# US 9,752,090 B2 · High-carbon biogenic reagents and uses thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,752,090 B2 - Document ID: US9752090B2 - Status: Granted - Kind: B2 - Application number: 14/548,874 - Filed: 2014-11-20 - Published: 2015-03-19 - Granted: 2017-09-05 - Earliest claimed: 2011-04-15 - Assignees: Carbon Technology Holdings, LLC - Applicants: Biogenic Reagents Ventures, LLC - Inventors: Daniel J. Despen; James A. Mennell; Steve Filips - Web page: https://patentgrep.com/patent/US9752090B2 ## CPC - C10L 5/447: {Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass} - B01J 21/18: Carbon - C01B 32/312: Preparation - C01B 32/318: characterised by the starting materials - C10B 39/00: Cooling or quenching coke - C10B 39/02: Dry cooling outside the oven - C10B 41/00: Safety devices, e.g. signalling or controlling devices for use in the discharge of coke - C10B 43/02: Removing incrustations - C10B 45/00: Other details - C10B 47/30: in rotary ovens or retorts - C10B 49/02: with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge - C10B 53/02: of cellulose-containing material (production of pyroligneous acid C10C5/00) - C10B 57/02: Multi-step carbonising or coking processes - C10B 57/06: containing additives - C10B 57/10: Drying - C10L 5/04: Raw material {of mineral origin} to be used; Pretreatment thereof {(pretreatment of fuels of non-mineral origin C10L5/40)} - C10L 5/36: Shape - C10L 5/363: {Pellets or granulates} - C10L 5/365: {Logs} - C10L 5/366: {Powders} - C10L 5/442: {Wood or forestry waste} - C21B 5/007: {Conditions of the cokes or characterised by the cokes used} - C21C 5/52: Manufacture of steel in electric furnaces {(C21C5/005 takes precedence)} - C22B 4/02: Light metals {(C22B4/005 takes precedence)} - H01B 1/04: mainly consisting of carbon-silicon compounds, carbon or silicon - C10L 2200/0204: Metals or alloys - C10L 2200/025: Halogen containing compounds - C10L 2200/0469: Renewables or materials of biological origin - C10L 2290/02: Combustion or pyrolysis - C10L 2290/06: Heat exchange, direct or indirect - C10L 2290/08: Drying or removing water - C10L 2290/145: of air - C10L 2290/28: Cutting, disintegrating, shredding or grinding - C10L 2290/30: Pressing, compressing or compacting - C10L 2290/50: Screws or pistons for moving along solids - C10L 2290/52: Hoppers - C10L 2290/58: Control or regulation of the fuel preparation of upgrading process - C10L 2290/60: Measuring or analysing fractions, components or impurities or process conditions during preparation or upgrading of a fuel - C21B 13/0066: {Preliminary conditioning of the solid carbonaceous reductant} - Y02E 50/10: Biofuels, e.g. bio-diesel - Y02E 50/30: Fuel from waste, e.g. synthetic alcohol or diesel - Y02E 60/10: Energy storage using batteries - Y02P 10/143: of methane [CH4] - Y02P 20/129: Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines - Y02P 20/133: Renewable energy sources, e.g. sunlight - Y02P 20/145: the feedstock being materials of biological origin - Y02W 10/30: Wastewater or sewage treatment systems using renewable energies - Y02W 10/37: using solar energy - C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - C10B: DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS (cracking oils C10G; underground gasification of minerals E21B43/295) - C21B: MANUFACTURE OF IRON OR STEEL (preliminary treatment of ferrous ores or scrap C22B1/00) - C21C: PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS - C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS - H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K}) - 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 - Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT ## Abstract This invention provides processes and systems for converting biomass into high-carbon biogenic reagents that are suitable for a variety of commercial applications. Some embodiments employ pyrolysis in the presence of an inert gas to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases, followed by separation of vapors and gases, and cooling of the hot pyrolyzed solids in the presence of the inert gas. Additives may be introduced during processing or combined with the reagent, or both. The biogenic reagent may include at least 70 wt %, 80 wt %, 90 wt %, 95 wt %, or more total carbon on a dry basis. The biogenic reagent may have an energy content of at least 12,000 Btu/lb, 13,000 Btu/lb, 14,000 Btu/lb, or 14,500 Btu/lb on a dry basis. The biogenic reagent may be formed into fine powders, or structural objects. The structural objects may have a structure and/or strength that derive from the feedstock, heat rate, and additives. ## Claims ### Claim 1 A process for producing high-carbon biogenic reagent comprising the steps of: (a) providing a carbon-containing feedstock comprising biomass, said biomass comprising not more than about 50% water, by weight; (b) in a pyrolysis zone, pyrolyzing said carbon-containing feedstock in the presence of a substantially inert gas for at least about 10 minutes and with a pyrolysis temperature selected from about 250° C. to about 700° C., to generate hot pyrolyzed solids, condensable vapors, and non-condensable gases; (c) separating at least a portion of said condensable vapors and at least a portion of said non-condensable gases from said hot pyrolyzed solids; (d) in a cooling zone, cooling said hot pyrolyzed solids, in the presence of said substantially inert gas for at least about 5 minutes and with a cooling zone temperature less than said pyrolysis temperature, to generate warm pyrolyzed solids; (e) in a cooling unit that is separate from said cooling zone, cooling said warm pyrolyzed solids to generate cool pyrolyzed solids; (f) recovering a high-carbon biogenic reagent comprising at least a portion of said cool pyrolyzed solids, and (g) introducing at least one additive selected from acids, bases, or salts thereof, and/or introducing at least one additive selected from the group consisting of a metal, a metal oxide, a metal hydroxide, a metal halide, and combinations thereof. ### Claim 2 (depends on 1) The process of claim 1, wherein each of said zones is located within a single reactor, or wherein each of said zones is located in a separate reactor. ### Claim 3 (depends on 1) The process of claim 1, wherein at least some of said substantially inert gas includes one or more non-condensable gas species recycled from step (c). ### Claim 4 (depends on 1) The process of claim 1, wherein said pyrolysis zone and said cooling zone each comprise a gas phase containing less than about 5 wt % oxygen, or about 1 wt % oxygen or less. ### Claim 5 (depends on 1) The process of claim 1, wherein said process is continuous or semi-continuous. ### Claim 6 (depends on 5) The process of claim 5, wherein said inert gas flows substantially countercurrent relative to the direction of solids flow, or wherein said inert gas flows substantially cocurrent relative to the direction of solids flow. ### Claim 7 (depends on 1) The process of claim 1, said process further comprising monitoring and controlling said process with at least one reaction gas probe, or with at least two reaction gas probes. ### Claim 8 (depends on 1) The process of claim 1, said process further comprising one or more of: process gas heating of at least a portion of said condensable vapors with an oxygen-containing gas, optionally assisted with combustion of natural gas, using process gas heating, at least in part, for drying said feedstock to remove at least a portion of moisture contained within said feedstock, and using process gas heating, at least in part, to heat said substantially inert gas, and optionally introducing the heated substantially inert gas to said pyrolysis zone. ### Claim 9 (depends on 1) The process of claim 1, said process further comprising combining at least a portion of said condensable vapors, in at least partially condensed form, with said cooled pyrolyzed solids and/or with said warm pyrolyzed solids, to increase the carbon content of said high-carbon biogenic reagent. ### Claim 10 (depends on 1) The process of claim 1, wherein: the at least one additive is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof, and/or the at least one additive is selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide, lime, and combinations thereof. ### Claim 11 (depends on 1) The process of claim 1, wherein the at least one additive is introduced: prior to or during step (b), during step (d), during step (e), between steps (d) and (e), after step (e), or to said warm pyrolyzed solids in an aqueous solution, vapor, or aerosol to assist with cooling of said warm pyrolyzed solids in step (e). ### Claim 12 (depends on 1) The process of claim 1, said process further comprising: introducing at least a portion of said cool pyrolyzed solids to a separate unit for additional pyrolysis, in the presence of a second substantially inert gas for at least 30 minutes and with a pyrolysis temperature selected from about 200° C. to about 600° C., to generate a solid product having higher carbon content than said cool pyrolyzed solids; and optionally process gas heating at least a portion of said condensable vapors with an oxygen-containing gas, wherein heat produced from said process gas heating is utilized, at least in part, to heat said second substantially inert gas prior to introduction to said separate unit for additional pyrolysis. ### Claim 13 (depends on 1) The process of claim 1 further comprising a step of drying the carbon-containing feedstock prior to step (b), wherein the cooling unit is operated: to cool said warm pyrolyzed solids with steam to generate cool pyrolyzed solids and superheated steam and wherein the step of drying is carried out, at least in part, with said superheated steam; and/or to first cool said warm pyrolyzed solids with steam to reach a first cooler temperature, and then with air to reach a second cooler temperature, wherein said second cooler temperature is lower than said first cooler temperature and is associated with a reduced combustion risk for said warm pyrolyzed solids in the presence of said air. ### Claim 14 (depends on 1) The process of claim 1, wherein said high-carbon biogenic reagent contains at least 35%, at least 50%, or at least 70% of the carbon contained in said feedstock. ### Claim 15 (depends on 1) The process of claim 1, wherein said high-carbon biogenic reagent contains at least 70 wt %, at least 80 wt %, at least 90 wt %, or at least 95 wt % carbon on a dry basis, wherein said carbon optionally includes fixed carbon and carbon from volatile matter. ### Claim 16 (depends on 1) The process of claim 1, wherein said high-carbon biogenic reagent has an energy content, on a dry basis, of at least 11,000 Btu/lb, at least 12,000 Btu/lb on a dry basis, at least 13,000 Btu/lb, at least 14,000 Btu/lb, at least 14,500 Btu/lb, or at least 14,700 Btu/lb. ### Claim 17 (depends on 1) The process of claim 1, wherein said high-carbon biogenic reagent is formed into a fine powder by particle-size reduction, is formed into a structural object by pressing, binding, pelletizing, or agglomeration, or is in the form of structural objects whose structure and/or strength substantially derive from said feedstock, optionally wherein said high-carbon biogenic reagent is in substantially the same structural form as said feedstock.