Process and system for producing biocoke in a kinetic interfacial reactor and biocoke produced therefrom

Abstract

A process for producing biocoke is provided that includes providing a heated biogas stream containing carbon-containing steam, providing a kinetic interfacial medium in solid form, introducing the kinetic interfacial medium and the heated biogas stream into a kinetic interfacial reactor operated to convert at least a portion of the carbon-containing steam to biocoke, removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor, and recovering the solid biocoke-containing kinetic interfacial medium. Another variation provides a process for producing biocoke that includes providing a bioliquid stream containing a carbon-containing liquid, providing a kinetic interfacial medium in solid form, introducing the kinetic interfacial medium and the bioliquid stream into a kinetic interfacial reactor operated to convert at least a portion of the carbon-containing liquid to biocoke, removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor, and recovering the solid biocoke-containing kinetic interfacial medium. Many embodiments are described.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 320,050, filed March 15, 2022, which is incorporated herein by reference in its entirety.

[0002] The present invention relates generally to processes and systems for making bio-coke and bio-coke compositions obtained therefrom. [Background technology]

[0003] Traditionally, coke is a hard, black form of coal containing about 80-90% carbon by weight. Coke has many industrial uses, including metallurgical coke for metal fabrication, such as steel production. Coke is commercially made from destructive distillation, in which coal is heated without air.

[0004] Coke is used in foundries, in the production of iron alloys, in the generation of calcium carbide from calcium oxide, and as a fuel to provide energy. Coke can serve an energetic role to provide process heat, a chemical role as a source of elemental carbon for the reduction of metal ores or the carburization of metals, or a physical role as a support for charge material, bed gas permeability, or liquid metal drainage. For example, foundry coke is used as a support matrix, reducing agent, and energy carrier during the cast iron production process.

[0005] Due to the rising economic, environmental, and social costs associated with fossil resources such as coal, there is a need in the industry for technologies that provide for the use of renewable biomass to produce coke and similar carbon products. Summary of the Invention

[0006] Some variations of the disclosed technology are processes for producing biocoke, the process comprising: providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a heated biogas stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert carbon-containing vapors into bio-coke, wherein the bio-coke contains at least 75% by weight of fixed carbon and the total carbon in the bio-coke is less than 0.05% by weight of the total carbon. 14 C / 12 converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the solid bio-coke-containing kinetic interfacial medium.

[0007] In some embodiments, the kinetic interfacial medium is in the form of pellets, which can be characterized by an average pellet effective diameter of at least about 1 millimeter and up to about 10 centimeters.

[0008] In some embodiments, the kinetic interfacial medium is in the form of a powder, which can be characterized by an average particle size of at least about 1 micron to a maximum of about 500 microns.

[0009] In some embodiments, the kinetic interfacial medium is in the form of granules, which can be characterized by an average effective granule diameter of at least about 100 microns to a maximum of about 10 millimeters.

[0010] In some embodiments, the kinetic interfacial medium has a bed depth within the kinetic interfacial reactor of at least about 10 centimeters to a maximum of about 10 meters.

[0011] The kinetic interface medium can include a pyrolysis form of a first biomass feedstock. In some embodiments, the first biomass feedstock is selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, and fruit husks. stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0012] In some embodiments, the kinetic interface medium comprises a crude biomass feedstock, such as softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0013] In some embodiments, the kinetic interfacial medium comprises a mixture of crude biomass feedstock and pyrolyzed biomass feedstock.

[0014] In some embodiments, the kinetic interfacial medium comprises pre-formed bio-coke or another pre-formed carbon source.

[0015] In some embodiments, the process further comprises producing a heated biogas stream by pyrolyzing the second biomass feedstock, wherein the carbon-containing steam comprises pyrolysis steam. The second biomass feedstock can include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper bales, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof.

[0016] In some embodiments, the kinetic interfacial medium comprises a pyrolytic form of a first biomass feedstock, a heated biogas stream is produced during the pyrolysis of the first biomass feedstock, and the kinetic interfacial medium and the heated biogas stream are obtained from a common pyrolysis reactor.

[0017] In some embodiments, the heated biogas stream comprises CO, CO, alkanes (e.g., methane), olefins (e.g., ethylene), aromatics (e.g., xylene), aldehydes (e.g., formaldehyde), ketones (e.g., acetone), acids (e.g., acetic acid), alcohols (e.g., methanol), or combinations thereof.

[0018] In some embodiments, during the converting step, bio-coke forms on the surface of the kinetic interfacial medium. Alternatively or additionally, during the converting step, bio-coke forms in the internal phase of the kinetic interfacial medium.

[0019] In some embodiments, during the converting step, the effective reaction conditions include a coking temperature of at least about 400°C up to about 1200°C.

[0020] In some embodiments, during the converting step, the effective reaction conditions include a coking pressure of at least about 1 bar up to about 40 bar.

[0021] In some embodiments, during the converting step, the effective reaction conditions include a coking vapor phase residence time of at least about 1 second up to about 1 hour.

[0022] In some embodiments, during the converting step, the effective reaction conditions include a coking solids residence time of at least about 1 minute up to about 24 hours.

[0023] In some embodiments, during the converting step, the effective reaction conditions comprise a kinetic interfacial medium residence time of at least about 1 minute up to about 24 hours.

[0024] In some embodiments, during the conversion step, the effective reaction conditions include a coking reaction seeded by a kinetic interfacial medium as the reaction matrix. In these embodiments, the kinetic interfacial medium seeds or initiates carbon growth but does not function as a true catalyst.

[0025] In some embodiments, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium.

[0026] In certain embodiments, during the converting step, the effective reaction conditions include a coking reaction catalyzed and seeded by a kinetic interfacial medium.

[0027] In some embodiments, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a separate coking catalyst other than the kinetic interfacial medium introduced into the kinetic interfacial reactor.

[0028] In some embodiments, the carbon conversion of the carbon-containing steam is at least 25% in the step of converting the carbon-containing steam to biocoke. In certain embodiments, the carbon conversion is at least 50%, at least 75%, or at least 90%.

[0029] In some embodiments, the process further includes separating the solid bio-coke-containing kinetic interfacial medium into a bio-coke-rich product and recovered kinetic interfacial medium, which is optionally recycled, at least in part, to the kinetic interfacial reactor, and the bio-coke-rich product can be stored, sold, distributed, converted into another product, or used in other ways.

[0030] In some embodiments, the process further includes conveying at least a portion of the solid bio-coke-containing kinetic interfacial medium to a pyrolysis reactor and producing a pyrolyzed solid bio-coke-containing kinetic interfacial medium. The pyrolyzed solid bio-coke-containing kinetic interfacial medium can be returned to the kinetic interfacial reactor via an inlet.

[0031] In some embodiments, the process further comprises recovering a kinetic interfacial reactor exhaust gas stream comprising unconverted carbon-containing vapors.

[0032] The kinetic interfacial reactor exhaust gas stream can be combusted, thereby producing energy. Some embodiments utilize the energy to heat a pyrolysis reactor, such as a pyrolysis reactor configured to provide a pyrolytic form of the biomass feedstock as a kinetic interfacial medium in the kinetic interfacial reactor.

[0033] Alternatively or additionally, the kinetic interfacial reactor exhaust gas stream may be partially oxidized, thereby producing a reducing gas containing at least H2 and / or CO.

[0034] In some embodiments, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after the recovering step, thereby forming a regenerated kinetic interfacial medium, and recycling the regenerated kinetic interfacial medium to the inlet of the kinetic interfacial reactor.

[0035] In some embodiments, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after the recovery step, thereby forming a regenerated kinetic interfacial medium comprising carbon, and conveying the regenerated kinetic interfacial medium to the pyrolysis reactor.

[0036] In various processes, the kinetic interfacial reactor may be, for example, a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, a rotary kiln, or a combination thereof. When the kinetic interfacial reactor is a rotary kiln, the rotary kiln may be configured such that the kinetic interfacial medium rotates radially and the heated biogas stream flows axially.

[0037] In some embodiments, the kinetic interfacial reactor is configured with a mechanical conveyor. The mechanical conveyor can introduce the kinetic interfacial medium into the kinetic interfacial reactor, or can transport the kinetic interfacial medium through the kinetic interfacial reactor, or both. Additionally or alternatively, the mechanical conveyor can transport the solid bio-coke-containing kinetic interfacial medium out of the kinetic interfacial reactor in a removal step. The mechanical conveyor can be a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, a recirculating conveyor, or a combination thereof.

[0038] In some embodiments utilizing a heated biogas stream, the removal step is performed continuously or semi-continuously. The removal step may be performed immediately after forming the solid bio-coke-containing kinetic interfacial medium. In other embodiments, there is an accumulation of solid bio-coke-containing kinetic interfacial medium, and the removal step is performed periodically or intermittently. In some embodiments utilizing a bio-liquid stream, the removal step is performed batchwise. Regardless of whether the removal step is continuous, semi-continuous, or batch, it may be desirable for the process not to result in a spatially continuous mass of solids packed within the kinetic interfacial reactor.

[0039] In some processes, the kinetic interfacial medium comprises at least about 25% by weight total carbon, at least about 50% by weight total carbon, or at least about 75% by weight total carbon.

[0040] In some processes, the solid bio-coke-containing kinetic interfacial medium comprises at least about 50% by weight fixed carbon, at least about 75% by weight fixed carbon, or at least about 90% by weight fixed carbon.

[0041] In some processes, the biocoke comprises at least about 80% by weight fixed carbon, at least about 90% by weight fixed carbon, at least about 95% by weight fixed carbon, or at least about 99% by weight fixed carbon. In some embodiments, the biocoke has a higher total carbon content than the kinetic interfacial medium.

[0042] The total carbon in bio-coke is 14 C / 12 In some embodiments, the total carbon in the biocoke can be at least about 75% renewable as determined from C isotope ratio measurements. 14 C / 12 In certain embodiments, the total carbon in the biocoke is at least about 90% renewable, as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0043] The solid bio-coke-containing kinetic interface medium generally has a different composition, including carbon content, compared to the bio-coke itself. The total carbon in the solid bio-coke-containing kinetic interface medium is 14 C / 12 In some embodiments, the total carbon in the solid biocoke-containing kinetic interfacial medium can be at least about 50% renewable, as determined from C isotope ratio measurements. 14 C / 12 In certain embodiments, the total carbon in the solid biocoke-containing kinetic interfacial medium is at least about 90% renewable, as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0044] In some embodiments, the bio-coke is essentially free of ash. In these or other embodiments, the bio-coke has a lower ash content than the kinetic interfacial medium.

[0045] In some embodiments, the process further includes producing free bio-coke particles from the carbon-containing vapor, wherein the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. The free bio-coke particles may originate solely from the carbon-containing vapor and not directly from the kinetic interfacial medium. Alternatively, if the kinetic interfacial medium contains carbon, the free bio-coke particles may originate from both the carbon-containing vapor and the kinetic interfacial medium. In some embodiments in which the free bio-coke particles are produced from the carbon-containing vapor, the formation of the free bio-coke particles is catalyzed or seeded by the kinetic interfacial medium.

[0046] In some processes, the carbonizing agent is added in one or more steps. The carbonizing agent may include a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a metal salt, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0047] In another variation of this technology, the process for producing biocoke comprises: providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a biological fluid stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert a carbon-containing liquid into bio-coke, wherein the bio-coke contains at least 75 wt. % fixed carbon and the total carbon in the bio-coke is less than 0.05 wt. 14 C / 12 converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the solid bio-coke-containing kinetic interfacial medium.

[0048] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of pellets, which can be characterized by an average pellet effective diameter of at least about 1 millimeter and up to about 10 centimeters.

[0049] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of a powder, which can be characterized by an average particle size of at least about 1 micron to a maximum of about 500 microns.

[0050] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of granules, which can be characterized by an average granule effective diameter of at least about 100 microns to a maximum of about 10 millimeters.

[0051] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium has a bed depth within the kinetic interfacial reactor of at least about 10 centimeters to a maximum of about 10 meters.

[0052] In some embodiments utilizing a biological liquid stream, the kinetic interface is the pyrolysis form of a first biomass feedstock, which may be softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, or fruit peels. , fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0053] In some embodiments utilizing a biological liquid stream, the kinetic interface medium comprises a crude biomass feedstock, such as softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0054] In some embodiments utilizing a biological liquid stream, the kinetic interfacial medium comprises a mixture of crude biomass feedstock and pyrolyzed biomass feedstock. In these embodiments, the pyrolyzed biomass may be from the same type of feedstock as the crude biomass (e.g., pine and pyrolyzed pine), or they may be from a different type of feedstock (e.g., non-pyrolyzed pine and pyrolyzed corn stover).

[0055] In some embodiments utilizing a bio-liquid stream, the kinetic interfacial medium comprises previously formed bio-coke.

[0056] In some embodiments utilizing a biological liquid stream, the process further includes producing a biological liquid stream from the pyrolysis of a second biomass feedstock. The second biomass feedstock can include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper bales, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof. The biological liquid stream may include condensed pyrolysis vapors, pyrolysis liquids not derived from vapor condensation (eg, tar), or a combination thereof.

[0057] In some embodiments utilizing a bioliquid stream, the bioliquid stream is produced from the pyrolysis of a first biomass feedstock, and the kinetic interfacial medium and the bioliquid stream are obtained from a common pyrolysis reactor.

[0058] The biological liquid stream may include one or more alkanes, olefins, aromatics, aldehydes, ketones, acids, alcohols, or combinations thereof. The biological liquid stream may contain tar, lignin, and / or high molecular weight components from biomass pyrolysis.

[0059] In some embodiments utilizing a biological liquid stream, bio-coke forms on the surface of the kinetic interfacial medium during the converting step. In these or other embodiments, bio-coke forms in the internal phase of the kinetic interfacial medium during the converting step.

[0060] In some embodiments utilizing a bioliquid stream, during the converting step, the effective reaction conditions include a coking temperature of at least about 400°C up to about 1200°C.

[0061] In some embodiments utilizing a bioliquid stream, during the converting step, the effective reaction conditions include a coking pressure of at least about 1 bar to a maximum of about 40 bar.

[0062] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking liquid phase residence time of at least about 1 minute to up to about 1 hour.

[0063] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking solids residence time of at least about 1 minute up to about 24 hours.

[0064] In some embodiments utilizing a biological fluid stream, during the converting step, the effective reaction conditions include a kinetic interfacial medium residence time of at least about 1 minute up to about 24 hours.

[0065] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction seeded by a kinetic interfacial medium as the reaction matrix.

[0066] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium.

[0067] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a separate coking catalyst other than the kinetic interfacial medium introduced into the kinetic interfacial reactor.

[0068] The carbon conversion of the carbon-containing liquid can be at least 25% in the step of converting the carbon-containing liquid to biocoke. In some embodiments, the carbon conversion is at least 50%, at least 75%, or at least 90%.

[0069] In some processes utilizing a bioliquid stream, the process further includes separating the solid bio-coke-containing kinetic interfacial medium into a bio-coke-rich product and recovered kinetic interfacial medium.

[0070] In some processes utilizing a bioliquid stream, the process further includes conveying at least a portion of the solid bio-coke-containing kinetic interfacial medium to a pyrolysis reactor and producing a pyrolyzed solid bio-coke-containing kinetic interfacial medium, and the pyrolyzed solid bio-coke-containing kinetic interfacial medium may be recycled to the inlet to the kinetic interfacial reactor.

[0071] In some processes utilizing a bioliquid stream, the process further includes recovering a kinetic interfacial reactor exhaust gas stream. The kinetic interfacial reactor exhaust gas stream can be combusted, thereby producing energy. The energy can be used to heat a pyrolysis reactor configured to provide a kinetic interfacial medium as a pyrolysis form of the biomass feedstock. Alternatively or additionally, the kinetic interfacial reactor exhaust gas stream can be partially oxidized, thereby producing a reducing gas.

[0072] In some processes utilizing the bioliquid stream, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after the recovery step, thereby forming a regenerated kinetic interfacial medium, and recycling the regenerated kinetic interfacial medium to the inlet of the kinetic interfacial reactor.

[0073] In some processes utilizing the bioliquid stream, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after the recovery step, thereby forming a regenerated kinetic interfacial medium comprising carbon, and conveying the regenerated kinetic interfacial medium to the pyrolysis reactor.

[0074] In various embodiments utilizing a biological liquid flow, the kinetic interfacial reactor is a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, a rotary kiln, or a combination thereof (e.g., a gravity-driven vertical falling bed vessel). When the kinetic interfacial reactor is a rotary kiln, the rotary kiln can be configured so that the kinetic interfacial medium rotates radially and the biological liquid flow flows axially.

[0075] In some embodiments utilizing a bioliquid flow, the kinetic interfacial reactor is configured with a mechanical conveyor. The mechanical conveyor can introduce the kinetic interfacial medium into the kinetic interfacial reactor, or can transport the kinetic interfacial medium through the kinetic interfacial reactor, or both. Additionally or alternatively, the mechanical conveyor can transport the solid biocoke-containing kinetic interfacial medium out of the kinetic interfacial reactor in a removal step. The mechanical conveyor can be a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, a recirculating conveyor, or a combination thereof.

[0076] In some embodiments utilizing a bioliquid stream, the removal step is performed continuously or semi-continuously. The removal step can be performed immediately after forming the solid bio-coke-containing kinetic interfacial medium. In other embodiments, there is an accumulation of solid bio-coke-containing kinetic interfacial medium, and the removal step is performed periodically or intermittently. In some embodiments utilizing a bioliquid stream, the removal step is performed batchwise. Regardless of whether the removal step is continuous, semi-continuous, or batch, it may be desirable for the process not to result in a spatially continuous mass of solids packed within the kinetic interfacial reactor.

[0077] In some processes utilizing biological fluid streams, the kinetic interfacial medium comprises at least about 25% by weight total carbon, at least about 50% by weight total carbon, or at least about 75% by weight total carbon.

[0078] In some processes utilizing a bioliquid stream, the solid bio-coke-containing kinetic interfacial medium comprises at least about 50% by weight fixed carbon, at least about 75% by weight fixed carbon, or at least about 90% by weight fixed carbon.

[0079] In some processes utilizing a bioliquid stream, the biocoke comprises at least about 80% by weight fixed carbon, at least about 90% by weight fixed carbon, at least about 95% by weight fixed carbon, or at least about 99% by weight fixed carbon. In certain embodiments, the biocoke has a higher total carbon content than the kinetic interfacial medium.

[0080] The total carbon in bio-coke is 14 C / 12 In some processes utilizing bioliquid streams, the total carbon in the biocoke can be at least about 75% renewable, as determined from C isotope ratio measurements. 14 C / 12 In certain embodiments, the total carbon in the biocoke is at least about 90% renewable, as determined from C isotope ratio measurements. 14 C / 12It is determined from measurements of C isotope ratios and is fully reproducible.

[0081] In processes utilizing a bioliquid stream, the solid bio-coke-containing kinetic interfacial medium generally has a different composition, including carbon content, compared to the bio-coke itself. The total carbon in the solid bio-coke-containing kinetic interfacial medium is 14 C / 12 In some embodiments, the total carbon in the solid biocoke-containing kinetic interfacial medium can be at least about 50% renewable, as determined from C isotope ratio measurements. 14 C / 12 In certain embodiments, the total carbon in the solid biocoke-containing kinetic interfacial medium is at least about 90% renewable, as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0082] In some embodiments utilizing a bio-liquid stream, the bio-coke is essentially free of ash. In these or other embodiments, the bio-coke has a lower ash content than the kinetic interfacial medium.

[0083] In some embodiments utilizing a bioliquid stream, the process further includes producing free bio-coke particles from the carbon-containing liquid, wherein the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. The free bio-coke particles may originate solely from the carbon-containing liquid and not directly from the kinetic interfacial medium. Alternatively, if the kinetic interfacial medium contains carbon, the free bio-coke particles may originate from both the carbon-containing liquid and the kinetic interfacial medium. In some embodiments where the free bio-coke particles are produced from the carbon-containing liquid, the formation of the free bio-coke particles is catalyzed or seeded by the kinetic interfacial medium.

[0084] In some processes utilizing biological liquid streams, a carbonizing agent is added in one or more steps. The carbonizing agent may include a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a metal salt, a non-metal salt, an organic halide, an inorganic halide, or derivatives or combinations thereof.

[0085] A biocoke product is provided by the disclosed technology. In some variations, the biocoke product comprises: providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a heated biogas stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert carbon-containing vapors into bio-coke, wherein the bio-coke contains at least 75% by weight of fixed carbon and the total carbon in the bio-coke is less than 0.05% by weight of the total carbon. 14 C / 12 converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the bio-coke product from the solid bio-coke-containing kinetic interfacial medium.

[0086] In another variation, the biocoke product comprises: providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a biological fluid stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert a carbon-containing liquid into bio-coke, wherein the bio-coke contains at least 75 wt. % fixed carbon and the total carbon in the bio-coke is less than 0.05 wt. 14 C / 12 converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the bio-coke product from the solid bio-coke-containing kinetic interfacial medium.

[0087] Yet another variation is a system for producing biocoke, the system comprising: a kinetic interfacial reactor; a first inlet configured to feed a heated biogas stream and / or a bioliquid stream into the kinetic interfacial reactor, the heated biogas stream comprising a carbon-containing vapor and the bioliquid stream comprising a carbon-containing liquid; a kinetic interfacial medium contained within a kinetic interfacial reactor, the kinetic interfacial medium being in solid form, the kinetic interfacial reactor being configured to operate under effective reaction conditions for converting carbon-containing vapors into bio-coke chemically or physically bound with the kinetic interfacial medium; a first outlet configured to remove bio-coke.

[0088] In some systems, the first inlet is configured to feed a heated biogas stream into the kinetic interfacial reactor. In other systems, the first inlet is configured to feed a bioliquid stream into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed a mixture of a heated biogas stream and a bioliquid stream (e.g., a supersaturated wet steam stream) into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed a heated biogas stream, a bioliquid stream, or both at different times when the kinetic interfacial reactor is designed to operate with either a heated biogas stream, a bioliquid stream, or a mixture thereof.

[0089] In some systems, the kinetic interfacial reactor is selected from a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, a rotary kiln, or a combination thereof. In systems using a rotary kiln as the kinetic interfacial reactor (or one of the kinetic interfacial reactors), the rotary kiln may be configured such that the kinetic interfacial medium rotates radially and the heated biogas stream and / or bioliquid stream flows axially.

[0090] Some systems are configured with a mechanical conveyor for feeding the kinetic interfacial medium into, through, and / or out of the kinetic interfacial reactor. The mechanical conveyor can be a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, a recirculating conveyor, or a combination thereof.

[0091] Some variations of this technology are continuous processes for producing biocoke, the continuous process comprising: providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; introducing the heated biogas stream into a kinetic interfacial reactor; converting carbon-containing vapors into solid bio-coke using a kinetic interfacial reactor; continuously withdrawing solid bio-coke; continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, wherein the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor; recovering the solid bio-coke as a bio-coke product, wherein the bio-coke product contains at least 75% by weight of fixed carbon, and the total carbon in the bio-coke product is less than or equal to 100% of the total carbon. 14 C / 12 and recovering the carbon dioxide, which is at least 50% renewable, as determined from measurements of the C isotope ratios; The process provides a continuous process in which the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0092] In some embodiments, the process further includes producing a heated biogas stream by pyrolyzing a biomass feedstock, wherein the carbon-containing steam is pyrolysis steam. The biomass feedstock may be selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0093] In some embodiments, the carbon-containing vapor is selected from CO, CO, an alkane (e.g., ethane), an olefin (e.g., propylene), an aromatic (e.g., toluene), an aldehyde (e.g., acetaldehyde), a ketone (e.g., acetylacetone), an acid (e.g., formic acid), an alcohol (e.g., propanol), or a combination thereof.

[0094] In some embodiments, the kinetic interfacial medium is in the form of pellets, which can be characterized by an average pellet effective diameter of at least about 1 millimeter and up to about 10 centimeters.

[0095] In some embodiments, the kinetic interfacial medium is in the form of a powder, which can be characterized by an average particle size of at least about 1 micron to a maximum of about 500 microns.

[0096] In some embodiments, the kinetic interfacial medium is in the form of granules, which can be characterized by an average effective granule diameter of at least about 100 microns to a maximum of about 10 millimeters.

[0097] In some embodiments, during the converting step, solid bio-coke forms on the surface of the kinetic interfacial medium. Alternatively or additionally, during the converting step, solid bio-coke forms in the internal phase of the kinetic interfacial medium.

[0098] In some embodiments, during the converting step, the effective reaction conditions include a coking temperature of at least about 400°C up to about 1200°C.

[0099] In some embodiments, during the converting step, the effective reaction conditions include a coking pressure of at least about 1 bar up to about 40 bar.

[0100] In some embodiments, during the converting step, the effective reaction conditions include a coking vapor phase residence time of at least about 1 second up to about 1 hour.

[0101] In some embodiments, during the converting step, the effective reaction conditions include a coking solids residence time of at least about 1 minute up to about 24 hours.

[0102] In some embodiments, during the converting step, the effective reaction conditions comprise a kinetic interfacial medium residence time of at least about 1 minute up to about 24 hours.

[0103] In some embodiments, during the conversion step, the effective reaction conditions include a coking reaction seeded by a kinetic interfacial medium as the reaction matrix. In these embodiments, the kinetic interfacial medium seeds or initiates carbon growth but does not function as a true catalyst.

[0104] In some embodiments, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium.

[0105] In some embodiments, during the conversion step, the effective reaction conditions include a coking reaction catalyzed by a separate coking catalyst other than the kinetic interfacial medium introduced into the kinetic interfacial reactor. In certain embodiments, the separate coking catalyst is continuously or periodically regenerated for reuse within the kinetic interfacial reactor. For example, if the separate coking catalyst is an aluminosilicate and the catalyst is deactivated by a refractory form of carbon, oxidation in air can regenerate the catalyst.

[0106] In some embodiments, during the converting step, the effective reaction conditions include a non-catalytic coking reaction that produces free bio-coke particles from the carbon-containing vapor. In certain embodiments, the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. In other embodiments, the free bio-coke particles are chemically or physically bound to the kinetic interfacial medium after they are formed.

[0107] In some embodiments, the carbon conversion from the carbon-containing vapor to solid biocoke is at least 25% in the converting step. In certain embodiments, the carbon conversion is at least 50%, at least 75%, or at least 90%.

[0108] In some embodiments, the process further includes recovering a kinetic interfacial reactor exhaust gas stream containing unconverted carbon-containing vapor. The kinetic interfacial reactor exhaust gas stream can be combusted with air or oxygen, thereby producing energy. The energy can be used to heat a pyrolysis reactor configured to provide a kinetic interfacial medium, the kinetic interfacial medium comprising a pyrolyzed form of the first biomass feedstock. Alternatively or additionally, the kinetic interfacial reactor exhaust gas stream can be partially oxidized with air or oxygen, thereby producing a reducing gas containing H and / or CO.

[0109] In some embodiments, the kinetic interfacial reactor is a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, or a rotary kiln, which may be configured such that the kinetic interfacial medium rotates radially and the heated biogas stream flows axially.

[0110] In some embodiments, the kinetic interfacial reactor is configured with a mechanical conveyor to convey the recycled bio-coke to the kinetic interfacial reactor, to convey the kinetic interfacial medium to the kinetic interfacial reactor, and / or to convey the solid bio-coke product out of the kinetic interfacial reactor, etc. The mechanical conveyor may be selected from, for example, a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, or a recirculation conveyor.

[0111] In some embodiments, the biocoke product comprises at least about 80% by weight fixed carbon, at least about 90% by weight fixed carbon, at least about 95% by weight fixed carbon, or at least about 99% by weight fixed carbon.

[0112] In some embodiments, the total carbon in the biocoke product is 14 C / 12 In certain embodiments, the total carbon in the biocoke product is at least about 75% renewable as determined from C isotope ratio measurements. 14 C / 12 At least about 90% renewable or at least about 100% (fully) renewable, as determined from measurements of C isotope ratios.

[0113] In some embodiments, the bio-coke product is essentially free of ash.

[0114] In some embodiments, during recovery, the solid bio-coke and the kinetic interfacial medium are separated from each other.

[0115] In some embodiments, the process further comprises adding a carbonizing agent, wherein the carbonizing agent comprises a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a metal salt, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0116] Another variation of this technology is a continuous process for producing biocoke, comprising: providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; introducing a biological fluid stream into a kinetic interfacial reactor; converting a carbon-containing liquid into solid bio-coke using a kinetic interfacial reactor; continuously withdrawing solid bio-coke; continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, wherein the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor; recovering the solid bio-coke as a bio-coke product, wherein the bio-coke product contains at least 75% by weight of fixed carbon, and the total carbon in the bio-coke product is less than or equal to 100% of the total carbon. 14 C / 12 and recovering the carbon dioxide, which is at least 50% renewable, as determined from measurements of the C isotope ratios; The process provides a continuous process in which the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0117] In some processes utilizing a bioliquid stream, the process further includes generating a bioliquid stream by pyrolyzing a biomass feedstock and collecting condensed pyrolysis vapors as a carbon-containing liquid. The biomass feedstock may be selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0118] In some embodiments utilizing a biological liquid stream, the biological liquid stream comprises one or more alkanes (e.g., n-hexane), olefins (e.g., cyclopentene), aromatics (e.g., lignin fragments), aldehydes (e.g., n-hexanal), ketones (e.g., cyclohexanone), acids (e.g., lignosulfonic acid), alcohols (e.g., cyclohexanol), or combinations thereof.

[0119] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of pellets, which can be characterized by an average pellet effective diameter of at least about 1 millimeter and up to about 10 centimeters.

[0120] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of a powder, which can be characterized by an average particle size of at least about 1 micron to a maximum of about 500 microns.

[0121] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of granules, which can be characterized by an average granule effective diameter of at least about 100 microns to a maximum of about 10 millimeters.

[0122] In some embodiments utilizing a bioliquid stream, solid bio-coke forms on the surface of the kinetic interfacial medium during the converting step. Alternatively or additionally, solid bio-coke forms in the internal phase of the kinetic interfacial medium during the converting step.

[0123] In some embodiments utilizing a bioliquid stream, during the converting step, the effective reaction conditions include a coking temperature of at least about 400°C up to about 1200°C.

[0124] In some embodiments utilizing a bioliquid stream, during the converting step, the effective reaction conditions include a coking pressure of at least about 1 bar to a maximum of about 40 bar.

[0125] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking liquid phase residence time of at least about 1 minute to up to about 1 hour.

[0126] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking solids residence time of at least about 1 minute up to about 24 hours.

[0127] In some embodiments utilizing a biological fluid stream, during the converting step, the effective reaction conditions include a kinetic interfacial medium residence time of at least about 1 minute up to about 24 hours.

[0128] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction seeded by a kinetic interfacial medium as the reaction matrix.

[0129] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium.

[0130] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a separate coking catalyst other than the kinetic interfacial medium introduced into the kinetic interfacial reactor. In certain embodiments, the separate coking catalyst is continuously or periodically regenerated for reuse within the kinetic interfacial reactor. For example, if the separate coking catalyst is a metal or metal hydride and the catalyst is poisoned by sulfur, regeneration in hydrogen can return the catalyst to the metal or metal hydride form.

[0131] In some embodiments utilizing a bio-liquid stream, during the converting step, the effective reaction conditions include a non-catalytic coking reaction that produces free bio-coke particles from the carbon-containing vapor. In certain embodiments, the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. In other embodiments, the free bio-coke particles are chemically or physically bound to the kinetic interfacial medium after they are formed.

[0132] In some embodiments utilizing a bioliquid stream, the carbon conversion from the carbon-containing vapor to solid bio-coke is at least 25% in the converting step, hi certain embodiments, the carbon conversion is at least 50%, at least 75%, or at least 90%.

[0133] In some embodiments utilizing a bioliquid stream, the process further includes recovering a kinetic interfacial reactor exhaust gas stream comprising carbon-containing vapors formed within the reactor (e.g., from evaporation of bioliquid components or from a chemical reaction). The kinetic interfacial reactor exhaust gas stream can be combusted with air or oxygen, thereby producing energy. The energy can be used to heat a pyrolysis reactor configured to provide a kinetic interfacial medium comprising the pyrolyzed form of the first biomass feedstock. Alternatively or additionally, the kinetic interfacial reactor exhaust gas stream can be partially oxidized with air or oxygen, thereby producing a reducing gas containing H and / or CO.

[0134] In some embodiments utilizing a biological liquid flow, the kinetic interfacial reactor is a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, or a rotary kiln. The rotary kiln may be configured so that the kinetic interfacial medium rotates radially and the biological liquid flow flows axially.

[0135] In some embodiments utilizing a bioliquid stream, the kinetic interfacial reactor is configured with a mechanical conveyor to transport recycled bio-coke to the kinetic interfacial reactor, to transport the kinetic interfacial medium to the kinetic interfacial reactor, and / or to transport the solid bio-coke product out of the kinetic interfacial reactor, etc. The mechanical conveyor may be selected from, for example, a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, or a recirculation conveyor.

[0136] In some embodiments utilizing a bioliquid stream, the biocoke product comprises at least about 80% by weight fixed carbon, at least about 90% by weight fixed carbon, at least about 95% by weight fixed carbon, or at least about 99% by weight fixed carbon.

[0137] In some embodiments utilizing a bioliquid stream, the total carbon in the biocoke product is 14 C / 12In certain embodiments, the total carbon in the biocoke product is at least about 75% renewable as determined from C isotope ratio measurements. 14 C / 12 At least about 90% renewable or at least about 100% (fully) renewable, as determined from measurements of C isotope ratios.

[0138] In some embodiments utilizing a bio-liquid stream, the bio-coke product is essentially ash-free.

[0139] In some embodiments utilizing a bioliquid stream, in the recovery step, the solid biocoke and the kinetic interfacial medium are separated from one another.

[0140] In some embodiments utilizing a biological liquid stream, the process further comprises adding a carbonizing agent, wherein the carbonizing agent comprises a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a metal salt, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0141] Yet another variation is providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; introducing the heated biogas stream into a kinetic interfacial reactor; converting carbon-containing vapors into solid bio-coke using a kinetic interfacial reactor; continuously withdrawing solid bio-coke; continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, wherein the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor; recovering the solid bio-coke as a bio-coke product, wherein the bio-coke product contains at least 75% by weight of fixed carbon, and the total carbon in the bio-coke product is less than or equal to 100% of the total carbon.14 C / 12 and recovering the carbon dioxide, which is at least 50% renewable, as determined from measurements of the C isotope ratios; Provided is a biocoke product produced by a continuous process, where the process does not result in a spatially continuous solid mass packed within a kinetic interfacial reactor.

[0142] Yet another variation is providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; introducing a biological fluid stream into a kinetic interfacial reactor; converting a carbon-containing liquid into solid bio-coke using a kinetic interfacial reactor; continuously withdrawing solid bio-coke; continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, wherein the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor; recovering the solid bio-coke as a bio-coke product, wherein the bio-coke product contains at least 75% by weight of fixed carbon, and the total carbon in the bio-coke product is less than or equal to 100% of the total carbon. 14 C / 12 and recovering the carbon dioxide, which is at least 50% renewable, as determined from measurements of the C isotope ratios; Provided is a biocoke product produced by a continuous process, where the process does not result in a spatially continuous solid mass packed within a kinetic interfacial reactor.

[0143] One particular variation provides a system for continuously producing bio-coke, the system comprising a kinetic interfacial reactor, the kinetic interfacial reactor comprising a first inlet configured to feed a heated biogas stream and / or a bio-liquid stream into the kinetic interfacial reactor, the heated biogas stream comprising a carbon-containing vapor and the bio-liquid stream comprising a carbon-containing liquid, the kinetic interfacial reactor configured to operate under effective reaction conditions for converting the carbon-containing vapor and / or the carbon-containing liquid to solid bio-coke, the kinetic interfacial reactor comprising a first outlet configured to continuously or semi-continuously remove the solid bio-coke, the kinetic interfacial reactor comprising a second inlet configured to feed at least a portion of the solid bio-coke removed from the outlet, and the first outlet or the second outlet configured to remove and recover the bio-coke product.

[0144] In some systems designed to continuously produce biocoke, the first inlet is configured to feed a heated biogas stream into the kinetic interfacial reactor. In other systems, the first inlet is configured to feed a bioliquid stream into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed a mixture of a heated biogas stream and a bioliquid stream (e.g., a liquid stream entrained with heated biogas bubbles) into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed the heated biogas stream, the bioliquid stream, or both at different times when the kinetic interfacial reactor is designed to operate with either the heated biogas stream or the bioliquid stream, or a mixture thereof.

[0145] In some systems designed to continuously produce bio-coke, the kinetic interfacial reactor is selected from a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, a rotary kiln, or a combination thereof. In systems using a rotary kiln as the kinetic interfacial reactor (or one of multiple kinetic interfacial reactors), the rotary kiln can be configured so that the kinetic interfacial medium rotates radially and the heated biogas stream and / or bioliquid stream flows axially.

[0146] In some systems designed to continuously produce biocoke, the system includes a mechanical conveyor configured to feed the kinetic interfacial medium into, through, and / or out of the kinetic interfacial reactor. The mechanical conveyor can be a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, a recirculating conveyor, or a combination thereof. [Brief explanation of the drawings]

[0147] [Figure 1] FIG. 1 is an exemplary process schematic illustrating the coking of biogas onto carbon pellets as a kinetic interfacial medium, thereby producing high yield carbon pellets.

[0148] [Figure 2] FIG. 1 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from heated biogas derived from biomass pyrolysis.

[0149] [Figure 3] FIG. 1 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from heated biogas.

[0150] [Figure 4]FIG. 1 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from bioliquids derived from biomass pyrolysis.

[0151] [Figure 5] FIG. 1 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from a bio-liquid.

[0152] [Figure 6] FIG. 1 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from heated biogas with internal recycle of bio-coke as the kinetic interfacial medium.

[0153] [Figure 7] FIG. 1 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from a bio-liquid with internal recycle of bio-coke as the kinetic interfacial medium. DETAILED DESCRIPTION OF THE INVENTION

[0154] Carbon is a platform element in a wide variety of industries and has a vast array of chemical, material, and fuel applications. Carbon is used as a fuel to generate energy, including electricity. Carbon also has great chemical value for a variety of commercial and advanced materials, including metals, metal alloys, composites, carbon fibers, electrodes, and catalyst supports. For metal fabrication, carbon used in certain forms, such as coke, is useful as a reactant, specifically to reduce metal oxides to metals during processing, as a fuel to provide heat for processing, and as a component of metal alloys.

[0155] Coke is a carbon-rich material with many industrial uses. Blast furnace ironmaking traditionally utilizes coke as a primary source of both energy and iron oxide reduction. In the blast furnace process, coke has multiple functions, playing an important role as a reducing agent, load carrier, and fuel. Fuel-grade coke (shot coke or sponge coke) is used in cement production and in fluidized-bed boilers to generate steam and electricity. Partial oxidation of coke in gasification processes allows for the production of synthesis gas. Coke combustion allows for the production of steam and electricity. Some calcined coke is used in titanium dioxide production, such as in chloride processes, as a feedstock for continuous thermal desulfurization of specialty low-sulfur carbon raisers, such as steel ladle additives, or as a carbon raiser in cast iron and steelmaking. Coke suitable for calcination is used in making carbon anodes for the aluminum industry. High-quality coke can be used for graphite electrodes in steel arc furnaces.

[0156] Most cokers are delayed cokers. Delayed coking is a thermal, non-catalytic process carried out at temperatures of approximately 500°C to crack heavy petroleum-based feedstocks into a range of lighter components and a significant amount of petroleum coke, which may be in the form of solid carbon. The short residence time in the furnace tubes "delays" the coking reaction until the coke reaches large coking drums. In the large drums, the solid coke settles, and lighter liquids or vapors are removed and sent to fractionators. Once the drum is filled with coke, the feed is switched to another drum. The full drum is cooled with water and then opened so that the solid coke can be drilled using high-pressure water jets. The coke can be cut directly into rail cars, cut into crushing cars and hydraulically pumped, or cut into pits or pads and removed by crane or end loader.

[0157] Coke can theoretically be produced from virtually any carbonaceous material. Carbonaceous materials generally include fossil resources, including natural gas, petroleum, coal, and lignite. Carbonaceous materials also include renewable resources, such as lignocellulosic biomass and various carbon-rich wastes. Energy produced from biomass-derived coke results in lower net CO2 emissions compared to coke derived from coal or petroleum. Materials (such as metal alloys) produced using biocoke have lower carbon intensity compared to materials produced using coke derived from coal or petroleum. Biocoke is of commercial interest as a replacement for conventional coke and to enable new applications. Improved processes and systems for producing coke, particularly biocoke, are desirable. It is particularly desirable to produce biocoke without the need to periodically remove large amounts of solid carbon from the reactor, which, in the case of coke produced from crude oil, traditionally requires water blasting, mechanical cutting, or even explosives to recover the coke from the delayed coke drum.

[0158] definition As used herein, when the indefinite article "a" or "an" is used in connection with a statement or description of the presence of a step in a process disclosed herein, unless the statement or description expressly provides to the contrary, the use of such an indefinite article does not limit the presence of a step in the process to one. As used herein, when an amount, concentration, or other value or parameter is given as either a range or a list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range or value and any lower range or value, regardless of whether the ranges are individually disclosed.

[0159] Where a range of numerical values ​​is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values ​​recited when defining a range.

[0160] As used herein, the terms "comprise," "comprising," "includes," "including," "has," "having," "contains," or "containing," or other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, mixture, process, method, article, or device that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or device. Such terms also include, but are not equivalent to, the terms "consisting essentially of" or "consisting of." Thus, when the term "comprising" appears, it can be replaced with "consisting essentially of" or "consisting of."

[0161] Further, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or. Unless the word "or" is expressly limited in reference to a list of two or more items to mean only one item exclusively of the other items, the use of "or" in such a list should be interpreted to include (a) any one item in the list, (b) all items in the list, or (c) any combination of items in the list. As used herein, a phrase "and / or," such as "A and / or B," refers to A alone, B alone, and both A and B. Where the context allows, singular or plural terms may also include the plural or singular term, respectively.

[0162] As used herein, the term "about" refers to possible variations in a reported numerical quantity. The term "about" means within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% of the reported numerical value.

[0163] Furthermore, as used herein, the term "substantially" refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, an object that is "substantially" enclosed would mean that the object is completely enclosed or nearly completely enclosed. The precise degree of acceptable deviation from absolute completeness may, in some cases, depend on the particular context. Generally speaking, however, near completeness would be such that one would have the same overall result as if absolute and total completeness had been achieved. The use of "substantially" is equally applicable when used in a negative sense to refer to the complete or nearly complete absence of an action, characteristic, property, state, structure, item, or result.

[0164] An "additive" or "additives" can be introduced throughout the process before, during, or after any step disclosed herein. Additives can be broadly categorized as process additives selected to improve process performance, such as carbon yield or pyrolysis time / temperature to achieve a desired carbon purity, and product additives selected to improve one or more properties of the high-carbon bioreagent or downstream products incorporating the reagent. Certain additives can provide enhanced process and product (bioreagent or product containing bioreagent) properties.

[0165] The additives can be added before, during, or after any one or more steps of the process, including adding them to the feedstock itself at any time before or after the feedstock is harvested. The additive treatment can be incorporated before, during, or after sizing, drying, or other preparation of the feedstock. The additives can be incorporated into or on the feedstock supply facility, transport truck, unloading equipment, storage bin, conveyor (including open or closed conveyors), dryer, process heater, or any other unit. The additives can be added anywhere in the pyrolysis process itself, using a suitable means for introducing the additive. If desired, the additives can be added after carbonization or even after pulverization.

[0166] In the art, "coke" typically refers to a product obtained from low-ash and low-sulfur bituminous coal through a process called coking. A similar product, called petroleum coke or pet coke, is obtained from crude oil in oil refineries. The definition of "coke" herein includes coke produced from either coal or crude oil, but not from biomass. As used herein, "biocoke" refers to coke produced from biomass or a mixture of biomass and another carbon source, which may be biogenic, nonbiogenic, or a mixture of biogenic and nonbiogenic carbon.

[0167] As used herein, a "biological" is a material (either a feedstock, product, or intermediate) that contains elements such as carbon that are renewable on time scales of months, years, or decades. Non-biological materials (e.g., fossil fuels) can be non-renewable or renewable on time scales of centuries, thousands, millions of years, or even longer geological time scales.

[0168] As used herein, "biomass" describes biologically produced or living matter. The chemical energy contained in biomass comes from solar energy using the natural process of photosynthesis. Photosynthesis is the process by which plants take carbon dioxide and water from their surroundings and convert them into sugars, starch, cellulose, hemicellulose, and lignin using energy from sunlight. Of all renewable energy sources, biomass is unique in that it is effectively stored solar energy. Furthermore, biomass is the only renewable source of carbon.

[0169] The three naturally occurring isotopes of carbon, 12 C. 13 C, and 14 There is C. 12 C and 13 C is stable and occurs in a natural ratio of approximately 93:1. 14C is produced by thermal neutrons from cosmic radiation in the upper atmosphere and transported to Earth where it is absorbed by living biological material. 14 Although C constitutes a negligible portion, it is radioactive with a half-life of 5,700 years and is therefore detectable radiometrically. 14 Because it does not absorb C, 14 Measurement of the amount of C can be used for radiometric dating of biological materials.

[0170] Plants fix atmospheric carbon through photosynthesis 14 C. Then, when animals consume the plants, or other animals that consume the plants, 14 Therefore, living plants and animals absorb the same amount of CO2 as the atmosphere. 14 C vs. 12 When an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer produces new carbon. 14 C is not incorporated. Radioactive decay then occurs in living organisms. 14 It gradually depletes C. This effect is the basis of radiocarbon dating.

[0171] Fossil fuels such as coal are primarily made from plant material deposited millions of years ago. 14 This is equivalent to thousands of half-lives of C, and therefore essentially all of the carbon in fossil fuels. 14 C is decaying. Also, fossil fuels are not toxic to the atmosphere because they were originally formed from living organisms. 13 C is depleted. Therefore, carbon from fossil fuels is 13 C and 14 Both C are depleted.

[0172] This difference between the carbon isotopes of recently depleted organic matter, such as from renewable sources, and the carbon isotopes of fossil fuels, such as coal or crude oil, allows for the determination of the source of carbon in a composition. Specifically, carbon isotope analysis can indicate whether the carbon in a composition is derived from a renewable resource or a fossil fuel, or in other words, whether a renewable resource or a fossil fuel was used to produce the composition.

[0173] The Hardgrove Grindability Index ("HGI") is a measure of the grindability of a material such as biomass or coal. The HGI parameter for coal is important in power applications such as pulverized coal boilers, where the coal is pulverized and burned in suspension, and in steelmaking, such as pulverized coal injection, where the pulverized coal is injected into a blast furnace through a lance and can replace coke to reduce iron ore to metallic iron.

[0174] As used herein, a "pellet" is an agglomerated object, not a loose powder. The geometric shape of a pellet is not limited to a spherical or nearly spherical shape. Also, in this disclosure, "pellet" is synonymous with "briquette." The geometric shape of a pellet may be spherical (round or ball-shaped), cylindrical, cubic (square), octagonal, hexagonal, honeycomb / honeycomb, elliptical, oval, cylindrical, rod-shaped, pillow-shaped, random, or a combination thereof. For convenience of disclosure, the term "pellet" is used generally for any object containing powder agglomerated using a binder. The present invention is in no way limited to any of the disclosed compositions being in the form of pellets.

[0175] As used herein, the unmodified term "reagent" broadly refers to a material such as a fuel, chemical, material, compound, additive, blend component, or solvent. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. In some embodiments, a reagent is a chemical reactant that is consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in adjusting the mechanical, physical, or hydrodynamic properties of a material to which it may be added. For example, a reagent may be introduced into a metal to impart certain strength properties to the metal. A reagent may be a substance of sufficient purity (in the present context, typically carbon purity) to be used in chemical analysis or physical testing.

[0176] As used herein, "low fixed carbon" and "high fixed carbon" describe materials that can be produced by the processes and systems disclosed herein. Any limitations on carbon content or any other concentration are not to be implied from the terms themselves, but rather only by reference to specific embodiments and their equivalents.

[0177] In this disclosure, a "product" can be, for example, a composition, a material, an object, or a structure. The term "product" is not intended to be limited by its commercial fate, such as whether it is sold, stored, traded, further processed, sold, or the like, to another party as an intermediate for further processing.

[0178] Process for producing biocoke using a biogas stream Disclosed herein is a process for producing bio-coke that may include providing a heated biogas stream, where the heated biogas stream includes carbon-containing vapors, providing a kinetic interfacial medium, where the kinetic interfacial medium is in solid form, introducing the kinetic interfacial medium and the heated biogas stream into a kinetic interfacial reactor, converting the carbon-containing vapors to bio-coke using the kinetic interfacial reactor, where the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium, removing the solid bio-coke-containing kinetic interfacial medium from the kinetic interfacial reactor, and recovering the solid bio-coke-containing kinetic interfacial medium.

[0179] A "kinetic interfacial medium" is a material effective to cause, enhance, or support coke formation on the surface of a material, or within the material, or both on the surface and within the material. Carbon atoms are transported across the interface formed with an external vapor, liquid, or solid phase containing a carbon source, so that solid bio-coke is formed kinetically and / or thermodynamically upon or after entering the material or on the surface of the material.

[0180] Some variations of the disclosed technology are processes for producing biocoke, the process comprising: providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a heated biogas stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert carbon-containing vapors into bio-coke, wherein the bio-coke contains at least 75% by weight of fixed carbon and the total carbon in the bio-coke is less than 0.05% by weight of the total carbon. 14 C / 12converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the solid bio-coke-containing kinetic interfacial medium.

[0181] In some embodiments, the kinetic interfacial medium is in the form of pellets. The pellets can be characterized by an average pellet effective diameter of at least about 1 millimeter to at most about 10 centimeters. In various embodiments, the average pellet effective diameter can be about, at least about, or at most about 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 1 cm, 1.5 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, or 10 cm, inclusive of all intervening ranges.

[0182] In some embodiments, the kinetic interfacial medium is in the form of a powder. The powder can be characterized by an average particle size of at least about 1 micron to at most about 500 microns. In various embodiments, the average particle size of the powder is about, at least about, or at most about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, or 500 microns, inclusive of all intervening ranges.

[0183] In some embodiments, the kinetic interfacial medium is in the form of granules. The granules can be characterized by an average granule effective diameter of at least about 100 microns to at most about 10 millimeters. In various embodiments, the average granule effective diameter is about, at least about, or at most about 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1000 microns, inclusive of all intervening ranges. In various embodiments, the average granule effective diameter is about, at least about, or at most about 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm, inclusive of all intervening ranges.

[0184] Particle size can be measured by various techniques, including, for example, dynamic light scattering, laser diffraction, image analysis, or sieving. Dynamic light scattering is a non-invasive, well-established technique for measuring particle size and size distribution down to 1 nanometer, typically in the submicron range. Laser diffraction is a widely used particle sizing technique for materials ranging in size from hundreds of nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction instruments for measuring particle size are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis to estimate particle size and distribution can be performed directly on photomicrographs, scanning electron photomicrographs, or other images. Finally, sieving is a prior art technique for separating particles by size.

[0185] The kinetic interfacial medium can be analyzed using imaging techniques, including, but not limited to, optical microscopy, dark-field microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray tomography (XRT). Alternatively or additionally, spectroscopic techniques can be utilized in various embodiments, including, but not limited to, energy dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.

[0186] In some embodiments, the kinetic interfacial medium has a bed depth of at least about 10 centimeters and up to about 10 meters. "Bed depth" is defined as the distance from the top to the bottom of a fixed or fluidized bed of kinetic interfacial medium in its largest dimension (which may be vertical or horizontal). In various embodiments, the kinetic interfacial medium bed depth is about, at least about, or up to about 10 cm, 25 cm, 50 cm, 100 cm, 250 cm, 500 cm, 750 cm, 1 m, 1.5 m, 2 m, 2.5 m, 3 m, 4 m, or 5 m, inclusive of all intervening ranges.

[0187] In some embodiments, the kinetic interface medium comprises a pyrolytic form of a first biomass feedstock, the first biomass feedstock being softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, or fruit peels. , fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0188] In some embodiments, the kinetic interfacial medium comprises previously formed bio-coke. The previously formed bio-coke can be fed to the kinetic interfacial reactor. The previously formed bio-coke can be formed according to any method disclosed herein or another method for making bio-coke. Alternatively or additionally, the kinetic interfacial medium can be another type of coke that is not necessarily bio-coke.

[0189] In some embodiments, the kinetic interface medium comprises a crude biomass feedstock, such as softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0190] In many embodiments, the kinetic interface medium contains carbon. In other embodiments, the kinetic interface medium does not contain carbon. For example, in certain embodiments, the kinetic interface medium contains a metal, metal alloy, metal oxide, metal hydride, metal nitride, or a combination thereof. Examples include, but are not limited to, iron, nickel, nickel oxide, cobalt, cobalt oxide, copper, copper oxide, zinc, zinc oxide, silica, sand, alumina, silica-alumina composites, or a combination thereof. In certain embodiments, biomass ash (which is generally silica-rich) is utilized as the kinetic interface medium. For example, biomass ash can be recovered from processes that combust, partially oxidize, and / or pyrolyze biomass. In certain embodiments, the kinetic interface medium contains carbon, but only as a compound with a metal. Examples include iron carbide, nickel carbide, cobalt carbide, zinc carbide, silicon carbide (silicon is considered a metal herein), aluminum carbide, or a combination thereof. The carbon in these metal carbide materials is not coke, and the bio-coke formed on or within the metal carbide is readily observable using analytical techniques and also recoverable via separation for bio-coke recovery.

[0191] In some embodiments, the process may further include generating a heated biogas stream (rather than receiving it from an external source). The generation of a heated biogas stream may be achieved by pyrolyzing the second biomass feedstock. The second biomass feedstock can include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper bales, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof.

[0192] In some embodiments, the carbon-containing vapor comprises pyrolysis vapor. The pyrolysis vapor may include CO, CO, alkanes, olefins, aromatic compounds, aldehydes, ketones, acids, alcohols, or combinations thereof. Exemplary alkanes include, but are not limited to, methane, ethane, propane, butane, and pentane. Exemplary olefins include, but are not limited to, ethylene, propylene, butene, and butadiene. Exemplary aromatic compounds include, but are not limited to, benzene, toluene, xylene, and lignin. Exemplary aldehydes include, but are not limited to, formaldehyde, acetaldehyde, and furfural. Exemplary ketones include, but are not limited to, acetone and butanone. Exemplary acids include, but are not limited to, formic acid, acetic acid, and levulinic acid. Exemplary alcohols include, but are not limited to, methanol, ethanol, and propanol.

[0193] In certain embodiments, the heated biogas stream is produced during pyrolysis of a biomass feedstock that is the same biomass feedstock that is also used to create the kinetic interfacial medium via pyrolysis.

[0194] In some embodiments, the kinetic interfacial medium comprises a pyrolysis form of a first biomass feedstock, a heated biogas stream is produced during pyrolysis of the first biomass feedstock, and the kinetic interfacial medium and the heated biogas stream are obtained from a common pyrolysis reactor. The heated biogas stream may comprise CO, CO, alkanes, olefins, aromatics, aldehydes, ketones, acids, alcohols, or combinations thereof. Alternatively or additionally, the heated biogas stream may comprise non-carbon-containing gases such as hydrogen or water vapor.

[0195] Various classes of compounds may be present in the heated biogas stream. C1 compounds may be present, including but not limited to, carbon monoxide, carbon dioxide, methane, formic acid, methanol, and formaldehyde. C2-C4 linear hydroxyl- and oxo-substituted aldehydes and ketones may be present, such as but not limited to, hydroxyacetaldehyde and hydroxyacetone. C2-C4 acids may be present, such as but not limited to, acetic acid or butyric acid. C5-C6 hydroxyl-, hydroxymethyl-, or oxo-substituted furans, furanones, lactones, and pyranones may be present. Anhydrosugars may be present, including C5 and C6 anhydrosugars (such as levoglucosan). Monomeric methoxyl-substituted phenols may be present. Lignin or lignin fragments may be present. Water vapor may be present in the heated biogas stream. Hydrogen may be present in the heated biogas stream.

[0196] The heated biogas can be at a biogas temperature of, for example, about 50° C. to about 800° C. before being introduced into the kinetic interfacial reactor. In various embodiments, the heated biogas is at a temperature of about, at least about, or up to about 50° C., 75° C., 100° C., 150° C., 200° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., or 800° C., including any intervening range. It is recognized that some components of the heated biogas stream are vapors at the heated biogas temperature but liquids at ambient temperature of 25° C. (e.g., methanol is a vapor at 100° C. but a liquid at 25° C., respectively, at 1 bar pressure), and other components (such as CO) are vapors at any temperature between 25° C. and 800° C. This depends on the liquid-vapor thermodynamic equilibrium properties of the particular species and conditions (including temperature and pressure) as well as the multicomponent thermodynamics involved.

[0197] In some embodiments, during conversion, bio-coke forms on the surface of the kinetic interfacial medium. In some embodiments, during conversion, bio-coke forms in the internal phase of the kinetic interfacial medium. When bio-coke forms in the internal phase, it may be in the same material phase as the kinetic interfacial medium solid phase, for example, forming a solid solution or alloy. Alternatively, bio-coke can phase separate within the kinetic interfacial medium and form its own solid phase. The separate phases can be located at or near the surface of the kinetic interfacial medium, which is beneficial for downstream separations.

[0198] As used herein, "during transformation" is synonymous with "during a transformation step," with the understanding that the transformation may actually be performed in one or more process steps. Similarly, this equivalence (i.e., the presence of a "step" or the implication of the presence of the word "step") applies with respect to other process steps, such as providing, introducing, removing, withdrawing, etc.

[0199] In some embodiments, during conversion, effective reaction conditions used to achieve the conversion include a coking temperature of at least about 400° C. to up to about 1200° C., including any intervening range, for example, about, at least about, or up to about 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., 800° C., 850° C., 900° C., 950° C., 1000° C., 1050° C., 1100° C., 1150° C., or 1200° C. Generally speaking, higher temperatures will promote the coking reaction, although other factors, including time, pressure, and catalytic effects, should be considered.

[0200] In some embodiments, during conversion, the effective reaction conditions used to achieve the conversion include a coking pressure of at least about 1 bar to up to about 40 bar, e.g., about, at least about, or up to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, or 40 bar, including any intervening range.

[0201] In some embodiments, during conversion, effective reaction conditions used to achieve the conversion include a coking vapor phase residence time of at least about 1 second to up to about 1 hour, including any intervening range, for example, about, at least about, or up to about 1 second, 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 45 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes, or 60 minutes. Generally speaking, longer vapor phase residence times will promote the coking reaction, although other factors, including temperature, pressure, and catalytic effects, should be considered.

[0202] In some embodiments, during conversion, effective reaction conditions used to achieve the conversion include a coking solids residence time of at least about 1 minute to up to about 24 hours, including any intervening range, for example, about, at least about, or up to about 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 45 minutes, 60 minutes, 1.5 hours, 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, or 24 hours. The coking solids residence time is a parameter independent of the gas phase residence time, as is known in multiphase reactor engineering.

[0203] In some embodiments, during the conversion, the effective reaction conditions used to achieve the conversion include a kinetic interfacial medium residence time of at least about 1 minute to up to about 24 hours, e.g., about, at least about, or up to about 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 45 minutes, 60 minutes, 1.5 hours, 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, or 24 hours, including any intervening range. The kinetic interfacial medium residence time can be the same as the coking solid phase residence time. Alternatively, the kinetic interfacial medium residence time can be longer than the coking solid phase residence time or shorter than the coking solid phase residence time. The kinetic interfacial medium residence time is an independent parameter from the coking solid phase residence time, although in practice they tend to be coupled, at least to some extent.

[0204] In some embodiments, during the conversion, the effective reaction conditions used to achieve the conversion comprise a coking reaction seeded by a kinetic interfacial medium as a reaction matrix. Alternatively or additionally, during the conversion, the effective reaction conditions used to achieve the conversion may comprise a coking reaction catalyzed by a kinetic interfacial medium. In some embodiments, during the conversion, the effective reaction conditions used to achieve the conversion comprise a coking reaction catalyzed by a separate coking catalyst introduced into the kinetic interfacial reactor.

[0205] The separate coking catalyst may include, for example, iron, nickel, nickel oxide, cobalt, cobalt oxide, copper, copper oxide, zinc, zinc oxide, silica, alumina, silica-alumina composites, sand, aluminosilicates, zeolites (e.g., ZSM-5 zeolite), silicon carbide, or combinations thereof.

[0206] In many hydrocarbon processes, industrially or in the laboratory, catalyst coking is avoided. For example, in the partial oxidation of methane over a Pt-containing catalyst to produce syngas, the production of solid carbon quickly deactivates the catalyst, essentially ceasing syngas production. However, in the present disclosure, when a separate coking catalyst is utilized, biocoke is the intended product. The separate coking catalyst may eventually be deactivated by the formation of refractory carbon (e.g., glassy carbon) or may become poisoned (e.g., by sulfur), in which case the coking catalyst may be regenerated, if desired.

[0207] In some embodiments, the carbon conversion of the carbon-containing steam in the converting step is about or at least about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, including any intervening range. For example, the converting step can be optimized to achieve conversion of about 25-75% of the carbon-containing steam to solid biocoke.

[0208] In some embodiments, the process further includes conveying at least a portion of the solid bio-coke-containing kinetic interfacial medium to a pyrolysis reactor. In some embodiments, conveying at least a portion of the solid bio-coke-containing interfacial medium to the pyrolysis reactor results in the production of a pyrolyzed solid bio-coke-containing kinetic interfacial medium. Some or all of the pyrolyzed solid bio-coke-containing kinetic interfacial medium can optionally be returned to the kinetic interfacial reactor.

[0209] In some embodiments, the process further comprises introducing a pyrolytic solid bio-coke-containing kinetic interfacial medium into the kinetic interfacial reactor.

[0210] In some embodiments, the process further includes recovering a kinetic interfacial reactor exhaust gas stream comprising unconverted carbon-containing vapor. In some embodiments, the process further includes combusting the kinetic interfacial reactor exhaust gas stream, thereby generating energy. The process may further include utilizing the energy to thereby heat a pyrolysis reactor, which may be configured to provide a kinetic interfacial medium, where the kinetic interfacial medium may comprise a pyrolyzed form of the first biomass feedstock. Alternatively or additionally, the process may further include partially oxidizing the kinetic interfacial reactor exhaust gas stream, thereby generating a reducing gas, typically containing H and / or CO. In some embodiments, the process further includes recycling some or all of the kinetic interfacial reactor exhaust gas stream to an inlet of the kinetic interfacial reactor, e.g., to increase biocoke yield.

[0211] In some embodiments, the process further comprises recycling the solid biocoke-containing kinetic interfacial medium to the inlet of the kinetic interfacial reactor.

[0212] In some embodiments, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after recovery, thereby forming a regenerated kinetic interfacial medium, and recycling the regenerated kinetic interfacial medium to the inlet of the kinetic interfacial reactor.

[0213] In some embodiments, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after recovery, thereby forming a regenerated kinetic interfacial medium, wherein the regenerated kinetic interfacial medium comprises carbon, and conveying the regenerated kinetic interfacial medium to a pyrolysis reactor.

[0214] In some embodiments, the process further includes carbonizing the carbon-containing kinetic interfacial medium in a kinetic interfacial reactor, wherein the carbonization is separate from the conversion of the carbon-containing vapor to bio-coke. In other words, in some embodiments in which the kinetic interfacial medium includes carbon, additional carbonization of the kinetic interfacial medium can occur in the kinetic interfacial reactor separately from the carbon-containing vapor being converted to bio-coke. In these embodiments, the kinetic interfacial medium can be or include crude biomass feedstock, a pyrolytic form thereof, or a combination of the foregoing.

[0215] The kinetic interfacial reactor can be a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a rotary kiln, or another type of reactor. The kinetic interfacial reactor can be a vertical vessel, a horizontal vessel, or an inclined vessel. The kinetic interfacial reactor can be fixed or rotating. When the kinetic interfacial reactor is a rotary kiln, the rotary kiln can be configured so that the kinetic interfacial medium rotates radially and the heated biogas stream flows axially.

[0216] In some embodiments, the kinetic interfacial reactor is configured with a mechanical conveyor. In some embodiments, the mechanical conveyor is a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, or a recirculating conveyor. In some embodiments, the conveyor is another type of conveyor known in the art. The mechanical conveyor can introduce the kinetic interfacial medium into the kinetic interfacial reactor, or can transport the kinetic interfacial medium through the kinetic interfacial reactor, or both. Additionally or alternatively, the mechanical conveyor can transport the solid biocoke-containing kinetic interfacial medium out of the kinetic interfacial reactor in a removal step. Multiple mechanical conveyors may be present in a single kinetic interfacial reactor.

[0217] In some embodiments, the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor. A "spatially continuous solid mass" refers to a mass that is completely packed within the vessel, up to the wall, and cannot be easily removed without severe mechanical means such as drilling or water jetting. A spatially continuous solid mass can be avoided by removing the solid bio-coke-containing kinetic interfacial medium before it is completely packed within the open volume of the kinetic interfacial reactor.

[0218] In some embodiments, the removal step occurs continuously or semi-continuously. In some embodiments, such as in FIG. 1, the removal occurs simultaneously with the conversion (and formation) step. In some embodiments, the removal occurs immediately after forming the solid bio-coke-containing kinetic interfacial medium. In other embodiments, the removal occurs only periodically or intermittently, but still occurs before a spatially continuous solid mass is formed.

[0219] In some embodiments, the removal is performed batchwise. For example, after a period of time during the conversion (and formation) step to allow biocoke formation, the reaction can be stopped, the reactor opened, and the solid biocoke-containing kinetic interface medium removed. However, even in batch mode, it may be desirable to avoid the formation of a spatially continuous solid mass.

[0220] In some embodiments, the kinetic interfacial medium comprises at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% total carbon by weight, including any intervening range. In various embodiments, the kinetic interfacial medium comprises at least about 10%, at least about 25%, at least about 50%, at least about 75%, or at least about 90% total carbon by weight. Total carbon includes fixed carbon and volatile carbon.

[0221] In some embodiments, the kinetic interfacial medium comprises at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% by weight of fixed carbon, including any intervening range. In various embodiments, the kinetic interfacial medium comprises at least about 25%, at least about 50%, at least about 70%, at least about 80%, or at least about 90% by weight of fixed carbon.

[0222] In some embodiments, the kinetic interfacial medium comprises up to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, or 50% by weight volatile carbon, including any intervening range.

[0223] In some embodiments, the solid biocoke-containing kinetic interfacial medium comprises at least about 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or 85 wt.% fixed carbon, including any intervening range. For example, the solid biocoke-containing kinetic interfacial medium can contain at least about 50 wt.% or at least about 80 wt.% fixed carbon.

[0224] In some embodiments, the biocoke comprises at least about 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% by weight of fixed carbon, including any intervening range. For example, the biocoke may contain at least about 80%, at least about 90%, at least about 95%, or at least about 99% by weight of fixed carbon.

[0225] In some embodiments, the bio-coke has a higher carbon content than the kinetic interfacial medium, and it is also possible for the carbon content of the bio-coke to be about the same as the average carbon content of the solid bio-coke-containing kinetic interfacial medium.

[0226] In some embodiments, the bio-coke is essentially free of ash. In some embodiments, the bio-coke has a lower ash content than the kinetic interfacial medium.

[0227] In some embodiments, the process further includes producing free bio-coke particles from the carbon-containing vapor, wherein the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. In some embodiments, the free bio-coke particles are derived solely from the carbon-containing vapor and not directly from the kinetic interfacial medium. In some embodiments, the kinetic interfacial medium comprises carbon, and the free bio-coke particles are derived from both the carbon-containing vapor and the kinetic interfacial medium. In some embodiments, the free bio-coke particles are derived from the carbon-containing vapor, and the formation of the free bio-coke particles is catalyzed or seeded by the kinetic interfacial medium.

[0228] In some embodiments, the total carbon in the solid biocoke-containing kinetic interfacial medium is 14 C / 12 In certain embodiments, the total carbon in the solid biocoke-containing kinetic interfacial medium is about or at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, or 100% ("fully") renewable, as determined from C isotope ratio measurements. 14 C / 12 At least about 50%, at least about 90%, or completely renewable, as determined from measurements of C isotope ratios.

[0229] In some embodiments, the total carbon in the biocoke is 14 C / 12 96, 97, 98, 99, 100% renewable as determined from C isotope ratio measurements. 14 C / 12 At least about 50%, at least about 90%, at least about 95%, at least about 99%, or about 100% renewable, as determined from C isotope ratio measurements. Even if the biocoke itself is fully renewable, the remainder of the solid biocoke-containing kinetic interfacial medium is optionally not fully renewable.

[0230] The process may be a continuous process, a semi-continuous process, a batch process, or a combination thereof, where combination means, for example, that one step may be batch and then the other step may be continuous, or that the process may start out batchwise but then run continuously at steady state for a period of time.

[0231] In some embodiments, the process further comprises adding a carbonizing agent, wherein the carbonizing agent comprises a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0232] Process for producing bio-coke using bioliquid streams Additional processes for producing bio-coke are disclosed herein. These processes for producing bio-coke may include providing a bio-liquid stream, where the bio-liquid stream comprises a carbon-containing liquid, providing a kinetic interfacial medium, where the kinetic interfacial medium is in solid form, introducing the kinetic interfacial medium and the bio-liquid stream into a kinetic interfacial reactor, converting the carbon-containing liquid to bio-coke using the kinetic interfacial reactor, where the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium, removing the solid bio-coke-containing kinetic interfacial medium from the kinetic interfacial reactor, and recovering the solid bio-coke-containing kinetic interfacial medium.

[0233] In some embodiments of the present technology, the process for producing biocoke comprises: providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a biological fluid stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert a carbon-containing liquid into bio-coke, wherein the bio-coke contains at least 75 wt. % fixed carbon and the total carbon in the bio-coke is less than 0.05 wt. 14 C / 12converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the solid bio-coke-containing kinetic interfacial medium.

[0234] In some embodiments, the kinetic interfacial medium is in the form of pellets. The pellets can be characterized by an average pellet effective diameter of at least about 1 millimeter to at most about 10 centimeters. In various embodiments, the average pellet effective diameter can be about, at least about, or at most about 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 1 cm, 1.5 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, or 10 cm, inclusive of all intervening ranges.

[0235] In some embodiments, the kinetic interfacial medium is in the form of a powder. The powder can be characterized by an average particle size of at least about 1 micron to at most about 500 microns. In various embodiments, the average particle size of the powder is about, at least about, or at most about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, or 500 microns, inclusive of all intervening ranges.

[0236] In some embodiments, the kinetic interfacial medium is in the form of granules. The granules can be characterized by an average granule effective diameter of at least about 100 microns to at most about 10 millimeters. In various embodiments, the average granule effective diameter is about, at least about, or at most about 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1000 microns, inclusive of all intervening ranges. In various embodiments, the average granule effective diameter is about, at least about, or at most about 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm, inclusive of all intervening ranges.

[0237] In some embodiments, the kinetic interfacial medium has a bed depth of at least about 10 centimeters to a maximum of about 10 meters. In various embodiments, the kinetic interfacial medium bed depth is about, at least about, or up to about 10 cm, 25 cm, 50 cm, 100 cm, 250 cm, 500 cm, 750 cm, 1 m, 1.5 m, 2 m, 2.5 m, 3 m, 4 m, or 5 m, inclusive of all intervening ranges.

[0238] In some embodiments, the kinetic interface medium is a pyrolysis form of a first biomass feedstock, such as softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, or fruit peels. , fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0239] In some embodiments, the kinetic interfacial medium comprises previously formed bio-coke. Alternatively or additionally, the kinetic interfacial medium can be another type of coke that is not necessarily bio-coke.

[0240] In some embodiments, the kinetic interface medium comprises or consists essentially of a crude biomass feedstock, such as softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0241] In many embodiments using a biological fluid stream, the kinetic interface medium contains carbon. In other embodiments, the kinetic interface medium does not contain carbon. For example, in certain embodiments, the kinetic interface medium contains a metal, metal alloy, metal oxide, metal hydride, metal nitride, or a combination thereof. Examples include, but are not limited to, iron, nickel, nickel oxide, cobalt, cobalt oxide, copper, copper oxide, zinc, zinc oxide, silica, sand, alumina, silica-alumina composites, or a combination thereof. In certain embodiments, biomass ash (which is generally silica-rich) is utilized as the kinetic interface medium. In certain embodiments, the kinetic interface medium contains carbon, but only as a compound with a metal. Examples include iron carbide, nickel carbide, cobalt carbide, zinc carbide, silicon carbide (silicon is considered a metal herein), aluminum carbide, or a combination thereof. The carbon in these materials is not coke, and the bio-coke formed on or within the metal carbides is readily observable using analytical techniques and recoverable via separation for bio-coke recovery.

[0242] In some embodiments, the process further comprises producing a biological liquid stream rather than obtaining the biological liquid stream from an external source. The production of the biological liquid stream can be achieved by pyrolyzing the second biomass feedstock. The second biomass feedstock can include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper bales, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof.

[0243] In some embodiments, the bioliquid stream is produced from the pyrolysis of a first biomass feedstock, in which case the bioliquid stream may include heavy pyrolysis liquids (e.g., tar) and / or condensed pyrolysis vapors. The bioliquid stream optionally further includes non-condensed pyrolysis vapors, such as entrained bubbles or dissolved gases. The condensed pyrolysis vapors may be, for example, alkanes, olefins, aromatics, aldehydes, ketones, acids, alcohols, water, or combinations thereof. The condensed pyrolysis vapors may utilize a condensation system having one or more condenser stages. The condenser liquid may be the condensation product of an individual stage (e.g., the first stage) of the multiple condenser stages.

[0244] In some embodiments, the kinetic interfacial medium is a pyrolyzed form of a first biomass feedstock, the bioliquid stream is produced from the pyrolysis of the first biomass feedstock, and the kinetic interfacial medium and the bioliquid stream are obtained from a common pyrolysis reactor.

[0245] In some embodiments, the biological liquid stream comprises alkanes, olefins, aromatics, aldehydes, ketones, acids, alcohols, or combinations thereof. In some embodiments, the biological liquid stream further comprises non-carbon-containing species, such as water. The biological liquid stream may be characterized as being substantially liquid at a pressure of 1 bar and a temperature of 25°C or another temperature, such as the temperature of the biological liquid feed stream fed into the kinetic interfacial reactor. The biological liquid feed stream may be at a temperature of about, at least about, or up to about 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C or higher, including any intervening range. By "substantially liquid" is meant that the bioliquid stream can be pumped using a liquid pump (e.g., a positive displacement pump, a centrifugal pump, or an axial pump) or gravity fed into a kinetic interfacial reactor. The liquid is generally recognized as being in equilibrium with a vapor, governed by the vapor-liquid phase equilibrium of the bioliquid stream.

[0246] Various classes of compounds may be present in biological fluid streams. C1 compounds may be present, including but not limited to, formic acid, methanol, and formaldehyde. C2-C4 linear hydroxyl- and oxo-substituted aldehydes and ketones may be present, such as, but not limited to, hydroxyacetaldehyde and hydroxyacetone. C2-C4 acids may be present, such as, but not limited to, acetic acid and levulinic acid. C5-C6 hydroxyl-, hydroxymethyl-, or oxo-substituted furans, furanones, lactones, and pyranones may be present. Anhydrosugars, including C5 and C6 anhydrosugars (such as levoglucosan), and anhydrooligosaccharides may be present. Monomeric methoxyl-substituted phenols may be present. Oligomeric and polymeric species derived from water-soluble carbohydrates may be present. Various forms of lignin may be present, such as monomeric lignin, low molecular weight lignin, high molecular weight lignin, condensed lignin, or pyrolytic lignin. Water may be present.

[0247] In some embodiments, providing a biological liquid stream provides a combination of biogas and biological liquid that includes both a carbon-containing vapor and a carbon-containing liquid. In such embodiments, the carbon-containing liquid can be condensed carbon-containing vapor or other liquid from another source. The carbon-containing vapor can be derived from evaporation of a carbon-containing liquid. The carbon-containing vapor and the carbon-containing liquid can be in equilibrium. Alternatively, the carbon-containing vapor and the carbon-containing liquid can exist in a non-equilibrium state, such as a kinetically controlled state or a mass-transfer limited state.

[0248] In some embodiments, during conversion, bio-coke forms on the surface of the kinetic interfacial medium. Alternatively or additionally, during conversion, bio-coke forms in the internal phase of the kinetic interfacial medium. When bio-coke forms in the internal phase, it may be in the same material phase as the kinetic interfacial medium solid phase, for example, forming a solid solution or alloy. Alternatively, bio-coke can phase separate within the kinetic interfacial medium and form its own solid phase. The separate phases can be located at or near the surface of the kinetic interfacial medium, which is beneficial for downstream separations.

[0249] In some embodiments, during conversion, effective reaction conditions for conversion include a coking temperature of at least about 400°C to at most about 1200°C, e.g., about, at least about, or at most about 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, or 1200°C, including any intervening range.

[0250] In some embodiments, during the conversion, effective reaction conditions for the conversion include a coking pressure of at least about 1 bar to up to about 40 bar, for example, about, at least about, or up to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, or 40 bar, including any intervening range.

[0251] In some embodiments, effective reaction conditions for conversion include a coking liquid phase residence time of at least about 1 minute to up to about 8 hours, including any intervening range, e.g., at least about, or up to about, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes, or 60 minutes, or 1 hour, 2 hours, 3 hours, 4 hours, 6 hours, or 8 hours.

[0252] In some embodiments, during the conversion, effective reaction conditions for the conversion include a coking solids residence time of at least about 1 minute to up to about 24 hours, including any intervening range, for example, about, at least about, or up to about 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 45 minutes, 60 minutes, 1.5 hours, 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, or 24 hours.

[0253] In some embodiments, during the conversion, effective reaction conditions for the conversion include a kinetic interfacial medium residence time of at least about 1 minute to up to about 24 hours, including any intervening range, for example, about, at least about, or up to about 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 45 minutes, 60 minutes, 1.5 hours, 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, or 24 hours. The kinetic interfacial medium residence time can be the same as the coking solid phase residence time. Alternatively, the kinetic interfacial medium residence time can be longer or shorter than the coking solid phase residence time.

[0254] In some embodiments, during the converting step, the effective reaction conditions for the conversion include a coking reaction seeded by a kinetic interfacial medium as a reaction matrix. Alternatively or additionally, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium. Alternatively or additionally, the effective reaction conditions may include a coking reaction catalyzed by a separate coking catalyst introduced into the kinetic interfacial reactor.

[0255] In some embodiments, the conversion (i.e., resulting in) of carbon from the carbon-containing liquid to biocoke is about or at least about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, including any intervening range.

[0256] In some embodiments, the process further includes conveying at least a portion of the solid bio-coke-containing kinetic interfacial medium to a pyrolysis reactor and producing a pyrolyzed solid bio-coke-containing kinetic interfacial medium. Optionally, the pyrolyzed solid bio-coke-containing kinetic interfacial medium can be returned to the kinetic interfacial reactor.

[0257] In some embodiments, the process further includes recovering a kinetic interfacial reactor exhaust gas stream, wherein the kinetic interfacial reactor exhaust gas stream comprises carbon-containing vapors. The kinetic interfacial reactor exhaust gas stream can be combusted to produce energy. The energy can be utilized, for example, to heat a pyrolysis reactor configured to provide a kinetic interfacial medium comprising, or consisting essentially of, a pyrolyzed form of the first biomass feedstock. The kinetic interfacial reactor exhaust gas stream can be partially oxidized to produce a reducing gas. The kinetic interfacial reactor exhaust gas stream can be recycled to the inlet of the kinetic interfacial reactor.

[0258] In some embodiments, the process further comprises recycling the solid biocoke-containing kinetic interfacial medium to the inlet of the kinetic interfacial reactor.

[0259] In some embodiments, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after recovery, thereby forming a regenerated kinetic interfacial medium, and recycling the regenerated kinetic interfacial medium to the inlet of the kinetic interfacial reactor.

[0260] In some embodiments, the process further includes removing at least a portion of the bio-coke from the solid bio-coke-containing kinetic interfacial medium during or after recovery, thereby forming a regenerated kinetic interfacial medium, wherein the regenerated kinetic interfacial medium comprises carbon, and conveying the regenerated kinetic interfacial medium to a pyrolysis reactor.

[0261] In some embodiments, the process further comprises carbonizing the kinetic interfacial medium in a kinetic interfacial reactor, wherein the kinetic interfacial medium comprises carbon, and wherein the carbonization is separate from converting the carbon-containing vapors to bio-coke.

[0262] In some embodiments, the kinetic interfacial medium comprises or consists essentially of a crude biomass feedstock, hi some embodiments, the kinetic interfacial medium comprises a mixture of crude biomass and pyrolyzed biomass, or another type of pretreated biomass, with or without the presence of crude biomass.

[0263] In some embodiments, the kinetic interfacial reactor is a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, or a rotary kiln. In some embodiments, the kinetic interfacial reactor is a vertical vessel, an inclined vessel, or a horizontal vessel. When the kinetic interfacial reactor is a rotary kiln, the rotary kiln can be configured so that the kinetic interfacial medium rotates radially and the biological liquid stream flows axially.

[0264] In some embodiments, the kinetic interfacial reactor is configured with a mechanical conveyor. In some embodiments, the mechanical conveyor is a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, or a recirculating conveyor. The mechanical conveyor moves solid material into, through, and / or out of the kinetic interfacial reactor.

[0265] In some embodiments, the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0266] In some embodiments, the removal is performed continuously or semi-continuously. In some embodiments, the removal is performed concomitantly with formation. In some embodiments, the removal is performed batchwise.

[0267] In some embodiments, the entire process (i.e., all process steps) is a continuous or semi-continuous process.

[0268] In some embodiments, the kinetic interfacial medium comprises at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 5, 70, 75, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 wt.% total carbon, inclusive of all intervening ranges.

[0269] In some embodiments, the kinetic interfacial medium comprises at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 5, 70, 75, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 wt. % fixed carbon, inclusive of all intervening ranges.

[0270] In some embodiments, the solid biocoke-containing kinetic interfacial medium comprises at least about 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or 85 wt. % fixed carbon, including all intervening ranges.

[0271] In various embodiments, the solid biocoke-containing kinetic interfacial medium comprises about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 wt.% fixed carbon.

[0272] In some embodiments, the biocoke comprises about, or at least about 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt.% fixed carbon, including all intervening ranges.

[0273] It is not uncommon for the bio-coke to have a higher carbon content than the kinetic interfacial medium, and it is also possible for the carbon content of the bio-coke to be approximately the same as the average carbon content of the solid bio-coke-containing kinetic interfacial medium.

[0274] In some embodiments, the bio-coke is essentially free of ash. In some embodiments, the bio-coke has a lower ash content than the kinetic interfacial medium.

[0275] In some embodiments, the process further includes producing free bio-coke particles from the carbon-containing liquid, wherein the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. In some embodiments, the free bio-coke particles are derived solely from the carbon-containing liquid and not directly from the kinetic interfacial medium. In other embodiments, the free bio-coke particles are derived from both the carbon-containing liquid and the kinetic interfacial medium (if it initially or transiently contains carbon).

[0276] In some embodiments, the kinetic interfacial medium comprises carbon and the free bio-coke particles are derived from both the carbon-containing liquid and the kinetic interfacial medium, hi some embodiments, the free bio-coke particles are derived from a carbon-containing vapor and the formation of the free bio-coke particles is catalyzed or seeded by the kinetic interfacial medium.

[0277] The total carbon in the solid bio-coke-containing kinetic interfacial medium is 14 C / 12 It may be at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99%, 100% ("fully") renewable as determined from measurements of C isotope ratios.

[0278] The total carbon in bio-coke is the total carbon in solid bio-coke.14 C / 12 It may be at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99%, or 100% renewable as determined from measurements of C isotope ratios.

[0279] In some embodiments, the process further comprises adding a carbonizing agent, which may comprise a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0280] Continuous or semi-continuous process for producing bio-coke using biogas streams Disclosed herein is a continuous or semi-continuous process for producing bio-coke. Such a process may include providing a heated biogas stream, where the heated biogas stream includes carbon-containing vapors, introducing the heated biogas stream into a kinetic interfacial reactor, converting the carbon-containing vapors to solid bio-coke using the kinetic interfacial reactor, continuously or semi-continuously removing the solid bio-coke, continuously, semi-continuously, or periodically returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, where the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor, and recovering the solid bio-coke as product bio-coke, wherein the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0281] In some embodiments, such a process may include producing a heated biogas stream, where the production is achieved by pyrolyzing a biomass feedstock. The heated biogas stream may include pyrolysis vapors, which may include CO, CO, alkanes, olefins, aromatics, aldehydes, ketones, acids, alcohols, or combinations thereof. Carbon-free pyrolysis vapors, such as, but not limited to, H, HO, and N, may also be present.

[0282] In some embodiments, during conversion, the carbon conversion of the carbon-containing vapor is at least about: 45, 50, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, inclusive of all intervening ranges, e.g., at least about 50% or at least about 75%.

[0283] In some embodiments, the biocoke product comprises at least about: 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.9, or 100 wt.% fixed carbon, including all intervening ranges, for example, at least about 90 wt.% fixed carbon.

[0284] In some embodiments, the total carbon in the biocoke product is 14 C / 12 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, or 100% (or "fully") renewable, including all intervening ranges, as determined from measurements of C isotope ratios. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0285] Continuous process for producing bio-coke using heated biogas Also disclosed herein are continuous processes for producing bio-coke. These continuous processes for producing bio-coke may include providing a bio-liquid stream, where the bio-liquid stream comprises a carbon-containing liquid, introducing the bio-liquid stream into a kinetic interfacial reactor, converting the carbon-containing liquid to solid bio-coke using the kinetic interfacial reactor, continuously removing the solid bio-coke from the kinetic interfacial reactor, continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, where the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor, and recovering the solid bio-coke as product bio-coke, wherein the continuous process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0286] Some variations of this technology are continuous processes for producing biocoke, the continuous process comprising: providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; introducing the heated biogas stream into a kinetic interfacial reactor; converting carbon-containing vapors into solid bio-coke using a kinetic interfacial reactor; continuously withdrawing solid bio-coke; continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, wherein the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor; recovering the solid bio-coke as a bio-coke product, wherein the bio-coke product contains at least 75% by weight of fixed carbon, and the total carbon in the bio-coke product is less than or equal to 100% of the total carbon. 14 C / 12 and recovering the carbon dioxide, which is at least 50% renewable, as determined from measurements of the C isotope ratios; The process provides a continuous process in which the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0287] In some embodiments, the process further includes producing a heated biogas stream by pyrolyzing a biomass feedstock, wherein the carbon-containing steam is pyrolysis steam. The biomass feedstock may be selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0288] In some embodiments, the carbon-containing vapor is selected from CO, CO, alkanes (e.g., ethane), olefins (e.g., propylene), aromatics (e.g., toluene), aldehydes (e.g., acetaldehyde), ketones (e.g., acetylacetone), acids (e.g., formic acid), alcohols (e.g., propanol), or combinations thereof. Carbon-free pyrolysis liquids, such as water, may also be present.

[0289] In some embodiments, the kinetic interfacial medium is in the form of pellets, which can be characterized by an average pellet effective diameter of at least about 1 millimeter and up to about 10 centimeters.

[0290] In some embodiments, the kinetic interfacial medium is in the form of a powder, which can be characterized by an average particle size of at least about 1 micron to a maximum of about 500 microns.

[0291] In some embodiments, the kinetic interfacial medium is in the form of granules, which can be characterized by an average effective granule diameter of at least about 100 microns to a maximum of about 10 millimeters.

[0292] In some embodiments, during the converting step, solid bio-coke forms on the surface of the kinetic interfacial medium. Alternatively or additionally, during the converting step, solid bio-coke forms in the internal phase of the kinetic interfacial medium.

[0293] In some embodiments, during the converting step, the effective reaction conditions include a coking temperature of at least about 400°C up to about 1200°C.

[0294] In some embodiments, during the converting step, the effective reaction conditions include a coking pressure of at least about 1 bar up to about 40 bar.

[0295] In some embodiments, during the converting step, the effective reaction conditions include a coking vapor phase residence time of at least about 1 second up to about 1 hour.

[0296] In some embodiments, during the converting step, the effective reaction conditions include a coking solids residence time of at least about 1 minute up to about 24 hours.

[0297] In some embodiments, during the converting step, the effective reaction conditions comprise a kinetic interfacial medium residence time of at least about 1 minute up to about 24 hours.

[0298] In some embodiments, during the conversion step, the effective reaction conditions include a coking reaction seeded by a kinetic interfacial medium as the reaction matrix. In these embodiments, the kinetic interfacial medium seeds or initiates carbon growth but does not function as a true catalyst.

[0299] In some embodiments, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium.

[0300] In some embodiments, during the conversion step, the effective reaction conditions include a coking reaction catalyzed by a separate coking catalyst other than the kinetic interfacial medium introduced into the kinetic interfacial reactor. In certain embodiments, the separate coking catalyst is continuously or periodically regenerated for reuse within the kinetic interfacial reactor. For example, if the separate coking catalyst is an aluminosilicate and the catalyst is deactivated by a refractory form of carbon, oxidation in air can regenerate the catalyst.

[0301] In some embodiments, during the converting step, the effective reaction conditions include a non-catalytic coking reaction that produces free bio-coke particles from the carbon-containing vapor. In certain embodiments, the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. In other embodiments, the free bio-coke particles are chemically or physically bound to the kinetic interfacial medium after they are formed.

[0302] In some embodiments, the carbon conversion of the carbon-containing vapor to solid biocoke is at least 25% during the converting step. In certain embodiments, the carbon conversion is at least 50%, at least 75%, or at least 90%. In various embodiments, the carbon conversion of the carbon-containing liquid during the converting step is at least about 45, 50, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, including any intervening range.

[0303] In some embodiments, the process further includes recovering a kinetic interfacial reactor exhaust gas stream containing unconverted carbon-containing vapor. The kinetic interfacial reactor exhaust gas stream can be combusted with air or oxygen, thereby producing energy. The energy can be used to heat a pyrolysis reactor configured to provide a kinetic interfacial medium, the kinetic interfacial medium comprising a pyrolyzed form of the first biomass feedstock. Alternatively or additionally, the kinetic interfacial reactor exhaust gas stream can be partially oxidized with air or oxygen, thereby producing a reducing gas containing H and / or CO.

[0304] In some embodiments, the kinetic interfacial reactor is a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, or a rotary kiln, which may be configured such that the kinetic interfacial medium rotates radially and the heated biogas stream flows axially.

[0305] In some embodiments, the kinetic interfacial reactor is configured with a mechanical conveyor to convey the recycled bio-coke to the kinetic interfacial reactor, to convey the kinetic interfacial medium to the kinetic interfacial reactor, and / or to convey the solid bio-coke product out of the kinetic interfacial reactor, etc. The mechanical conveyor may be selected from, for example, a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, or a recirculation conveyor.

[0306] In some embodiments, the biocoke product comprises at least about 80% by weight fixed carbon, at least about 90% by weight fixed carbon, at least about 95% by weight fixed carbon, or at least about 99% by weight fixed carbon. In various embodiments, the biocoke product comprises about, or at least about 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, or 99.9% by weight fixed carbon, including any intervening range.

[0307] In some embodiments, the total carbon in the biocoke product is 14 C / 12 In certain embodiments, the total carbon in the biocoke product is at least about 75% renewable as determined from C isotope ratio measurements. 14 C / 12 In various embodiments, the total carbon in the biocoke product is at least about 90% renewable or at least about 100% (fully) renewable, as determined from C isotope ratio measurements. 14 C / 12 It is 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99%, or 100% renewable, as determined from measurements of the C isotope ratio.

[0308] In some embodiments, the bio-coke product is essentially free of ash.

[0309] In some embodiments, during recovery, the solid bio-coke and the kinetic interfacial medium are separated from each other.

[0310] In some embodiments, the process further comprises adding a carbonizing agent, wherein the carbonizing agent comprises a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0311] A continuous process for producing bio-coke using biofluids Another variation of this technology is a continuous process for producing biocoke, comprising: providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; introducing a biological fluid stream into a kinetic interfacial reactor; converting a carbon-containing liquid into solid bio-coke using a kinetic interfacial reactor; continuously withdrawing solid bio-coke; continuously returning a recycled portion of the solid bio-coke to the kinetic interfacial reactor, wherein the recycled portion of the solid bio-coke is a kinetic interfacial medium contained within the kinetic interfacial reactor; recovering the solid bio-coke as a bio-coke product, wherein the bio-coke product contains at least 75% by weight of fixed carbon, and the total carbon in the bio-coke product is less than or equal to 100% of the total carbon. 14 C / 12 and recovering the carbon dioxide, which is at least 50% renewable, as determined from measurements of the C isotope ratios; The process provides a continuous process in which the process does not result in a spatially continuous solid mass packed within the kinetic interfacial reactor.

[0312] In some processes utilizing a bioliquid stream, the process further includes generating a bioliquid stream by pyrolyzing a biomass feedstock and collecting condensed pyrolysis vapors as a carbon-containing liquid. The biomass feedstock may be selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, The waste may include fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0313] In some embodiments utilizing a biological liquid stream, the biological liquid stream comprises one or more alkanes (e.g., n-hexane), olefins (e.g., cyclopentene), aromatics (e.g., lignin fragments), aldehydes (e.g., n-hexanal), ketones (e.g., cyclohexanone), acids (e.g., lignosulfonic acid), alcohols (e.g., cyclohexanol), or combinations thereof.

[0314] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of pellets, which can be characterized by an average pellet effective diameter of at least about 1 millimeter and up to about 10 centimeters.

[0315] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of a powder, which can be characterized by an average particle size of at least about 1 micron to a maximum of about 500 microns.

[0316] In some embodiments utilizing a biological fluid flow, the kinetic interfacial medium is in the form of granules, which can be characterized by an average granule effective diameter of at least about 100 microns to a maximum of about 10 millimeters.

[0317] In some embodiments utilizing a bioliquid stream, solid bio-coke forms on the surface of the kinetic interfacial medium during the converting step. Alternatively or additionally, solid bio-coke forms in the internal phase of the kinetic interfacial medium during the converting step.

[0318] In some embodiments utilizing a bioliquid stream, during the converting step, the effective reaction conditions include a coking temperature of at least about 400°C up to about 1200°C.

[0319] In some embodiments utilizing a bioliquid stream, during the converting step, the effective reaction conditions include a coking pressure of at least about 1 bar to a maximum of about 40 bar.

[0320] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking liquid phase residence time of at least about 1 minute to up to about 1 hour.

[0321] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking solids residence time of at least about 1 minute up to about 24 hours.

[0322] In some embodiments utilizing a biological fluid stream, during the converting step, the effective reaction conditions include a kinetic interfacial medium residence time of at least about 1 minute up to about 24 hours.

[0323] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction seeded by a kinetic interfacial medium as the reaction matrix.

[0324] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a kinetic interfacial medium.

[0325] In some embodiments utilizing a biological liquid stream, during the converting step, the effective reaction conditions include a coking reaction catalyzed by a separate coking catalyst other than the kinetic interfacial medium introduced into the kinetic interfacial reactor. In certain embodiments, the separate coking catalyst is continuously or periodically regenerated for reuse within the kinetic interfacial reactor. For example, if the separate coking catalyst is a metal or metal hydride and the catalyst is poisoned by sulfur, regeneration in hydrogen can return the catalyst to the metal or metal hydride form.

[0326] In some embodiments utilizing a bio-liquid stream, during the converting step, the effective reaction conditions include a non-catalytic coking reaction that produces free bio-coke particles from the carbon-containing vapor. In certain embodiments, the free bio-coke particles are not chemically or physically bound to the kinetic interfacial medium. In other embodiments, the free bio-coke particles are chemically or physically bound to the kinetic interfacial medium after they are formed.

[0327] In some embodiments utilizing a bioliquid stream, the carbon conversion from the carbon-containing vapor to solid bio-coke is at least 25% during the converting step. In certain embodiments, the carbon conversion is at least 50%, at least 75%, or at least 90%. In various embodiments, the carbon conversion of the carbon-containing liquid during the converting step is at least about 45, 50, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99%, including any intervening range.

[0328] In some embodiments utilizing a bioliquid stream, the process further includes recovering a kinetic interfacial reactor exhaust gas stream comprising carbon-containing vapors formed within the reactor (e.g., from evaporation of bioliquid components or from a chemical reaction). The kinetic interfacial reactor exhaust gas stream can be combusted with air or oxygen, thereby producing energy. The energy can be used to heat a pyrolysis reactor configured to provide a kinetic interfacial medium comprising the pyrolyzed form of the first biomass feedstock. Alternatively or additionally, the kinetic interfacial reactor exhaust gas stream can be partially oxidized with air or oxygen, thereby producing a reducing gas containing H and / or CO.

[0329] In some embodiments utilizing a biological liquid flow, the kinetic interfacial reactor is a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, or a rotary kiln. The rotary kiln may be configured so that the kinetic interfacial medium rotates radially and the biological liquid flow flows axially.

[0330] In some embodiments utilizing a bioliquid stream, the kinetic interfacial reactor is configured with a mechanical conveyor to transport recycled bio-coke to the kinetic interfacial reactor, to transport the kinetic interfacial medium to the kinetic interfacial reactor, and / or to transport the solid bio-coke product out of the kinetic interfacial reactor, etc. The mechanical conveyor may be selected from, for example, a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, or a recirculation conveyor.

[0331] In some embodiments utilizing a bioliquid stream, the biocoke product comprises at least about 80% by weight fixed carbon, at least about 90% by weight fixed carbon, at least about 95% by weight fixed carbon, or at least about 99% by weight fixed carbon. In various embodiments, the biocoke product comprises about, or at least about 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, or 99.9% by weight fixed carbon, including any intervening range.

[0332] In some embodiments utilizing a bioliquid stream, the total carbon in the biocoke product is 14 C / 12 In certain embodiments, the total carbon in the biocoke product is at least about 75% renewable as determined from C isotope ratio measurements. 14 C / 12 In various embodiments, the total carbon in the biocoke product is at least about 90% renewable or at least about 100% ("fully") renewable, as determined from C isotope ratio measurements. 14 C / 12 It is 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99%, or 100% renewable, as determined from measurements of the C isotope ratio.

[0333] In some embodiments utilizing a bio-liquid stream, the bio-coke product is essentially ash-free.

[0334] In some embodiments utilizing a bioliquid stream, in the recovery step, the solid biocoke and the kinetic interfacial medium are separated from one another.

[0335] In some embodiments utilizing a biological liquid stream, the process further comprises adding a carbonizing agent, wherein the carbonizing agent comprises a metal, a metal alloy, a metal oxide, a metal hydroxide, a metal hydride, a metal sulfide, a metal nitride, a metal halide, a metal salt, a mineral, a natural polymer, a synthetic polymer, an acid, a base, a non-metal salt, an organic halide, an inorganic halide, or a derivative or combination thereof.

[0336] System for producing biocoke Disclosed herein are systems configured to perform any of the disclosed processes.

[0337] Yet another variation is a system for producing biocoke, the system comprising: a kinetic interfacial reactor; a first inlet configured to feed a heated biogas stream and / or a bioliquid stream into the kinetic interfacial reactor, the heated biogas stream comprising a carbon-containing vapor and the bioliquid stream comprising a carbon-containing liquid; a kinetic interfacial medium contained within a kinetic interfacial reactor, the kinetic interfacial medium being in solid form, the kinetic interfacial reactor being configured to operate under effective reaction conditions for converting carbon-containing vapors into bio-coke chemically or physically bound with the kinetic interfacial medium; a first outlet configured to remove bio-coke.

[0338] In some systems, the first inlet is configured to feed a heated biogas stream into the kinetic interfacial reactor. In other systems, the first inlet is configured to feed a bioliquid stream into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed a mixture of a heated biogas stream and a bioliquid stream (e.g., a supersaturated wet steam stream) into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed a heated biogas stream, a bioliquid stream, or both at different times when the kinetic interfacial reactor is designed to operate with either a heated biogas stream, a bioliquid stream, or a mixture thereof.

[0339] In some systems, the kinetic interfacial reactor is selected from a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, a rotary kiln, or a combination thereof. In systems using a rotary kiln as the kinetic interfacial reactor (or one of the kinetic interfacial reactors), the rotary kiln may be configured such that the kinetic interfacial medium rotates radially and the heated biogas stream and / or bioliquid stream flows axially.

[0340] Some systems are configured with a mechanical conveyor for feeding the kinetic interfacial medium into, through, and / or out of the kinetic interfacial reactor. The mechanical conveyor can be a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, a recirculating conveyor, or a combination thereof.

[0341] One particular variation provides a system for continuously producing bio-coke, the system comprising a kinetic interfacial reactor, the kinetic interfacial reactor comprising a first inlet configured to feed a heated biogas stream and / or a bio-liquid stream into the kinetic interfacial reactor, the heated biogas stream comprising a carbon-containing vapor and the bio-liquid stream comprising a carbon-containing liquid, the kinetic interfacial reactor configured to operate under effective reaction conditions for converting the carbon-containing vapor and / or the carbon-containing liquid to solid bio-coke, the kinetic interfacial reactor comprising a first outlet configured to continuously or semi-continuously remove the solid bio-coke, the kinetic interfacial reactor comprising a second inlet configured to feed at least a portion of the solid bio-coke removed from the outlet, and the first outlet or the second outlet configured to remove and recover the bio-coke product.

[0342] In some systems designed to continuously produce biocoke, the first inlet is configured to feed a heated biogas stream into the kinetic interfacial reactor. In other systems, the first inlet is configured to feed a bioliquid stream into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed a mixture of a heated biogas stream and a bioliquid stream (e.g., a liquid stream entrained with heated biogas bubbles) into the kinetic interfacial reactor. In certain systems, the first inlet is configured to feed the heated biogas stream, the bioliquid stream, or both at different times when the kinetic interfacial reactor is designed to operate with either the heated biogas stream or the bioliquid stream, or a mixture thereof.

[0343] In some systems designed to continuously produce bio-coke, the kinetic interfacial reactor is selected from a fluidized bed reactor, a falling bed reactor, a gravity-driven vessel, a vertical vessel, an inclined vessel, a horizontal vessel, a rotary kiln, or a combination thereof. In systems using a rotary kiln as the kinetic interfacial reactor (or one of multiple kinetic interfacial reactors), the rotary kiln can be configured so that the kinetic interfacial medium rotates radially and the heated biogas stream and / or bioliquid stream flows axially.

[0344] In some systems designed to continuously produce biocoke, the system includes a mechanical conveyor configured to feed the kinetic interfacial medium into, through, and / or out of the kinetic interfacial reactor. The mechanical conveyor can be a screw conveyor, a belt conveyor, a chain conveyor, a continuous flow conveyor, a recirculating conveyor, or a combination thereof.

[0345] Compositions and Products Disclosed herein are biocoke compositions produced according to any of the processes disclosed herein; such compositions may also be described as "biocoke products."

[0346] In some variations, the biocoke product comprises: providing a heated biogas stream, the heated biogas stream comprising carbon-containing steam; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a heated biogas stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert carbon-containing vapors into bio-coke, wherein the bio-coke contains at least 75% by weight of fixed carbon and the total carbon in the bio-coke is less than 0.05% by weight of the total carbon. 14 C / 12converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the bio-coke product from the solid bio-coke-containing kinetic interfacial medium.

[0347] In another variation, the biocoke product comprises: providing a biological liquid stream, the biological liquid stream comprising a carbon-containing liquid; providing a kinetic interface medium, wherein the kinetic interface medium is in solid form; introducing a kinetic interfacial medium and a biological fluid stream into a kinetic interfacial reactor; 1. Using a kinetic interfacial reactor to convert a carbon-containing liquid into bio-coke, wherein the bio-coke contains at least 75 wt. % fixed carbon and the total carbon in the bio-coke is less than 0.05 wt. 14 C / 12 converting the bio-coke to a kinetic interfacial medium that is at least 50% renewable as determined from C isotope ratio measurements, and the bio-coke is chemically or physically bound to the kinetic interfacial medium, thereby forming a solid bio-coke-containing kinetic interfacial medium; removing the solid biocoke-containing kinetic interfacial medium from the kinetic interfacial reactor; and recovering the bio-coke product from the solid bio-coke-containing kinetic interfacial medium.

[0348] The bio-coke product can be in the form of, for example, a powder or pellets. The pellets can utilize a pellet binder. If the kinetic interface medium is in the form of pellets, or if the bio-coke product is in the form of pellets, a pellet binder can be present.

[0349] Binders include, for example, starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, The binder may comprise or consist essentially of wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, formaldehyde, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, peat, sphagnum peat, derivatives thereof, or any combination of the foregoing. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations of the foregoing.

[0350] In some embodiments, no external binder is used, in which materials already present, such as lignin or condensed steam, can act as an in-situ binder for the pellets.

[0351] When the kinetic interfacial medium comprises pyrolyzed biomass, the pyrolyzed biomass can be obtained by subjecting the biomass to a pyrolysis temperature of at least about 300° C. and up to about 1200° C. for a pyrolysis time of at least about 10 seconds and up to about 24 hours. Pyrolysis conditions are discussed in more detail further herein.

[0352] In some embodiments, the pyrolysis biomass, the solid bio-coke-containing kinetic interfacial medium, or the solid bio-coke is pulverized using a mechanical processing device. The mechanical processing device may include, for example, a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof. In some embodiments, the intermediate material can be pulverized using a mechanical processing device such as, for example, a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0353] The biocoke composition can comprise at least about 50% by weight fixed carbon, at least about 60% by weight fixed carbon, at least about 70% by weight fixed carbon, at least about 75% by weight fixed carbon, at least about 80% by weight fixed carbon, at least about 85% by weight fixed carbon, or at least about 90% by weight fixed carbon. In various embodiments, the biocoke composition comprises about, at least about, or up to about 55, 60, 65, 70, 75, 80, 85, or 90% by weight fixed carbon.

[0354] The biocoke composition can comprise at least about 55 wt.% total carbon, at least about 60 wt.% total carbon, at least about 70 wt.% total carbon, at least about 75 wt.% total carbon, at least about 80 wt.% total carbon, at least about 85 wt.% total carbon, at least about 90 wt.% total carbon, or at least about 95 wt.% total carbon. In various embodiments, the biocoke composition comprises about, at least about, or up to about 60, 65, 70, 75, 80, 85, 90, or 95 wt.% total carbon, including all intervening ranges.

[0355] In some embodiments, the biocoke composition comprises up to about 10 wt.% ash, up to about 5 wt.% ash, up to about 2 wt.% ash, or up to about 1 wt.% ash. In various embodiments, the biocoke composition contains about or up to about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.2, or 0.1 wt.% ash, including all intervening ranges.

[0356] In some processes, the bio-coke composition is characterized by a Hardgrove Grindability Index of at least 30 or at least 50. In various embodiments, the bio-coke composition is characterized by a Hardgrove Grindability Index of about, at least about, or up to about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, including all intervening ranges.

[0357] In some processes, the biocoke composition has a dry weight of at least about 35 lb / ft 3 or at least about 45 lb / ft on a dry basis 3 In various embodiments, the bio-coke composition has a bulk density of about, or at least about, 25, 30, 35, 40, 45, or 50 lb / ft, on a dry basis, including all intervening ranges. 3 is.

[0358] In some processes, the bio-coke composition is characterized as a hydrophobic bio-coke or a partially hydrophobic bio-coke.

[0359] In some processes, the bio-coke composition in pellet form is characterized by a crush strength of at least 1 psi according to ASTM D 4179. In various embodiments, the crush strength is about, or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 psi or more according to ASTM D 4179.

[0360] In some processes, bio-coke compositions are characterized as non-self-heating when subjected to a self-heating test in accordance with Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances."

[0361] In some processes, the bio-coke composition is characterized by a lack of odor production at 25° C. over 24 hours. In some embodiments, the bio-coke composition is characterized by a lack of odor production at 50° C. over 24 hours. In some embodiments, the bio-coke composition is characterized by a lack of odor production at 25° C. over 48 hours. "Odor production" in this context refers to organic molecules that volatilize from the bio-carbon composition; such organic molecules are typically detectable by humans. Examples include formaldehyde, acetic acid, ethanol, methanol, and mercaptans.

[0362] In any of the processes disclosed herein, a carbonization agent can be added at one point (or multiple points) in the process. The carbonization agent can remain in the final composition produced. A "carbonization agent" is a material that improves the rate, selectivity, or yield of bio-coke formation from a carbon-containing precursor. The carbonization agent can be a reactant, catalyst, promoter, functional filler, or another material that improves the rate, selectivity, or yield of bio-coke formation.

[0363] A wide variety of carbonizing agents are available, including, but not limited to, classes of carbonizing agents: metals, metal alloys, metal oxides, metal hydroxides, metal hydrides, metal sulfides, metal nitrides, metal halides, minerals, natural polymers, synthetic polymers, acids, bases, salts (metal salts or non-metal salts), organic halides (e.g., organic chlorides or fluorides), inorganic halides (e.g., inorganic chlorides or fluorides), and derivatives or combinations thereof.

[0364] The carbonizing agent may comprise or consist essentially of, for example, iron, steel, nickel, cobalt, copper, zinc, aluminum, manganese, magnesium, iron ore concentrate, alloys thereof, salts thereof, oxides thereof, hydroxides thereof, hydrides thereof, nitrides thereof, derivatives or combinations of the foregoing.

[0365] Alternatively, or additionally, the carbonizing agent may include or consist essentially of, for example, silica, alumina, silica-alumina, sand, aluminosilicate, zeolite (e.g., ZSM-5 zeolite), Gilsonite, bentonite clay, borax (sodium borate), limestone, lime, silica fume, gypsum, fly ash, or derivatives or combinations thereof.

[0366] Alternatively, or additionally, the carbonizing agent may comprise or consist essentially of, for example, starch, cross-linked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, wax, vegetable wax, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, formaldehyde, phenol-formaldehyde resin, vegetable resin, or derivatives or combinations thereof.

[0367] Alternatively or additionally, the carbonizing agent may comprise or consist essentially of, for example, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium chloride, ammonium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, diammonium phosphate, potassium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, kaolin, olivine, augite, hornblende, biotite, anorthite, albite, orthoclase, muscovite, quartz, and calcite, or derivatives or combinations thereof.

[0368] In some embodiments, the carbonizing agent comprises or consists essentially of a metal halide. Metal halides are compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are generally obtained by direct combination of a basic metal salt with a hydrohalic acid, or more commonly, by neutralization. In some embodiments, the carbonizing agent comprises or consists essentially of iron chloride (FeCl2 or FeCl3), iron bromide (FeBr2 or FeBr3), or hydrates thereof, or combinations thereof.

[0369] Alternatively or additionally, the carbonizing agent can be a carbon-rich material such as coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolytic tar, activated carbon, carbon black (e.g., recovered from recycled tires), graphite, graphene, graphene oxide, holey graphene, graphene platelets, carbon nanotubes, fullerenes, carbon fibers, pitch coke, petroleum coke, amorphous carbon, glassy carbon, pyrolytic carbon-containing molecules, pyrolytic parylene (e.g., parylene-N, parylene-C, or parylene-AF-4), polyaromatic hydrocarbons (e.g., pentacene, rubrene, hexabenzocoronene, or coronene), peat, sphagnum peat, or derivatives or combinations thereof.

[0370] The carbonizing agent can be introduced into the process in the form of solid particulates or as a solution, suspension, or slurry. The carbonizing agent can be combined with a solvent or liquid carrier, such as water or a hydrocarbon, for addition to the process. In certain embodiments, it may be desirable for the solvent or liquid carrier to contain significant carbon and further contribute to carbon formation in the kinetic interfacial reactor. For example, pyrolysis liquid can be used to dissolve or suspend the carbonizing agent.

[0371] The carbonization agent can be introduced directly into the kinetic interfacial reactor. Alternatively or additionally, the carbonization agent can be introduced into the pyrolysis reactor. Alternatively or additionally, the carbonization agent can be applied to the initial biomass prior to pyrolysis. Alternatively or additionally, the carbonization agent can be introduced into the pelletization unit (the carbonization agent can also function as a binder in certain embodiments). Alternatively or additionally, the carbonization agent can be introduced into a biocoke recovery unit, and the recovered kinetic interfacial medium can be recycled to the kinetic interfacial reactor so that the recycled carbonization agent is present in the reactor. Alternatively or additionally, the carbonization agent can be added to the heated biogas stream. For example, a liquid form of the carbonization agent can be sprayed into the heated biogas stream, or a solid form of the carbonization agent can be entrained in the heated biogas stream as a powder. Alternatively or additionally, the carbonization agent can be added to the bioliquid stream. The carbonization agent can be added at other points in the process.

[0372] The biocoke product can be material obtained from a biocoke recovery unit or from elsewhere in the process. The biocoke product will necessarily contain biocoke, although the concentration of biocoke can vary widely. In some embodiments, the biocoke-containing kinetic interfacial medium is recovered as a product and stored, marketed, or sold.

[0373] Additives (e.g., carbonization agents) can reduce the reactivity of a bio-coke product compared to an otherwise equivalent bio-coke product without the additive. The reactivity can be thermal reactivity. For example, a bio-coke product with an additive can have lower self-heating compared to an otherwise equivalent bio-carbon composition without the additive. Alternatively or additionally, the reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, or metals (e.g., iron).

[0374] If an additive is present, the additive (or at least one additive, if more than one additive is present) may be pore-filled within the bio-coke product. Alternatively or additionally, the additive may be disposed on the outer surface of the bio-coke product.

[0375] In some embodiments, the bio-coke product is in the form of a powder. In other embodiments, the bio-coke product is in the form of pellets. When in pellet form, the additive may include a binder for the pellets. Alternatively or additionally, the pellets may utilize the low fixed carbon material itself as a binder within the pellets.

[0376] In some embodiments, the bio-coke product is characterized as non-self-heating when subjected to a self-heating test in accordance with Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances" (incorporated herein by reference).

[0377] Fixed carbon concentration can be an important parameter for bio-coke-containing products, and the present disclosure, in various embodiments, allows for maximizing or optimizing, but not necessarily maximizing, fixed carbon concentration.

[0378] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the energy content associated with the bio-coke product.

[0379] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the bulk density associated with the bio-coke product.

[0380] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the hydrophobicity associated with the bio-coke product.

[0381] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the pore size associated with the bio-coke product.

[0382] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the pore size ratio associated with the bio-coke product.

[0383] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the surface area associated with the bio-coke product.

[0384] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the reactivity associated with the bio-coke product.

[0385] In some embodiments, the fixed carbon concentration of the bio-coke-containing product, and optionally the type or concentration of additives, are selected to optimize the ion exchange capacity associated with the bio-coke product.

[0386] In some embodiments, the bio-coke-containing product is in the form of pellets, and the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the Hardgrove Grindability Index associated with the pellets.

[0387] In some embodiments, the bio-coke-containing product is in the form of pellets, and the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the pellet durability index associated with the pellets.

[0388] In some embodiments, varying the fixed carbon content allows for optimization of the Hardgrove Grindability Index ("HGI"). The incorporation of binders or other additives may also allow for HGI tailoring for the bio-coke product.

[0389] The ability to adjust the HGI of bio-coke is beneficial because downstream applications utilizing pellets (e.g., replacing coal in a boiler) have varying HGI requirements. HGI adjustability addresses well-known problems industrially: the difficulty in grinding crude biomass and the difficulty in grinding pellets. Furthermore, because there are so many downstream uses for bio-carbon pellets, each with its own unique requirements, being able to adjust the pellet grindability is highly advantageous. It is desirable to be able to adjust the HGI to suit a particular application, such as combustion in a boiler to make syngas, metal production, or gasification.

[0390] In many applications, pellets are preferred over powders (isolated biomass particles) based on delivery, storage, and safety advantages. Finally, pellets may, at some point, be reconstituted into powder, or at least smaller bodies, if desired. Thus, pellet grindability is often a critical parameter that impacts operational and capital costs.

[0391] In some embodiments, the pellets need to be crushed or pulverized into a powder, such as when a boiler or gasifier utilizes a fluidized bed or a suspension of carbon particles. Another example is pulverized carbon injection into a blast furnace to reduce metal ore to metal. In these embodiments, high pellet crushability is desirable, but not too high so that the pellets break down during shipping and handling. In other embodiments, it is desirable to feed the pellets themselves into a process, such as a metal fabrication process. In these embodiments, lower crushability may be desirable because some pellet strength may be needed to support the bed of material in the reactor. Different technologies have different pellet crushability requirements.

[0392] The Hardgrove Grindability Index of the bio-coke-containing pellets can be at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, at least about 80, at least about 90, or at least about 100. In some embodiments, the Hardgrove Grindability Index is from about 30 to about 50, or from about 50 to about 70. ASTM Standard D409 / D409M for "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method" is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to Hardgrove Grindability Index or HGI in this disclosure refer to ASTM Standard D409 / D409M.

[0393] In various embodiments, the Hard Glove Crushability Index is about, at least about, or up to about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 43, 44, 45, 46, 47, 48, 49, 51, 52, 43, 44, 45, 46, 47, 48, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, , 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0394] Bio-coke-containing pellets can be characterized by a pellet durability index of at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%. Bio-carbon pellets can be characterized by a pellet durability index of up to about 99%, up to about 95%, up to about 90%, up to about 85%, or up to about 80%. Unless otherwise indicated, all references to pellet durability index in this disclosure refer to ISO 17831-1:2015 "Solid biofuels - Determination of mechanical durability of pellets and briquettes - Part 1: Pellets," which is incorporated herein by reference in its entirety.

[0395] In some embodiments, bio-coke-containing pellets are utilized as starting materials for making smaller objects; "pellets" is not limited to a specific geometry and may also be referred to as bio-carbon pellets. For example, initial pellets having an average pellet diameter of 10 mm can be produced. These initial pellets can then be crushed using various mechanical means (e.g., using a hammer mill). The crushed pellets can be separated according to size, such as by screening. In this manner, smaller pellets can be produced having an average pellet diameter of, for example, about, at least about, or up to about 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, or 5000 microns. The average pellet diameter of the smaller pellets is preferably greater than the average particle diameter of the initial carbon-containing particles used to make the pellets with the binder.

[0396] When the biocarbon pellets are crushed to produce smaller pellets, the crushing (and optionally screening) step can be integrated with other process steps, potentially including points of industrial use. The optional step to produce smaller pellets can utilize crushing equipment such as a hammer mill, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, rock crusher, or combinations thereof.

[0397] In various embodiments, the Hard Glove Crushability Index is at least about 40, at least about 50, at least about 60, at least about 70, at least about 80, at least about 90, or at least about 100. For example, the Hard Glove Crushability Index can be at least about 30 and up to about 50, or at least about 50 and up to about 70.

[0398] In various processes, the process conditions may range from about, at least about, or up to about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, , 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0399] In some processes, the bio-coke-containing pellets are characterized by a pellet durability index of at least about 80%, at least about 90%, or at least about 95%.

[0400] In some embodiments, the process includes preselecting a Hardgrove grindability index for the bio-coke-containing pellets, adjusting process conditions based on the preselected Hardgrove grindability index, and achieving within ±20% of the preselected Hardgrove grindability index for the bio-carbon pellets, where the adjusted process conditions include adjusting one or more of pyrolysis temperature, pyrolysis time, mechanical treatment conditions, pelletizing conditions, binder type, binder concentration, binding conditions, or drying. Certain embodiment processes may achieve within ±10% or ±5% of the preselected Hardgrove grindability index for the pellets.

[0401] The size and geometry of bio-coke-containing pellets (or other objects) can vary. Bio-coke-containing pellets can be characterized by an average pellet diameter, which is the true diameter in the case of a sphere or cylinder, or the equivalent diameter in the case of any other 3D geometric shape. The equivalent diameter of a non-spherical pellet is the diameter of a sphere of equivalent volume to the actual pellet. In some embodiments, the average pellet diameter is about or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters, inclusive of all intervening ranges. In some embodiments, the average pellet diameter is about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns, inclusive of all intervening ranges.

[0402] In some embodiments, there are a plurality of pellets (sometimes simply referred to as "pellets") that are relatively uniform in size, such as a standard deviation of up to about ±100%, up to about ±50%, up to about ±25%, up to about ±10%, or up to about ±5% of the average pellet diameter. In other embodiments, there are pellets with a wide range of sizes, which may be advantageous in some applications.

[0403] Bio-coke-containing pellets may contain moisture. The moisture present in the pellets may be water chemically bound to the carbon or binder, water physically bound (absorbed or adsorbed) to the carbon or binder, free water present in the water phase that is not chemically or physically bound to the carbon or binder, or a combination thereof. When moisture is desired during the binding process, it may be preferable for such moisture to be chemically or physically bound to the carbon or binder rather than being free water.

[0404] Various moisture levels can be present. For example, the pellets can contain at least about 1% to up to about 30% (e.g., 32%) by weight moisture, e.g., at least about 5% to up to about 15% by weight moisture, at least about 2% to up to about 10% by weight moisture, or at least about 0.1% to up to about 1% by weight moisture. In some embodiments, the pellets contain at least about 4% to up to about 8% by weight moisture. In various embodiments, the pellets contain about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% by weight moisture, including all intervening ranges. The moisture level of the pellets can be optimized to vary the density within the pellets.

[0405] In some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. In other market applications, such as metallurgy, lower moisture levels may be desirable (e.g., 1% moisture by weight or even lower). Note that water may be present during the process of making the pellets, but these pellets are then optionally dried, which means that the final pellets do not necessarily contain moisture.

[0406] In some bio-coke-containing pellets, the pellets comprise at least about 2% to about 25% by weight of binder, at least about 5% to about 20% by weight of binder, or at least about 1% to about 5% by weight of binder. In various embodiments, the pellets comprise about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, or 30% by weight of binder, including all intervening ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0407] The binder may be pore-filling within the carbon. Alternatively or additionally, the binder may be disposed on a surface of the carbon, such as on the pore walls.

[0408] The binder can be an organic binder or an inorganic binder. In some embodiments, the binder comprises or consists essentially of renewable materials. In some embodiments, the binder comprises or consists essentially of biodegradable materials. In some embodiments, the binder is capable of being partially oxidized or burned.

[0409] In various embodiments, the binder comprises starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, peat, sphagnum peat, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, formaldehyde, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations of the foregoing. The binder may comprise or consist essentially of a grindable plasticizer.

[0410] In certain embodiments, the binder comprises starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., amylose- and amylopectin-based polymers), derivatives thereof, or combinations of the foregoing. The starch can be a nonionic starch, anionic starch, cationic starch, or zwitterionic starch.

[0411] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and easily chemically modified. The cyclic structure of starch molecules, along with strong hydrogen bonds, gives starch a rigid structure, resulting in highly ordered crystalline and granular regions. Starch in its granular state is generally not suitable for thermoplastic processing. To obtain thermoplastic starch, semicrystalline starch granules can be decomposed by thermal and mechanical forces. Because the melting point of pure starch is significantly higher than its decomposition temperature, plasticizers such as water or glycol can be added. The native crystallinity can then be destroyed by vigorous mixing (shearing) at high temperatures, resulting in thermoplastic starch. Starch can be plasticized (decomposed) with relatively low levels of molecules capable of hydrogen bonding with starch hydroxyl groups, such as water, glycerol, or sorbitol.

[0412] Thermoplastic starch can be chemically modified or blended with other biopolymers to produce stronger, more ductile, and resilient bioplastics. For example, starch can be blended with natural or synthetic (biodegradable) polyesters such as polylactic acid, polycaprolactone, or polyhydroxybutyrate. To improve the compatibility of starch / polyester blends, suitable compatibilizers such as poly(ethylene-co-vinyl alcohol) or polyvinyl alcohol can be added. The hydrophilic hydroxyl groups (-OH) of starch can be replaced with hydrophobic reactive groups, such as by esterification or etherification.

[0413] In some embodiments, the starch-containing binder comprises or consists essentially of cross-linked starch. Various methods for cross-linking starch are known in the art. Starch materials can be cross-linked, for example, under acidic or alkaline conditions after dissolving or dispersing in an aqueous medium. Starch can be cross-linked using aldehydes (e.g., glutaraldehyde or formaldehyde).

[0414] An example of a cross-linked starch is the reaction product of starch with glycerol or another polyol, such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination thereof. The reaction product can be formed from a cross-linking reaction catalyzed by an acid, such as (but not limited to) formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof. Inorganic acids, such as sulfuric acid, can also be utilized to catalyze the cross-linking reaction. In some embodiments, the thermoplastic or cross-linked reaction product can alternatively be formed from a cross-linking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0415] In some embodiments, the binder is designed to be a water-resistant binder, for example, in the case of starch, the hydrophilic groups can be replaced by hydrophobic groups that better resist water.

[0416] In some embodiments, the binder serves other purposes such as (but not limited to) moisture retention within the biocarbon pellets and a food source for microorganisms.

[0417] In some embodiments, the binder reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the binder, which may refer to thermal or chemical reactivity.

[0418] If thermally reactive, the biocarbon pellets can have low self-heating compared to otherwise equivalent biocarbon pellets that do not contain a binder. "Self-heating" refers to biocarbon pellets that undergo a spontaneous exothermic reaction in the absence of any external ignition, at a relatively low temperature and in an oxidizing atmosphere, to raise the internal temperature of the biocarbon pellets.

[0419] The chemical reactivity can be reactivity with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. The chemical reactivity can be associated with reaction with or against, for example, CO, CO2, HO, pyrolysis oil, or heat.

[0420] Optionally, the pellets include additives (not necessarily binders), such as inorganic bentonite clay, limestone, starch, cellulose, lignin, or acrylamide. When lignin is used as a binder or other additive, the lignin can be obtained from the same biomass feedstock used in the pyrolysis process. For example, the starting biomass feedstock can be subjected to a lignin extraction step to remove some amount of lignin for use as a binder or additive.

[0421] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additive is selected from an acid, a base, or a salt thereof. In some embodiments, the additive comprises or consists essentially of a metal, a metal oxide, a metal hydroxide, a metal halide, or a derivative or combination thereof. For example, the additive may include sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or a derivative or combination thereof. The additive can be added before, during, or after any one or more steps of the process, including adding it to the feedstock itself at any time before or after the feedstock is harvested.

[0422] The bio-coke-containing pellets disclosed herein have a wide variety of downstream uses. They can be stored, sold, distributed, and converted into other products. They can be pulverized for use in boilers to burn the carbon and generate electrical energy or heat. They can be pulverized, crushed, or milled for feeding into furnaces, such as blast furnaces in metal production. They can be fed directly into furnaces, such as Tecnored furnaces in metal fabrication. They can be pulverized, crushed, or milled for feeding into gasifiers for the purpose of producing syngas from the bio-carbon pellets.

[0423] In many embodiments, the bio-coke-containing pellets are fed directly, or after a step of pulverizing, crushing, milling, or otherwise reducing the particle size, into a furnace. The furnace can be a blast furnace, a top gas recirculation blast furnace, a shaft furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a silencer furnace, a retort furnace, a flash furnace, a Tecnored furnace, an Ausmelt furnace, an ISASMELT furnace, a Puddle furnace, a bogie hearth furnace, a continuous chain furnace, a pusher furnace, a rotary hearth furnace, a walking beam furnace, an electric arc furnace, an induction furnace, a basic oxygen furnace, a Puddle furnace, a Bessemer furnace, a direct reduction metal furnace, or a combination or derivative thereof.

[0424] It should be noted that despite the Hardgrove Grindability Index of bio-coke-containing pellets, they do not necessarily subsequently undergo a grinding process. For example, the pellets can be used directly in agricultural applications. As another example, the pellets can be directly incorporated into engineered structures, such as landscape walls. At the end of the life of the structure containing the pellets, the pellets can then be crushed, combusted, gasified, or otherwise reused or recycled.

[0425] In some embodiments, the total carbon in the bio-coke-containing product is 14 C / 12Preferably, the total carbon is at least about 50% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon is at least about 50% renewable as determined from C isotope ratio measurements. 14 C / 12 In certain embodiments, the total carbon is at least 90% renewable as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0426] The surface area of ​​biocoke can vary widely. An exemplary surface area (e.g., BET surface area) for biocoke is about 400 m², including any intervening range. 2 / g~about 2000m 2 / g or more, e.g., about 500m 2 / g, 600m 2 / g, 800m 2 / g, 1000m 2 / g, 1200m 2 / g, 1400m 2 / g, 1600m 2 / g, or 1800m 2 / g. Bio-coke surface area can be important for a range of commercial applications, for example, that depend on the kinetic availability of carbon or that are mass-transfer limited. In some cases, low bio-coke surface area is desirable, such as for better gas permeability through the bio-coke bed. In other cases, high bio-coke surface area is desirable, such as when bio-coke is a chemical reducing agent in metallurgy.

[0427] In the disclosed technology, the use of biomass to produce biocoke results in a low carbon intensity of the biocoke product and process. The "carbon intensity" of a product (or process) is the net amount of carbon dioxide by weight produced per ton of product, or per ton of raw material processed to make the product, as the case may be. CO2-equivalent carbon intensity can also be defined as the net amount of carbon dioxide equivalent produced per ton of product. "Carbon dioxide equivalent" or "CO2e" represents the amount of CO2 that would have an equivalent global warming effect. A typical unit of carbon intensity is kilograms of carbon dioxide equivalent per metric ton (1000 kg) of product.

[0428] A greenhouse gas (or "GHG") is any gas in the atmosphere that absorbs and re-emits heat, thereby keeping the planet's atmosphere warmer than it would otherwise be. The primary GHGs in Earth's atmosphere are water vapor, carbon dioxide, methane, nitrous oxide, and ozone. By convention, the global warming potential of CO2 is defined as 1. The global warming potential of CH4 is about 30, i.e., methane is 30 times more potent as a greenhouse gas than CO2. See "IPCC Fourth Assessment Report: Climate Change 2007," Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge (2007) (incorporated herein by reference).

[0429] Generally, to calculate the carbon intensity of products and processes, it is necessary to estimate the carbon intensity of the starting material, the carbon intensity associated with the conversion of the starting material to intermediates, and the carbon intensity associated with the conversion of the intermediates to the final product. Those skilled in the art of chemical engineering can perform these calculations, which can be assisted by software such as life cycle analysis software (e.g., GREET® or SimaPro® software). Life cycle assessment (LCA) is a known method used to evaluate the environmental impact of a product throughout its life cycle, including raw material processing, manufacture, distribution, use, recycling, and final disposal. When multiple products are manufactured, allocation rules are used to calculate the LCA impacts attributable to each product.

[0430] In some embodiments of this technology, the biocoke product is characterized by a carbon intensity that is less than about 500 kg CO2e per metric ton of biocoke product, e.g., about 400, 300, 200, 100, 50, 25, or 0 kg CO2e per metric ton of biocoke product. In various embodiments of this technology, the biocoke product is characterized by a negative carbon intensity that is less than 0 kg CO2e per metric ton of biocoke product, e.g., a carbon intensity of less than about -100, -200, -300, -400, or -500 kg CO2e per metric ton of biocoke product.

[0431] While renewable biocarbon compositions may be desired, the principles of the present invention can be applied to non-renewable materials. In certain embodiments, the biomass-containing feedstock includes biomass (such as the biomass sources listed herein) as well as non-renewable feedstocks such as coal. Thus, a biomass-coal mixture can be utilized as the biomass-containing feedstock, which can be substituted for "biomass" in, for example, any of Figures 2, 4, or 6. Other non-biomass feedstocks that can be used in the feedstock mixture include, for example, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or derivatives or combinations thereof.

[0432] Disclosed herein are systems configured to perform the processes disclosed herein.

[0433] Some embodiments of the present invention will now be described with reference to the accompanying drawings, Figures 1-7, which illustrate various processes and systems. In the block flow diagrams, dotted boxes and lines indicate optional units and flows, respectively.

[0434] Figure 1 is an exemplary process schematic illustrating the coking of biogas onto carbon pellets as a kinetic interface medium to produce high-yield carbon pellets. Hot combustion gases or steam can be injected directly into the biogas. Alternatively, or additionally, the heat content of the hot combustion gases or steam can be indirectly transferred to the biogas stream, thereby increasing its temperature.

[0435] 2 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form biocoke from heated biogas derived from biomass pyrolysis. The biomass feedstock is pyrolyzed to form a bioreagent and a biogas stream. The bioreagent, optionally pelletized, is introduced into the kinetic interfacial reactor along with the heated biogas. The biogas is heated with heat injected into the pyrolysis reactor and, optionally, further heated, such as via direct or indirect steam heating. The biocoke-containing kinetic interfacial medium is recovered from the reactor and, optionally, sent to a biocoke recovery unit to produce a biocoke product.

[0436] 3 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form biocoke from heated biogas. A kinetic interfacial medium is introduced into the kinetic interfacial reactor along with the heated biogas. The biocoke-containing kinetic interfacial medium is recovered from the reactor and optionally sent to a biocoke recovery unit, thereby producing a biocoke product.

[0437] 4 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from bio-liquids derived from biomass pyrolysis. The biomass feedstock is pyrolyzed to form bio-reagents and pyrolysis vapors. The bio-reagents, optionally pelletized, are introduced into the kinetic interfacial reactor along with a bio-liquid stream from a condenser for the pyrolysis vapors. The bio-coke-containing kinetic interfacial medium is recovered from the reactor and optionally sent to a bio-coke recovery unit, thereby producing a bio-coke product.

[0438] 5 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from a bio-liquid. The bio-coke-containing kinetic interfacial medium is recovered from the reactor and optionally sent to a bio-coke recovery unit, thereby producing a bio-coke product.

[0439] FIG. 6 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to continuously form biocoke from heated biogas with internal recirculation of biocoke as the kinetic interfacial medium. Optionally, the kinetic interfacial reactor can use a coking catalyst (e.g., metal, metal alloy, metal oxide, metal hydride, metal carbide, aluminosilicate) that is different from the kinetic interfacial medium. If desired, the coking catalyst may be regenerated. The biocoke product can be obtained from a biocoke recovery unit. The catalyst can be a carbonizing agent, as described above, or another catalyst. In some embodiments that use air oxidation to perform catalyst regeneration as shown in FIG. 6, the catalyst is preferably not a carbon-rich catalyst (e.g., graphite) because the catalyst itself is likely to be oxidized. Also, in FIG. 6, a carbonizing agent may be present as a separate material in addition to the kinetic interfacial medium and catalyst.

[0440] FIG. 7 is an exemplary process block flow diagram illustrating the use of a kinetic interfacial reactor to form bio-coke from a bioliquid with internal recirculation of bio-coke as the kinetic interfacial medium. Optionally, the kinetic interfacial reactor can use a coking catalyst different from the kinetic interfacial medium. The coking catalyst can be, for example, a metal, metal alloy, metal oxide, metal hydride, metal carbide, or aluminosilicate. If desired, the coking catalyst can be regenerated. The bio-coke product can be obtained from a bio-coke recovery unit. The catalyst can be a carbonizing agent, as described herein, or another catalyst. In some embodiments using air oxidation to perform catalyst regeneration as shown in FIG. 7, the catalyst is preferably not a carbon-rich catalyst because the catalyst itself is likely to be oxidized. (Carbon-rich catalyst refers to a material that has carbon in an oxidizable form. Thus, a mixture of 1 wt. % silica and 99 wt. % graphite is a carbon-rich catalyst, while silicon carbide would not be considered a carbon-rich catalyst.) Also, in FIG. 7, a carbonizing agent may be present as a separate material in addition to the kinetic interfacial medium and catalyst.

[0441] Some processes use at least two separate pyrolysis reactors. In such embodiments, the pyrolysis reactors are typically all continuous or all batch, although in principle a mixture of reaction modes can be used. Also, when separate pyrolysis reactors are used, they may be at a common location or they may be at different locations.

[0442] In some embodiments, the processes are carried out in a common pyrolysis reactor at different times, such as separate production campaigns. If a single pyrolysis reactor is used, it can be operated in batch mode, for example, with separate batches of low and high fixed carbon material, or using different pyrolysis conditions. Alternatively, a single pyrolysis reactor can be operated continuously or semi-continuously to produce a first material over a first period of time, then a second material over a second period of time, after which the reactor can be returned to producing the first material or something else.

[0443] In some process embodiments, the first pyrolysis reactor is operated at a first pyrolysis temperature of at least about 250° C. and up to about 1250° C., e.g., at least about 300° C. and up to about 700° C. The second pyrolysis reactor can be operated at a second pyrolysis temperature of at least about 250° C. and up to about 1250° C., e.g., at least about 300° C. and up to about 700° C. The second pyrolysis temperature can be the same as or different from the first pyrolysis temperature.

[0444] In some embodiments, the first pyrolysis reactor is operated for a first pyrolysis time of at least about 10 seconds up to about 24 hours. In these or other embodiments, the second pyrolysis reactor can be operated for a second pyrolysis time of at least about 10 seconds up to about 24 hours. The second pyrolysis time can be the same as or different from the first pyrolysis time.

[0445] Some embodiments are based on optimized pyrolysis of biomass with carbon recapture using the principles taught herein to produce a carbon substrate, mechanical size reduction of the carbon substrate, and the use of a binder to agglomerate the carbon substrate to form bio-carbon pellets. The carbon substrate may comprise or consist essentially of a blend of low and high fixed carbon materials.

[0446] Pyrolysis Processes and Systems Suitable processes and systems for pyrolyzing biomass feedstocks are now described in further detail. References to a pyrolysis reactor (or reaction) will in some cases be understood as references to a reactor (or reaction) for producing a kinetic interfacial medium or a precursor thereof.

[0447] As used herein, "pyrolysis" and "pyrolyzing" refer to the thermal decomposition of a carbonaceous material. In pyrolysis, less oxygen is present than is required for complete combustion of the material, such as less than about 10%, 5%, 1%, 0.5%, 0.1%, or 0.01% of the oxygen (on an O molar basis) required for complete combustion. In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0448] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from the heat source increases the temperature within the feedstock; (ii) the initiation of primary pyrolysis reactions at this higher temperature liberates volatiles and forms char; (iii) the flow of hot volatiles toward the cooler solids results in heat transfer between the hot volatiles and the cooler, non-pyrolyzed feedstock; (iv) some of the volatiles in the cooler portions of the feedstock may condense, followed by secondary reactions to produce tar; (v) autocatalytic secondary pyrolysis reactions may proceed while competing primary pyrolysis reactions occur simultaneously; and (vi) further pyrolysis, reforming, water-gas shift reaction, free-radical recombination, or dehydration may also occur, which are functions of residence time, temperature, and pressure profiles.

[0449] Pyrolysis can at least partially dewater the starting material (e.g., lignocellulosic biomass). In various embodiments, pyrolysis removes about 50%, 75%, 90%, 95%, 99% or more of the water from the starting material.

[0450] In some embodiments, the starting biomass feedstock is selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit extracts, and the like. The biomass feedstock may be selected from the group consisting of shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. Note that typical biomass feedstocks include at least carbon, hydrogen, and oxygen.

[0451] The bioreagent may comprise at least about 50%, at least about 75%, or at least about 90% total carbon by weight. In various embodiments, the bioreagent contains about, at least about, or up to about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% carbon by weight. Total carbon is the sum of fixed carbon and non-fixed carbon present in the volatile materials. In some embodiments, component weight percentages are on an absolute basis, which is assumed unless otherwise stated. In other embodiments, component weight percentages are on a dry and ash-free basis. The compositions of low-fixed carbon and high-fixed carbon materials are discussed in detail above.

[0452] Pyrolysis conditions can vary widely depending on the desired composition of the bioreagent and pyrolysis exhaust gas, the starting materials, the reactor configuration, and other factors.

[0453] In some embodiments, multiple reactor zones are designed and operated to optimize carbon yield and product quality from pyrolysis while maintaining flexibility and adjustability to feedstock variations and product requirements.

[0454] In some non-limiting embodiments, the temperature and residence time are selected to achieve a relatively slow pyrolysis chemical reaction. An advantage can be substantial preservation of the cell walls contained in the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, it is preferable to utilize equipment that does not mechanically disrupt cell walls or otherwise convert biomass particles into small fines. Certain suitable reactor configurations are discussed in accordance with the process description below.

[0455] Additionally, if the feedstock is a milled or sized feedstock, such as wood chips or pellets, it may be desirable to carefully mill or size the feedstock. Careful initial processing tends to preserve the strength and cell wall integrity present in the natural feedstock source (e.g., wood). This may also be important if the final product is to retain some, most, or all of the shape and strength of the starting biomass.

[0456] In some embodiments, the first zone of the pyrolysis reactor is configured to feed biomass (or another carbon-containing feedstock) in a manner that does not "shock" the biomass, which ruptures cell walls and initiates rapid decomposition of the solid phase into steam and gas. This first zone can be considered mild pyrolysis.

[0457] In some embodiments, the second zone of the pyrolysis reactor is configured as a primary reaction zone, where preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, leaving behind a significant amount of solid material that is a high-carbon reaction intermediate. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to create vapors that escape by penetrating pores or by creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0458] In some embodiments, the third zone of the pyrolysis reactor is configured to receive the high-carbon reaction intermediates and provide some cooling of the solids. Typically, the third zone is at a lower temperature than the second zone. In the third zone, chemical reactions and mass transfer can be surprisingly complex. Without being limited by a particular theory or proposed mechanism, it is believed that secondary reactions can occur in the third zone. Essentially, carbon-containing components in the gas phase can decompose to form additional fixed carbon or become adsorbed onto carbon. Thus, in some embodiments, the final carbonaceous material is not simply the solid, degassed residue of the processing step, but rather may include additional carbon deposited from the gas phase, such as by the decomposition of organic vapors (e.g., tars) that can form carbon.

[0459] Certain embodiments extend the concept of additional carbon formation by including a separate unit in which the cooled carbon is subjected to an environment containing carbon-containing species to enhance the carbon content of the product. If the temperature of this unit is below the pyrolysis temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0460] There are numerous options with regard to intermediate input and output (purge or probe) streams of one or more phases present in any particular zone, various mass and energy recycle schemes, various additives that can be introduced anywhere in the process, adjustability of process conditions, including both reaction and separation conditions to tailor product distribution, etc. Zone-specific input and output streams allow for better process monitoring and control, such as by FTIR sampling and dynamic process adjustment.

[0461] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis. Surprisingly, high quality carbon materials, including compositions with very high percentages of fixed carbon, can be obtained from the disclosed processes and systems.

[0462] In some embodiments, the pyrolysis process for producing a bio-reagent comprises the following steps: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in the presence of a substantially inert gas phase at at least one temperature selected from about 250°C to about 700°C for at least 10 minutes to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the high temperature pyrolysis solid to produce a cooled pyrolysis solid; (g) recovering the biological reagent comprising at least a portion of the cooled pyrolysis solid.

[0463] The present invention can also be used with carbon-containing feedstocks other than biomass, such as fossil fuels (e.g., coal or petroleum coke), or any mixture of biomass and fossil fuels (e.g., biomass / coal blends). In some embodiments, the biofeedstock is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Feedstocks can include scrap tires, recycled plastics, recycled paper, construction waste, demolition waste, and other waste or recycled materials. For clarity, any method, apparatus, or system described herein can be used with any carbonaceous feedstock. The carbon-containing feedstock can be transportable by any known means, such as truck, train, ship, barge, tractor-trailer, or any other vehicle or conveyance.

[0464] The selection of the particular raw material(s) is not considered technically critical, but is carried out in a manner that tends to favor an economical process. Typically, regardless of the raw material selected, there may (in some embodiments) be screening to remove undesirable materials. The raw material may optionally be dried before processing.

[0465] The raw materials used can be provided or processed into a wide variety of particle sizes or shapes. For example, the feed material can be a fine powder or a mixture of fine and coarse particles. The feed material can be in the form of larger pieces of material, such as wood chips or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the feed material comprises pellets or other agglomerated forms of particles that are pressed together or otherwise bound, for example, with a binder.

[0466] It should be noted that size reduction is an expensive and energy-intensive process. Pyrolyzed materials can be sized with significantly less energy input, i.e., it may be preferable to reduce the particle size of the product rather than the feedstock. This is an option in the present invention because the process does not require fine starting material and there is not necessarily any significant particle size reduction during processing. The ability to process very large feedstock pieces is an important economic advantage of the present invention. In particular, some market applications of high-carbon products actually require large sizes (e.g., on the order of centimeters), and therefore in some embodiments, large pieces are sourced, produced, and sold.

[0467] If it is desired to produce a final carbonaceous bio-reagent with structural integrity, such as a cylindrical shape, there are at least two options in the context of the present invention. First, the material produced from the process can be collected and then further mechanically processed into the desired form. For example, the product can be pressed or pelletized with a binder. A second option is to utilize a feed material that generally has the desired size or shape for the final product and use processing steps that do not destroy the basic structure of the feed material. In some embodiments, the feed and product have similar geometric shapes, such as spheres, cylinders, or cubes.

[0468] The ability to maintain the approximate size of the feed material throughout the process is beneficial when product strength is important, and it avoids the difficulty and cost of pelletizing high fixed carbon materials.

[0469] The starting feedstock may be provided at a range of moisture levels, as will be appreciated. In some embodiments, the feedstock may already be sufficiently dry that further drying prior to pyrolysis is not necessary. Typically, it is desirable to utilize commercial sources of biomass that normally contain moisture and to feed the biomass through a drying step before introducing it into the pyrolysis reactor. However, in some embodiments, dry feedstock may be utilized.

[0470] Typically, it is desirable to provide a relatively low oxygen environment in the pyrolysis reactor, such as about or up to about 10 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.02 mol%, or 0.01 mol% O in the gas phase. First, uncontrolled combustion should be avoided in the pyrolysis reactor for safety reasons. Some amount of total carbon oxidation to CO may occur, and the heat released from the exothermic oxidation may support the endothermic pyrolysis chemical reaction. Large amounts of carbon oxidation, including partial oxidation to syngas, reduce the carbon yield to solids.

[0471] In practice, achieving a strictly oxygen-free environment in the reactor can be difficult. This limit can be approached, and in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that little or no oxygen is present in the pyrolysis reactor, it may be desirable to remove air from the feed before it is introduced into the reactor. There are various methods for removing or reducing air in the feed.

[0472] In some embodiments, a degassing unit is utilized before or after drying, in which the feedstock is conveyed in the presence of another gas that can remove adsorbed oxygen and penetrate the feedstock pores to remove oxygen from the pores. Essentially, any gas with less than 21% O by volume can be used with varying effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO or CO is used. Mixtures can be used, such as a mixture of nitrogen and small amounts of oxygen. Water vapor may be present in the degassing gas, but adding significant moisture back to the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or an effluent treatment unit) or recycled.

[0473] In principle, the effluent from the degassing unit (or a portion thereof) could be introduced into the pyrolysis reactor itself, since the oxygen removed from the solids would be highly diluted. In this embodiment, it may be advantageous to introduce the degassed effluent gas into the last zone of the reactor if the reactor is operated in a countercurrent configuration.

[0474] Various types of degassing units can be used. If drying is performed, it may be inefficient to clean soluble oxygen from the moisture present, so drying and then degassing may be preferred. In certain embodiments, the drying and degassing steps are combined in a single unit, or some amount of degassing is achieved during drying, etc.

[0475] The optionally dried and optionally degassed feedstock is introduced into a pyrolysis reactor or multiple reactors in series or parallel. The feedstock can be introduced using any known means, including, for example, a screw feeder or a lock hopper. In some embodiments, the material feed system incorporates an air knife.

[0476] When a single reactor is used, there can be multiple zones, such as two, three, four, or more zones, which can allow for separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, or pressure to adjust overall process performance.

[0477] References to "zones" shall be interpreted broadly to include regions of space within a single physical unit, physically separated units, or any combination thereof. With respect to continuous reactors, zone boundaries may relate to structures such as the presence of flights within the reactor or separate heating elements for providing heat to separate zones. Alternatively or additionally, zone boundaries in continuous reactors may relate to functions such as, for example, separate temperatures, fluid flow patterns, solids flow patterns, extent of reaction, etc. In single batch reactors, a "zone" is an operating regime in time rather than space. Multiple batch reactors may also be used.

[0478] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary, and some amount of pyrolysis may occur in part of the preheat zone, while some amount of "preheating" may continue to occur in the pyrolysis zone. The temperature profile in the reactor is typically continuous, including at zone boundaries within the reactor.

[0479] Some embodiments employ a first zone operated under preheat or mild pyrolysis conditions. The temperature of the first zone can be selected from about 150° C. to about 500° C., e.g., about 300° C. to about 400° C. Preferably, the temperature of the first zone is not so high as to bombard the biomass material, rupture cell walls, and initiate rapid decomposition of the solid phase into vapors and gases.

[0480] All references to zone temperatures herein should be interpreted non-limitingly to include temperatures that may be applied to the bulk solids present, or the gas phase, or the reactor wall (process side). It will be understood that temperature gradients exist in each zone, both axially and radially, and over time (i.e., after start-up or due to transients). Thus, references to zone temperatures may be to average temperatures or other effective temperatures that may affect actual kinetics. Temperatures may be measured directly by thermocouples or other temperature probes, or may be measured or estimated indirectly by other means.

[0481] The second zone, or generally the primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone can be selected from about 250°C to about 700°C, e.g., about, or as low as, or as high as about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemical reactions, releasing gases and condensable vapors, leaving behind a significant amount of solid material as a high-carbon reaction intermediate. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or creating new pores. The appropriate temperature depends at least on the residence time in the second zone, as well as the nature of the feedstock and the desired product characteristics.

[0482] The third zone, or cooling zone, is operated to cool the high-carbon reaction intermediate to various degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone can be selected from about 100°C to about 550°C, for example, from about 150°C to about 350°C.

[0483] Chemical reactions can continue to occur in the cooling zone. Without being limited to a particular theory, it is believed that a secondary pyrolysis reaction can be initiated in the third zone. Carbon-containing components that are in the gas phase can condense (due to the decrease in temperature in the third zone). However, the temperature remains high enough to promote reactions that can form additional fixed carbon from the condensed liquid (secondary pyrolysis), or at least reactions that can form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that can occur is the Boudouin reaction to convert carbon monoxide to carbon dioxide and fixed carbon.

[0484] The residence time of the reactor zones can vary. There is an interaction of time and temperature, such that for a desired amount of pyrolysis, higher temperatures can allow for shorter reaction times, and vice versa. The residence time in a continuous reactor (zone) is the volume divided by the volumetric flow rate. The residence time in a batch reactor is the batch reaction time after heating to the reaction temperature.

[0485] It should be recognized that in a multiphase reactor, multiple residence times exist. In the present context, there are residence times (and residence time distributions) for both the solid and vapor phases in each zone. For a given apparatus using multiple zones, at a given throughput, the residence times across the zones are generally coupled on the solid side, but if multiple inlet and outlet ports are utilized in the individual zones, the residence times may not be coupled on the vapor side. The solid and vapor residence times are not coupled.

[0486] The solids residence time in the preheat zone can be selected from about 5 minutes to about 60 minutes, e.g., about 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a time sufficient to allow the biomass to reach the desired preheat temperature is desirable. Heat transfer rates, which depend on particle type and size, physical equipment, and heating parameters, dictate the minimum residence time required to allow the solids to reach the desired preheat temperature. In some embodiments, additional time is undesirable because it contributes to higher capital costs unless some amount of mild pyrolysis is intended in the preheat zone.

[0487] The solids residence time in the pyrolysis zone can be selected from about 10 minutes to about 120 minutes, for example, about 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be sufficient time for the necessary heat transfer followed by the carbonization chemical reaction. For times less than about 10 minutes, the temperature needs to be very high, such as above 700°C, to remove a significant amount of non-carbon elements. This temperature promotes fast pyrolysis and the production of vapors and gases derived from the carbon itself, but should be avoided if the intended product is solid carbon.

[0488] In a static system, there will be an equilibrium conversion that can be substantially reached at a certain time. When, as in certain embodiments, steam is continuously flowing over the solids with continuous devolatilization, the equilibrium constraint can be removed to allow pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times tend not to substantially change the remaining refractory solids.

[0489] The solids residence time in the cooling zone can be selected from about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be sufficient time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature dictate the minimum residence time required to allow the carbon to cool. In some embodiments, additional time is not desirable unless some amount of secondary pyrolysis is desired.

[0490] As discussed above, the vapor phase residence times can be independently selected and controlled. The vapor residence time in the preheating zone can be selected from about 0.1 minutes to about 15 minutes, e.g., about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time in the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, e.g., about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time in the cooling zone can be selected from about 0.1 minutes to about 15 minutes, e.g., about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. A short vapor residence time promotes rapid clearing of volatiles from the system, while a longer vapor residence time promotes reaction of components in the vapor phase with the solid phase.

[0491] The mode of operation of the reactor, and the overall system, can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the reactor is a continuous countercurrent reactor, in which solids and vapor flow in substantially opposite directions. The reactor can also be operated in batch, but with simulated countercurrent flow of vapor, for example, by periodically introducing and removing the vapor phase from the batch vessel.

[0492] A variety of flow patterns may be desired or observed. In chemical reactions and simultaneous separations involving multiple phases in multiple reactor zones, the fluid dynamics can become very complex. Typically, solids flow can approach plug flow (well mixed in the radial dimension), while vapor flow can approach perfectly mixed flow (high velocity transport in both the radial and axial dimensions). Multiple inlet and outlet ports for vapor can contribute to overall mixing.

[0493] The pressure in each zone can be separately selected and controlled. The pressure in each zone can be independently selected from about 1 kPa to about 3000 kPa, for example, about 101.3 kPa (standard atmospheric pressure). Independent zone control of pressure is possible when multiple gas inlets and outlets are used, including vacuum ports for withdrawing gas when subatmospheric zone pressures are desired.

[0494] The process can, in some embodiments, be conveniently operated at atmospheric pressure. Operation at atmospheric pressure has many advantages, ranging from mechanical simplicity to improved safety. In certain embodiments, the pyrolysis zone is operated at a pressure of about 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute).

[0495] Vacuum operation (e.g., 10-100 kPa) promotes rapid sweeping of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) can be useful when exhaust gas is fed to high-pressure operation. Higher pressures can also be useful to promote heat transfer, chemical reactions, or separations.

[0496] The step of separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high-temperature pyrolysis solids can be accomplished in the reactor itself or using a separate separation unit. A substantially inert sweep gas can be introduced into one or more zones. The condensable vapors and non-condensable gases are then carried away from the zones in the sweep gas and exit the reactor.

[0497] The sweep gas may be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweep gas may be initially preheated before introduction, or may be cooled if obtained from a heated source.

[0498] The sweep gas more completely removes volatile components by removing them from the system before they can condense or further react. The sweep gas allows volatiles to be removed at a higher rate than would be possible from volatilization alone at a given process temperature. Alternatively, the use of a sweep gas allows more moderate temperatures to be used to remove a given amount of volatiles. The reason the sweep gas improves volatile removal is because the mechanism of separation is not simply relative volatility, but rather liquid / vapor phase separation assisted by the sweep gas. The sweep gas can reduce the mass transfer limitation of volatilization as well as the thermodynamic limitation by continuously depleting a given volatile species, allowing more volatile species to evaporate and achieve thermodynamic equilibrium.

[0499] Some embodiments remove gases full of volatile organic carbon from subsequent processing stages to produce products with high fixed carbon. Otherwise, the volatile carbon may be adsorbed or absorbed onto the pyrolyzed solids, thereby requiring additional energy (cost) to achieve a purer form of carbon that may be desired. It is also speculated that rapid removal of vapors can increase porosity in the pyrolysis solids. Higher porosity is desirable for some products.

[0500] In certain embodiments, the sweep gas, in conjunction with a relatively low process pressure, such as atmospheric pressure, provides rapid vapor removal without requiring large amounts of inert gas.

[0501] In some embodiments, the sweep gas flows countercurrently to the feed flow direction. In other embodiments, the sweep gas flows cocurrently to the feed flow direction. In some embodiments, the flow pattern of the solids approaches plug flow, while the flow patterns of the sweep gas and vapor phase generally approach perfectly mixed flow in one or more zones.

[0502] Sweeping can be performed in any one or more of the reactor zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted (along with generated volatiles) from the cooling or pyrolysis zone. In some embodiments, the sweep gas is introduced into the pyrolysis zone and extracted from the pyrolysis or preheating zone. In some embodiments, the sweep gas is introduced into the preheating zone and extracted from the pyrolysis zone. In these or other embodiments, the sweep gas can be introduced into each of the preheating zone, pyrolysis zone, and cooling zone, and can also be extracted from each of the zones.

[0503] In some embodiments, the zone or zones in which separation is performed are units physically separate from the reactor. Separation units or zones can be located between reactor zones, if desired. For example, a separation unit can be located between a pyrolysis unit and a cooling unit.

[0504] The sweep gas can be introduced continuously, especially when the solids flow is continuous. If the pyrolysis reaction is operated as a batch process, the sweep gas can be introduced after a certain amount of time or periodically to remove volatiles. Even if the pyrolysis reaction is operated continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, using suitable valves and controls.

[0505] The volatile-containing sweep gas can exit one or more reactor zones or can be combined if obtained from multiple zones. The resulting gas stream containing various vapors can then be fed to a thermal oxidizer for controlled air emissions. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are fed to the thermal oxidizer to reach a temperature sufficient to substantially destroy the volatiles contained therein.

[0506] The effluent of the thermal oxidizer is a hot gas stream containing water, carbon dioxide, and nitrogen. This effluent stream can be purged directly to the air exhaust, if desired. Preferably, the energy content of the thermal oxidizer effluent is recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (such as a sweep gas). The energy content can be utilized by directly or indirectly heating or assisting in heating units elsewhere in the process, such as a dryer or reactor. In some embodiments, essentially all of the thermal oxidizer effluent is used to indirectly heat (the utility side) the dryer. The thermal oxidizer can use fuels other than natural gas.

[0507] The yield of carbonaceous materials can vary depending on the factors mentioned above, including the type of feedstock and process conditions. In some embodiments, the net yield of solids as a percentage of the starting material on a dry basis is at least 25%, 30%, 35%, 40%, 45%, 50%, or more. The remainder is divided between condensable vapors, such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases, such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on process conditions, including the presence of water.

[0508] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or more. For example, in some embodiments, the carbonaceous material contains from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon forms, to varying degrees, methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones.

[0509] In alternative embodiments, some portion of these compounds are combined with carbon-rich solids to enrich the carbon and energy content of the product. In these embodiments, some or all of the gas stream obtained from the reactor, containing various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids from a cooling zone or a separate cooling unit. These embodiments are described in more detail below.

[0510] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids can be introduced into a separate cooling unit. In some embodiments, the solids are collected and simply cooled at a slow rate. If the carbonaceous solids are reactive or unstable in air, it may be desirable to maintain an inert atmosphere or to rapidly cool the solids to a temperature below 40°C, e.g., ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. "Cooling unit" should be interpreted broadly to include vessels, tanks, pipes, or portions thereof.

[0511] In some embodiments, the process further includes operating a cooling unit to cool the warm pyrolyzed solids with steam, thereby producing cooler pyrolyzed solids and superheated steam, and drying is performed at least in part using superheated steam obtained from an external cooler. Optionally, the cooling unit can be operated to first cool the warm pyrolyzed solids with steam to reach a first cooling unit temperature, and then with air to reach a second cooling unit temperature, the second cooling unit temperature being lower than the first cooling unit temperature and associated with a reduced risk of combustion of the warm pyrolyzed solids in the presence of air.

[0512] Following cooling to ambient conditions, the carbonaceous solids may be collected and stored, conveyed to another on-site operation, transported to another site, or otherwise disposed of, traded, or sold. The solids may be fed to a unit to reduce particle size. A variety of size reduction units are known in the art, including crushers, shredders, grinders, pulverizers, jet mills, pin mills, and ball mills.

[0513] Some other means for screening or particle size-based separation may be included. Grinding, if present, may be upstream or downstream of the grinding. A portion of the screened material (e.g., large chunks) may be returned to the grinding unit. Small and large particles may be recovered for separate downstream uses. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as a pulverized carbon or activated carbon product.

[0514] Various additives can be introduced throughout the process before, during, or after any step disclosed herein. Additives can be broadly categorized as process additives selected to improve process performance, such as carbon yield or pyrolysis time / temperature to achieve a desired carbon purity, and as process additives selected to improve one or more properties of the bioreagent or downstream products incorporating the reagent. Certain additives can provide enhanced process and product (bioreagent or bioreagent-containing products) properties.

[0515] The additives can be added before, during, or after any one or more steps of the process, including adding them to the feedstock itself at any time before or after the feedstock is harvested. The additive treatment can be incorporated before, during, or after sizing, drying, or other preparation of the feedstock. The additives can be incorporated into or on the feedstock supply facility, transport truck, unloading equipment, storage bin, conveyor (including open or closed conveyors), dryer, process heater, or any other unit. The additives can be added anywhere in the pyrolysis process itself, using a suitable means for introducing the additive. If desired, the additives can be added after carbonization or even after pulverization.

[0516] In some embodiments, the additive is selected from a metal, a metal oxide, a metal hydroxide, or a combination thereof. For example, the additive may be selected from, but is in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0517] In some embodiments, the additive is selected from an acid, a base, or a salt thereof. For example, the additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof.

[0518] In some embodiments, the additive is selected from metal halides. Metal halides are compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are generally obtained by direct combination of a basic metal salt with a hydrohalic acid, or more commonly, by neutralization. In some embodiments, the additive is selected from iron chloride (FeCl2 or FeCl3), iron bromide (FeBr2 or FeBr3), or hydrates thereof, and any combination thereof.

[0519] The additives can result in a final product with a higher energy content (energy density). The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content can result from the removal of non-combustible materials or materials with a lower energy density than carbon. In some embodiments, the additives reduce the degree of liquid formation in favor of solid and gas formation, or in favor of solid formation.

[0520] Without being limited to any particular hypothesis, the additives can chemically modify the starting biomass or treated biomass prior to pyrolysis to reduce cell wall breakdown for greater strength / integrity. In some embodiments, the additives can increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0521] Additives can result in bioreagents with improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. Additives can improve mechanical properties simply by their presence (e.g., the additive itself imparts strength to the mixture) or by some transformation that occurs in the additive phase or in the resulting mixture. For example, a reaction such as vitrification can occur within a portion of the bioreagent that contains the additive, thereby improving the final strength.

[0522] Chemical additives can be applied to wet or dry biomass feedstock. The additives can be applied as a solid powder, spray, mist, liquid, or vapor. In some embodiments, the additives can be introduced by spraying from a liquid solution (such as in an aqueous solution or solvent) or by immersion in a tank, bin, bag, or other container.

[0523] In certain embodiments, an immersion pretreatment is used, in which the solid feedstock is immersed, either batchwise or continuously, in a bath containing the additive for a time sufficient to impregnate the additive into the solid feed material.

[0524] In some embodiments, additives applied to the feedstock can reduce the energy requirements for pyrolysis or increase the yield of the carbonaceous product. In these or other embodiments, additives applied to the feedstock can provide desirable functionality for the intended use of the carbonaceous product.

[0525] Throughput or process capacity can vary widely from small laboratory-scale units to full operations, including any pilot-, demonstration-, or semi-commercial-scale. In various embodiments, process capacities (of feedstock, product, or both) are at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 ton / day, 100 ton / day, 500 ton / day, 1000 ton / day, 2000 ton / day, or more.

[0526] In some embodiments, a portion of the solids produced may be recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the reactor. By returning to the front end and passing through the process again, the treated solids may be higher in fixed carbon. The solids, liquids, and gas streams produced or present in the process may be independently recycled, passed to subsequent steps, or removed / purged from the process at any point.

[0527] In some embodiments, the pyrolyzed material is recovered and then fed to a separate unit for further pyrolysis to create a product with higher carbon purity (e.g., conversion of low fixed carbon material to high fixed carbon material). In some embodiments, the secondary process can be carried out in a simple container such as a steel drum through which a heated inert gas (such as heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas containing volatiles can be sent, for example, to a thermal oxidizer or returned to the main process reactor. To cool the product, another stream of inert gas, initially at, for example, ambient temperature, can be passed through the solids to cool them and then returned to the inert gas preheat system.

[0528] Some variations of the present invention include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the supplying apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor configured to contain at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone and having an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solids cooler disposed in operable communication with the multi-zone reactor; (e) a biological reagent production system comprising a biological reagent recovery unit disposed in operable communication with the solid-state cooler.

[0529] Some variations are: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the supplying apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) an optional preheater disposed in operable communication with the dryer and configured to heat or gently pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operable communication with the preheater and configured to pyrolyze the feedstock; (e) a cooler disposed in operable communication with the pyrolysis reactor and configured to cool the pyrolysis solids; (f) a biological reagent collection unit disposed in operative communication with the cooler, A bioreagent production system is utilized, wherein the system is configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0530] The feed system can be physically integrated with the multi-zone reactor, such as through the use of a screw feed system or auger mechanism to introduce the feed solids into the first reaction zone.

[0531] In some embodiments, the system further comprises a preheating zone disposed in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) can be located within a single unit or can be located in separate units.

[0532] Optionally, the dryer can be configured as a drying zone within a multi-zone reactor. Optionally, a solids cooler can be located within the multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0533] The system may include a purging means for removing oxygen from the system. For example, the purging means may comprise one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the system. In some embodiments, the purging means is a degasser disposed in operative communication between the dryer and the multi-zone reactor.

[0534] The multi-zone reactor can be configured with at least a first gas inlet and a first gas outlet, which can be disposed in communication with different zones or the same zone.

[0535] In some embodiments, the multi-zone reactor is configured with a second gas inlet or a second gas outlet. In some embodiments, the multi-zone reactor is configured with a third gas inlet or a third gas outlet. In some embodiments, the multi-zone reactor is configured with a fourth gas inlet or a fourth gas outlet. In some embodiments, each zone present in the multi-zone reactor is configured with a gas inlet and a gas outlet.

[0536] Gas inlets and outlets not only allow for the introduction and removal of vapors, but the gas outlets (probes) in particular allow for accurate process monitoring and control over various stages of the process, up to and potentially including all stages of the process. Accurate process monitoring is expected to result in improved yields and efficiencies, both dynamically and over time, when operating history can be utilized to adjust process conditions.

[0537] In certain embodiments, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful for sampling and analyzing gases to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as by adjusting the feed rate, the rate of inert gas sweep, the temperature (in one or more zones), the pressure (in one or more zones), additives, etc.

[0538] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more sampling via the reactive gas probe, and optionally, if deemed necessary or desirable, making process or equipment adjustments based on the measurements using well-known principles of process control (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0539] The reaction gas probe can be configured to extract a gas sample in many ways. For example, the sampling line can have a pressure lower than the pyrolysis reactor pressure, so that when the sampling line is opened, a quantity of gas can be easily extracted from the pyrolysis zone. The sampling line can be under vacuum, such as when the pyrolysis zone is at near atmospheric pressure. Typically, the reaction gas probe is associated with one gas output or a portion thereof (e.g., a line branching off from the gas output line).

[0540] In some embodiments, both the gas input and gas output are utilized as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with a process sample (a "sample sweep"). Such a configuration can be used in zones that do not have a gas inlet / outlet for a substantially inert gas for processing, or the reactive gas probe can be associated with a separate gas inlet / outlet in addition to the process inlet and outlet. The sampling inert gas that is periodically introduced and withdrawn for sampling (in embodiments utilizing a sample sweep) can be different from the process inert gas, as desired, either for reasons of analytical accuracy or to introduce an analytical tracer.

[0541] For example, the acetic acid concentration in the gas phase of the pyrolysis zone can be measured using a gas probe to extract a sample, which is then analyzed using a suitable technique (gas chromatography, GC; mass spectrometry, MS; GC-MS, or Fourier transform infrared spectroscopy, FTIR, etc.). The CO or CO2 concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity to gases / vapors. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity to liquids.

[0542] In some embodiments, the system further comprises at least one additional gas probe disposed in operative communication with the cooling zone, or the drying zone (if present) or the preheating zone (if present).

[0543] A gas probe for the cooling zone can be useful, for example, to determine the extent of any additional chemical reactions occurring in the cooling zone. A gas probe in the cooling zone can also be useful as an independent measurement of temperature (e.g., in addition to a thermocouple located in the cooling zone). This independent measurement can be a correlation between cooling temperature and a measured quantity of a particular species. The correlation can be developed separately or can be established after a period of process operation.

[0544] A gas probe for the drying zone can be useful to determine the degree of drying, for example, by measuring moisture content. A gas probe in the preheat zone can be useful, for example, to determine the extent of any mild pyrolysis that occurs.

[0545] In certain embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the preheating zone (if present) can be configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the drying zone can be configured with a gas outlet to generate a substantially countercurrent flow.

[0546] The one or more pyrolysis reactors may be selected from any suitable reactor configuration capable of carrying out a pyrolysis process. Exemplary reactor configurations include, but are not limited to, a fixed bed reactor, a fluidized bed reactor, an entrained bed reactor, an auger, an ablation reactor, a rotating cone, a rotating drum kiln, a calciner, a roaster, a moving bed reactor, a transport bed reactor, an ablation reactor, a rotating cone, or a microwave-assisted pyrolysis reactor.

[0547] In some embodiments where an auger is used, sand or another heat carrier can optionally be used. For example, the feedstock and sand can be fed at one end of the screw. The screw mixes the sand and feedstock and conveys them through the reactor. The screw can provide good control of feedstock residence time and does not dilute the pyrolysis products with carrier or fluidizing gas. The sand can be reheated in a separate vessel.

[0548] In some embodiments where an ablation process is used, the feedstock is moved at high velocity relative to the hot metal surface. Ablation of any char that forms on the surface can maintain a high heat transfer rate. Such an arrangement can prevent dilution of the product. Alternatively, the feedstock particles can be suspended in a carrier gas and introduced at high velocity through a cyclone with heated walls.

[0549] In some embodiments where a fluidized bed reactor is used, the feedstock may be introduced into a bed of hot sand fluidized by a gas, typically a recycled product gas. References herein to "sand" also include similar substantially inert materials such as glass particles, recovered ash particles, and the like. The high heat transfer rate from the fluidized sand can result in rapid heating of the feedstock. There may be some abrasion due to friction with the sand particles. Heat is typically provided by heat exchanger tubes through which the hot combustion gases flow.

[0550] A circulating fluidized bed reactor can be used, in which gas, sand, and feedstock move together. Exemplary transport gases include recycled product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the feedstock, and ablation is expected to be stronger than in a conventional fluidized bed. A separator can be used to separate the product gas from the sand and char particles. The sand particles can be reheated in a fluidized burner vessel and recycled to the reactor.

[0551] In some embodiments, the multi-zone reactor is a continuous reactor comprising a feedstock inlet, a plurality of spatially separated reaction zones configured to separately control the temperature and mixing within each of the reaction zones, and a carbonaceous solids outlet, one of the reaction zones configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the reaction zones configured with a first gas outlet.

[0552] In various embodiments, the reactor comprises at least two, three, four, or more reaction zones. Each of the reaction zones is disposed in communication with separately adjustable heating means independently selected from electrical heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat heat transfer, or combinations thereof. In some embodiments, at least one reactor zone is heated with an effluent stream from a thermal oxidizer, if present.

[0553] The reactor can be configured to separately adjust the gas phase composition and gas phase residence time of at least two reaction zones up to all reaction zones present in the reactor.

[0554] The reactor can be equipped with a second gas inlet or a second gas outlet. In some embodiments, the reactor is configured with a gas inlet for each reaction zone. In these or other embodiments, the reactor is configured with a gas outlet for each reaction zone. The reactor can be a co-current or counter-current reactor.

[0555] In some embodiments, the feedstock inlet comprises a screw or auger feed mechanism, hi some embodiments, the carbonaceous solids outlet comprises a screw or auger output mechanism.

[0556] Certain embodiments utilize a rotary calciner equipped with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotational speed affects solids flow patterns and heat and mass transfer. Each reaction zone can be configured with flights disposed on the interior walls to provide agitation of the solids. The flights can be independently adjustable in each reaction zone.

[0557] Other means of agitating the solids can be used, such as an auger, screw, or paddle conveyor. In some embodiments, the reactor contains a single continuous auger positioned throughout each of the reaction zones. In other embodiments, the reactor contains twin screws positioned throughout each of the reaction zones.

[0558] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., the ability to process biomass feedstock without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not contain augers, screws, or rakes, which tend to significantly reduce the size of the feedstock being pyrolyzed.

[0559] In some embodiments of the present invention, the system further includes a thermal oxidizer disposed in operable communication with the outlet through which the condensable vapors and non-condensable gases are removed. The thermal oxidizer is preferably configured to receive separate fuel (such as natural gas) and oxidant (such as air) into a combustion chamber adapted to combust at least a portion of the fuel and condensable vapors. Certain non-condensable gases, such as CO or CH4, can also be oxidized to CO2.

[0560] When a thermal oxidizer is used, the system may include a heat exchanger disposed between the thermal oxidizer and the dryer and configured to utilize at least a portion of the heat of combustion for the dryer. This embodiment can significantly contribute to the overall energy efficiency of the process.

[0561] In some embodiments, the system further comprises a carbon enrichment unit disposed in operative communication with the solids cooler and configured to combine the condensable vapor in at least partially condensed form with the solids, The carbon enrichment unit may increase the carbon content of the biological reagent obtained from the recovery unit.

[0562] The system may further include a separate pyrolysis unit adapted to further pyrolyze the bio-reagent to further increase its carbon content. The separate pyrolysis unit may be a relatively simple container, unit, or device, such as a tank, barrel, bin, drum, tote, sack, or roll-off.

[0563] The entire system may be at a fixed location or may be distributed over several locations. The system may be constructed using modules that can be easily replicated for practical scale-up. The system may also be constructed using economy of scale principles, as is well known in the process industries.

[0564] Some variations on solid carbon enrichment will now be further described. In some embodiments, the process for producing a bio-reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) optionally cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; (h) then passing at least a portion of the condensable vapors or at least a portion of the non-condensable gases from step (e) through a warm or cold pyrolysis solid to form an enhanced pyrolysis solid having an increased carbon content; (i) recovering the biological reagent comprising at least a portion of the enhanced pyrolysis solid.

[0565] In some embodiments, step (h) comprises passing at least a portion of the condensable vapors from step (e), in vapor or condensed form, through warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gases from step (e) through warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content.

[0566] Alternatively or additionally, the vapor or gas can be contacted with the low temperature pyrolytic solid. In some embodiments, step (h) comprises passing at least a portion of the condensable vapor from step (e), in vapor or condensed form, through the low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gas from step (e) through the low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0567] In certain embodiments, step (h) comprises passing substantially all of the condensable vapors from step (e), in vapor or condensed form, through a low-temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content. In certain embodiments, step (h) comprises passing substantially all of the non-condensable gases from step (e) through a low-temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0568] The process may include various methods of treating or separating the steam or gas prior to using the steam or gas for carbon enrichment. For example, the intermediate feed stream comprising or consisting essentially of at least a portion of the condensable steam and at least a portion of the non-condensable gas obtained from step (e) may be fed to a separation unit configured to produce at least first and second output streams. In certain embodiments, the intermediate feed stream comprises all of the condensable steam, all of the non-condensable gas, or both.

[0569] Separation techniques can include or use distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separations can be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and can exploit differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to a stationary phase, and any combination thereof.

[0570] In some embodiments, the first and second output streams are separated from the intermediate feed stream based on relative volatility. For example, the separation unit can be a distillation column, a flash tank, or a condenser.

[0571] Thus, in some embodiments, the first output stream includes condensable vapors and the second output stream includes non-condensable gases. The condensable vapors may include at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapors from pyrolysis may include aromatic compounds such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic compounds such as refractory tars may be present in the vapors. The non-condensable gases may include at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, or methane.

[0572] In some embodiments, the first and second output streams are intermediate feed streams that have been separated based on their relative polarity. For example, the separation unit can be a stripping column, a packed bed, a chromatography column, or a membrane.

[0573] Thus, in some embodiments, the first output stream comprises polar compounds and the second output stream comprises non-polar compounds. The polar compounds may comprise at least one carbon-containing molecule selected from methanol, furfural, or acetic acid. The non-polar compounds may comprise at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, methane, terpene, or terpene derivatives.

[0574] Step (h) may increase the total carbon content of the bio-reagent relative to an otherwise identical process without step (h). The increase in carbon content may be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more in various embodiments.

[0575] In some embodiments, step (h) increases the fixed carbon content of the bioreagent. In these or other embodiments, step (h) increases the volatile carbon content of the bioreagent. Volatile carbon content is carbon attributable to volatile materials in the reagent. Volatile materials can be, but are not limited to, aliphatic or aromatic compounds (e.g., terpenes); oxygenates, including alcohols, aldehydes, or ketones; and hydrocarbons, including various tars. Volatile carbon typically remains bound or adsorbed to solids at ambient conditions but is released upon heating before the fixed carbon is oxidized, gasified, or otherwise released as vapor.

[0576] Depending on the conditions associated with step (h), it is possible for some amount of volatile carbon to become fixed carbon (e.g., via Boudoir carbon formation from CO). Typically, volatiles enter the micropores of the fixed carbon and exist as condensed / adsorbed species, but remain relatively volatile. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0577] Step (h) can increase the energy content (i.e., energy density) of the biological reagent. The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. The degree of increase in energy content can be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher in various embodiments.

[0578] Further separation can be used to recover one or more non-condensable gases or condensable vapors for use within the process or further processing, for example, to produce purified carbon monoxide or hydrogen.

[0579] As another example, separation of acetic acid can be performed, followed by reduction of the acetic acid to ethanol, which can be achieved, at least in part, using hydrogen derived from the non-condensable gases produced.

[0580] Condensable vapors can be used for energy in the process (such as by thermal oxidation) or as carbon enrichment to increase the carbon content of the bioreagent. Certain non-condensable gases, such as CO or CH4, can be utilized for energy in the process or as part of the substantially inert gas for the pyrolysis step. Any combination of the foregoing is also possible.

[0581] A potential advantage of including step (h) is that the gas stream is scrubbed and the resulting gas stream is enriched in CO and CO. The resulting gas stream can be utilized for energy recovery, recycled for carbon enrichment of solids, or used as an inert gas in the reactor. Similarly, by separating non-condensable gases from condensable vapors, a CO / CO stream is prepared for use as an inert gas in, for example, a reactor system or a cooling system.

[0582] Other variations are premised on the recognition that the principles of the carbon enrichment step can be applied to any feedstock to which it is desired to add carbon.

[0583] In some embodiments, a batch or continuous process for manufacturing a bioreagent comprises: (a) providing a solids stream comprising a carbon-containing material; (b) providing a gas stream comprising a condensable carbon-containing vapor, a non-condensable carbon-containing gas, or a mixture of a condensable carbon-containing vapor and a non-condensable carbon-containing gas; (c) passing the gas stream through the solid stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0584] In some embodiments, the starting carbon-containing material is pyrolyzed biomass or torrefied biomass. The gas stream can be obtained during an integrated process to provide the carbon-containing material. Alternatively, the gas stream can be obtained from a separate processing of the carbon-containing material. The gas stream, or a portion thereof, can be obtained from an external source (e.g., a sawmill oven). Mixtures of gas streams from various sources are possible, as well as mixtures of carbon-containing materials.

[0585] In some embodiments, the process further comprises repeating the process to recycle or reuse the gas stream to further increase the carbon or energy content of the carbon-containing product. In some embodiments, the process further comprises performing the process to recycle or reuse the gas stream to increase the carbon or energy content of another feedstock different from the carbon-containing material.

[0586] In some embodiments, the process further includes introducing the gas stream into a separation unit configured to produce at least first and second output streams, the gas streams comprising a mixture of condensable carbon-containing vapors and non-condensable carbon-containing gases. The first and second output streams can be separated based on relative volatility, relative polarity, or any other characteristic. The gas streams can be obtained from separate processing of carbon-containing materials.

[0587] In some embodiments, the process further comprises repeating the process to recycle or reuse the gas stream to further increase the carbon content of the carbon-containing product. In some embodiments, the process further comprises performing the process to recycle or reuse the gas stream to increase the carbon content of another feedstock.

[0588] The carbon-containing product can have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, relative to the starting carbon-containing material.

[0589] In a related variation, the biological reagent manufacturing system comprises: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the supplying apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor configured to contain at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone and having an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solids cooler disposed in operable communication with the multi-zone reactor; (e) a material enrichment unit disposed in operable communication with the solids cooler and configured to pass a condensable vapor or a non-condensable gas through the solids to form an enriched solid having an increased carbon content; (f) a biological reagent recovery unit disposed in operable communication with the material concentration unit.

[0590] The system may further include a preheating zone disposed in operable communication with the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within the multi-zone reactor. Each of the zones may be located within a single unit or in separate units. Additionally, a solids cooler may be disposed within the multi-zone reactor.

[0591] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet, thereby creating a substantially countercurrent flow of the gas phase relative to the solid phase. In these or other embodiments, the preheating zone or drying zone (or dryer) is configured with a gas outlet, thereby creating a substantially countercurrent flow of the gas phase relative to the solid phase.

[0592] In certain embodiments, the system incorporates a material enrichment unit, the material enrichment unit comprising: (i) a housing having an upper portion and a lower portion; (ii) an inlet at the bottom of the lower portion of the housing configured to carry condensable vapors and non-condensable gases; (iii) an outlet at the top of the upper portion of the housing configured to carry a concentrated gas stream derived from the condensable vapors and non-condensable gases; (iv) a passageway defined between the upper and lower portions of the housing; (v) a transport system following the pathway, the transport system configured to transport the solid, the housing shaped such that the solid adsorbs at least a portion of the condensable vapor or at least a portion of the non-condensable gas.

[0593] The present invention can produce a variety of compositions useful as bioreagents, and products incorporating such reagents. In some variations, the bioreagents can be prepared using any of the processes disclosed herein, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; and (h) recovering the bio-reagent comprising at least a portion of the low temperature pyrolysis solid.

[0594] In some embodiments, the reagent comprises, on a dry basis, about at least 70%, at least 80%, at least 90%, or at least 95% total carbon by weight. Total carbon includes at least fixed carbon and may further include carbon from volatile materials. In some embodiments, carbon from volatile materials is about at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the bioreagent. For example, fixed carbon can be measured using ASTM D3172, and volatile carbon can be measured using ASTM D3175.

[0595] The bioreagent may contain about 10% by weight or less, e.g., about 5% by weight or less, hydrogen on a dry basis. The bioreagent may contain about 1% by weight or less, e.g., about 0.5% by weight or less, nitrogen on a dry basis. The bioreagent may contain about 0.5% by weight or less, e.g., about 0.2% by weight or less, phosphorus on a dry basis. The bioreagent may contain about 0.2% by weight or less, e.g., about 0.1% by weight or less, sulfur on a dry basis.

[0596] Carbon, hydrogen, and nitrogen can be measured, for example, using ASTM D5373 for elemental analysis. Oxygen can be measured, for example, using ASTM D3176. Sulfur can be measured, for example, using ASTM D3177.

[0597] Certain embodiments provide reagents that are substantially free of hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture that may be present. Thus, some embodiments provide bioreagents that have 100% or less carbon on a dry / ash-free (DAF) basis.

[0598] Generally speaking, feedstocks such as biomass contain non-volatile species, including silica and various metals, that are not readily released during pyrolysis. Of course, ashless feedstocks can also be utilized, in which case there should be no substantial amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0599] Varying amounts of non-combustible materials, such as ash, may be present. The bioreagent may include about 10% or less by weight of non-combustible materials on a dry basis, e.g., about 5%, about 2%, about 1% or less by weight. In certain embodiments, the reagent contains little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon, including 100% carbon on a dry basis.

[0600] Varying amounts of moisture may be present. On a total mass basis, the bioreagent may contain at least 1%, 2%, 5%, 10%, 15%, 25%, 35%, 50%, or more by weight of moisture. As intended herein, "moisture" should be interpreted to include any form of water present in the bioreagent, including absorbed moisture, adsorbed water molecules, chemical hydrates, and physical hydrates. The equilibrium moisture content may vary depending on at least the local environment, such as relative humidity. Moisture may also vary during transportation, preparation for use, and other logistics. Moisture can be measured, for example, using ASTM D3173.

[0601] The bioreagents can have a variety of energy contents, which for the present purposes refers to energy density based on the higher calorific value associated with the total combustion of the bone-dry reagent. For example, the bioreagents can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In certain embodiments, the energy content is about 14,000-15,000 Btu / lb. Energy content can be measured, for example, using ASTM D5865.

[0602] The biological reagents can be formed into a powder, such as a coarse or fine powder. For example, the reagents can, in embodiments, be formed into a powder having an average mesh size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0603] In some embodiments, the biological reagents are formed into structural objects comprising compressed, bonded, or aggregated particles. The starting material for forming these objects can be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The objects can be formed by mechanical pressing or other forces, optionally with the use of binders or other means to aggregate the particles together.

[0604] In some embodiments, the bioreagent is manufactured in the form of a structural object whose structure is substantially derived from the source material. For example, a source chip can produce a bioreagent product chip. Or, a source cylinder can produce a bioreagent cylinder, which may be somewhat smaller but otherwise maintain the basic structure and geometry of the starting material.

[0605] Bioreagents according to the present invention can be produced or formed into objects having a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or more. In various embodiments, the minimum or maximum dimension can be a length, width, or diameter.

[0606] Other variations of the invention relate to the incorporation of additives into the process, into the product, or both. In some embodiments, the biological reagent includes at least one process additive that is incorporated during the process. In these or other embodiments, the reagent includes at least one product additive that is introduced into the reagent after the process.

[0607] In some embodiments, the biological reagent, on a dry basis, comprises: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5 wt. % or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

[0608] The additives may be selected from, but are in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0609] In some embodiments, the biological reagent, on a dry basis, comprises: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5 wt. % or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from an acid, a base, or a salt thereof.

[0610] The additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0611] In certain embodiments, the biological reagents, on a dry basis, include: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5 wt. % or less of phosphorus; 0.2% by weight or less of sulfur; a first additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; a second additive selected from an acid, a base, or a salt thereof; The first additive is different from the second additive.

[0612] The first additive may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof, and the second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0613] Certain bioreagents consist essentially, on a dry basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, a non-combustible material, and an additive selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0614] Certain biological reagents consist essentially, on a dry basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, a non-flammable material, and an additive selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, or combinations thereof.

[0615] The amount of additive (or total additives) can vary widely, such as from about 0.01% to about 25% by weight, including about 0.1%, about 1%, about 5%, about 10%, or about 20% by weight. It will be appreciated, therefore, that when a relatively large amount of additive, such as greater than about 1% by weight, is incorporated, the energy content calculated based on the total reagent weight (including additives) will be reduced. Furthermore, in various embodiments, a bioreagent with additives can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0616] The above discussion regarding product form also applies to embodiments incorporating additives, and indeed certain embodiments incorporate additives as binders, fluxing agents, or other modifiers to improve final properties for particular applications.

[0617] In certain embodiments, the majority of the carbon contained in the bioreagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. There may be certain market mechanisms (e.g., renewable identification numbers, tax credits, etc.) where value is attributed to the renewable carbon content in the bioreagent.

[0618] In certain embodiments, the fixed carbon can be classified as non-renewable carbon (e.g., from coal), while the volatile carbon, which can be added separately, can be renewable carbon to increase not only the energy content but also the renewable carbon value.

[0619] The bioreagents produced as described herein are useful for a wide variety of carbonaceous products. The bioreagents may themselves be desirable market products. Bioreagents as provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including higher renewable carbon content) compared to the state of the art.

[0620] In variations, the product comprises any of the biological reagents obtainable by the disclosed processes or described in the compositions set forth herein, or any portion, combination, or derivative thereof.

[0621] Generally speaking, bioreagents can be combusted to produce energy (including electricity and heat); partially oxidized, gasified, or steam reformed to produce syngas; utilized for their adsorption or absorption properties; utilized for their reactive properties in metal refining (such as reduction of metal oxides) or other industrial processes; or utilized for their material properties in carbon steel and various other metal alloys. Essentially, bioreagents can be utilized in any market application of carbon-based commodities or advanced materials, including specialized uses to be developed.

[0622] Prior to suitability or actual use in any product application, the disclosed bioreagents can be analyzed, measured, and optionally modified (such as by additives) in a variety of ways. Some potentially important properties beyond chemical composition and energy content include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, and basicity, to name a few.

[0623] Products or materials into which these bio-reagents can be incorporated include, but are in no way limited to, carbon-based blast furnace additive products, carbon-based taconite pellet additive products, ladle additive carbon-based products, metcoke carbon-based products, coal replacement products, ...

Claims

1. To provide a heated biogas stream, wherein the heated biogas stream contains carbon-containing steam, The heated biogas stream is introduced into a kinetic interface reactor. Using the kinetic interfacial reactor, the carbon-containing steam is converted into solid biocoke. Continuously extracting the solid biocoke, The recirculating portion of the solid biocoke is continuously returned to the kinetic interface reactor, wherein the recirculating portion of the solid biocoke is a kinetic interface medium contained within the kinetic interface reactor, and The solid biocoke is recovered as a biocoke product, wherein the biocoke product contains at least 75% by weight of fixed carbon, and the total carbon in the biocoke product is equal to the total carbon １４ C / １２ Based on measurements of the C isotope ratio, it is determined that at least 50% of the recovered material is recyclable. A continuous method for producing biocoke, including, The method wherein the method does not result in a spatially continuous solid mass filling the kinetic interface reactor.

2. The method according to claim 1, further comprising generating the heated biogas flow by thermal decomposition of a biomass raw material, wherein the carbon-containing steam is thermal decomposition steam.

3. The aforementioned biomass raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, The method according to claim 2, comprising vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging materials, paper scraps, food packaging materials, construction or demolition waste, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

4. The carbon-containing vapor is CO, CO ２ The method according to any one of claims 1 to 3, wherein the material is selected from alkanes, olefins, aromatic compounds, aldehydes, ketones, acids, alcohols, or combinations thereof.

5. The method according to any one of claims 1 to 3, wherein during the conversion, the solid biocoke is formed on the surface of the kinetic interface medium.

6. The method according to any one of claims 1 to 3, wherein during the conversion, the solid biocoke is formed in the internal phase of the kinetic interface medium.

7. The method according to any one of claims 1 to 3, wherein during the conversion, the carbon conversion rate of the carbon-containing vapor is at least 25%.

8. The method according to any one of claims 1 to 3, wherein the biocoke product contains at least about 80% by weight of fixed carbon.

9. The total carbon in the biocoke product is １４ C / １２ The method according to any one of claims 1 to 3, which is fully reproducible, determined from the measurement of the 1C isotope ratio.

10. The method according to any one of claims 1 to 3, wherein the biocoke product essentially does not contain ash.

11. To provide a bioliquid flow, wherein the bioliquid flow includes a carbon-containing liquid, To introduce the bio-liquid flow into a kinetic interface reactor, Using the kinetic interfacial reactor, convert the carbon-containing liquid into solid biocoke. Continuously extracting the solid biocoke, The recirculating portion of the solid biocoke is continuously returned to the kinetic interface reactor, wherein the recirculating portion of the solid biocoke is a kinetic interface medium contained within the kinetic interface reactor, and The solid biocoke is recovered as a biocoke product, wherein the biocoke product contains at least 75% by weight of fixed carbon, and the total carbon in the biocoke product is equal to the total carbon １４ C / １２ Based on measurements of the C isotope ratio, it is determined that at least 50% of the recovered material is recyclable. A continuous method for producing biocoke, including, The method, which does not result in a spatially continuous solid mass being filled into the kinetic interface reactor.

12. The method according to claim 11, further comprising generating the bioliquid flow by thermal decomposition of a biomass raw material, wherein the carbon-containing liquid is condensation pyrolysis vapor.

13. The aforementioned biomass raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, The method according to claim 12, comprising vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, walnut shells, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging materials, paper scraps, food packaging materials, construction or demolition waste, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

14. The method according to any one of claims 11 to 13, wherein the bioliquid stream comprises one or more alkanes, olefins, aromatic compounds, aldehydes, ketones, acids, alcohols, or combinations thereof.

15. The method according to any one of claims 11 to 13, wherein during the conversion, the carbon conversion rate of the carbon-containing liquid is at least 25%.

16. The method according to any one of claims 11 to 13, wherein the biocoke product contains at least about 80% by weight of fixed carbon.

17. The total carbon in the bio-coke product is determined from the measurement of the １４ C / １２ C isotope ratio and is completely renewable, the method according to any one of claims 11 to 13. １４ C / １２ ​

18. The method according to any one of claims 11 to 13, wherein the biocoke product is essentially ash-free.

19. To provide a heated biogas stream, wherein the heated biogas stream contains carbon-containing steam, The heated biogas stream is introduced into a kinetic interface reactor. Using the kinetic interfacial reactor, the carbon-containing steam is converted into solid biocoke. Continuously extracting the solid biocoke, The recirculating portion of the solid biocoke is to be continuously returned to the kinetic interface reactor, wherein the recirculating portion of the solid biocoke is a kinetic interface medium contained within the kinetic interface reactor, and The solid biocoke is recovered as a biocoke product, wherein the biocoke product contains at least 75% by weight of fixed carbon, and the total carbon in the biocoke product is equal to the total carbon １４ C / １２ A continuous method comprising recovering, determined from the measurement of the C isotope ratio, such that at least 50% is recyclable, A biocoke product produced by the method which does not result in a spatially continuous solid mass being filled into the kinetic interfacial reactor.

20. To provide a bioliquid flow, wherein the bioliquid flow includes a carbon-containing liquid, To introduce the bio-liquid flow into a kinetic interface reactor, Using the kinetic interfacial reactor, convert the carbon-containing liquid into solid biocoke. Continuously extracting the solid biocoke, The recirculating portion of the solid biocoke is continuously returned to the kinetic interface reactor, wherein the recirculating portion of the solid biocoke is a kinetic interface medium contained within the kinetic interface reactor, and The solid biocoke is recovered as a biocoke product, wherein the biocoke product contains at least 75% by weight of fixed carbon, and the total carbon in the biocoke product is equal to the total carbon １４ C / １２ A continuous method comprising recovering, determined from the measurement of the C isotope ratio, such that at least 50% is recyclable, A biocoke product produced by the method which does not result in a spatially continuous solid mass being filled into the kinetic interfacial reactor.

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