catalyst is methyltrioxorhenium (VII) (MeReC ⁇ ).
  • a method of obtaining 1 ,2,4- trihydroxybenzene from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce 1 ,2,4-trihydroxybenzene.
  • the method comprises contacting lignin with hydrogen peroxide and MeReOs.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein.
  • the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non- limiting example, heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • Figure 5 illustrates a process of producing 1,2,4-trihydroxybenzene from lignin according to one embodiment of a process described herein.
  • lignin is oxidized to an oxidative chemical suite, wherein the oxidative chemical suite is a combination of aromatic compounds, by use of an oxidizing system comprising, e.g., an enzyme (e.g., ligninase, peroxidase, oxidase, or combination thereof); a metal catalyst; nitroarene (e.g., nitrobenzene); oxygen; peroxide; or a combination thereof.
  • an enzyme e.g., ligninase, peroxidase, oxidase, or combination thereof
  • nitroarene e.g., nitrobenzene
  • oxygen peroxide
  • peroxide or a combination thereof.
  • lignin is oxidized with nitroarene (e.g., nitrobenzene and/or substituted nitrobenzene).
  • the oxidative chemical suite obtained by oxidizing lignin is further deconvo luted to 1,2,4-trihydroxybenzene, e.g., by 1) oxidative cleavage; 2) reduction; and 3) optional thermal decarboxylation, decarbonylation, and/or demethylation, as illustrated in Sche
  • R 1 C-i and C 2 chains (5 identities)
  • R 2 H, OCH 3 , or C-i chain (5 identities)
  • the combination of oxidative compounds are subjected to conditions suitable for oxidative cleavage using an enzyme (e.g., Lacasse, ligninase, peroxidase, oxidase, or combination thereof); a metal catalyst (e.g., NaN0 2 /H + ); oxygen; peroxide; a mediator molecule; or a combination thereof.
  • an enzyme e.g., Lacasse, ligninase, peroxidase, oxidase, or combination thereof
  • a metal catalyst e.g., NaN0 2 /H +
  • oxygen peroxide
  • a mediator molecule e.g., oxide
  • Figure 6 illustrates oxidation of the chemical suite and recycling of laccase without a mediator molecule according to one embodiment of a process described herein.
  • Figure 7 illustrates oxidation of the chemical suite recycling of laccase in the presence of a mediator molecule according to one embodiment of a process described herein.
  • the oxidative cleavage mixture is optionally heated to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • oxidation of the oxidative chemical suite provides intermediate quinones, e.g. as illustrated in Figure 5. In other embodiments, the intermediate quinones are not observed.
  • decarboxylation/decarbonylation/demethylation occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a mixture containing combination includes, by way of non-limiting example, heating to at least room temperature, at least 25° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 60° C, at least 70° C, at least 80° C, at least 90° C, at least 100° C, at least 125° C, at least 150° C, at least 175° C, at least 180° C, or at least 200° C.
  • demethylation occurs by heating the mixture of intermediates to greater than 100° C.
  • decarboxylation/decarbonylation/demethylation occurs in the presence of water.
  • reduction of the optional quinone intermediate occurs in the presence of hydrogen.
  • reduction of the optional quinone intermediate occurs in water and at 1 atm of hydrogen.
  • the reducing mixture is optionally heated to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • the optional quinone intermediate is subjected to reaction conditions suitable for decarboxylation/decarbonylation/demethylation prior to reaction conditions suitable for reduction. In other embodiments, the optional quinone intermediate is subjected to reaction conditions suitable for reduction prior to reaction conditions suitable for decarboxylation/decarbonylation/demethylation. In further or additional embodiments, the optional quinone intermediate is subjected to conditions suitable for reduction and decarboxylation/decarbonylation/demethylation concurrently.
  • Figure 8 illustrates a specific embodiment of this process, i.e., oxidation of the combination of aromatic compounds obtained by oxidizing lignin with molecular oxygen and Laccase, optionally reducing, and optionally decarboxylating, decarbonylating, and/or demethylating, e.g., by thermal mechanisms.
  • other oxidizing agent(s) and optional catalysts are utilized.
  • a process described herein comprises preparing 1,2,4- trihydroxybenzene from lignin, whereby 1,2,4-trihydroxybenzene is prepared from the lignin in a yield of about 5% to about 60% by weight of the lignin. In some embodiments, 1,2,4-trihydroxybenzene is prepared from the lignin in a yield of about 15% to about 50% by weight of the lignin.
  • the 1,2,4-trihydroxybenzene is isolated from the remaining lignin. In some embodiments, 1,2,4-trihydroxybenzene is isolated by any method suitable.
  • the 1,2,4-trihydroxybenzene is separated from the lignin by use of a solvent. In some embodiments, the 1,2,4-trihydroxybenzene is separated from the lignin by use of a solvent in which the 1,2,4-trihydroxybenzene is soluble and the lignin is either insoluble or sparingly soluble. In some embodiments, the 1,2,4-trihydroxybenzene is separated from the lignin by use of a solvent in which 1,2,4-trihydroxybenzene is either insoluble or sparingly soluble and lignin is soluble. In some embodiments, the solvent and the soluble components are separated from the insoluble components by any suitable method (e.g., filtration). Where the 1,2,4-trihydroxybenzene is soluble, in some
  • the 1,2,4-trihydroxybenzene is precipitated from the solvent.
  • the method comprises washing the 1,2,4-trihydroxybenzene with a second solvent to further remove impurities.
  • the solvent with which the purified 1,2,4-trihydroxybenzene is extracted is a tunable solvent, such as a gas-expanded liquid.
  • the 1,2,4-trihydroxybenzene/residual lignin material is washed with a first solvent in which 1,2,4-trihydroxybenzene is either insoluble or sparingly soluble and subsequently washed with a second solvent in which 1,2,4-trihydroxybenzene is soluble.
  • (a) 1,2,4-trihydroxybenzene and the residual lignin material are washed with a first solvent; (b) the first solvent is removed (e.g., by evaporation or filtration); and (c) the 1,2,4-trihydroxybenzene is further purified (i) by washing the 1,2,4- trihydroxybenzene with a second solvent in which the 1,2,4-trihydroxybenzene is insoluble (or sparingly soluble) and in which at least some of the contaminants are at least partially soluble, (ii) by dissolving the 1,2,4-trihydroxybenzene in a second solvent in which at least some of the contaminants are insoluble (or sparingly soluble), and/or (iii) by dissolving the 1,2,4-trihydroxybenzene and at least some of the contaminants in a second solvent and selectively precipitating 1,2,4-trihydroxybenzene and/or the various contaminants from the second solvent.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • any compound processed from 1,2,4- trihydroxybenzene wherein the 1,2,4-trihydroxybenzene is obtained from lignin.
  • hydroquinone obtained from lignin is hydroquinone obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining hydroquinone from lignin. It is to be understood that provided in various embodiments herein are both (1) hydroquinone prepared according to any of the processes described herein; and (2) any method described herein for obtaining hydroquinone from a lignin source.
  • a method of obtaining hydroquinone from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to hydroquinone.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • heating comprises heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • converting 1,2,4-trihydroxybenzene to hydroquinone comprises hydro genolyzing 1,2,4-trihydroxybenzene.
  • hydro genolyzing 1,2,4-trihydroxybenzene comprises contacting 1,2,4-trihydroxybenzene with a metal catalyst and hydrogen under conditions that instigate or maximize the catalytic reaction.
  • hydro genolyzing 1,2,4-trihydroxybenzene comprises contacting 1,2,4- trihydroxybenzene with a metal catalysts and hydrogen followed by heating the
  • hydro genolyzing 1,2,4-trihydroxybenzene comprises contacting 1,2,4-trihydroxybenzene with super critical or near critical water.
  • supercritical water is water heated to about 400° C and at about 23 MPa.
  • near critical water is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • hydrogen and 1,2,4-trihydroxybenzene are present in a ratio of molecules of hydrogen to molecules of 1,2,4-trihydroxybenzene of about 2: 1 to about 50: 1.
  • the catalyst is a multicomponent metal oxide comprising a Group VB, VIB, VIII, IB, IIB, IVA and/or VA metal.
  • the catalyst is Pd, Pt, or Rh.
  • the catalyst is Rh/Al 2 0 3 , Rh/C, Pt/C or Pd/C.
  • the catalyst is BfVO 4 , CuW0 4 , Cuo.75Zno. 2 5W0 4 , or CuW0 4 + Ce, CuO-Al 2 0 3 .
  • the metal catalyst/hydrogen/l,2,4-trihydroxybenzene combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • 1,2,4-trihydroxybenzene, hydrogen, and the catalyst are contacted at a pressure of about 1- 100 bar.
  • 1,2,4-trihydroxybenzene, hydrogen, and the catalyst are contacted at a temperature of about 250° C to about 500° C and a pressure of about 1-100 bar.
  • the hydroquinone product is obtained from lignin without isolation of 1,2,4-trihydroxybenzene.
  • methanol is isolated from the reaction mixture.
  • the hydroquinone is isolated from the remaining 1,2,4- trihydroxybenzene. In some embodiments, hydroquinone is isolated by any method suitable.
  • the hydroquinone is isolated from the remaining 1,2,4- trihydroxybenzene by use of a solvent. In some embodiments, the hydroquinone is isolated from the remaining 1,2,4-trihydroxybenzene by use of a solvent in which the 1,2,4- trihydroxybenzene is soluble and the hydroquinone is either insoluble or sparingly soluble. In some embodiments, the 1,2,4-trihydroxybenzene is separated from the hydroquinone by use of a solvent in which 1,2,4-trihydroxybenzene is either insoluble or sparingly soluble and hydroquinone is soluble. In some embodiments, the solvent and the soluble components are separated from the insoluble components by any suitable method (e.g., filtration).
  • the hydroquinone is precipitated from the solvent.
  • the method comprises washing the hydroquinone with a second solvent to further remove impurities.
  • the solvent with which the purified hydroquinone is extracted is a tunable solvent, such as a gas-expanded liquid.
  • the 1,2,4-trihydroxybenzene/hydroquinone combination is washed with a first solvent in which hydroquinone is either insoluble or sparingly soluble and subsequently washed with a second solvent in which hydroquinone is soluble.
  • hydroquinone and the residual 1,2,4-trihydroxybenzene material are washed with a first solvent; (b) the first solvent is removed (e.g., by
  • the hydroquinone is further purified (i) by washing the hydroquinone with a second solvent in which the hydroquinone is insoluble (or sparingly soluble) and in which at least some of the contaminants are at least partially soluble, (ii) by dissolving the hydroquinone in a second solvent in which at least some of the contaminants are insoluble (or sparingly soluble), and/or (iii) by dissolving the hydroquinone and at least some of the contaminants in a second solvent and selectively precipitating hydroquinone and/or the various contaminants from the second solvent. iii. Use of a Reactor
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • 4-aminophenol (4-AP) obtained from lignin is 4-aminophenol (4-AP) obtained from lignin.
  • the 4-AP is suitable for use in dyes, acetaminophen production, and as an antioxidant.
  • a method of obtaining 4-aminophenol from lignin is a method of obtaining 4-aminophenol from lignin. It is to be understood that provided in various embodiments herein are both (1) 4-aminophenol prepared according to any of the processes described herein; and (2) any method described herein for obtaining 4- aminophenol from a lignin source.
  • a method of obtaining 4-aminophenol from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to 4-aminophenol.
  • a method of obtaining 4-aminophenol from lignin comprises (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to 2-hydroxy-4-aminophenol; and (c) subjecting 2-hydroxy-4-aminophenol to conditions sufficient to convert 2-hydroxy-4- aminophenol to 4-aminophenol.
  • a method of obtaining 4- aminophenol from lignin comprises (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to hydroquinone; and (c) subjecting hydroquinone to conditions sufficient to convert hydroquinone to 4-aminophenol.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating comprises heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to 2-hydroxy-4-aminophenol, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 2-hydroxy-4-aminophenol.
  • any residual material e.g., lignin
  • 1,2,4-trihydroxybenzene is converted to 2-hydroxy-4- aminophenol by amination.
  • 1,2,4-trihydroxybenzene is contacted with ammonia (NH 3 ) and a metal catalyst and/or a zeolite catalyst.
  • the metal catalyst is Zn, Pd, Pt, A1 2 0 3 , MgO, Zr0 2 , Ti0 2 , Nb 2 0 5 , Va oxides, Sn, La, Cu, and/or spinel.
  • 1,2,4-trihydroxybenzene is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210, which is incorporated herein for such disclosure.
  • the contacting occurs under conditions sufficient to convert 1,2,4-trihydroxybenzene to 2- hydroxy-4-aminopheno 1.
  • the amination reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 100° C, at least 125° C, at least 140° C, at least 165° C, at least 200° C, at least 225° C, at least 250° C, at least 300° C, at least 350° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 250 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • 2-hydroxy-4-aminophenol is separated or extracted from any residual material (e.g., lignin and/or 1,2,4-trihydroxybenzene) prior to converting it to 4-aminophenol, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 4-aminophenol.
  • any residual material e.g., lignin and/or 1,2,4-trihydroxybenzene
  • 2-hydroxy-4-aminophenol is converted to 4- aminophenol.
  • converting 2-hydroxy-4-aminophenol to 4- aminophenol comprises hydro genolyzing 2-hydroxy-4-aminophenol such that 4- aminophenol is produced.
  • hydro geno lysis comprises contacting the 2-hydroxy-4-aminophenol with supercritical or near critical water.
  • “supercritical water” is water heated to about 400° C and at about 23 MPa.
  • “near critical water” is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • hydro genolyzing 2-hydroxy-4-aminophenol comprises contacting 2-hydroxy-4-aminophenol with a metal catalyst and hydrogen under conditions that instigate or maximize the catalytic reaction.
  • hydro genolyzing 2-hydroxy-4- aminophenol comprises contacting 2-hydroxy-4-aminophenol with a metal catalysts and hydrogen followed by heating the combination.
  • hydrogen and 2- hydroxy-4-aminophenol are present in a ratio of molecules of hydrogen to molecules of 2- hydroxy-4-aminophenol of about 2: 1 to about 50: 1.
  • the catalyst is a multi-component metal oxide comprising a Group VB, VIB, VIII, IB, IIB, IVA and/or VA metal.
  • the catalyst is Pd, Pt, or Rh.
  • the catalyst is Rh/Al 2 0 3 , Rh/C, Pt/C or Pd/C.
  • the metal catalyst/hydrogen/2-hydroxy-4-aminophenol combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • 2-hydroxy-4-aminophenol, hydrogen, and the catalyst are contacted at a pressure of about 1- 100 bar.
  • 2-hydroxy-4-aminophenol, hydrogen, and the catalyst are contacted at a temperature of about 250° C to about 500° C and a pressure of about 1-100 bar.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to hydroquinone, and in other embodiments, is not separated or extracted from any residual material prior to converting it to hydroquinone.
  • 1,2,4-trihydroxybenzene is converted to hydroquinone by any method disclosed herein.
  • hydroquinone is separated or extracted from any residual material (e.g., lignin, 1,2,4-trihydroxybenzene) prior to converting it to 4-aminophenol, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 4-aminophenol.
  • hydroquinone is converted to 4-aminophenol by amination.
  • hydroquinone is contacted with ammonia (NH 3 ) and a metal catalyst and/or a zeolite catalyst.
  • hydroquinone is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210.
  • the metal catalyst is Zn, Pd, Pt, A1 2 0 3 , MgO, Zr0 2 , Ti0 2 , Nb 2 C"5, Va oxides, Sn, La, Cu, and/or spinel.
  • the contacting occurs under conditions sufficient to convert hydroquinone to 4-aminophenol.
  • the amination reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 100° C, at least 125° C, at least 140° C, at least 165° C, at least 200° C, at least 225° C, at least 250° C, at least 300° C, at least 350° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 250 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • the 4-aminophenol is isolated from any remaining lignin, 1,2,4-trihydroxybenzene, hydroquinone and/or 2-hydroxy-4-aminophenol. In some embodiments, 4-aminophenol is isolated by any suitable method. In some embodiments, 4- aminophenol is isolated from any remaining lignin, 2-hydroxy-4-aminophenol, 1,2,4- trihydroxybenzene, and/or hydroquinone by use of a solvent. In some embodiments, 4- aminophenol is isolated from any remaining lignin, 2-hydroxy-4-aminophenol, 1,2,4- trihydroxybenzene, and/or hydroquinone by use of at least two solvents,
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • p-phenylenediamine obtained from lignin is suitable for use in dyes, polymer synthesis, and as an antioxidant.
  • a method of obtaining p-phenylenediamine from lignin is both (1) p-phenylenediamine prepared according to any of the processes described herein; and (2) any method described herein for obtaining p- phenylenediamine from a lignin source.
  • a method of obtaining p- phenylenediamine from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to p-phenylenediamine.
  • a method of obtaining p-phenylenediamine from lignin comprises (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4- trihydroxybenzene to 2,5-diaminophenol; and (c) subjecting 2,5-diaminophenol to conditions sufficient to convert 2,5-diaminophenol to p-phenylenediamine.
  • a method of obtaining p-phenylenediamine from lignin comprises (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1 ,2,4- trihydroxybenzene to hydroquinone; and (c) subjecting hydroquinone to conditions sufficient to convert hydroquinone to p-phenylenediamine.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to 2,5-diaminophenol, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 2,5-diaminophenol.
  • any residual material e.g., lignin
  • 1,2,4-trihydroxybenzene is converted to 2,5- diaminophenol by amination.
  • 1,2,4-trihydroxybenzene is contacted with ammonia (NH 3 ) and a metal catalyst and/or a zeolite catalyst.
  • the metal catalyst is Zn, Pd, Pt, A1 2 0 3 , MgO, Zr0 2 , Ti0 2 , Nb 2 0 5 , Va oxides, Sn, La, Cu, and/or spinel.
  • 1,2,4-trihydroxybenzene is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210, which is incorporated herein for such disclosure.
  • the contacting occurs under conditions sufficient to convert 1,2,4-trihydroxybenzene to 2,5- diaminophenol.
  • the amination reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 100° C, at least 125° C, at least 140° C, at least 165° C, at least 200° C, at least 225° C, at least 250° C, at least 300° C, at least 350° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 250 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • 2,5-diaminophenol is separated or extracted from any residual material (e.g., lignin and/or 1 ,2,4-trihydroxybenzene) prior to converting it to p- phenylenediamine, and in other embodiments, is not separated or extracted from any residual material prior to converting it to p-phenylenediamine.
  • any residual material e.g., lignin and/or 1 ,2,4-trihydroxybenzene
  • 2,5-diaminophenol is converted to p-phenylenediamine.
  • converting 2,5-diaminophenol to p-phenylenediamine comprises hydro genolyzing 2,5-diaminophenol such that p-phenylenediamine is produced.
  • hydro geno lysis comprises contacting the 2,5-diaminophenol with
  • supercritical water is water heated to about 400° C and at about 23 MPa.
  • near critical water is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • hydro genolyzing 2,5-diaminophenol comprises contacting 2,5-diaminophenol with a metal catalyst and hydrogen under conditions that instigate or maximize the catalytic reaction.
  • hydro genolyzing 2,5-diaminophenol comprises contacting 2,5-diaminophenol with a metal catalysts and hydrogen followed by heating the combination.
  • hydrogen and 2,5-diaminophenol are present in a ratio of molecules of hydrogen to molecules of 2,5-diaminophenol of about 2: 1 to about 50: 1.
  • the catalyst is a multi-component metal oxide comprising a Group VB, VIB, VIII, IB, IIB, IVA and/or VA metal.
  • the catalyst is Pd, Pt, or Rh.
  • the catalyst is Rh/Al 2 0 3 , Rh/C, Pt/C or Pd/C.
  • the metal catalyst/hydrogen/2,5-diaminophenol combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • 2,5-diaminophenol, hydrogen, and the catalyst are contacted at a pressure of about 1-100 bar.
  • 2,5-diaminophenol, hydrogen, and the catalyst are contacted at a temperature of about 250° C to about 500° C and a pressure of about 1-100 bar.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to hydroquinone, and in other embodiments, is not separated or extracted from any residual material prior to converting it to hydroquinone.
  • 1,2,4-trihydroxybenzene is converted to hydroquinone by any method disclosed herein.
  • hydroquinone is separated or extracted from any residual material (e.g., lignin, 1,2,4-trihydroxybenzene) prior to converting it to p-phenylenediamine, and in other embodiments, is not separated or extracted from any residual material prior to converting it to p-phenylenediamine.
  • hydroquinone is converted to p-phenylenediamine by amination.
  • hydroquinone is contacted with ammonia (NH 3 ) and a metal catalyst and/or a zeolite catalyst.
  • hydroquinone is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210.
  • the metal catalyst is Zn, Pd, Pt, A1 2 0 3 , MgO, Zr0 2 , Ti0 2 , Nb 2 C"5, Va oxides, Sn, La, Cu, and/or spinel.
  • the contacting occurs under conditions sufficient to convert hydroquinone to p- pheny lenediamine .
  • the amination reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 100° C, at least 125° C, at least 140° C, at least 165° C, at least 200° C, at least 225° C, at least 250° C, at least 300° C, at least 350° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 250 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • iii Isolation of p-phenylenediamine
  • the p-phenylenediamine is isolated from any remaining lignin, 1,2,4-trihydroxybenzene, hydroquinone and/or 2,5-diaminophenol. In some embodiments, p-phenylenediamine is isolated by any suitable method. In some
  • p-phenylenediamine is isolated from any remaining lignin, 2,5- diaminophenol, 1,2,4-trihydroxybenzene, and/or hydroquinone by use of a solvent. In some embodiments, p-phenylenediamine is isolated from any remaining lignin, 2,5- diaminophenol, 1,2,4-trihydroxybenzene, and/or hydroquinone by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • terephthalic acid obtained from lignin is terephthalic acid obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining terephthalic acid from lignin. It is to be understood that provided in various embodiments herein are both (1) terephthalic acid prepared according to any of the processes described herein; and (2) any method described herein for obtaining terephthalic acid from a lignin source.
  • a method of obtaining terephthalic acid from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to terephthalic acid.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to terephthalic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to terephthalic acid.
  • any residual material e.g., lignin
  • converting 1,2,4-trihydroxybenzene to terephthalic acid comprises contacting 1,2,4-trihydroxybenzene with a catechol dioxygenase (e.g., catechol 2,3-dioxygenase).
  • a catechol dioxygenase e.g., catechol 2,3-dioxygenase
  • the pyrone intermediate is optionally observed.
  • conversion of the optional pyrone intermediate to terephthalic acid comprises contacting the optional pyrone with ethylene under conditions suitable for cyclocondensation.
  • the conversion to terephthalic acid occurs under conditions that instigate or maximize the reaction.
  • any suitable metal catalyst is used to promote cyclocondensation.
  • conversion of 1,2,4- trihydroxybenzene to terephthalic acid comprises contacting 1,2,4-trihydroxybenzene with a catechol dioxygenase, ethylene, and optionally a metal catalysts followed by heating the combination.
  • the catechol dioxygenase /ethylene/1, 2,4- trihydroxybenzene combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • 1,2,4-trihydroxybenzene, ethylene, and the enzyme are contacted at a pressure of about 1-150 bar.
  • 1,2,4-trihydroxybenzene, ethylene, and the enzyme are contacted at a temperature of about 200° C to about 400° C and a pressure of about 1-150 bar.
  • the terephthalic acid product can be obtained from lignin without isolation of 1,2,4-trihydroxybenzene.
  • the terephthalic acid is isolated from the remaining 1,2,4- trihydroxybenzene. In some embodiments, terephthalic acid is isolated by any method suitable. [00140] In some embodiments, the terephthalic acid is isolated from the remaining 1,2,4- trihydroxybenzene by use of a solvent. In some embodiments, the terephthalic acid is isolated from the remaining 1,2,4-trihydroxybenzene by use of a solvent in which the 1,2,4- trihydroxybenzene is soluble and the terephthalic acid is either insoluble or sparingly soluble.
  • the 1,2,4-trihydroxybenzene is separated from the terephthalic acid by use of a solvent in which 1,2,4-trihydroxybenzene is either insoluble or sparingly soluble and terephthalic acid is soluble.
  • the solvent and the soluble components are separated from the insoluble components by any suitable method (e.g., filtration). Where the terephthalic acid is soluble, in some embodiments, the terephthalic acid is precipitated from the solvent.
  • the method comprises washing the terephthalic acid with a second solvent to further remove impurities.
  • the solvent with which the purified terephthalic acid is extracted is a tunable solvent, such as a gas-expanded liquid.
  • the 1,2,4-trihydroxybenzene/terephthalic acid [00141] In some embodiments, the 1,2,4-trihydroxybenzene/terephthalic acid
  • terephthalic acid and the residual 1,2,4- trihydroxybenzene material are washed with a first solvent;
  • the first solvent is removed (e.g., by evaporation or filtration); and
  • the terephthalic acid is further purified (i) by washing the terephthalic acid with a second solvent in which the terephthalic acid is insoluble (or sparingly soluble) and in which at least some of the contaminants are at least partially soluble, (ii) by dissolving the terephthalic acid in a second solvent in which at least some of the contaminants are insoluble (or sparingly soluble), and/or (iii) by dissolving the terephthalic acid and at least some of the contaminants in a second solvent and selectively precipitating terephthalic acid and/or the various contaminants from the second solvent, iii.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch-flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor. E. t-Butylhydroquinone
  • t-butylhydroquinone obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining t- butylhydroquinone from lignin. It is to be understood that provided in various embodiments herein are both (1) t-butylhydroquinone prepared according to any of the processes described herein; and (2) any method described herein for obtaining t-butylhydroquinone from a lignin source.
  • a method of obtaining t- butylhydroquinone from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1 ,2,4-trihydroxybenzene, and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to t-butylhydroquinone.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to t-butylhydroquinone, and in other embodiments, is not separated or extracted from any residual material prior to converting it to t-butylhydroquinone.
  • any residual material e.g., lignin
  • converting 1,2,4-trihydroxybenzene to t- butylhydroquinone comprises contacting 1,2,4-trihydroxybenzene with t-butanol or isobutylene. In some embodiments, converting 1,2,4-trihydroxybenzene to t- butylhydroquinone further comprises contacting 1,2,4-trihydroxybenzene with a suitable acid (e.g. HCl) to promote alkylation. In some embodiments, the t-butylated intermediate is optionally observed. [00148] In some embodiments, converting the optional t-butylated intermediate to t- butylhydroquinone comprises hydro genolyzing the optional intermediate.
  • a suitable acid e.g. HCl
  • hydro geno lysis comprises contacting the optional intermediate with a metal catalyst and hydrogen under conditions that instigate or maximize the catalytic reaction. In some hydro genolyzing comprises contacting the optional intermediate with a metal catalysts and hydrogen followed by heating the combination. In some embodiments,
  • hydro genolyzing the optional t-butylated intermediate comprises contacting the optional t- butylated intermediate with super critical or near critical water.
  • “supercritical water” is water heated to about 400° C and at about 23 MPa.
  • “near critical water” is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • hydrogen and 1,2,4-trihydroxybenzene are present in a ratio of molecules of hydrogen to molecules of 1,2,4-trihydroxybenzene of about 2: 1 to about 50: 1.
  • the catalyst is a multicomponent metal oxide comprising a Group VB, VIB, VIII, IB, IIB, IVA and/or VA metal.
  • the catalyst is Pd, Pt, or Rh.
  • the catalyst is Rh/Al 2 0 3 , Rh/C, Pt/C or Pd/C.
  • the metal catalyst/hydrogen/optional t-butylated intermediate combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • the optional t-butylated intermediate, hydrogen, and the catalyst are contacted at a pressure of about 1-100 bar.
  • the optional t-butylated intermediate, hydrogen, and the catalyst are contacted at a temperature of about 250° C to about 500° C and a pressure of about 1-100 bar.
  • the conversion to t-butylhydroquinone occurs under conditions that instigate or maximize the reaction.
  • the 1,2,4- trihydroxybenzene/hydrogen/metal catalyst combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • 1,2,4-trihydroxybenzene, hydrogen, and the metal catalyst are contacted at a pressure of about 1-150 bar.
  • 1,2,4- trihydroxybenzene, hydrogen, and the metal catalyst are contacted at a temperature of about 200° C to about 400° C and a pressure of about 1-150 bar.
  • the t-butylhydroquinone product can be obtained from lignin without isolation of 1,2,4-trihydroxybenzene.
  • the t-butylhydroquinone is isolated from the remaining 1,2,4-trihydroxybenzene. In some embodiments, t-butylhydroquinone is isolated by any method suitable.
  • the t-butylhydroquinone is isolated from the remaining 1,2,4-trihydroxybenzene by use of a solvent.
  • the t- butylhydroquinone is isolated from the remaining 1,2,4-trihydroxybenzene by use of a solvent in which the 1,2,4-trihydroxybenzene is soluble and the t-butylhydroquinone is either insoluble or sparingly soluble.
  • the 1,2,4-trihydroxybenzene is separated from the t-butylhydroquinone by use of a solvent in which 1,2,4- trihydroxybenzene is either insoluble or sparingly soluble and t-butylhydroquinone is soluble.
  • the solvent and the soluble components are separated from the insoluble components by any suitable method (e.g., filtration).
  • any suitable method e.g., filtration.
  • the t-butylhydroquinone is soluble, in some embodiments, the t-butylhydroquinone is
  • the method comprises washing the t- butylhydroquinone with a second solvent to further remove impurities.
  • the solvent with which the purified t-butylhydroquinone is extracted is a tunable solvent, such as a gas-expanded liquid.
  • the 1,2,4-trihydroxybenzene/t-butylhydroquinone combination is washed with a first solvent in which t-butylhydroquinone is either insoluble or sparingly soluble and subsequently washed with a second solvent in which t- butylhydroquinone is soluble.
  • t-butylhydroquinone and the residual 1,2,4- trihydroxybenzene material are washed with a first solvent;
  • the first solvent is removed (e.g., by evaporation or filtration); and
  • the t-butylhydroquinone is further purified (i) by washing the t-butylhydroquinone with a second solvent in which the t-butylhydroquinone is insoluble (or sparingly soluble) and in which at least some of the contaminants are at least partially soluble, (ii) by dissolving the t-butylhydroquinone in a second solvent in which at least some of the contaminants are insoluble (or sparingly soluble), and/or (iii) by dissolving the t-butylhydroquinone and at least some of the contaminants in a second solvent and selectively precipitating t-butylhydroquinone and/or the various contaminants from
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • butylated hydro xyanisole obtained from lignin is butylated hydro xyanisole obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining butylated hydro xyanisole from lignin. It is to be understood that provided in various embodiments herein are both (1) butylated hydro xyanisole prepared according to any of the processes described herein; and (2) any method described herein for obtaining butylated hydro xyanisole from a lignin source.
  • a method of obtaining butylated hydro xyanisole from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1 ,2,4-trihydroxybenzene, and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to butylated hydro xyanisole.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to butylated hydro xyanisole, and in other embodiments, is not separated or extracted from any residual material prior to converting it to butylated hydroxyanisole.
  • any residual material e.g., lignin
  • 1,2,4-trihydroxybenzene is converted to t- butylhydroquinone by any method disclosed herein.
  • t- butylhydroquinone is separated or extracted from any residual material (e.g., lignin, 1,2,4- trihydroxybenzene) prior to converting it to butylated hydroxyanisole, and in other embodiments, is not separated or extracted from any residual material prior to converting it to butylated hydroxyanisole.
  • t-butylhydroquinone is converted to butylated
  • hydroquinone is contacted with a methylating agent (e.g., MeBr or Mel).
  • a methylating agent e.g., MeBr or Mel
  • the alkylation reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 100° C, at least 125° C, at least 140° C, at least 165° C, at least 200° C, at least 225° C, at least 250° C, at least 300° C, at least 350° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 250 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • the butylated hydroxyanisole is isolated from any remaining lignin, 1,2,4-trihydroxybenzene, and/or t-butylhydroquinone.
  • butylated hydroxyanisole is isolated by any suitable method. In some embodiments, butylated hydroxyanisole is isolated from any remaining lignin, 1,2,4- trihydroxybenzene, and/or t-butylhydroquinone by use of a solvent. In some embodiments, the butylated hydroxyanisole is isolated from any remaining lignin, 1,2,4- trihydroxybenzene, and/or t-butylhydroquinone by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch-flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • ⁇ -acetylacrylic acid obtained from lignin is a method of obtaining ⁇ - acetylacrylic acid from lignin. It is to be understood that provided in various embodiments herein are both (1) ⁇ -acetylacrylic acid prepared according to any of the processes described herein; and (2) any method described herein for obtaining ⁇ -acetylacrylic acid from a lignin source.
  • a method of obtaining ⁇ - acetylacrylic acid from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1 ,2,4-trihydroxybenzene, and (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to ⁇ -acetylacrylic acid.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • 1,2,4-trihydroxybenzene is separated or extracted from any residual material (e.g., lignin) prior to converting it to ⁇ -acetylacrylic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to ⁇ -acetylacrylic acid.
  • any residual material e.g., lignin
  • the method comprises contacting 1,2,4- trihydroxybenzene with a base such as, by way of non-limiting example, pyridine, t-BuOK or the like.
  • the method further comprises contacting the 1,2,4- trihydroxybenzene with an oxidizing agent.
  • the method further comprises contacting the 1,2,4-trihydroxybenzene with 0 2 , H 2 0 2 , or combinations thereof.
  • the method optionally comprises contacting 1,2,4- trihydroxybenzene with a metal (e.g., a metal cation) or metal catalyst (e.g., a metal cation) such as, by way of non-limiting example, iron (II, III), copper (I, II) or the like.
  • a metal e.g., a metal cation
  • metal catalyst e.g., a metal cation
  • the method comprises contacting 1,2,4- trihydroxybenzene with a catechol dioxygenase (e.g., a 1,2-catechol dioxygenase).
  • a catechol dioxygenase e.g., a 1,2-catechol dioxygenase
  • the method further comprises decarboxylating the oxidative cleavage product.
  • the conversion to ⁇ -acetylacrylic acid occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • the ⁇ -acetylacrylic acid is isolated from any remaining lignin and/or 1,2,4-trihydroxybenzene. In some embodiments, ⁇ -acetylacrylic acid is isolated by any suitable method. In some embodiments, ⁇ -acetylacrylic acid is isolated from any remaining lignin and/or 1,2,4-trihydroxybenzene by use of a solvent. In some embodiments, the ⁇ -acetylacrylic acid is isolated from any remaining lignin and/or 1,2,4- trihydroxybenzene by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch-flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor. H. ⁇ -Aminolevulinic Acid
  • ⁇ -aminolevulinic acid obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining ⁇ - aminolevulinic acid from lignin. It is to be understood that provided in various
  • embodiments herein are both (1) ⁇ -aminolevulinic acid prepared according to any of the processes described herein; and (2) any method described herein for obtaining ⁇ - aminolevulinic acid from a lignin source.
  • a method of obtaining ⁇ - aminolevulinic acid from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to ⁇ -acetylacrylic acid, and (c) subjecting ⁇ -acetylacrylic acid to conditions sufficient to convert ⁇ -acetylacrylic acid to ⁇ - aminolevulinic acid.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • 1,2,4-trihydroxybenzene is converted to ⁇ -acetylacrylic acid by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • ⁇ -acetylacrylic acid is separated or extracted from any residual material (e.g., lignin) prior to converting it to ⁇ -aminolevulinic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to ⁇ -aminolevulinic acid.
  • any residual material e.g., lignin
  • the method comprises contacting ⁇ -acetylacrylic acid with ethyl nitrite. In additional embodiments, the method comprises contacting ⁇ - acetylacrylic acid with an acid such as, by way of non-limiting example, HCl, acetic acid or the like. In some embodiments, the method further comprises contacting the ⁇ -acetylacrylic acid with a reducing agent.
  • the reducing agent comprises hydrogen and an acid such as, by way of non-limiting example, HCl, acetic acid or the like. In additional specific embodiments, the reducing agent comprises tin, stannous chloride, and HCl. In some embodiments, the method comprises converting ⁇ -acetylacrylic acid to an ester before treatment with ethyl nitrite and the reducing agent.
  • the conversion to ⁇ -aminolevulinic acid occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • the ⁇ -aminolevulinic acid is isolated from any remaining lignin, ⁇ -acetylacrylic acid, and/or 1,2,4-trihydroxybenzene.
  • ⁇ - aminolevulinic acid is isolated by any suitable method.
  • ⁇ - aminolevulinic acid is isolated from any remaining lignin, ⁇ -acetylacrylic acid, and/or 1,2,4- trihydroxybenzene by use of a solvent.
  • the ⁇ -aminolevulinic acid is isolated from any remaining lignin, ⁇ -acetylacrylic acid, and/or 1,2,4-trihydroxybenzene by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch-flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • levulinate esters obtained from lignin are levulinate esters obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining levulinate esters from lignin. It is to be understood that provided in various embodiments herein are both (1) levulinate esters prepared according to any of the processes described herein; and (2) any method described herein for obtaining levulinate esters from a lignin source.
  • a method of obtaining levulinate esters from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce 1,2,4-trihydroxybenzene, (b) subjecting 1,2,4-trihydroxybenzene to conditions sufficient to convert 1,2,4-trihydroxybenzene to ⁇ -acetylacrylic acid, and (c) subjecting ⁇ - acetylacrylic acid to conditions sufficient to convert ⁇ -acetylacrylic acid to levulinate esters.
  • lignin is converted to 1,2,4-trihydroxybenzene by any method disclosed herein.
  • 1,2,4-trihydroxybenzene is converted to ⁇ - acetylacrylic acid by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass. In some embodiments, the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating comprises heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • ⁇ -acetylacrylic acid is separated or extracted from any residual material (e.g., lignin) prior to converting it to levulinate esters, and in other embodiments, is not separated or extracted from any residual material prior to converting it to levulinate esters.
  • any residual material e.g., lignin
  • ⁇ -acetylacrylic acid is esterified under conditions sufficient to yield the ester.
  • the ester is subjected to hydrogenation conditions sufficient to yield levulinate esters.
  • the ester is contacted with hydrogen (e.g., hydrogen gas) and a metal catalyst.
  • the metal catalyst is platinum, palladium (e.g., Pd/C), rhodium, ruthenium, Raney nickel, and Urushibara nickel.
  • the ⁇ -acetylacrylic acid is subjected to hydrogenation conditions sufficient to reduce the carbon-carbon unsaturated group (e.g., alkenyl group) on ⁇ -acetylacrylic acid.
  • the ⁇ -acetylacrylic acid is contacted with hydrogen (e.g., hydrogen gas) and a metal catalyst.
  • the metal catalyst is platinum, palladium (e.g., Pd/C), rhodium, ruthenium, Raney nickel, and Urushibara nickel.
  • the levulinic acid intermediate is esterified under conditions sufficient to yield the levulinate ester.
  • the conversion to levulinate esters occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • the levulinate esters is isolated from any remaining lignin, ⁇ -acetylacrylic acid, and/or 1,2,4-trihydroxybenzene. In some embodiments, levulinate esters is isolated by any suitable method. In some embodiments, levulinate esters is isolated from any remaining lignin, ⁇ -acetylacrylic acid, and/or 1,2,4-trihydroxybenzene by use of a solvent. In some embodiments, the levulinate esters is isolated from any remaining lignin, ⁇ -acetylacrylic acid, and/or 1,2,4-trihydroxybenzene by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch-flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • vanillic acid obtained from lignin is vanillic acid obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining vanillic acid from lignin. It is to be understood that provided in various embodiments herein are both (1) vanillic acid prepared according to any of the processes described herein for preparing vanillic acid from a lignin source; and (2) any process described herein for preparing vanillic acid from a li nin source.
  • a method of obtaining vanillic acid from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce vanillic acid.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein.
  • the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non-limiting example, heating to at least room
  • temperature at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • a method of obtaining vanillic acid from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce vanillic acid.
  • the method comprises contacting lignin with a ligninase.
  • the enzymatic reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the ligninase is an oxidative ligninase.
  • the ligninase is a peroxidase, an oxidase, or combinations thereof.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein.
  • the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non-limiting example, heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • the peroxidase is an isolated peroxidase. In some embodiments, the peroxidase is produced by fermentation methods and/or recombinant methods. In some embodiments, the peroxidase is a modified form of a known or naturally- occurring peroxidase and/or has been selected from a library of naturally-occurring and/or modified peroxidases.
  • the oxidase is an isolated oxidase. In some embodiments, the oxidase is produced by fermentation methods and/or recombinant methods. In some embodiments, the oxidase is a modified form of a known or naturally-occurring oxidase and/or has been selected from a library of naturally-occurring and/or modified oxidases.
  • a method of obtaining vanillic acid from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce vanillic acid.
  • the method comprises contacting lignin with an oxidizing agent.
  • the oxidizing agent is hydrogen peroxide (H 2 O 2 ).
  • the oxidizing agent is molecular oxygen (i.e., O 2 ).
  • the oxidizing agent is a nitroarene, such as nitrobenzene (e.g., catalytic nitrobenzene) or substituted nitrobenzene.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein.
  • the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non-limiting example, heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the oxidizing agent is a nitroarene.
  • the use of non- catalytic amounts of nitroarene in oxidizing lignin can be commercially cost prohibitive.
  • the oxidizing agent is catalytic nitroarene (e.g., catalytic nitrobenzene and/or substituted nitrobenzene). Oxidation of lignin produces inactive (i.e., reduced) nitroarene byproducts.
  • Figure 1 illustrates the reduction of nitrobenzene and various byproducts resulting from use of such oxidants according to one embodiment of a process described herein.
  • a method described herein further comprises recycling these inactive nitroarene byproducts, e.g., by re-oxidizing the reduced nitroarene byproducts to an active oxidizing agent, e.g., a catalytic nitroarene.
  • an active oxidizing agent e.g., a catalytic nitroarene.
  • the nitroarene oxidizes lignin and is recycled in a single pot.
  • the nitroarene byproducts are removed from the lignin oxidation system, re-oxidized, and returned to the lignin oxidation system.
  • nitroarene oxidation of lignin is performed at ambient or low pressure (e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm).
  • nitroarene oxidation of lignin is performed at ambient or low temperature (e.g., less than 80 °C, less than 50 °C, or less than 30 °C).
  • an additional additive is added to the lignin/nitroarene combination.
  • the additive is an additive for improving aldehyde yields (e.g., an anthraquinone).
  • the nitroarene byproducts are re-oxidized utilizing any suitable system.
  • the nitroarene byproducts are re-oxidized utilizing an oxidizing agent (e.g., molecular oxygen) and a metal catalyst (e.g., a molybdenum catalyst, a rhenium catalyst, a tungsten catalyst, a cobalt (e.g., Co 2+ ) catalyst, or the like).
  • Figure 2 illustrates oxidation of lignin and recycling of nitroarene catalysts according to one embodiment of a process described herein. Specifically, Figure 2 illustrates an electron transport from lignin to, eventually, molecular oxygen.
  • the metal catalyst is utilized in an amount of less than 5 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In some embodiments, the metal catalyst is utilized in an amount of less than 1 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In some embodiments, the metal catalyst is utilized in an amount of less than 0.5 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In some embodiments, the metal catalyst is utilized in an amount of less than 0.1 mol % (e.g., compared to the amount of nitroarene catalyst utilized).
  • the metal catalyst is utilized in an amount of less than 0.01 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In other specific embodiments, the metal catalyst is utilized in an amount of 0.01 mol % to about 1 mol % (e.g., compared to the amount of nitroarene catalyst utilized). In certain embodiments, re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low pressure (e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm).
  • re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low temperature (e.g., less than 80 °C, less than 50 °C, or less than 30 °C).
  • ambient or low temperature e.g., less than 80 °C, less than 50 °C, or less than 30 °C.
  • a composition comprising lignin, nitroarene, and a metal catalyst.
  • the composition further comprises any compound of Formula I:
  • R a is CHO, COOH, CH 2 OH, COCH 3 , or CHOHCH 3 ; and R b is H, OCH 3 , or COOH.
  • the nitroarene catalytic byproducts are re-oxidized by contacting the nitroarene byproducts with an N-oxygenase (e.g., the N-oxygenase AurF, such as from Streptomyces thioluteus).
  • an oxidizing agent such as molecular oxygen (e.g., air) is utilized in combination with the N-oxygenase, e.g., as a terminal oxidant of the catalytic nitroarene recycling process.
  • Figure 3 illustrates recycling of nitroarene catalytic byproducts with AurF according to one embodiment of a process described herein.
  • Figure 4 illustrates oxidation of lignin and recycling of nitroarene catalysts according to one embodiment of a process described herein. Specifically, Figure 4 illustrates an electron transport from lignin to, eventually, molecular oxygen.
  • re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low pressure (e.g., less than 5 atm, less than 3 atm, less than 2 atm, or less than 1.2 atm).
  • re-oxidation or recycling of nitroarene catalytic byproducts is performed at ambient or low temperature (e.g., less than 80 °C, less than 50 °C, or less than 30 °C).
  • a composition comprising lignin, nitroarene, and an N-oxygenase (e.g., AurF).
  • the composition further comprises any or more compound of Formula I.
  • a nitroarene group described herein is a compound of Formula II:
  • R is 0-4 substituents, each of which independently are, by way of non-limiting example, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
  • Q is, by way of non-limiting example, H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, cyano, nitro, hydroxy, thiol, arylthio, Ci-Cealkylsulfoxide, arylsulfoxide, Ci-Cealkylsulfone, arylsulfone, cyano, halo, C 2 -Csacyl, C 2 -Csacyloxy, Ci-C 6 haloalkyl, Ci-Cefluoroalkyl, and amino, including Ci-Cealkylamino, or L q R q , wherein each L q is independently selected from a bond, -0-,
  • the method further comprises contacting lignin with a metal catalyst.
  • the metal catalyst is a transition metal.
  • the metal catalyst is a Group VII transition metal.
  • the metal catalyst is Co, Rh, Ir, or combinations thereof.
  • the catalyst is a Cobalt catalyst (e.g., a Co(II) catalyst).
  • the metal catalyst is a Group VA metal.
  • the metal catalyst is Bi.
  • the metal catalyst is methyltrioxorhenium (VII) (MeReC ⁇ ).
  • a method of obtaining vanillic acid from lignin comprising: subjecting lignin to oxidative conditions sufficient to produce vanillic acid.
  • the method comprises contacting lignin with hydrogen peroxide and MeReOs.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein.
  • the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating a lignin containing combination includes, by way of non-limiting example, heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • a process described herein comprises preparing vanillic acid from lignin, whereby vanillic acid is prepared from the lignin in a yield of about 5% to about 60% by weight of the lignin. In some embodiments, vanillic acid is prepared from the lignin in a yield of about 15% to about 50% by weight of the lignin.
  • Figure 9 illustrates a process of producing vanillic acid from lignin in high yield according to one embodiment of a process described herein.
  • lignin is oxidized to a combination of aromatic compounds (e.g., as illustrated in Figure 9) by use of an oxidizing system comprising, e.g., an enzyme (e.g., ligninase, peroxidase, oxidase, or combination thereof); a metal catalyst; nitroarene (e.g., nitrobenzene); oxygen; peroxide; or a combination thereof.
  • an enzyme e.g., ligninase, peroxidase, oxidase, or combination thereof
  • nitroarene e.g., nitrobenzene
  • oxygen peroxide
  • peroxide or a combination thereof.
  • lignin is oxidized with nitroarene (e.g., nitrobenzene and/or substituted nitrobenzene).
  • the combination of aromatic compound obtained by oxidizing lignin can then be further oxidized, and optionally thermally o-decarboxylated, to convert a number of different aromatic compounds in the combination of aromatic compounds to one or more like compounds.
  • Figure 9 illustrates a specific embodiment of this process, i.e., oxidation of the combination of aromatic compounds obtained by oxidizing lignin with molecular oxygen and catalytic Co(II), and optionally thermally o-decarboxylating, e.g., by thermal mechanism.
  • other oxidizing agent(s) and optional catalysts are utilized.
  • the combination of oxidative compounds are further oxidized using an enzyme (e.g., ligninase, peroxidase, oxidase, or combination thereof); a metal catalyst; oxygen; peroxide; or a combination thereof, as illustrated in Scheme 2:
  • an enzyme e.g., ligninase, peroxidase, oxidase, or combination thereof
  • a metal catalyst e.g., oxygen; peroxide; or a combination thereof
  • R 2 H, OCH 3 , or COOH
  • R 2 H, OCH3, or C, chain (5 identities)
  • a vanillic acid composition comprising (i) 50-98%) w/w vanillic acid, and (ii) 1-30% w/w compound of Formula 4, wherein R 2 is OCH 3 and/or 1-30% w/w compound of Formula 4, wherein R 2 is COOH.
  • the vanillic acid composition comprises 2-15% w/w compound of Formula 4, wherein R 2 is OCH 3 and/or 2-15% w/w compound of Formula 4, wherein R 2 is COOH.
  • the yield of vanillic acid is further improved by o-decarboxylating (e.g., thermally) the compound of Formula 4 wherein R 2 is COOH.
  • the vanillic acid is isolated from the remaining lignin. In some embodiments, vanillic acid is isolated by any method suitable.
  • the vanillic acid is separated from the lignin by use of a solvent. In some embodiments, the vanillic acid is separated from the lignin by use of a solvent in which the vanillic acid is soluble and the lignin is either insoluble or sparingly soluble. In some embodiments, the vanillic acid is separated from the lignin by use of a solvent in which vanillic acid is either insoluble or sparingly soluble and lignin is soluble. In some embodiments, the solvent and the soluble components are separated from the insoluble components by any suitable method (e.g., filtration). Where the vanillic acid is soluble, in some embodiments, the vanillic acid is precipitated from the solvent.
  • the method comprises washing the vanillic acid with a second solvent to further remove impurities.
  • the solvent with which the purified vanillic acid is extracted is a tunable solvent, such as a gas-expanded liquid.
  • the vanillic acid/residual lignin material is washed with a first solvent in which vanillic acid is either insoluble or sparingly soluble and subsequently washed with a second solvent in which vanillic acid is soluble.
  • vanillic acid and the residual lignin material are washed with a first solvent;
  • the first solvent is removed (e.g., by evaporation or filtration); and
  • the vanillic acid is further purified (i) by washing the vanillic acid with a second solvent in which the vanillic acid is insoluble (or sparingly soluble) and in which at least some of the contaminants are at least partially soluble, (ii) by dissolving the vanillic acid in a second solvent in which at least some of the contaminants are insoluble (or sparingly soluble), and/or (iii) by dissolving the vanillic acid and at least some of the contaminants in a second solvent and selectively precipitating vanillic acid and/or the various contaminants from the second solvent.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • 2-methoxyphenol obtained from lignin is 2-methoxyphenol obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining 2- methoxyphenol from lignin. It is to be understood that provided in various embodiments herein are both (1) 2-methoxyphenol prepared according to any of the processes described herein; and (2) any method described herein for obtaining 2-methoxyphenol from a lignin source.
  • 2-Methoxyphenol [00215] Disclosed herein, in certain embodiments, is a method of obtaining 2- methoxyphenol from lignin, comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, and (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to 2-methoxyphenol.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • converting vanillic acid to 2-methoxyphenol comprises decarboxylating vanillic acid.
  • decarboxylating vanillic acid comprises contacting vanillic acid with a decarboxylase under conditions that instigate or maximize the enzymatic reaction.
  • decarboxylating vanillic acid comprises contacting vanillic acid with a decarboxylase and heating the combination.
  • the decarboxylase/vanillic acid combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • decarboxylating vanillic acid comprises contacting vanillic acid with super critical or near critical water.
  • the 2-methoxyphenol is isolated from the remaining vanillic acid. In some embodiments, 2-methoxyphenol is isolated by any method suitable.
  • the 2-methoxyphenol is isolated from the remaining vanillic acid by use of a solvent.
  • the 2-methoxyphenol is isolated from the remaining vanillic acid by use of a solvent in which the vanillic acid is soluble and the 2-methoxyphenol is either insoluble or sparingly soluble.
  • the vanillic acid is separated from the 2-methoxyphenol by use of a solvent in which vanillic acid is either insoluble or sparingly soluble and 2-methoxyphenol is soluble.
  • the solvent and the soluble components are separated from the insoluble components by any suitable method (e.g., filtration).
  • the 2-methoxyphenol is precipitated from the solvent.
  • the method comprises washing the 2-methoxyphenol with a second solvent to further remove impurities.
  • the solvent with which the purified 2- methoxyphenol is extracted is a tunable solvent, such as a gas-expanded liquid.
  • the vanillic acid/2-methoxyphenol combination is washed with a first solvent in which 2-methoxyphenol is either insoluble or sparingly soluble and subsequently washed with a second solvent in which 2-methoxyphenol is soluble.
  • the 2-methoxyphenol is further purified (i) by washing the 2-methoxyphenol with a second solvent in which the 2-methoxyphenol is insoluble (or sparingly soluble) and in which at least some of the contaminants are at least partially soluble, (ii) by dissolving the 2-methoxyphenol in a second solvent in which at least some of the contaminants are insoluble (or sparingly soluble), and/or (iii) by dissolving the 2- methoxyphenol and at least some of the contaminants in a second solvent and selectively precipitating 2-methoxyphenol and/or the various contaminants from the second solvent, iii.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • catechol is obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining catechol from lignin. It is to be understood that provided in various embodiments herein are both (1) catechol prepared according to any of the processes described herein; and (2) any method described herein for obtaining catechol from a lignin source.
  • a method of obtaining catechol from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, and (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to catechol.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • vanillic acid is converted to 2-methoxyphenol by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • converting vanillic acid to catechol comprises (a) decarboxylating vanillic acid such that 2-methoxyphenol is produced; and (b) contacting the 2-methoxyphenol with supercritical or near critical water to demethylate 2-methoxyphenol.
  • supercritical water is water heated to about 400° C and at about 23 MPa.
  • near critical water is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • decarboxylating vanillic acid comprises contacting vanillic acid with a decarboxylase under conditions that instigate or maximize the enzymatic reaction.
  • decarboxylating vanillic acid comprises contacting vanillic acid with a decarboxylase and heating the combination.
  • the decarboxylase/vanillic acid combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • 2-methoxyphenol is converted to catechol without isolating 2-methoxyphenol from vanillic acid.
  • 2-methoxyphenol is isolated from vanillic acid before it is converted into catechol.
  • 2- methoxyphenol is isolated from vanillic acid by any method disclosed herein.
  • subjecting vanillic acid to conditions sufficient to convert vanillic acid directly to catechol includes, e.g., subjecting vanillic acid to supercritical water or subjecting vanillic acid to near-critical water, both of which are as defined herein for converting 2-methoxyphenol to catechol.
  • methanol is generated from the demethylation of 2- methoxyphenol.
  • methanol is isolated from the reaction mixture, ii. Improved Yield
  • a process described herein comprises preparing catechol from lignin, whereby catechol is prepared from the lignin in a yield of about 5% to about 60% by weight of the lignin. In some embodiments, catechol is prepared from the lignin in a yield of about 15% to about 50%> by weight of the lignin.
  • Figure 11 illustrates a process of producing catechol from lignin in high yield according to one embodiment of a process described herein.
  • lignin is oxidized to a combination of aromatic compounds (e.g., comprising any one or more of the compounds as illustrated in Figure 11) by use of an oxidizing system comprising, e.g., an enzyme (e.g., ligninase, peroxidase, oxidase, or combination thereof); a metal catalyst; nitrobenzene; oxygen; peroxide; or a combination thereof.
  • the combination of aromatic compound obtained by oxidizing lignin can then be subjected to aqueous demethylation and/or dehydroxylation, and optionally catalytic decarboxylation and/or decarbonylation, to convert a number of different aromatic compounds in the combination of aromatic compounds to one or more like compounds.
  • the combination of aromatic compounds obtained from oxidizing lignin are purified, or partially purified, before further processing according to a process as illustrated in Figure 11.
  • the combination of oxidative compounds are further oxidized using an enzyme (e.g., ligninase, peroxidase, oxidase, or combination thereof); a metal catalyst; oxygen; peroxide; or a combination thereof, as illustrated in Scheme 3:
  • R 1 CT and C 2 chains (5 identities)
  • R 1 C-i and C 2 chains (2 identities)
  • R 2 H, OCH 3 , or C, chain (5 identities)
  • R 2 H, OH, or C, chain (4 identities)
  • R 2 H, OH
  • a catechol composition comprising (i) 70-98%) w/w catechol, and (ii) 2-30%> w/w compound 6, wherein R 2 is OH.
  • the catechol composition comprises 2-15% w/w compound 6.
  • the catechol is isolated from any remaining lignin, vanillic acid and/or 2-methoxyphenol. In some embodiments, catechol is isolated by any suitable method. In some embodiments, the catechol is isolated from the remaining lignin, vanillic acid, methanol, and/or 2-methoxyphenol by use of a solvent. In some embodiments, the catechol is isolated from any remaining lignin, vanillic acid, methanol, and/or 2- methoxyphenol by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • catechol obtained from lignin is a method of obtaining catechol from lignin. It is to be understood that provided in various embodiments herein are both (1) catechol prepared according to any of the processes described herein; and (2) any method described herein for obtaining catechol from a lignin source.
  • a method of obtaining catechol from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to catechol; and (c) subjecting catechol to conditions sufficient to convert catechol to phenol (e.g., hydrodeoxygenation).
  • the method comprises subjecting catechol to hydrodeoxygenation.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • vanillic acid is converted to 2-methoxyphenol by any method disclosed herein.
  • 2-methoxyphenol is converted to catechol by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass. In some embodiments, the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating comprises heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • catechol is separated or extracted from any residual material (e.g., lignin, vanillic acid, and/or 2-methoxyphenol) prior to converting it to phenol, and in other embodiments, is not separated or extracted from any residual material prior to converting it to phenol.
  • any residual material e.g., lignin, vanillic acid, and/or 2-methoxyphenol
  • hydrodeoxygenation of catechol comprises contacting catechol, hydrogen, and a catalyst.
  • hydrogen and catechol are present in a ratio of molecules of hydrogen to molecules of catechol of about 2: 1 to about 50: 1.
  • the catalyst is Bi or Nb.
  • the catalyst is a multicomponent metal oxide comprising a Group VB, VIB, VIII, IB, IIB, IVA and/or VA metal.
  • the catalyst has the formula Bi(i_x/3 ) V(i_ x)w Nb(i_ x )(i_ w) Mo x 04, wherein x is between 0 and 1 and w is between 0 and 1.
  • the catalyst has the formula Cu(i_ z) Zn z W(i_ y) Mo y 04, wherein y is between 0 and 1 and z is between 0 and 1.
  • the catalyst is BfVO 4 , CuW0 4 , Cuo.75Zno.25 W0 4 , CuW0 4 + Ce, CuO-Al 2 03 and combinations thereof.
  • catechol, hydrogen, and the catalyst are contacted at a temperature of about 250° C to about 500° C. In some embodiments, catechol, hydrogen, and the catalyst are contacted at a pressure of about 1-100 bar. In some embodiments, catechol, hydrogen, and the catalyst are contacted at a temperature of about 250° C to about 500° C and a pressure of about 1-100 bar.
  • methanol is generated from the demethylation of 2- methoxyphenol. In some embodiments, methanol is isolated from the reaction mixture. ii. Isolation of Phenol
  • the phenol is isolated from any remaining lignin, vanillic acid, methanol, 2-methoxyphenol, and/or catechol. In some embodiments, phenol is isolated by any suitable method. In some embodiments, the phenol is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, methanol, and/or catechol by use of a solvent. In some embodiments, the phenol is isolated from any remaining lignin, vanillic acid, 2- methoxyphenol, and/or catechol by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • muconic acid obtained from lignin is muconic acid obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining muconic acid from lignin. It is to be understood that provided in various embodiments herein are both (1) muconic acid prepared according to any of the processes described herein; and (2) any method described herein for obtainin muconic acid from a lignin source.
  • a method of obtaining muconic acid from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to catechol; and (c) subjecting catechol to conditions sufficient to convert catechol to muconic acid (e.g., under oxidative conditions).
  • lignin is converted to vanillic acid by any method disclosed herein.
  • vanillic acid is converted to 2-methoxyphenol by any method disclosed herein.
  • 2-methoxyphenol is converted to catechol by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass. In some embodiments, the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating comprises heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • catechol is separated or extracted from any residual material (e.g., lignin, vanillic acid, and/or 2-methoxyphenol) prior to converting it to muconic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to muconic acid.
  • any residual material e.g., lignin, vanillic acid, and/or 2-methoxyphenol
  • the method comprises contacting catechol with a metal (e.g., a metal cation) or metal catalyst (e.g., a metal cation) such as, by way of non-limiting example, iron (II, III), copper (I, II) or the like.
  • a metal e.g., a metal cation
  • metal catalyst e.g., a metal cation
  • the method further comprises contacting the catechol with an oxidizing agent.
  • the method further comprises contacting the catechol with 0 2 , H 2 0 2 , or combinations thereof.
  • the method comprises contacting catechol with a catechol dioxygenase (e.g., a 1,2-catechol dioxygenase).
  • a catechol dioxygenase e.g., a 1,2-catechol dioxygenase
  • the conversion to muconic acid occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • instigate or maximize the reaction e.g., heating or high pressure.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • methanol is generated from the dioxygenase induced cleavage of catechol. In some embodiments, methanol is isolated from the reaction mixture. ii. Isolation of Muconic Acid
  • the muconic acid is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, and/or catechol. In some embodiments, muconic acid is isolated by any suitable method. In some embodiments, muconic acid is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, methanol, and/or catechol by use of a solvent. In some embodiments, the muconic acid is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, methanol, and/or catechol by use of at least two solvents. iii. Use of a Reactor
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • adipic acid obtained from lignin is adipic acid obtained from lignin. Further disclosed herein, in certain embodiments, is a method of obtaining adipic acid from lignin. It is to be understood that provided in various embodiments herein are both (1) adipic acid prepared according to any of the processes described herein; and (2) any method described herein for obtaining adipic acid from a lignin source.
  • a method of obtaining adipic acid from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to catechol; (c) subjecting catechol to conditions sufficient to convert catechol to muconic acid (e.g., under oxidative conditions); and (d) subjecting muconic acid to conditions sufficient to convert muconic acid to adipic acid.
  • the method comprises subjecting muconic acid to reductive conditions.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • vanillic acid is converted to 2-methoxyphenol by any method disclosed herein.
  • 2-methoxyphenol is converted to catechol by any method disclosed herein.
  • catechol is converted to muconic acid by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass. In some embodiments, the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • heating comprises heating to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • muconic acid is separated or extracted from any residual material (e.g., lignin, vanillic acid, 2-methoxyphenol, and/or catechol) prior to converting it to adipic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to adipic acid.
  • any residual material e.g., lignin, vanillic acid, 2-methoxyphenol, and/or catechol
  • a carbon-carbon unsaturated group (e.g., an alkenyl group) on muconic acid is reduced.
  • muconic acid is catalytically hydrogenated.
  • muconic acid is contacted with hydrogen and (e.g., hydrogen gas) and a metal catalyst.
  • the metal catalyst is platinum, palladium (e.g., Pd/C), rhodium, ruthenium, Raney nickel, and Urushibara nickel.
  • the reduction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 30° C, at least 35° C, at least 40° C, at least 45° C, at least 50° C, at least 55° C, at least 60° C, at least 65° C, at least 70° C, at least 75° C, at least 80° C, at least 85° C, at least 90° C, at least 95° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like,
  • the muconic acid is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, catechol, methanol, and/or muconic acid.
  • adipic acid is isolated by any suitable method.
  • adipic acid is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, catechol, and/or muconic acid by use of a solvent.
  • the adipic acid is isolated from any remaining lignin, vanillic acid, 2-methoxyphenol, catechol, methanol, and/or muconic acid by use of at least two solvent,
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • acrylates and butadiene obtained from lignin is a method of obtaining acrylates and butadiene from lignin. It is to be understood that provided in various embodiments herein are both (1) acrylates and butadiene prepared according to any of the processes described herein; and (2) any method described herein for obtaining acrylates and butadiene from a lignin source.
  • a method of obtaining acrylates and butadiene from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to catechol; (c) subjecting catechol to conditions sufficient to convert catechol to hexa- 2,4-dienedioic acid; and (d) subjecting hexa-2,4-dienedioic acid to conditions (e.g., olefin metathesis) sufficient to convert hexa-2,4-dienedioic acid to acrylic acid and butadiene.
  • conditions e.g., olefin metathesis
  • the method comprises esterifying hexa-2,4-dienedioic acid before subjecting it to olefin metathesis.
  • olefin metathesis is performed by adding an additional olefin, e.g., ethylene, and is catalyzed, e.g., by the use of a metal, such as nickel, tungsten, ruthenium, molybdenum, or the like, or combinations thereof.
  • the olefin metathesis catalyst is a black box catalyst (e.g., WCWSnJV ⁇ or Re20yAl 2 03); a titanocene-based catalyst (3.g., Cp 2 Ti(u-Cl)(u-CH 2 )AlMe 2 ); a Schrock W, Mo, or Re catalyst, including an arylimido complex of Mo (e.g.,
  • Ar'N aryl, e.g., 2,6-diisopropylphenyl, and R' is any suitable substituent, e.g., alkyl or aryl, and R is neopentyl or neophyl (CMe 2 Ph)); or a Grubbs Ru catalyst.
  • a method of obtaining acrylates and butadiene from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to catechol; (c) subjecting catechol to conditions sufficient to convert catechol to hexa- 2,4-dienedioic acid; (d) esterifying hexa-2,4-dienedioic acid and (e) subjecting the ester to conditions sufficient to convert the ester to acrylate ester and butadiene.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • vanillic acid is converted to catechol by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • catechol is separated or extracted from any residual material (e.g., lignin, vanillic acid, and/or 2-methoxyphenol) prior to converting it to a downstream compound, e.g., hexa-2,4-dienedioic acid.
  • a downstream compound e.g., hexa-2,4-dienedioic acid.
  • catechol is contacted with a catechol dioxygenase (e.g., a 1,2-catechol dioxygenase) under conditions sufficient to yield hexa-2,4-dienedioic acid.
  • a catechol dioxygenase e.g., a 1,2-catechol dioxygenase
  • hexa-2,4-dienedioic acid is separated or extracted from any residual material (e.g., lignin, vanillic acid, 2-methoxyphenol, methanol, and/or catechol) prior to converting it to butadiene and acrylate, and in other embodiments, is not separated or extracted from any residual material prior to converting it to butadiene and acrylate.
  • hexa-2,4-dienedioic acid is subjected to olefin metathesis under conditions sufficient to yield butadiene and acrylic acid.
  • hexa- 2,4-dienedioic acid is esterified under conditions sufficient to yield the ester.
  • the ester is subjected to olefin metathesis under conditions sufficient to yield butadiene and acrylate ester.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • the butadiene is isolated from any remaining lignin, vanillic acid, catechol, hexa-2,4-dienedioic acid (or and ester thereof), and/or acrylate. In some embodiments, butadiene is isolated by any suitable method. In some embodiments, butadiene is isolated from any remaining lignin, methanol, vanillic acid, catechol, hexa-2,4- dienedioic acid (or and ester thereof), and/or acrylate by use of a solvent.
  • the butadiene is isolated from any remaining lignin, vanillic acid, methanol, catechol, hexa-2,4-dienedioic acid (or and ester thereof), and/or acrylate by use of at least two solvents.
  • the acrylate is isolated from any remaining lignin, vanillic acid, catechol, hexa-2,4-dienedioic acid (or an ester thereof) and/or butadiene. In some embodiments, an acrylate is isolated by any suitable method. In some embodiments, an acrylate is isolated from any remaining lignin, vanillic acid, catechol, methanol, hexa-2,4- dienedioic acid (or an ester thereof), and/or butadiene by use of a solvent.
  • an acrylate is isolated from any remaining lignin, vanillic acid, methanol, catechol, hexa-2,4-dienedioic acid (or an ester thereof), and/or butadiene by use of at least two solvent.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • 2-aminophenol (2-AP) obtained from lignin is 2-aminophenol (2-AP) obtained from lignin.
  • the 2-AP is suitable for use in azo dyes, photographic developer, paint corrosion inhibitor, and as a monomer in benzoxazole polymers.
  • a method of obtaining 2-aminophenol from lignin is both (1) 2- aminophenol prepared according to any of the processes described herein; and (2) any method described herein for obtaining 2-aminophenol from a lignin source.
  • a method of obtaining 2- aminophenol from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to 4-amino-3-methoxybenzoic acid; and (c) subjecting 4-amino-3- methoxybenzoic acid to conditions sufficient to convert 4-amino-3-methoxybenzoic acid to 2-aminophenol.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • vanillic acid is separated or extracted from any residual material (e.g., lignin) prior to converting it to 4-amino-3-methoxybenzoic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 4-amino-3-methoxybenzoic acid.
  • vanillic acid is converted to 4-amino-3-methoxybenzoic acid by amination.
  • vanillic acid is contacted with ammonia (NH 3 ) and a metal catalyst and/or a zeolite catalyst.
  • vanillic acid is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210, which is incorporated herein for such disclosure.
  • the contacting occurs under conditions sufficient to convert vanillic acid to 4-amino-3-methoxybenzoic acid.
  • 4-amino-3-methoxybenzoic acid is separated or extracted from any residual material (e.g., lignin and/or vanillic acid) prior to converting it to 2- aminophenol, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 2-aminophenol.
  • any residual material e.g., lignin and/or vanillic acid
  • 4-amino-3-methoxybenzoic acid is converted to 2- aminophenol.
  • converting 4-amino-3-methoxybenzoic acid to 2- aminophenol comprises (a) demethylating 4-amino-3-methoxybenzoic acid; and (b) decarboxylating 4-amino-3-methoxybenzoic acid such that 2-methoxyphenol is produced.
  • decarboxylation and demethylation comprise contacting the 4- amino-3-methoxybenzoic acid with supercritical or near critical water.
  • supercritical water is water heated to about 400° C and at about 23 MPa.
  • near critical water is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • decarboxylating 4-amino-3-methoxybenzoic acid comprises contacting 4-amino-3-methoxybenzoic acid with a decarboxylase under conditions that instigate or maximize the enzymatic reaction.
  • decarboxylating 4- amino-3-methoxybenzoic acid comprises contacting 4-amino-3-methoxybenzoic acid with a decarboxylase and heating the combination.
  • the decarboxylase/4- amino-3-methoxybenzoic acid combination is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • the demethylation and decarboxylation occur
  • the demethylation occurs before the
  • the demethylation product is isolated before decarboxylation. In some embodiments, the decarboxylation occurs before the demethylation. In some embodiments, the decarboxylation product is isolated before demethylation.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • methanol is generated from the demethylation of 4- amino-3-methoxybenzoic acid. In some embodiments, methanol is isolated from the reaction mixture.
  • 2-methoxyaniline is generated from the decarboxylation of 4-amino-3-methoxybenzoic acid. In some embodiments, 2-methoxyaniline is isolated from the reaction mixture.
  • vanillic acid is separated or extracted from any residual material (e.g., lignin) prior to converting it to 4-amino-3-methoxybenzoic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 4-amino-3-methoxybenzoic acid.
  • any residual material e.g., lignin
  • vanillic acid is converted to catechol by 4-demethylation and decarboxylation (e.g., following contact with super critical or near critical water).
  • decarboxylation e.g., following contact with super critical or near critical water.
  • the demethylation of catechol generates methanol.
  • the methanol is isolated.
  • catechol is contacted with ammonia (NH 3 ) and a metal catalyst and/or a zeolite catalyst. In some embodiments, catechol is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210. In some embodiments, the contacting occurs under conditions sufficient to convert catechol to 2-aminophenol.
  • the 2-aminophenol is isolated from any remaining lignin, vanillic acid, and/or 4-amino-3-methoxybenzoic acid.
  • 2- aminophenol is isolated by any suitable method.
  • 4-amino-3- methoxybenzoic acid is isolated from any remaining lignin, vanillic acid, and/or 4-amino-3- methoxybenzoic acid by use of a solvent.
  • the 4-amino-3- methoxybenzoic acid is isolated from any remaining lignin, vanillic acid, and/or 4-amino-3- methoxybenzoic acid by use of at least two solvents,
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • aniline obtained from lignin is suitable for use as MDI starting material, in dyes and pigments, in the generation of rubber, and in agro chemicals. Further disclosed herein, in certain embodiments, is a method of obtaining aniline from lignin. It is to be understood that provided in various embodiments herein are both (1) aniline prepared according to any of the processes described herein; and (2) any method described herein for obtaining aniline from a lignin source.
  • a method of obtaining aniline from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to 4-amino-3-methoxybenzoic acid; (c) subjecting 4-amino-3-methoxybenzoic acid to conditions sufficient to convert 4-amino-3-methoxybenzoic acid to 2-aminophenol; and (d) subjecting 2-aminophenol to conditions sufficient to convert 2-aminophenol to aniline.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • vanillic acid is converted to 2-aminophenol by any method disclosed herein.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • 2-aminophenol is separated or extracted from any residual material (e.g., lignin, vanillic acid, methanol, and/or 4-amino-3-methoxybenzoic) prior to converting it to aniline, and in other embodiments, is not separated or extracted from any residual material prior to converting it to aniline.
  • any residual material e.g., lignin, vanillic acid, methanol, and/or 4-amino-3-methoxybenzoic
  • methanol is generated from the demethylation of 4- amino-3-methoxybenzoic acid. In some embodiments, methanol is isolated from the reaction mixture.
  • the aniline is isolated from any remaining lignin, vanillic acid, 4-amino-3-methoxybenzoic acid, methanol, and/or 2-aminophenol. In some embodiments, aniline is isolated by any suitable method. In some embodiments, aniline is isolated from any remaining lignin, vanillic acid, methanol, 4-amino-3-methoxybenzoic acid, and/or 2-amiophenol by use of a solvent. In some embodiments, the aniline is isolated from any remaining lignin, vanillic acid, methanol, 4-amino-3-methoxybenzoic acid, and/or 2-aminophenol by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • o-Phenylenediamine obtained from lignin.
  • the OPDA obtained from lignin is suitable for use in Azo dyes, as a polymer monomer, or as an anti-oxidant.
  • a method of obtaining o-Phenylenediamine from lignin is both (1) o-Phenylenediamine prepared according to any of the processes described herein; and (2) any method described herein for obtaining o-Phenylenediamine from a lignin source. A particular benefit of the following process is it allows the generation of OPDA with the use of nitric acid.
  • a method of obtaining OPDA from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to 4-amino-3-methoxybenzoic acid; and (c) subjecting 4-amino-3-methoxybenzoic acid to conditions sufficient to convert 4-amino-3-methoxybenzoic acid to OPDA.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • the lignin is isolated from biomass (e.g., lignocellulose biomass) by any method disclosed herein. In some embodiments, the lignin is not isolated from biomass.
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing). In some embodiments, heating comprises heating to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • vanillic acid is separated or extracted from any residual material (e.g., lignin) prior to converting it to 4-amino-3-methoxybenzoic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to 4-amino-3-methoxybenzoic acid.
  • any residual material e.g., lignin
  • vanillic acid is converted to 4-amino-3-methoxybenzoic acid by amination.
  • vanillic acid is contacted with ammonia (NH 3 ) and a metal catalyst or a zeolite catalyst.
  • vanillic acid is contacted with ammonia (NH 3 ) and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210.
  • the contacting occurs under conditions sufficient to convert vanillic acid to 4-amino-3-methoxybenzoic acid.
  • 4-amino-3-methoxybenzoic acid is separated or extracted from any residual material (e.g., lignin and/or vanillic acid) prior to converting it to OPDA, and in other embodiments, is not separated or extracted from any residual material prior to converting it to OPDA.
  • any residual material e.g., lignin and/or vanillic acid
  • 4-amino-3-methoxybenzoic acid is converted to OPDA.
  • converting 4-amino-3-methoxybenzoic acid to OPDA comprises decarboxylating 4-amino-3-methoxybenzoic acid such that OPDA is produced.
  • decarboxylation comprises contacting the 4-amino-3-methoxybenzoic acid with supercritical or near critical water. As used herein, "supercritical water” is water heated to about 400° C and at about 23 MPa.
  • near critical water is water that has a temperature and/or pressure about 1% less than, about 2% less than, about 3% less than, about 5% less than, about 10% less than, or about 15% less than is necessary for the water to become supercritical.
  • decarboxylating 4-amino-3-methoxybenzoic acid comprises contacting 4-amino-3-methoxybenzoic acid with a decarboxylase under conditions that instigate or maximize the enzymatic reaction. In some embodiments, decarboxylating 4-amino-3-methoxybenzoic acid comprises contacting 4-amino-3- methoxybenzoic acid with a decarboxylase and/or heating the combination.
  • the decarboxylase/4-amino-3-methoxybenzoic acid combination or 4-amino- 3-methoxybenzoic acid is heated to about 50° C, to about 100° C, to about 150° C, to about 200° C, to about 250° C, to about 300° C, to about 350° C, or to about 400° C.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • methanol is generated from the demethylation of 4- amino-3-methoxybenzoic acid. In some embodiments, methanol is isolated from the reaction mixture.
  • the o-Phenylenediamine is isolated from any remaining lignin, vanillic acid, methanol, and/or 4-amino-3-methoxybenzoic acid. In some embodiments, o-Phenylenediamine is isolated by any suitable method. In some
  • o-Phenylenediamine is isolated from any remaining lignin, vanillic acid, methanol, and/or 4-amino-3-methoxybenzoic acid by use of a solvent.
  • the aniline is isolated from any remaining lignin, vanillic acid, methanol, and/or 4-amino-3-methoxybenzoic acid by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • caprolactam obtained from lignin is a method of obtaining caprolactam from lignin. It is to be understood that provided in various embodiments herein are both (1) caprolactam prepared according to any of the processes described herein; and (2) any method described herein for obtaining caprolactam from a lignin source.
  • a method of obtaining caprolactam from lignin comprising: (a) subjecting lignin to oxidative conditions sufficient to produce vanillic acid, (b) subjecting vanillic acid to conditions sufficient to convert vanillic acid to cyclohexanecarboxylic acid; and (d) subjecting cyclohexanecarboxylic acid to conditions sufficient to convert cyclohexanecarboxylic acid to caprolactam.
  • lignin is converted to vanillic acid by any method disclosed herein.
  • the reaction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • vanillic acid is separated or extracted from any residual material (e.g., lignin) prior to converting it to cyclohexanecarboxylic acid, and in other embodiments, is not separated or extracted from any residual material prior to converting it to cyclohexanecarboxylic acid. In some embodiments, vanillic acid is converted to cyclohexanecarboxylic acid under reducing conditions.
  • any residual material e.g., lignin
  • a carbon-carbon unsaturated group (e.g., an alkenyl group) on vanillic acid is reduced (e.g., so as to produce a cyclohexanecarboxylic acid).
  • vanillic acid is catalytically hydrogenated.
  • vanillic acid is contacted with hydrogen (e.g., hydrogen gas) and a metal catalyst.
  • the metal catalyst is platinum, palladium (e.g., Pd/C), rhodium, ruthenium, Raney nickel, and Urushibara nickel.
  • the reduction occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • cyclohexanecarboxylic acid is separated or extracted from any residual material (e.g., lignin, or vanillic acid) prior to converting it to caprolactam, and in other embodiments, is not separated or extracted from any residual material prior to converting it to caprolactam.
  • any residual material e.g., lignin, or vanillic acid
  • cyclohexanecarboxylic acid is converted to caprolactam by contacting cyclohexanecarboxylic acid with nitrosylsulfuric acid (NO(HS0 4 )).
  • NO(HS0 4 ) nitrosylsulfuric acid
  • nitrosulfuric acid is generated from ammonia, oxygen, and oleum.
  • the contacting occurs under conditions that instigate or maximize the reaction (e.g., heating or high pressure).
  • the contacting occurs under heating, pressurizing and/or agitating (e.g., stirring or mixing).
  • the reaction mixture is heated to at least room temperature, at least 25° C, at least 35° C, at least 50° C, at least 70° C, at least 80° C, at least 90° C, or at least 100° C.
  • the reaction mixture is pressurized to at least 20 psi, at least 30 psi, at least 40 psi, 50 psi, at least 100 psi, at least 200 psi, at least 300 psi, at least 500 psi, at least 1000 psi or the like.
  • methanol is generated from the reduction of
  • methanol is isolated from the reaction mixture.
  • the caprolactam is isolated from any remaining lignin, vanillic acid, methanol, and/or cyclohexanecarboxylic acid. In some embodiments, caprolactam is isolated by any suitable method. In some embodiments, caprolactam is isolated from any remaining lignin, vanillic acid, methanol, and/or cyclohexanecarboxylic acid by use of a solvent. In some embodiments, the aniline is isolated from any remaining lignin, vanillic acid, methanol, and/or cyclohexanecarboxylic acid by use of at least two solvents.
  • the biomass is contacted with an enzyme in a reactor.
  • the lignin is separated from the biomass in a reactor.
  • the reactor is, by way of non-limiting example, a flow reactor (e.g., a batch- flow reactor and a continuous flow reactor).
  • the reactor is a large scale industrial reactor.
  • 1,2,4-trihydroxybenzene wherein 1,2,4-trihydroxybenzene is obtained from lignin.
  • the 1,2,4- trihydroxybenzene has a 14 C/C ratio greater than 10 "15 .
  • the 1,2,4-trihydroxybenzene has a 14 C/C ratio greater than about 10 ⁇ 15 , greater than about 10 ⁇ 14 , greater than about 10 ⁇ 13 , or greater than about 10 ⁇ 12 .
  • the 1,2,4-trihydroxybenzene has a 14 C/C ratio greater than about 10 ⁇ 15 , greater than about 10 ⁇ 14 , greater than about 10 ⁇ 13 , or greater than about 10 ⁇ 12 .
  • the 1,2,4-trihydroxybenzene has a 14 C/C ratio greater than about 10 ⁇ 15 , greater than about 10 ⁇ 14 , greater than about 10 ⁇ 13 , or greater than about 10 ⁇ 12 .
  • concentration of 14 C in the compound can be quantified by use of any suitable analytical technique (e.g., accelerator mass spectrometry, isotope ratio mass spectrometry, liquid scintillation beta spectrometry, etc.).
  • any suitable analytical technique e.g., accelerator mass spectrometry, isotope ratio mass spectrometry, liquid scintillation beta spectrometry, etc.
  • any compound obtained from 1,2,4- trihydroxybenzene wherein the 1,2,4-trihydroxybenzene is obtained from lignin.
  • the compound obtained from 1,2,4-trihydroxybenzene has a 14 C/C ratio greater than 10 ⁇ 15 .
  • the compound obtained from 1,2,4- trihydroxybenzene has a 14 C/C ratio greater than about 10 ⁇ 15 , greater than about 10 ⁇ 14 , greater than about 10 ⁇ 13 , or greater than about 10 ⁇ 12 .
  • the concentration of 14 C in the compound can be quantified by use of any suitable analytical technique (e.g., accelerator mass spectrometry, isotope ratio mass spectrometry, liquid scintillation beta spectrometry, etc.).
  • vanillic acid wherein vanillic acid is obtained from lignin.
  • the vanillic acid has a 14 C/C ratio greater than 10 ⁇ 15 .
  • the vanillic acid has a 14 C/C ratio greater than about 10 ⁇ 15 , greater than about 10 ⁇ 14 , greater than about 10 ⁇ 13 , or greater than about 10 ⁇ 12 .
  • the concentration of 14 C in the compound can be quantified by use of any suitable analytical technique (e.g., accelerator mass spectrometry, isotope ratio mass spectrometry, liquid scintillation beta spectrometry, etc.).
  • any compound obtained from vanillic acid wherein the vanillic acid is obtained from lignin.
  • the compound obtained from vanillic acid has a 14 C/C ratio greater than 10 ⁇ 15 .
  • the compound obtained from vanillic acid has a 14 C/C ratio greater than about 10 ⁇ 15 , greater than about 10 ⁇ 14 , greater than about 10 ⁇ 13 , or greater than about 10 ⁇ 12 .
  • the concentration of 14 C in the compound can be quantified by use of any suitable analytical technique (e.g., accelerator mass spectrometry, isotope ratio mass spectrometry, liquid scintillation beta spectrometry, etc.).
  • Lignin is converted to 1,2,4-trihydroxybenzene by contacting lignin with molecular oxygen and laccase.
  • the metal catalyst NaN0 2 /H + can be used. Then the mixture of aromatic compounds is subjected to reductive conditions and decarboxylation, decarbonylation and/or demethylation conditions (e.g., H 2 /H 2 0).
  • Lignin is converted into hydroquinone by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is subjected to hydro geno lysis conditions. 1,2,4-trihydroxybenzene is treated with hydrogen and a metal catalyst (Pd/C) to generate hydroquinone.
  • Pd/C metal catalyst
  • Lignin is converted into 4-aminophenol by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is subjected to hydro geno lysis conditions. 1,2,4-trihydroxybenzene is treated with hydrogen and a metal catalyst (Pd/C) to generate hydroquinone. Finally, the hydroquinone is treated with ammonia and a metal oxide catalyst (e.g. Zr0 2 ) to generate 4- aminophenol.
  • a metal oxide catalyst e.g. Zr0 2
  • Lignin is converted into p-phenylenediamine by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is subjected to hydro geno lysis conditions. 1,2,4-trihydroxybenzene is treated with hydrogen and a metal catalyst (Pd/C) to generate hydroquinone. Finally, the hydroquinone is treated with ammonia and a metal oxide catalyst (e.g. Zr0 2 ) to generate p- pheny lenediamine .
  • a metal oxide catalyst e.g. Zr0 2
  • Lignin is converted into terephthalic acid by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is treated with catechol 2,3-dioxygenase to generate the pyrone intermediate. Finally, the pyrone intermediate is subjected to cyclocondensation conditions in the presence of ethylene to generate terephthalic acid.
  • Lignin is converted into t-butylhydroquinone by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is treated with isobutylene and acid (e.g., HCl). Finally, the alkylated intermediate is subjected to hydro geno lysis conditions (i.e., hydrogen and Pd/C catalyst) to generate t-butylhydroquinone.
  • hydro geno lysis conditions i.e., hydrogen and Pd/C catalyst
  • Lignin is converted into butylated hydro xyanisole by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is treated with isobutylene and acid (e.g., HCl), followed by hydrogen and Pd/C catalyst to generate t-butylhydroquinone. Finally t-butylhydroquinone is treated with a methylating agent (e.g., Mel) to generate the butylated hydroxyanisole.
  • a methylating agent e.g., Mel
  • Lignin is converted into ⁇ -acetylacrylic acid by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is treated with oxygen and a base (e.g., pyridine), to generate ⁇ - acetylacrylic acid.
  • a base e.g., pyridine
  • Lignin is converted into ⁇ -aminolevulinic acid by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is treated with oxygen and a base (e.g., pyridine), to generate ⁇ - acetylacrylic acid. Finally ⁇ -acetylacrylic acid is treated with ethyl nitrite and HCl followed by tin, stannous chloride, and HCl to generate ⁇ -aminolevulinic acid.
  • a base e.g., pyridine
  • Lignin is converted into the levulinate ethyl ester by first contacting lignin with molecular oxygen and laccase, followed by H 2 /H 2 0 to generate 1,2,4-trihydroxybenzene. Next, the 1,2,4-trihydroxybenzene is optionally isolated from the lignin. Then, the 1,2,4- trihydroxybenzene is treated with oxygen and a base (e.g., pyridine), to generate ⁇ - acetylacrylic acid. Finally ⁇ -acetylacrylic acid is subjected to ethyl esterification conditions followed by hydrogenation conditions (e.g., Pd/C catalyst and hydrogen) to generate the levulinate ethyl ester.
  • a base e.g., pyridine
  • Lignin is oxidized to vanillic acid by contacting lignin with molecular oxygen and a cobalt (II) metal catalyst.
  • a cobalt (II) metal catalyst In alternative instances, the metal catalyst MeReOs can be used.
  • Lignin is converted into 2-methoxyphenol by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is decarboxylated with a decarboxylase
  • Lignin is converted into catechol by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is decarboxylated with a decarboxylase, generating 2-methoxyphenol. Finally, 2-methoxyphenol is contacted with super critical water to generate catechol.
  • II cobalt
  • Lignin is converted into catechol by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is decarboxylated and demethylated by contacting it with super critical water to generate catechol. Finally, the catechol is contacted with hydrogen and catalyst (e.g., B1VO4, CuW0 4 , Cuo.75Zno. 25 W04, or CuW0 4 + Ce, CuO- A1 2 0 3 ) to generate phenol.
  • catalyst e.g., B1VO4, CuW0 4 , Cuo.75Zno. 25 W04, or CuW0 4 + Ce, CuO- A1 2 0 3
  • Lignin is converted into muconic acid by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is decarboxylated with a decarboxylase, generating 2-methoxyphenol. Next, 2-methoxyphenol is contacted with super critical water to generate catechol. Finally, the catechol is contacted with molecular oxygen and Fe(II) to generate muconic acid.
  • Lignin is converted into muconic acid by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is decarboxylated with a decarboxylase, generating 2-methoxyphenol. Next, 2-methoxyphenol is contacted with super critical water to generate catechol. Then, the catechol is contacted with molecular oxygen and Fe(II) to generate muconic acid. Finally, muconic acid is subjected to reducing conditions via exposure to H 2 and Pd.
  • II cobalt
  • Lignin is converted into muconic acid by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid.
  • vanillic acid is isolated from the lignin.
  • the vanillic acid is decarboxylated with a decarboxylase, generating 2-methoxyphenol.
  • 2-methoxyphenol is contacted with super critical water to generate catechol.
  • the catechol is contacted with catechol 1 ,2-dioxygenase to generate hexa- 2,4-dienedioic acid.
  • hexa-2,4-dienedioic acid is subjected to catalytic olefin metathesis to generate butadiene and acrylic acid.
  • Lignin is converted into 2-aminophenol by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is aminated by contacting it with ammonia and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210. Next, 4-amino-3-methoxybenzoic acid is contacted with near- critical water, generating 2- aminophenol.
  • II cobalt
  • Lignin is converted into aniline by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is aminated by contacting it with ammonia and Pd or 3 ⁇ 40 5 . Next, 4-amino-3-methoxybenzoic acid is contacted with near-critical water, generating 2- aminophenol. Finally, 2-aminophenol is reduced by contact with 3 ⁇ 4 and Pd.
  • II cobalt
  • Lignin is converted into OPDA by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is aminated by contacting it with ammonia and acid washed H-151 alumina or another catalyst as described in US Patent No. 5,214,210. Next, 4-amino- 3-methoxybenzoic acid is contacted with super critical water to produce OPDA.
  • II cobalt
  • Lignin is converted into caprolactam by first contacting lignin with molecular oxygen and a cobalt (II) catalyst to generate vanillic acid. Next, the vanillic acid is isolated from the lignin. Then, the vanillic acid is reduced to cyclohexanecarboxylic acid by contacting it with hydrogen and Pd. Next, cyclohexanecarboxylic acid is contacted with nitrosylsulfuric acid, generating caprolactam.
  • II cobalt

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Abstract

L'invention concerne un procédé d'oxydation de la lignine ainsi que des composés aromatiques et non aromatiques obtenus à partir de lignine oxydée.
PCT/US2011/062477 2010-11-30 2011-11-29 Oxydation de la lignine et produits dérivés Ceased WO2012075053A2 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013082264A1 (fr) * 2011-12-02 2013-06-06 Amyris, Inc. Synthèse d'oléfines
CN105541559A (zh) * 2016-01-24 2016-05-04 东北石油大学 钙钛矿类氧化物催化木质素生产芳香基含氧化合物的方法
WO2017037013A1 (fr) * 2015-08-28 2017-03-09 Universitaet Des Saarlandes Moyens et procédés pour la production de composés organiques
WO2020035548A2 (fr) 2018-08-14 2020-02-20 Cmblu Projekt Ag Composés à activité redox et leurs utilisations
US10745335B2 (en) 2016-07-14 2020-08-18 University Of Kansas Continuous process for the ozonolysis of lignin to yield aromatic monomers
US12234329B2 (en) 2019-06-20 2025-02-25 University Of Kansas Methods for forming lignin prepolymers and lignin resins

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7396974B2 (en) * 2002-02-08 2008-07-08 University Of Maine Oxidation using a non-enzymatic free radical system mediated by redox cycling chelators
US20120107886A1 (en) * 2009-06-01 2012-05-03 Strategic Enzyme Applications, Inc. Lignin Oxidation and Products Thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013082264A1 (fr) * 2011-12-02 2013-06-06 Amyris, Inc. Synthèse d'oléfines
WO2017037013A1 (fr) * 2015-08-28 2017-03-09 Universitaet Des Saarlandes Moyens et procédés pour la production de composés organiques
CN105541559A (zh) * 2016-01-24 2016-05-04 东北石油大学 钙钛矿类氧化物催化木质素生产芳香基含氧化合物的方法
CN105541559B (zh) * 2016-01-24 2018-08-10 东北石油大学 钙钛矿类氧化物催化木质素生产芳香基含氧化合物的方法
US10745335B2 (en) 2016-07-14 2020-08-18 University Of Kansas Continuous process for the ozonolysis of lignin to yield aromatic monomers
WO2020035548A2 (fr) 2018-08-14 2020-02-20 Cmblu Projekt Ag Composés à activité redox et leurs utilisations
WO2020035138A1 (fr) 2018-08-14 2020-02-20 Cmblu Projekt Ag Composés à activité redox et leurs utilisations
WO2020035549A2 (fr) 2018-08-14 2020-02-20 Cmblu Projekt Ag Composés à activité redox et leurs utilisations
US12234329B2 (en) 2019-06-20 2025-02-25 University Of Kansas Methods for forming lignin prepolymers and lignin resins

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