# US 9,518,076 B2 · Apparatus and process for preparing reactive lignin with high yield from plant biomass for production of fuels and chemicals > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,518,076 B2 - Document ID: US9518076B2 - Status: Granted - Kind: B2 - Application number: 14/397,035 - Filed: 2013-04-30 - Published: 2015-04-09 - Granted: 2016-12-13 - Earliest claimed: 2012-04-30 - Assignees: Washington State University - Applicants: Washington State University - Inventors: Bin Yang; Dhrubojyoti Dey Laskar - Web page: https://patentgrep.com/patent/US9518076B2 ## CPC - C07G 1/00: Low-molecular-weight derivatives of lignin (high-molecular-weight derivatives of lignin {C08H6/00}) - B01J 19/24: Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) - B01J 19/245: {placed in series} - C08H 6/00: {Macromolecular compounds derived from lignin, e.g. tannins, humic acids} - C08H 8/00: Macromolecular compounds derived from lignocellulosic materials {(pretreatment thereof B27N)} - C08L 97/005: {Lignin} - C10G 1/002: {in combination with oil conversion- or refining processes} - C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds} - B01J 2219/24: Stationary reactors without moving elements inside - C10G 2300/1014: of vegetal origin - C10G 2400/02: Gasoline - C10G 2400/04: Diesel oil - C10G 2400/08: Jet fuel - Y02P 30/20: using bio-feedstock - C07G: COMPOUNDS OF UNKNOWN CONSTITUTION (sulfonated fats, oils or waxes of undetermined constitution C07C309/62) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C08H: DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS (polysaccharides C08B; natural rubber C08C; natural resins or their derivatives C09F; bituminous materials C10) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract Provided are methods for aqueous isolation of depolymerized lignin in high yield from a lignin-containing biomass composition, comprising positioning a lignin-containing biomass composition into a flowthrough thermal reactor chamber to provide for passage of an aqueous fluid therethrough, contacting the lignin biomass composition with the aqueous fluid under elevated temperature conditions sufficient to provide for lignin release and depolymerization, flowing the aqueous fluid through the reactor chamber under the elevated temperature conditions, to provide an output aqueous fluid comprising released depolymerized lignin, and collecting the depolymerized lignin. Particular aspects further comprise hydrogenation and/or hydrodeoxygenation (HDO) of the released depolymerized lignin with a catalyst or catalyst system for deconstruction of the released depolymerized lignin into lower molecular weight reactive lignin moieties and oligomers amenable for subsequent removal of oxygen to produce hydrocarbon fuels and/or chemicals and/or compounds. Systems for practicing the methods are also provided, along with highly purified depolymerized lignin. ## Claims ### Claim 1 A method for aqueous isolation of depolymerized lignin in high yield from a lignin-containing biomass composition, comprising: positioning a lignin-containing biomass composition into a flowthrough thermal reactor chamber comprising an input opening and an output opening configured to provide for passage of an aqueous fluid through the reactor chamber, the input opening in communication with a source of aqueous fluid; contacting the lignin biomass composition in the thermal reactor with the aqueous fluid, under elevated temperature conditions sufficient to provide for lignin release and depolymerization, by flowing the aqueous fluid through the reactor chamber under the elevated temperature conditions, to provide an output aqueous fluid comprising released depolymerized lignin; collecting, from the output opening, the output aqueous fluid comprising the released depolymerized lignin; and contacting the released depolymerized lignin with a catalyst or catalyst system in a hydrogenation and/or hydrodeoxygenation reactor chamber to provide for hydrogenation and/or hydrodeoxygenation for deconstruction of the released polymerized lignin into lower molecular weight reactive lignin moieties and oligomers amenable for subsequent removal of oxygen to produce hydrocarbon fuels and/or chemicals and/or compounds, wherein the catalyst or catalyst system comprises a combination of one or more noble metal catalysts, with one or more solid supports, in the presence of one or a series of solid acids, and wherein the one or more noble metal catalysts comprises at least one selected from the group consisting of Pt, Pd, Ru, and Rh, wherein the one or more solid supports comprises at least one selected from the group consisting of Al2O3, C, ZrO2, and TiO2, and wherein the one or more solid acids are solid acidic zeolites. ### Claim 2 (depends on 1) The method of claim 1, wherein contacting the lignin biomass composition under elevated temperature conditions comprises contacting at temperature greater than about 200° C., or a temperature in a range of from 200° C. to 300° C., or in the range of from 220° C. to 260° C., or in the range from 220° C. to 240° C. ### Claim 3 (depends on 1) The method of claim 1, wherein at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 94%, or at least 95% of the original lignin in the lignin containing biomass composition is collected in the output aqueous fluid comprising the depolymerized lignin. ### Claim 4 (depends on 1) The method of claim 1, wherein collecting the output aqueous fluid under the flowthrough conditions results in dilution of the released, depolymerized lignin. ### Claim 5 (depends on 1) The method of claim 1, wherein the flowthrough elevated temperature conditions are sufficient to reduced or eliminate counterproductive recondensation/re-polymerization of the released depolymerized lignin, relative to non-flowthrough or batch conditions/methods. ### Claim 6 (depends on 1) The method of claim 1, wherein the depolymerized lignin comprises at least one selected from the group consisting of soluble depolymerized lignin, oligomeric lignin, and insoluble depolymerized lignin comprising native lignin structure. ### Claim 7 (depends on 1) The method of claim 1, wherein the syringyl/guaiacyl ratio of the depolymerized lignin is decreased relative to the original lignin in the lignin-containing biomass composition. ### Claim 8 (depends on 1) The method of claim 1, wherein contacting the lignin biomass composition by passing the aqueous fluid through the reactor chamber under the elevated temperature conditions, comprises passing the aqueous fluid through the reactor chamber in three different time zones, comprising a heating zone, a reaction zone at elevated temperature, and a colling zone, wherein the heating and the colling zone may optionally occur inside or outside the thermal reactor. ### Claim 9 (depends on 1) The method of claim 1, wherein the flowthrough thermal reactor chamber comprising the lignin-containing biomass composition is purged using an inert gas prior to contacting the lignin biomass composition in the thermal reactor with the aqueous fluid. ### Claim 10 (depends on 9) The method of claim 9 wherein the gas is selected from the group consisting of hydrogen, helium or nitrogen. ### Claim 11 (depends on 1) The method of claim 1, wherein the aqueous fluid is acidic. ### Claim 12 (depends on 11) The method of claim 11, wherein the acid comprises H2SO4 at a concentration in the range of 0.01% to 2%. ### Claim 13 (depends on 12) The method of claim 12 wherein the acid comprises H2SO4 at a concentration of at least 0.05% H2SO4. ### Claim 14 (depends on 1) The method of claim 1, wherein the one or more noble metal catalysts comprises at least one selected from the group consisting of Pd, Ru, and Rh. ### Claim 15 (depends on 1) The method of claim 1, wherein contacting the released depolymerized lignin with a catalyst or catalyst system in the hydrogenation and/or hydrodeoxygenation reactor chamber to provide for hydrogenation and/or hydrodeoxygenation occurs after the released depolymerized lignin exits the flowthrough thermal reactor. ### Claim 16 (depends on 15) The method of claim 15, wherein contacting the released depolymerized lignin with a catalyst or catalyst system in the hydrogenation and/or hydrodeoxygenation reactor chamber to provide for hydrogenation and/or hydrodeoxygenation occurs after the released depolymerized lignin exits the flowthrough thermal reactor in a subsequent hydrogenation and/or hydrodeoxygenation reactor chamber in communication with the flowthrough thermal reactor. ### Claim 17 (depends on 1) The method of claim 1, wherein contacting the released depolymerized ligning with a catalyst or catalyst system in the hydrogenation and/or hydrodeoxygenation reactor chamber to provide for hydrogenation and/or hydrodeoxygenation occurs within the flowthrough thermal reactor to provide for a simultaneous solubilization, depolymerization, and hydrodeoxygenation process comprising integration of depolymerized lignin production with hydrodeoxygenation in a single reactor. ### Claim 18 (depends on 1) The method of claim 1, wherein the hydrogenation and/or hydrodeoxygenation reactor chamber is purged using an inert gas prior to hydrogenation and/or hydrodeoxgenation. ### Claim 19 An aqueous-based system for depolymerizing lignin in high yield from a lignin-containing biomass composition, comprising: an aqueous flowthrough thermal reactor chamber comprising an input opening and an output opening configured to provide for passage of an aqueous fluid through the reactor chamber, the input opening in communication with a source of aqueous fluid, the reactor configured for positioning a lignin-containing biomass composition therein to provide for contact with an aqueous fluid flowing therethrough, the input configured to provide for communication with an aqueous fluid source, and with a pressure source suitable to provide for flowing an aqueous fluid with released depolymerized lignin through the flowthrough thermal reactor; and a source of heat suitable to provide for an aqueous fluid at a raised temperature within the aqueous flowthrough thermal reactor; and a hydrogenation and/or hydrodeoxygenation reactor chamber, in fluid communication with the output opening of the aqueous flowthrough thermal reactor chamber, and configured with a catalyst or catalyst system for contacting the released depolymerized lignin with the catalyst or catalyst system to provide for hydrogenation and/or hydrodeoxygenation for deconstruction of the released depolymerized lignin into lower molecular weight reactive lignin moieties and oligomers amenable for subsequent removal of oxygen to produce hydrocarbon fuels and/or chemicals and/or compounds, wherein the catalyst or catalyst system comprises a combination of one or more noble metal catalysts, with one or more solid supports, in the presence of one or a series of solid acids, and wherein the one or more noble metal catalysts comprises at least one selected from the group consisting of Pt, Pd, Ru, and Rh, wherein the one or more solid supports comprises at least one selected from the group consisting of Al2O3, C, ZrO2, and TiO2, and wherein the one or more solid acids are solid acidic zeolites. ### Claim 20 (depends on 19) The aqueous based system of claim 19, wherein the one or more noble metal catalysts comprises at least one selected from the group consisting of Pd, Ru, and Rh. ### Claim 21 (depends on 19) The aqueous-based system of claim 19, wherein the hydrogenation and/or hydrodeoxygenation reactor chamber is integrated with the aqueous flow through thermal reactor chamber, or is distinct from the aqueous flowthrough thermal reactor chamber.