# US 8,772,556 B2 · Bio-oil production with optimal byproduct processing > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,772,556 B2 - Document ID: US8772556B2 - Status: Granted - Kind: B2 - Application number: 12/888,193 - Filed: 2010-09-22 - Published: 2012-03-22 - Granted: 2014-07-08 - Earliest claimed: 2010-09-22 - Assignees: KiOR, Inc. - Applicants: Andre Ditsch - Inventors: Andre Ditsch - Web page: https://patentgrep.com/patent/US8772556B2 ## CPC - C10B 53/02: of cellulose-containing material (production of pyroligneous acid C10C5/00) - C01B 3/16: using catalysts - C01B 3/38: using catalysts - C10B 49/22: according to the "fluidised bed" technique - C10G 2/30: {from carbon monoxide with hydrogen} - C10G 3/52: {Hydrogen in a special composition or from a special source} - C10K 1/005: {Carbon dioxide} - C01B 2203/0233: the reforming step being a steam reforming step - C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step - C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration - C01B 2203/1241: Natural gas or methane - C10G 2300/1011: Biomass - C10G 2300/42: Hydrogen of special source or of special composition - C10G 2400/20: C2-C4 olefins - Y02E 50/10: Biofuels, e.g. bio-diesel - Y02E 50/30: Fuel from waste, e.g. synthetic alcohol or diesel - Y02P 20/145: the feedstock being materials of biological origin - Y02P 30/40: Ethylene production - C10B: DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS (cracking oils C10G; underground gasification of minerals E21B43/295) - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - 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 - C10K: PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A process and system for the conversion of biomass under high severity in the presence of a catalyst to produce a bio-oil, olefins, methane, and carbon monoxide (CO). The methane and/or CO can be used to generate hydrogen and the generated hydrogen can be used for hydrotreating the bio-oil. Additionally, or alternatively, a syngas stream, a carbon dioxide-rich stream, and/or a methane-rich stream can be recovered for use in the bio-oil production process and/or for use in a conventional petroleum refinery and/or petrochemical plant. ## Claims ### Claim 1 A process for producing bio-oil and processing byproducts of bio-oil production, said process comprising: (a) pyrolyzing biomass in a conversion reactor in the presence of a catalyst to thereby produce a reactor effluent comprising bio-oil, carbon monoxide (CO), and methane, wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 0.5:1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.05:1; (b) condensing and separating a substantial portion of said bio-oil from said reactor effluent, thereby leaving an uncondensed stream comprising at least a portion of said methane and at least a portion of said CO; and (c) generating hydrogen by reacting water with at least a portion of said CO and/or at least a portion of said methane, thereby producing a hydrogen-enriched stream comprising generated hydrogen, wherein said process produces said generated hydrogen at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 2 (depends on 1) The process of claim 1 wherein said generating of step (c) comprises methane reforming. ### Claim 3 (depends on 1) The process of claim 1 wherein said generating of step (c) comprises a water gas shift reaction. ### Claim 4 (depends on 1) The process of claim 1 wherein said generating of step (c) comprises methane reforming followed by a water gas shift reaction. ### Claim 5 (depends on 1) The process of claim 1 further comprising hydrodreating at least a portion of said condensed and separated bio-oil using at least a portion of said generated hydrogen. ### Claim 6 (depends on 5) The process of claim 5 wherein at least 75 weight percent of the hydrogen used in said hydrotreating is said generated hydrogen. ### Claim 7 (depends on 1) The process of claim 1 wherein said pyrolyzing is carried out at a temperature of at least 300° C. and not more than 1,000° C., wherein said pyrolyzing includes catalytic cracking, wherein the oxygen content of said condensed and separated bio-oil is less than 25 weight percent. ### Claim 8 (depends on 1) The process of claim 1 wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 1:1 and not more than 10:1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.1:1 and not more than 1:1. ### Claim 9 (depends on 1) The process of claim 1 wherein said generating of step (c) produces said generated hydrogen at a rate that is at least 1 percent and not more than 20 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 10 (depends on 1) The process of claim 1 wherein said reactor effluent further comprises olefins, wherein the weight ratio of said olefins to said bio-oil in said reactor effluent is at least 0.1:1. ### Claim 11 (depends on 10) The process of claim 10 further comprising, prior to said generating of step (c), removing at least 50 weight percent of said olefins originally present in said reactor effluent. ### Claim 12 (depends on 10) The process of claim 10 wherein ethylene and propylene in combination make up at least 50 weight percent of said olefins present in said reactor effluent. ### Claim 13 (depends on 1) The process of claim 1 wherein said conversion reactor produces said bio-oil at a rate that is at least 4 percent and not more than 50 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces said CO at a rate that is at least 10 percent and not more than 80 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces said methane at a rate that is at least 0.5 percent and not more than 30 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces olefins at a rate that is at least 2 percent and not more than 40 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces water at a rate that is at least 4 percent and not more than 50 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 14 (depends on 1) The process of claim 1 further comprising recovering from said hydrogen-enriched stream at least one of the following recovered streams: (i) a syngas stream comprising at least a portion of said generated hydrogen and at least a portion of said CO, wherein said generated hydrogen and said CO make up at least 75 weight percent of said syngas stream, (ii) a hydrogen-rich stream, wherein said generated hydrogen makes up at least 75 weight percent of said hydrogen-rich stream, (iii) a carbon dioxide-rich stream comprising at least 75 weight percent carbon dioxide (CO2), and/or (iv) a methane-rich stream, wherein said methane makes up at least 75 weight percent of said methane-rich stream. ### Claim 15 (depends on 14) The process of claim 14 wherein said generated hydrogen and said CO make up at least 95 weight percent of said syngas stream, wherein said generated hydrogen makes up at least 95 weight percent of said hydrogen-rich stream, wherein said CO2 comprises at least 95 weight percent of said CO2-rich stream, wherein said methane makes up at least 95 weight percent of said methane-rich stream. ### Claim 16 (depends on 14) The process of claim 14 wherein said recovering comprises pressure swing adsorption. ### Claim 17 (depends on 14) The process of claim 14 wherein said recovered streams include said syngas stream. ### Claim 18 (depends on 17) The process of claim 17 wherein said process produces said syngas stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 19 (depends on 17) The process of claim 17 further comprising converting at least a portion of said syngas stream to ethanol and/or Fischer-Tropsch liquids. ### Claim 20 (depends on 14) The process of claim 14 wherein said recovered streams include said hydrogen-rich stream and said CO2-rich stream. ### Claim 21 (depends on 20) The process of claim 20 wherein said process produces said hydrogen-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO2-rich stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 22 (depends on 20) The process of claim 20 further comprising using at least a portion of said hydrogen-rich stream to hydrotreat at least a portion of said condensed and separated bio-oil and sequestering at least a portion of said CO2-rich stream. ### Claim 23 (depends on 14) The process of claim 14 wherein said recovered streams include said hydrogen-rich stream, said CO2-rich stream, and said methane-rich stream. ### Claim 24 (depends on 23) The process of claim 23 wherein said process produces said hydrogen-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO2-rich stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said methane-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 25 (depends on 23) The process of claim 23 further comprising using at least a portion of said hydrogen-rich stream to hydrotreat at least a portion of said condensed and separated bio-oil, sequestering at least a portion of said CO2-rich stream, and using at least a portion of said methane-rich stream in a cogeneration process. ### Claim 26 A process for producing bio-oil and processing byproducts of bio-oil production, said process comprising: (a) pyrolyzing biomass in a riser reactor in the presence of a catalyst to thereby produce a reactor effluent comprising bio-oil, carbon monoxide (CO), olefins, and methane, wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 0.5:1, wherein the weight ratio of said olefins to said bio-oil in said reactor effluent is at least 0.1:1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.05:1; (b) condensing and separating a substantial portion of said bio-oil from said reactor effluent, thereby leaving an uncondensed stream comprising at least a portion of said methane and at least a portion of said CO; and (c) generating hydrogen from at least a portion of said uncondensed stream to thereby produce a hydrogen-enriched stream comprising generated hydrogen; (d) recovering from at least a portion of said hydrogen-enriched stream at least one of the following recovered streams: (i) a syngas stream comprising hydrogen and at least a portion of said CO, wherein said hydrogen and said CO make up at least 75 weight percent of said syngas stream, (ii) a hydrogen-rich stream, wherein hydrogen makes up at least 75 weight percent of said hydrogen-rich stream, (iii) a carbon dioxide-rich stream comprising at least 75 weight percent carbon dioxide (CO2), or (iv) a methane-rich stream, wherein said methane makes up at least 75 weight percent of said methane-rich stream, wherein when said syngas stream is recovered in step (d) said process produces said syngas stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein when said hydrogen-rich stream is recovered in step (d) said process produces said hydrogen-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein when said CO2-rich stream is recovered in step (d) said process produces said CO2-rich stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein when said methane-rich stream is recovered in step (d) said process produces said methane-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 27 (depends on 26) The process of claim 26 wherein said recovered streams include said syngas stream and not said hydrogen-rich stream and not said methane-rich stream and not said CO2-rich stream. ### Claim 28 (depends on 27) The process of claim of claim 27 further comprising converting at least a portion of said syngas stream to ethanol and/or Fischer-Tropsch liquids. ### Claim 29 (depends on 26) The process of claim 26 wherein said recovered streams include said hydrogen-rich stream and said CO2-rich stream and not said syngas stream and not said methane-rich stream. ### Claim 30 (depends on 29) The process of claim 29 wherein said process produces said hydrogen-rich stream at a rate that is at least 1 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO2-rich stream at a rate that is at least 10 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 31 (depends on 26) The process of claim 26 wherein said recovered streams include said hydrogen-rich stream, said CO2-rich stream, and said methane-rich stream and not said syngas stream. ### Claim 32 (depends on 31) The process of claim 31 wherein said process produces said hydrogen-rich stream at a rate that is at least 1 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO2-rich stream at a rate that is at least 10 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said methane-rich stream at a rate that is at least 1 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis. ### Claim 33 (depends on 26) The process of claim 26 wherein said generating of step (c) comprises reacting water with at least a portion of said CO and/or at least a portion of said methane to generate said hydrogen-enriched stream. ### Claim 34 (depends on 33) The process of claim 33 further comprising hydrotreating at least a portion of said condensed and separated bio-oil using at least a portion of said generated hydrogen. ### Claim 35 (depends on 26) The process of claim 26 wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 1:1, wherein the weight ratio of said olefins to said bio-oil in said reactor effluent is at least 0.4:1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.2:1, wherein said condensed and separated bio-oil has an oxygen content of less than 25 weight percent. ### Claim 36 A system for producing bio-oil, said system comprising: a biomass feedstock source for providing solid particulate biomass; a conversion reactor for thermally converting at least a portion of said solid particulate biomass feedstock into a reactor effluent comprising bio-oil, carbon monoxide (CO), olefins, and methane; a partial condenser for partially condensing at least a portion of said reactor effluent into a bio-oil stream and an uncondensed stream; an olefin removal unit for removing olefins from said uncondensed stream thereby providing an olefin-depleted stream; a hydrogen generation unit having a water inlet, wherein said hydrogen generation unit is operable to generate hydrogen by reacting water with CO and/or methane from said olefin-depleted stream; and a hydrotreater for reacting at least a portion of said bio-oil stream with at least a portion of the generated hydrogen from said hydrogen generation unit. ### Claim 37 (depends on 36) The system of claim 36 further comprising a pressure swing adsorption unit for recovering at least a portion of the generated hydrogen from said hydrogen generation unit. ### Claim 38 (depends on 36) The system of claim 36 wherein said hydrogen generation unit comprises a methane reformer and/or a water gas shift reactor. ### Claim 39 (depends on 36) The system of claim 36 wherein said conversion reactor is a riser reactor.