Process for producing biocarbon pellets with high fixed carbon content and optimized reactivity, and biocarbon pellets obtained therefrom

Abstract

Some variations provide a process for producing bio-carbon pellets, including pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor to produce a first bio-reagent and pyrolysis vapors, introducing the pyrolysis vapors into a separation unit to produce a pyrolysis precipitate in liquid or solid form, contacting the first bio-reagent with the pyrolysis precipitate to thereby produce an intermediate material, pelletizing the intermediate material to produce intermediate pellets, optionally drying the intermediate pellets, separately pyrolyzing the intermediate pellets in a second pyrolysis reactor to produce a second bio-reagent and a pyrolysis tail gas, and recovering the second bio-reagent as bio-carbon pellets. Some variations provide a similar process that utilizes a carbon-containing condensate material that is not necessarily a pyrolysis precipitate. The present disclosure provides improved processes for producing bio-carbon compositions, particularly with respect to carbon yield and bio-carbon properties, such as reactivity.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority benefit of U.S. Provisional Patent Application No. 63 / 220,073, filed July 9, 2021, which is incorporated by reference herein in its entirety.

[0002] The present disclosure relates generally to pyrolysis processes for making high yield bio-carbon compositions and the bio-carbon compositions produced therefrom. [Background technology]

[0003] Carbon is a platform element in a wide variety of industries with a vast array of chemical, material, and fuel applications. Carbon is used as a fuel to generate energy, including electricity. Carbon also has chemical value for a variety of commodity and advanced materials, including metals, metal alloys, composites, carbon fibers, electrodes, and catalyst supports. For metal fabrication, carbon is useful as a reactant for reducing metal oxides to metals during processing, as a fuel to provide heat for processing, and as a component of metal alloys.

[0004] Carbon can be produced from many sources of carbonaceous materials, which generally include fossil resources such as natural gas, petroleum, coal, and lignite, as well as renewable resources such as lignocellulosic biomass and various carbon-rich waste materials. Due to the rising economic, environmental, and social costs associated with fossil resources, it is preferable to utilize renewable biomass to produce carbon-based reagents. Summary of the Invention

[0005] The disclosed technology addresses the aforementioned needs in the art.

[0006] Some variations include a process for producing bio-carbon pellets, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, the pyrolysis precipitate being in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolytic precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolytic precipitate; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; The process includes: a thermogravimetric analysis of the second bio-reagent, the second bio-reagent having a lower oxygen reactivity than the first bio-reagent; and the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

[0007] In some embodiments, the second bioreagent requires at least 5% more time to reach 99% carbon oxidation compared to the first bioreagent according to a TGA graph of weight loss versus time from thermogravimetric analysis. In certain embodiments, the second bioreagent requires at least 10% more time to reach 99% carbon oxidation compared to the first bioreagent according to a TGA graph.

[0008] In some embodiments, the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon followed by a second carbon oxidation regime associated with the oxidation of fixed carbon.

[0009] In some embodiments, the volatile carbon oxidation time is defined as from the start of the first carbon oxidation regime to the start of the second carbon oxidation regime. During the volatile carbon oxidation time, the mass loss of the first biological reagent may be at least 25% or at least 50% greater than the mass loss of the second biological reagent.

[0010] In some embodiments, during the first carbon oxidation regime, thermogravimetric analysis indicates that the rate of mass loss of the first biological reagent is at least 25% or at least 50% greater than the rate of mass loss of the second biological reagent during the first carbon oxidation regime.

[0011] In some embodiments, thermogravimetric analysis indicates that the first biological reagent has an average mass loss rate that is at least 10% higher during the first carbon oxidation regime compared to the second carbon oxidation regime.

[0012] In some embodiments, the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the second biological reagent at a temperature of at least about 500°C, and the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the first biological reagent at a temperature between 200°C and 500°C.

[0013] Biomass-containing feedstocks 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 sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit husks, fruit stem ... The waste stream may be selected from peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0014] In some embodiments, the separation unit includes a condensation system. The condensation system may have multiple stages, in which case the pyrolysis precipitate may be a condensation product of a first condenser stage of the multiple stages. The pyrolysis precipitate may be a condensation product of another condenser stage of the multiple stages.

[0015] In various embodiments, the separation unit includes a condensation system, a liquid-vapor cyclone separator, a demister, a distillation unit, a filtration unit, a membrane unit, a scrubbing unit, a chemical precipitation unit, a liquid-liquid extraction unit, an electrostatic precipitator unit, or a combination thereof.

[0016] In some embodiments, the intermediate material comprises a pyrolysis precipitate adsorbed onto a surface of the first bio-reagent. Alternatively or additionally, the intermediate material may comprise a pyrolysis precipitate absorbed within the bulk phase of the first bio-reagent.

[0017] The pyrolysis precipitate can be in liquid form, solid form, or slurry form (slurry, meaning a suspension of solids in a liquid).

[0018] In some embodiments, steps (c) and (d) are combined.

[0019] A binder can be introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, 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 any combination of the foregoing.

[0020] In some embodiments, no external binder is introduced into the intermediate material during pelletization. Note that the pyrolysis precipitate itself (from the process) may function as an in-situ binder. An in-situ binder is not an external binder.

[0021] In some embodiments, a step (e) for drying is performed, in which case steps (d) and (e) may be combined. Additionally or alternatively, steps (e) and (f) may be combined.

[0022] In some embodiments, the first bio-reagent is pulverized using a first mechanical processing device selected from 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.

[0023] In some embodiments, the intermediate material is pulverized utilizing a second mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or combinations thereof.

[0024] In some embodiments, step (d) utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0025] The first pyrolysis reactor can be different from the second pyrolysis reactor. Alternatively, the first pyrolysis reactor and the second pyrolysis reactor can be the same unit, with steps (a) and (f) carried out at different times, such as in a campaign mode of the process.

[0026] In some embodiments, the first biological reagent acts as a catalyst or reaction matrix for the fixed carbon formation reaction of the pyrolytic precipitate.

[0027] Step (a) can be carried out at a first pyrolysis temperature selected, for example, from about 250° C. to about 700° C. Step (a) can be carried out for a first pyrolysis time selected, for example, from about 1 minute to about 4 hours.

[0028] Step (f) can be carried out at a second pyrolysis temperature selected, for example, from about 300° C. to about 1250° C. Step (f) can be carried out for a second pyrolysis time selected, for example, from about 1 minute to about 4 hours.

[0029] In some embodiments, a pyrolysis non-precipitate is produced in a separation unit, and the pyrolysis non-precipitate is optionally recovered and at least partially oxidized to produce heat, which is optionally used in the process.

[0030] In some embodiments, a portion of the pyrolysis vapors are at least partially oxidized to generate heat, which is optionally used in the process.

[0031] In some embodiments, the pyrolysis exhaust gas is at least partially oxidized to produce heat, which is optionally used in the process.

[0032] The pyrolysis exhaust gas is optionally conveyed to a separation unit. Alternatively or additionally, the pyrolysis exhaust gas can be conveyed to a second separation unit (different from the separation unit of step (b)) operated under precipitation conditions effective to produce a second pyrolysis precipitate, the second pyrolysis precipitate being in the form of a liquid, solid or slurry. The process may further comprise contacting the second pyrolysis precipitate with the first bioreagent or the second bioreagent.

[0033] The biocarbon pellets may contain at least 60% fixed carbon by weight. In various embodiments, the biocarbon pellets contain at least 70% fixed carbon by weight, at least 80% fixed carbon by weight, at least 85% fixed carbon by weight, or at least 90% fixed carbon by weight.

[0034] The bio-carbon pellets may contain up to 10% ash by weight. In various embodiments, the bio-carbon pellets contain up to 5% ash by weight or up to 1% ash by weight.

[0035] The pyrolysis precipitate itself may contain up to 1% ash by weight, up to 0.1% ash by weight, or may be essentially free of ash. A low ash pyrolysis precipitate is beneficial because no ash is added to the first bio-reagent, resulting in a low ash final product.

[0036] In some embodiments, the biocarbon pellets contain up to 20% total volatile matter by weight. In certain embodiments, the biocarbon pellets contain up to 10% total volatile matter by weight.

[0037] In some embodiments, at least 10% by weight of the carbon in the pyrolysis precipitate is converted to fixed carbon in the bio-carbon pellets. In various embodiments, at least 20% or at least 50% by weight of the carbon in the pyrolysis precipitate is converted to fixed carbon in the bio-carbon pellets. In certain embodiments, between 30% and 90% by weight of the carbon in the pyrolysis precipitate is converted to fixed carbon in the bio-carbon pellets.

[0038] In some embodiments, between 1% and 50% by weight of the fixed carbon in the biocarbon pellets is derived from the pyrolytic precipitation. In certain embodiments, between 10% and 40% by weight of the fixed carbon in the biocarbon pellets is derived from the pyrolytic precipitation.

[0039] In some embodiments, the intermediate material further comprises additional pyrolysis precipitate not provided from step (b) of the process.

[0040] In step (c), less than all or all of the first bio-reagent can be contacted with the pyrolysis precipitate.In step (c), less than all or all of the pyrolysis precipitate can be contacted with the first bio-reagent.

[0041] In some embodiments, the total carbon in the biocarbon pellets is 14 C / 12 The total carbon in the biocarbon pellets is at least 50% renewable, as determined by C isotope ratio measurements. 14 C / 12 The total carbon in the biocarbon pellets is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0042] The biocarbon pellets may be characterized, for example, by a Hardgrove Crushability Index of at least 30.

[0043] The biocarbon pellets, for example, have a dry weight of at least about 20 lb / ft 3 It can be characterized by its bulk density.

[0044] The biocarbon pellets can have an average pellet size selected from, for example, about 1 mm to about 10 cm, calculated as the effective diameter of the biocarbon pellet.

[0045] The biocarbon pellets may have an effective pellet diameter within 10% or within 5% of the effective pellet diameter of the intermediate pellets. In other embodiments, the biocarbon pellets have an effective pellet diameter that is greater than 110% or less than 90% of the effective pellet diameter of the intermediate pellets.

[0046] The biocarbon pellets may have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, cylinder-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

[0047] The biocarbon pellets, for example, are at least about 100 lbs. f / in 2 Or at least about 150 lbs. f / in 2 The composition can be characterized by its pellet compressive strength at 25°C.

[0048] The biocarbon pellets can be characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0049] Biocarbon pellets can be characterized as non-self-heating when subjected to a self-heating test in accordance with the 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”.

[0050] The process may further include introducing an additive into the process. The additive may be selected from an acid, a base, or a salt thereof. Alternatively or additionally, the additive may be selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. In some embodiments, the additive is selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof.

[0051] In some embodiments, the oxygen reactivity of the second biological reagent is reduced by adding an additive to the second biological reagent.

[0052] The additives can be selected to adjust the filtrate pH of the biocarbon pellets, which is measured by combining 20 grams of the biocarbon pellets, or a powder form thereof, on a dry basis, with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter.

[0053] An additive can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent, and the filtrate pH is measured by combining 20 grams of the second bioreagent on a dry basis with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter. In some embodiments, an additive is added to the second bioreagent to decrease the filtrate pH of the second bioreagent. In other embodiments, an additive is added to the second bioreagent to increase the filtrate pH of the second bioreagent.

[0054] In some embodiments, the process provides a total carbon yield of at least 50%, calculated as the carbon contained in the bio-carbon pellets as a percentage of the carbon contained in the biomass-containing feedstock. In various embodiments, the total carbon yield is at least 60%, at least 70%, or at least 80%.

[0055] The process can be continuous or semi-continuous.

[0056] In some embodiments, the bio-carbon pellets are mechanically processed to produce a bio-carbon powder. Alternatively or additionally, the bio-carbon pellets can be combined with another amount of a second bio-reagent to produce the bio-carbon object. The other amount of the second bio-reagent can be, for example, itself in pellet form or can be in powder form.

[0057] Another variation is a process for producing bio-carbon pellets, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensable matter material, the carbon-containing condensable matter material being a liquid, a solid, or a slurry; (c) contacting a first biological reagent with a carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; The process provides a method for determining whether a second bio-reagent has a lower oxygen reactivity than the first bio-reagent by thermogravimetric analysis using a temperature ramp of 40° C. / min from 25° C. to 950° C. in the presence of pure oxygen.

[0058] In some embodiments, the second bioreagent requires at least 5% or at least 10% more time to reach 99% oxidation compared to the first bioreagent, according to a TGA graph of weight loss versus time from thermogravimetric analysis.

[0059] In some embodiments, the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon followed by a second carbon oxidation regime associated with the oxidation of fixed carbon.

[0060] In some embodiments, the volatile carbon oxidation time is defined as from the start of the first carbon oxidation regime to the start of the second carbon oxidation regime. During the volatile carbon oxidation time, the first biological reagent may have a mass loss of at least 25% or at least 50% compared to the second biological reagent.

[0061] In some embodiments, thermogravimetric analysis indicates that the first biological reagent has a mass loss rate in the first carbon oxidation regime that is at least 25% or at least 50% higher than the mass loss rate of the second biological reagent in the first carbon oxidation regime.

[0062] In some embodiments, thermogravimetric analysis indicates that the first biological reagent has an average mass loss rate that is at least 10% higher during the first carbon oxidation regime compared to the second carbon oxidation regime.

[0063] In some embodiments, the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the second biological reagent at a temperature of at least about 500°C, and the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the first biological reagent at a temperature between 200°C and 500°C.

[0064] Biomass-containing feedstocks 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 sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit husks, fruit stem ... The waste stream may be selected from peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0065] In some embodiments, the carbon-containing condensable material is a pyrolysis precipitate derived from pyrolysis vapor. In other embodiments, the carbon-containing condensable material is a pyrolysis precipitate provided externally from a different process. The pyrolysis precipitate can also be a mixture of the foregoing.

[0066] In some embodiments, the carbon-containing condensable matter material comprises aromatic species. For example, the carbon-containing condensable matter material may be an off-spec or waste aromatic stream. In certain embodiments, the carbon-containing condensable matter material comprises lignin.

[0067] In some embodiments, the carbon-containing condensed matter comprises sugars or sugar degradation products.

[0068] In some embodiments, the carbon-containing condensed matter material comprises a polymer or a polymer decomposition product.

[0069] In some embodiments, the carbon-containing condensable matter material comprises a liquid product produced by chemical reaction of a syngas, the syngas optionally being derived from pyrolysis steam or pyrolysis exhaust gas.

[0070] In some embodiments, the carbon-containing condensed matter material comprises: 14 C / 12 Contains at least 50%, at least 90%, or 100% (fully) renewable carbon, as determined by C isotope ratio measurements.

[0071] In some embodiments, the intermediate material comprises a carbon-containing condensed matter material adsorbed onto a surface of the first biological reagent. Alternatively or additionally, the intermediate material may comprise a carbon-containing condensed matter material absorbed within the bulk phase of the first biological reagent.

[0072] In some embodiments, steps (c) and (d) are combined.

[0073] In some embodiments, a binder is introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, 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 any combination of the foregoing.

[0074] In some embodiments, no external binder is introduced into the intermediate material during pelletization. Note that the pyrolysis precipitate itself (from the process) may function as an in-situ binder. An in-situ binder is not an external binder.

[0075] In some embodiments, a step (e) for drying is performed. When step (e) is performed, steps (d) and (e) may be combined. Also, when step (e) is performed, steps (e) and (f) may be combined.

[0076] In some embodiments, the first bio-reagent is pulverized using a first mechanical processing device selected from 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.

[0077] In some embodiments, the intermediate material is pulverized utilizing a second mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or combinations thereof.

[0078] In some embodiments, step (d) utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0079] In some embodiments, the first pyrolysis reactor is different from the second pyrolysis reactor. Alternatively, the first pyrolysis reactor and the second pyrolysis reactor can be the same unit, and steps (a) and (f) are carried out at different times.

[0080] In some embodiments, the first biological reagent acts as a catalyst or reaction matrix for the fixed carbon formation reaction of the carbon-containing condensed matter.

[0081] In some embodiments, step (a) is conducted at a first pyrolysis temperature selected from about 250° C. to about 700° C., or for a first pyrolysis time selected from about 1 minute to about 4 hours.

[0082] In some embodiments, step (f) is conducted at a second pyrolysis temperature selected from about 300° C. to about 1250° C., or for a second pyrolysis time selected from about 1 minute to about 4 hours.

[0083] In some embodiments, the pyrolysis vapors are at least partially oxidized to produce heat, which is optionally used in the process.

[0084] In some embodiments, the pyrolysis exhaust gas is at least partially oxidized to produce heat, which is optionally used in the process.

[0085] In some embodiments, the pyrolysis exhaust gas is conveyed to a separation unit operated under precipitation conditions effective to produce a second pyrolysis precipitate, the second pyrolysis precipitate being in liquid or solid form. In certain embodiments, the process further comprises contacting a first bio-reagent with the second pyrolysis precipitate. In certain embodiments, the process further comprises contacting a second bio-reagent with the second pyrolysis precipitate.

[0086] In some embodiments, the biocarbon pellets contain at least 60% fixed carbon by weight. In certain embodiments, the biocarbon pellets contain at least 70%, at least 80%, at least 85%, or at least 90% fixed carbon by weight.

[0087] In some embodiments, the bio-carbon pellets contain up to 10% ash by weight. In certain embodiments, the bio-carbon pellets contain up to 5% ash by weight or up to 1% ash by weight.

[0088] In some embodiments, the biocarbon pellets comprise up to 20% total volatile matter by weight, such as up to 10% total volatile matter by weight.

[0089] In some embodiments, at least 25%, at least 50%, or at least 75% by weight of the carbon in the carbon-containing condensable matter material is converted to fixed carbon in the bio-carbon pellets.

[0090] In some embodiments, between 1% and 50% by weight of the fixed carbon in the bio-carbon pellets is derived from a carbon-containing condensable matter material. In one particular embodiment, between 10% and 40% by weight of the fixed carbon in the bio-carbon pellets is derived from a carbon-containing condensable matter material.

[0091] In some embodiments, step (c) involves contacting less than all or all of the first biological reagent with the carbon-containing condensed matter material.

[0092] In some embodiments, step (c) involves contacting less than all or all of the carbon-containing condensed material with the first biological reagent.

[0093] In some embodiments, the total carbon in the biocarbon pellets is 14 C / 12 At least 50% renewable as determined from C isotope ratio measurements. In one embodiment, the total carbon in the biocarbon pellets is at least 50% renewable as determined from C isotope ratio measurements. 14 C / 12 It is at least 90% renewable or fully renewable, as determined from C isotope ratio measurements.

[0094] In some embodiments, the biocarbon pellets are characterized by a Hardgrove Crushability Index of at least 30.

[0095] In some embodiments, the biocarbon pellets have a density of at least about 20 lb / ft on a dry basis. 3 It is characterized by its bulk density.

[0096] In some embodiments, the biocarbon pellets have an average pellet size selected from about 1 mm to about 10 cm, calculated as the effective diameter of the biocarbon pellets.

[0097] The biocarbon pellets may have an effective pellet diameter within 10% or within 5% of the effective pellet diameter of the intermediate pellets. In other embodiments, the biocarbon pellets have an effective pellet diameter that is greater than 110% or less than 90% of the effective pellet diameter of the intermediate pellets.

[0098] In some embodiments, the biocarbon pellets have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, cylinder-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

[0099] In some embodiments, the biocarbon pellets are at least about 100 lbs. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0100] In some embodiments, the biocarbon pellets are at least about 150 lbs. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0101] In some embodiments, the biocarbon pellets are characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0102] In some embodiments, the biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to the 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”.

[0103] In some embodiments, the process further comprises introducing an additive into the process. The additive can be selected from an acid, a base, or a salt thereof. The additive can be selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. For example, the additive can be selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof.

[0104] The additives can be selected to adjust the filtrate pH of the biocarbon pellets, which is measured by combining 20 grams of the biocarbon pellets, or a powder form thereof, on a dry basis, with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter.

[0105] An additive can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent, and the filtrate pH is measured by combining 20 grams of the second bioreagent on a dry basis with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter. An additive can be added to the second bioreagent to decrease the filtrate pH of the second bioreagent. Alternatively, an additive can be added to the second bioreagent to increase the filtrate pH of the second bioreagent. If the additive is added for a reason other than pH adjustment, the additive added to the second bioreagent may not result in a change in the filtrate pH of the second bioreagent.

[0106] In some embodiments, the oxygen reactivity of the second biological reagent is reduced by adding an additive to the second biological reagent.

[0107] In some embodiments, the process provides a total carbon yield of at least 50%, calculated as the carbon contained in the bio-carbon pellets as a percentage of the sum of the carbon in the biomass-containing feedstock and the carbon in the carbon-containing condensable matter material. In certain embodiments, the total carbon yield is at least 60%, at least 70%, or at least 80%.

[0108] The process can be continuous or semi-continuous.

[0109] Optionally, the bio-carbon pellets, after they are formed, are mechanically treated to produce a bio-carbon powder.

[0110] Optionally, the bio-carbon pellet is combined with another amount of a second bio-reagent to produce a bio-carbon object.

[0111] Some variations provide bio-carbon pellets comprising fixed carbon having a fixed carbon content of at least 60% by weight, wherein the bio-carbon pellets are characterized by thermogravimetric analysis to measure the oxygen reactivity of the bio-carbon pellets, the thermogravimetric analysis being performed in the presence of pure oxygen from 25° C. to 950° C. using a temperature ramp of 40° C. / min, and wherein the bio-carbon pellets require at least 240 minutes to reach 99% carbon oxidation according to a thermogravimetric analysis graph of weight loss versus time ("TGA graph").

[0112] In some embodiments of the bio-carbon pellets, according to TGA graphs of weight loss versus time from thermogravimetric analysis performed in the presence of pure oxygen from 25° C. to 950° C. using a temperature ramp of 40° C. / min, the bio-carbon pellets require at least 250 minutes, 260 minutes, 270 minutes, 280 minutes, 290 minutes, 300 minutes, 310 minutes, or 320 minutes to reach 99% carbon oxidation.

[0113] In some embodiments, thermogravimetric analysis is performed on an anthracite control sample, which requires a control time to reach 99% carbon oxidation, and the time required for the biocarbon pellets to reach 99% carbon oxidation is about 85% to about 100% of the control time. In various embodiments, the time required for the biocarbon pellets to reach 99% carbon oxidation is about 90% to about 100%, e.g., about 95% to about 98%, of the control time.

[0114] In some embodiments, the biocarbon pellets contain volatile carbon and the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon followed by a second carbon oxidation regime associated with the oxidation of fixed carbon. In certain embodiments, the thermogravimetric analysis shows a first derivative curve peak within the first carbon oxidation regime for the biocarbon pellets at a temperature of at least about 500° C.

[0115] In some embodiments, the biocarbon pellets contain at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, at least 85% by weight fixed carbon, or at least 90% by weight fixed carbon.

[0116] In some embodiments, the biocarbon pellets include up to 10% ash by weight, up to 5% ash by weight, or up to 1% ash by weight.

[0117] In some embodiments, the biocarbon pellets contain up to 20% total volatile matter by weight, or up to 10% total volatile matter by weight.

[0118] In some embodiments, the biocarbon pellets include a binder, which can be selected from starch, thermoplastic 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, 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 any combination of the foregoing.

[0119] In some embodiments, the bio-carbon pellets do not include a binder. In some embodiments, the bio-carbon pellets do not include a binder other than the pyrolytic precipitate.

[0120] In some embodiments, the biocarbon pellets include an additive. The additive can be selected from an acid, a base, or a salt thereof. The additive can be selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. In various embodiments, the additive is selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof.

[0121] In some embodiments, the total carbon in the biocarbon pellets is 14 C / 12 At least 50%, at least 90%, or completely renewable, as determined from C isotope ratio measurements.

[0122] In some embodiments, the biocarbon pellets are characterized by a Hardgrove Crushability Index of at least 30.

[0123] In some embodiments, the biocarbon pellets have a density of at least about 20 lb / ft on a dry basis. 3 It is characterized by its bulk density.

[0124] In some embodiments, the biocarbon pellets have an average pellet size selected from about 1 mm to about 10 cm, calculated as the effective diameter of the biocarbon pellets.

[0125] In some embodiments, the biocarbon pellets have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, cylinder-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

[0126] In some embodiments, the biocarbon pellets are at least about 100 lbs. f / in 2 Or at least about 150 lbs. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0127] In some embodiments, the biocarbon pellets are characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0128] In some embodiments, the biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to the 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”.

[0129] Biocarbon pellets, (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, the pyrolysis precipitate being in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolytic precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolytic precipitate; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; Thermogravimetric analysis shows that the second bio-reagent has a lower oxygen reactivity than the first bio-reagent, and the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

[0130] Biocarbon pellets, (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensable matter material, the carbon-containing condensable matter material being a liquid, a solid, or a slurry; (c) contacting a first biological reagent with a carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; A second bio-reagent can be produced by the process, which has a lower oxygen reactivity than the first bio-reagent by thermogravimetric analysis using a temperature ramp of 40 °C / min from 25 °C to 950 °C in the presence of pure oxygen.

[0131] Some variations provide a biocarbon composition comprising fixed carbon having a fixed carbon content of at least 60% by weight, the biocarbon composition being characterized by thermogravimetric analysis measuring the oxygen reactivity of the biocarbon pellets, the thermogravimetric analysis being performed in the presence of pure oxygen from 25° C. to 950° C. using a temperature ramp of 40° C. / min, and the biocarbon pellets requiring at least 240 minutes to reach 99% carbon oxidation according to a TGA graph of weight loss versus time from the thermogravimetric analysis.

[0132] The biocarbon composition (e.g., powder) is (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, the pyrolysis precipitate being in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolytic precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolytic precipitate; (d) separately from step (a), pyrolyzing the intermediate material in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (e) recovering the second bio-reagent as a bio-carbon composition; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; Thermogravimetric analysis shows that the second bio-reagent has a lower oxygen reactivity than the first bio-reagent, and the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

[0133] The biocarbon composition (e.g., powder) is (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensable matter material, the carbon-containing condensable matter material being a liquid, a solid, or a slurry; (c) contacting a first biological reagent with a carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; (d) separately from step (a), pyrolyzing the intermediate material in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (e) recovering the second bio-reagent as a bio-carbon composition; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; A second bio-reagent can be produced by the process, which has a lower oxygen reactivity than the first bio-reagent by thermogravimetric analysis using a temperature ramp of 40 °C / min from 25 °C to 950 °C in the presence of pure oxygen. [Brief description of the drawings]

[0134] [Figure 1]1 illustrates an exemplary block flow diagram of a process and system for pyrolyzing biomass in a first pyrolysis reactor to produce bioreagents and pyrolysis steam. The pyrolysis steam is sent to a separation unit that produces a pyrolysis precipitate and a pyrolysis non-precipitate. The pyrolysis precipitate is fed to an optional mixing unit, to which the bioreagents are also fed. The combined material is sent to a pelleting unit to produce intermediate pellets. Alternatively, there is no mixing unit, and the pyrolysis precipitate and bioreagent are fed directly to the pelleting unit. A binder is optionally added to the pelleting unit. The pellets are then fed to a second pyrolysis reactor that produces a biocarbon product. The second pyrolysis reactor also produces a pyrolysis exhaust gas, which can be recycled (e.g., returned to the separation unit) or otherwise treated (e.g., combusted). The dotted boxes and lines indicate optional units and flows, respectively.

[0135] [Diagram 2] 1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a first pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The carbon-containing condensable material is fed to an optional mixing unit, to which the bio-reagents are also fed. The combined material is sent to a pelleting unit to produce intermediate pellets. Alternatively, there is no mixing unit, and the carbon-containing condensable material and bio-reagents are fed directly to the pelleting unit. A binder is optionally added to the pelleting unit. The pellets are then fed to a second pyrolysis reactor to produce a bio-carbon product. The dotted boxes and lines indicate optional units and flows, respectively.

[0136] [Diagram 3] 1 shows the TGA results of the bio-carbon pellets of Example 1 with pyrolytic tar carbonization compared to the profile of the bio-carbon pellets without pyrolytic tar carbonization.

[0137] [Figure 4]1 shows TGA results of samples of Example 2 to characterize their oxygen reactivity compared to an anthracite control sample. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0138] Some variations are premised on the discovery that by pelleting the bio-reagent and simultaneously or sequentially adding pyrolysis precipitate derived from pyrolysis vapors, the pelleted solids enhance the reaction to form fixed carbon, thereby greatly increasing the yield of fixed carbon, and the bio-carbon pellets produced have been found to have optimized reactivity, particularly reduced oxygen reactivity, for many commercial applications.

[0139] Biomass is a term used to describe 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.

[0140] Various conversion technologies exist for biomass feedstocks to carbonaceous materials. Pyrolysis is a process for thermal conversion of solid materials in the complete absence of oxidizing agents (air or oxygen) and with limited supply such that oxidation does not occur appreciably. Depending on process conditions and additives, biomass pyrolysis can be adjusted to produce widely varying amounts of gas, liquids, and solids. Lower process temperatures and longer steam residence times favor the production of solids. High temperatures and longer residence times increase biomass conversion to syngas, while moderate temperatures and short steam residence times are generally optimal for producing liquids. Historically, slow pyrolysis of wood has been carried out in large piles, in simple batch processes, and without emissions controls. Traditional charcoal production techniques are not only energy inefficient, but also highly polluting.

[0141] Improved or optimized processes for producing bio-carbon compositions are desirable, particularly with respect to carbon yield and bio-carbon properties, such as reactivity.

[0142] The description enables one skilled in the art to make and use the invention and describes several embodiments, adaptations, variations, alternatives, and uses of the invention. These and other embodiments, features, and advantages of the invention will become more apparent to those skilled in the art upon review of the following detailed description of the disclosure in conjunction with the accompanying drawings.

[0143] For the purpose of enabling technical disclosure, various explanations, hypotheses, theories, speculations, assumptions, etc. are disclosed. The present invention does not depend on any of these being true in reality. None of the explanations, hypotheses, theories, speculations, or assumptions in this detailed description should be construed as limiting the scope of the present invention in any way.

[0144] definition As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0145] Unless otherwise indicated, all numbers expressing reaction conditions, stoichiometries, concentrations of ingredients, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending at least on certain analytical techniques.

[0146] As used herein, the term "about" means ±20% of a given range, value, or structure, unless otherwise indicated.

[0147] As used herein, any concentration range, percentage range, ratio range, or integer range should be understood to include any integer value within the recited range, and fractions thereof, where appropriate (such as tenths and hundredths of integers), unless otherwise indicated. Also, any numerical range recited herein should be understood to include any integer within the recited range, unless otherwise indicated.

[0148] As used herein, "a range from about or between," e.g., "a range from about X, Y, or Z, between or between," includes "at least X up to Z."

[0149] The term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional unrecited elements or method steps. "Comprising" is a term of art used in claim language that means that a specified claim element is essential, but that other claim elements may be added and still form a construct within the scope of the claim.

[0150] As used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase "consist of" (or variations thereof) appears in a section in the body of a claim rather than immediately following the preamble, the phrase limits only the elements recited in that section and does not exclude other elements from the claim as a whole. As used herein, the phrase "consisting essentially of" limits the scope of the claim to those specified elements or method steps, in addition to those that do not materially affect the basic and novel characteristics of the claimed subject matter.

[0151] With respect to the terms "comprising," "consisting of," and "consisting essentially of," when one of these three terms is used herein, the subject matter disclosed and claimed herein may include the use of either of the other two terms. Thus, in some embodiments not expressly recited otherwise, any instance of "comprising" can be replaced by "consisting of," or alternatively, by "consisting essentially of."

[0152] As used herein, unless expressly stated to the contrary, "or" refers to an inclusive "or" and 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 from 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 permits, singular or plural terms may also include the plural or singular terms, respectively.

[0153] As used herein, "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 can be non-renewable or renewable on time scales of centuries, millennia, millions of years, or even longer geological time scales. For example, traditional fuel sources of coal and petroleum are non-renewable and non-biological. Biological materials can consist essentially of biological sources. It will be understood by those skilled in the art that biological materials as natural sources or derived from nature can contain trace amounts of non-biological materials. Furthermore, the processes disclosed herein can be used with non-biological materials, although the beneficial environmental impact may not be as significant.

[0154] The three naturally occurring isotopes of carbon, 12 C. 13 C, and 14 C exists. 12 C and 13 C is stable and occurs in a natural ratio of approximately 93:1. 14 C is produced by thermal neutrons from cosmic radiation in the upper atmosphere and is transported to Earth where it is absorbed by living biological material. 14C constitutes a negligible portion, but it is radioactive with a half-life of 5,700 years and is therefore detectable by radiometric measurements. 14 Because it does not absorb C, 14 The amount of C is one of the methods used for radiometric dating of biological materials.

[0155] Plants fix atmospheric carbon through photosynthesis. 14 C. The animals then, when they consume the plant, or consume other animals that consume the plant, 14 Living plants and animals therefore absorb atmospheric CO 2 Same as 14 C vs. 12 C ratio. When an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer produces new 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.

[0156] Fossil fuels such as coal are derived primarily from plant material deposited millions of years ago. 14 This is equivalent to thousands of half-lives of C, so essentially all of the 14 C is decaying. Also, fossil fuels are not harmful to the atmosphere because they were originally formed from living organisms. 13 C is depleted. Thus, carbon from fossil fuels is 13 C and 14 Both C are depleted.

[0157] 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, allows for the determination of the source of carbon in the composition, specifically, whether the carbon in the composition is derived from a renewable resource or from a fossil fuel, in other words, whether a renewable resource or a fossil fuel was used in the production of the composition.

[0158] Biomass is a term used to describe biologically produced or living matter. Biomass refers to the mass of living organisms, including plants, animals, and microorganisms, or from a biochemical standpoint, cellulose, lignin, sugars, fats, and proteins. Biomass includes both above-ground and below-ground tissues of plants, such as leaves, twigs, branches, and stems, as well as the roots of trees and rhizomes of grasses. The chemical energy contained in biomass comes from solar energy using the natural process of photosynthesis. This 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. Biomass is useful in that it is effectively stored solar energy. Biomass is the only renewable source of carbon.

[0159] As used herein, "total carbon" is the sum of fixed and non-fixed carbon present in the volatile matter. 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.

[0160] As used herein, a "zone" is a region of space within a single physical unit, physically separated units, or any combination thereof. For continuous reactors, the boundaries of the zones may relate to structures such as the presence of flights within the reactor or separate heating elements to provide heat to separate zones. Alternatively or additionally, the boundaries of the zones in a continuous reactor may relate to functions such as separate temperatures, fluid flow patterns, solid flow patterns, or extent of reaction. In a single batch reactor, the "zones" are operating regimes in time rather than space. There is not necessarily an abrupt transition from one zone to another. For example, the boundaries between the preheat zone and the pyrolysis zone may be somewhat arbitrary, and some amount of pyrolysis may occur in a portion of the preheat zone, and some amount of "preheat" may continue to occur in the pyrolysis zone. The temperature profile within the reactor is typically continuous, including the zone boundaries within the reactor.

[0161] For the present purposes, "reagent" is intended to mean a material in its broadest sense, and a reagent may be a fuel, a chemical, a material, a compound, an additive, a blend component, a solvent, etc. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. A reagent may or may not be a chemical reactant and may or may not be 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 give the metal certain strength properties. A reagent may be a substance of sufficient purity (typically carbon purity in the present context) to be used in chemical analysis or physical testing.

[0162] As used herein, a "derivative" is a compound, molecule, or ion derived from another substance by chemical reaction. The substance from which the derivative is derived is an additive. A derivative is also an additive.

[0163] The terms "low fixed carbon" and "high fixed carbon" are used herein for practical purposes to describe materials that may be produced, in various embodiments, by the processes and systems as disclosed. Any limitations on carbon content or any other concentration should be implied only by reference to specific embodiments and their equivalents, and not from the terms themselves.

[0164] Some variations include a process for producing bio-carbon pellets, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, the pyrolysis precipitate being in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolytic precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolytic precipitate; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; The process includes: a thermogravimetric analysis of the second bio-reagent, the second bio-reagent having a lower oxygen reactivity than the first bio-reagent; and the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

[0165] Thermogravimetric analysis (TGA) is a well-known analytical method in which the mass of a sample is measured over time as the temperature changes. To perform TGA on both the first bioreagent and the second bioreagent, a sample of the first bioreagent can be collected after its generation in step (a), while a sample of the second bioreagent is provided by step (g). TGA measurements may be performed simultaneously on both samples and other samples (e.g., control samples) using a commercial TGA device that accommodates many samples (see, e.g., FIG. 4).

[0166] In some embodiments, the second bioreagent requires at least 5% more time to reach 99% carbon oxidation compared to the first bioreagent according to a TGA graph of weight loss versus time from thermogravimetric analysis. In certain embodiments, the second bioreagent requires at least 10% more time to reach 99% carbon oxidation compared to the first bioreagent according to a TGA graph.

[0167] In some embodiments, the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon followed by a second carbon oxidation regime associated with the oxidation of fixed carbon.

[0168] In some embodiments, the volatile carbon oxidation time is defined as from the start of the first carbon oxidation regime to the start of the second carbon oxidation regime. During the volatile carbon oxidation time, the mass loss of the first biological reagent may be at least 25% or at least 50% greater than the mass loss of the second biological reagent.

[0169] In some embodiments, during the first carbon oxidation regime, thermogravimetric analysis indicates that the rate of mass loss of the first biological reagent is at least 25% or at least 50% greater than the rate of mass loss of the second biological reagent during the first carbon oxidation regime.

[0170] In some embodiments, thermogravimetric analysis indicates that the first biological reagent has an average mass loss rate that is at least 10% higher during the first carbon oxidation regime compared to the second carbon oxidation regime.

[0171] In some embodiments, the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the second biological reagent at a temperature of at least about 500°C, and the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the first biological reagent at a temperature between 200°C and 500°C.

[0172] Biomass-containing feedstocks 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 sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit husks, fruit stem ... The waste stream may be selected from peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0173] In some embodiments, the separation unit is or includes a condensation system. In certain embodiments, the condensation system has multiple stages. The pyrolysis precipitate can be, for example, a condensation product of a first condenser stage of the multiple stages. Alternatively or additionally, the pyrolysis precipitate can be a condensation product of a second, third, or later condenser stage of the multiple stages. The pyrolysis precipitate can be a condensation product that is a combination of multiple condensation products of multiple stages that can be equal to or less than the multiple stages present in the condensation system.

[0174] The separation in step (b) may generally utilize thermal, chemical, mechanical, electrical / electrostatic, or other means, or a combination thereof. When utilizing thermal means, there may be indirect heat exchange (e.g., with air or oil on the other side of the separation unit wall) or direct heat exchange (e.g., direct injection of water or cooled pyrolysis precipitate). Chemical means may utilize, for example, adsorption, absorption, or extraction. Mechanical means may utilize, for example, centrifugal force or molecular size exclusion. Electrical / electrostatic means may utilize, for example, the presence of an electromagnetic field.

[0175] In various embodiments, the separation unit is or includes a condensation unit, a liquid-vapor cyclone separator, a demister, a distillation unit, a filtration unit, a membrane unit, a scrubbing unit, a chemical precipitation unit, a liquid-liquid extraction unit, an electrostatic precipitator unit, or combinations thereof.

[0176] When the separation unit includes a condensing unit, the condensing unit can be a single stage condenser or a multi-stage condensing system, as discussed above. Exemplary types of condensing units include, for example, liquid-cooled condensers (e.g., water-cooled condensers), gas-cooled condensers (e.g., air-cooled condensers), and evaporative condensers. The condensing unit can be a direct contact condenser or an indirect condenser (e.g., a surface condenser such as a shell-and-tube condenser).

[0177] Where the separation unit includes a liquid-vapor cyclone separator, exemplary types of liquid-vapor cyclone separators are commercially known (e.g., from Sulzer, Winterthur, Switzerland). Liquid-vapor cyclone separators utilize a combination of centrifugal force, buoyancy, and drag forces to cause liquid-vapor separation, especially when the centrifugal force is sufficient to overcome other forces. Exemplary centrifugal forces are from about 10 g to about 1000 g, e.g., from about 100 to 500 g, where g is gravity.

[0178] When the separation unit includes a demister, exemplary types of demisters include, for example, mesh demisters, vane demisters, cyclone demisters, and fiber bed demisters.

[0179] When the separation unit includes a distillation unit, exemplary types of distillation units include, for example, single column units, multiple column units, and reactive distillation units. The distillation unit may be vertical or horizontal and may be operated in continuous or batch mode.

[0180] When the separation unit includes a filtration unit, exemplary types of filtration units include, for example, gravity filters, vacuum filters, pressure filters, pneumatic press filters, centrifugal filters, and crossflow filters. The filtration media can be selected to separate components by, for example, molecular weight, particle size, or viscosity.

[0181] When the separation unit includes a membrane unit, exemplary types of membrane units include, for example, microfiltration units, ultrafiltration units, nanofiltration units, reverse osmosis units, and electrodialysis units.

[0182] When the separation unit includes a scrubbing unit, exemplary types of scrubbing units include, for example, suction scrubbers and vent scrubbers. In some embodiments, the scrubbing utilizes recovered / recycled pyrolysis precipitate.

[0183] Where the separation unit includes a chemical precipitation unit, for example, the chemical precipitation can be catalyzed or assisted using a solvent, acid, or base to induce precipitation of the pyrolysis vapor components from the vapor into a liquid or solid.

[0184] When the separation unit includes a liquid-liquid extraction unit, exemplary types of liquid-liquid extraction units include, for example, mixer settlers, centrifugal extractors, static extraction columns, stirred extraction columns, and multi-stage countercurrent extraction units. Liquid-liquid extraction can use, for example, an extraction solvent that is or includes an aromatic hydrocarbon. In some embodiments, the extraction solvent is the recovered pyrolysis precipitate. The liquid-liquid extraction unit can be operated in a continuous or batch mode.

[0185] When the separation unit includes an electrostatic precipitator unit, exemplary types of electrostatic precipitator units include electrostatic precipitators, electrostatic separators, electrodynamic separators, capacitor-based separators, and other means or devices that use the principle of separation by electrical forces. Electrostatic precipitators can be designed to collect droplets using electric field forces. Electrostatic precipitators work by charging particles (e.g., droplets) and then collecting the charged particles in an electric field. Charging occurs by two mechanisms: diffusion charging and field charging. In diffusion charging, ions in a gas bounce off by Brownian motion, collide with particles, and transfer their charge to the particles. Field charging occurs when particles are located in an electric field that contains ions. Electrostatic precipitators use a high-voltage power supply to create a potential difference between a discharge electrode and a collection electrode to capture charged or polarized droplets.

[0186] In some embodiments, the electrostatic precipitator comprises one or more tubes, channels, or ducts through which the material flows, acting as an electrical ground and collection surface for the droplets. A discharge electrode can be suspended in the center of the pipe and acts as a high voltage (e.g., ±10-100 kV DC) electrode. The high voltage applied to the electrode creates an electrostatic field between the electrode and the grounded channel. This field projects a force on particles passing through it. As the particles pass through the field, they move towards the grounded wall and therefore collect on the wall. Gravity causes the collected liquid to flow down the electrostatic precipitator and be collected. Electrostatic precipitators use a positive or negative polarity power supply.

[0187] Combinations of separation units are possible. For example, a separation unit may include a single stage condenser as a first subunit for producing a primary pyrolysis precipitate and a fractional condenser or distiller as a second subunit for fractionating the primary pyrolysis precipitate into multiple fraction precipitates. In another example, a separation unit may include a liquid-vapor cyclone separator as a first subunit for producing a liquid stream and a vapor stream, a liquid-liquid extraction unit as a second subunit for recovering a portion of the liquid stream as a pyrolysis precipitate, and a filtration unit for recovering a portion of the vapor stream as an additional pyrolysis precipitate. Other embodiments utilize a combination of a condensation unit and an electrostatic precipitator to collect the individual liquid products.

[0188] In some embodiments, the intermediate material comprises a pyrolytic precipitate adsorbed onto a surface of the first bio-reagent, hi these or other embodiments, the intermediate material may comprise a pyrolytic precipitate absorbed within the bulk phase of the first bio-reagent.

[0189] The pyrolysis precipitate may be in liquid form (one or more liquid phases), solid form (one or more solid phases), or a combination of one or more liquid and one or more solid phases (e.g., a slurry). The solid phase may vary widely in viscosity and density. For example, the solid phase, or the combined solid-liquid material, may be a gel-like material, a sticky material, or a rubber-like material.

[0190] The ratio of pyrolysis precipitate to the first bioreagent can be varied to achieve different properties (e.g., reactivity) of the final pellet. Varying the ratio can be achieved by diverting a portion of the first bioreagent and blending the remaining portion of the first bioreagent with the pyrolysis precipitate. Alternatively or additionally, two pyrolysis reactors can be operated in parallel with the pyrolysis precipitate collected from the first pyrolysis reactor being diverted to the second pyrolysis reactor. In one scenario, one pyrolysis reactor produces a less reactive product incorporating additional pyrolysis of twice the portion of pyrolysis precipitate, while the other pyrolysis reactor produces a more reactive product without additional pyrolysis of pyrolysis precipitate.

[0191] In some embodiments, steps (c) and (d) are integrated, for example, the pyrolyzed precipitate can be contacted with the first bio-reagent in a pelleting unit.

[0192] A binder can be introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations 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.

[0193] In other embodiments, no external binder is introduced into the intermediate material during pelletization. Certain components within the intermediate material, particularly the pyrolyzed precipitate itself or components contained therein, for example, can function as binders.

[0194] In some processes, a step (e) for drying is performed. Steps (d) and (e) may be integrated such that drying occurs along with pelletizing. Also, steps (e) and (f) may be integrated such that both pyrolysis and drying of the intermediate pellets occurs. In certain embodiments, steps (d), (e), and (f) are all integrated.

[0195] In some embodiments, the first bio-reagent is ground utilizing a mechanical processing device selected from 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 these or other embodiments, the intermediate material can be ground utilizing a mechanical processing device selected from 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. The intermediate material can be ground instead of or in addition to the first bio-reagent.

[0196] In some embodiments, step (d) utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0197] In some processes, the first pyrolysis reactor is different from the second pyrolysis reactor. Alternatively, the first pyrolysis reactor and the second pyrolysis reactor can be the same unit, and steps (a) and (f) are carried out at different times.

[0198] In some embodiments, step (a) is carried out at a first pyrolysis temperature selected from about 250° C. to about 1250° C., e.g., from about 300° C. to about 700° C. In these or other embodiments, step (f) is carried out at a second pyrolysis temperature selected from about 250° C. to about 1250° C., e.g., from about 400° C. to about 1000° C. The second pyrolysis temperature can be, but is not required to be, at least about the first pyrolysis temperature.

[0199] In some embodiments, step (a) is carried out for a first pyrolysis time selected from about 10 seconds to about 24 hours, e.g., from about 1 minute to about 4 hours. In these or other embodiments, step (f) is carried out for a second pyrolysis time selected from about 10 seconds to about 24 hours, e.g., from about 1 minute to about 4 hours. The second pyrolysis time can be, but is not required to be, longer than the first pyrolysis time.

[0200] In a process such as during step (f), the first bio-reagent may act as a catalyst or reaction matrix for the fixed carbon forming reaction of the pyrolytic precipitate.

[0201] The pyrolysis non-precipitates are typically produced in a separation unit. The pyrolysis non-precipitates are typically a vapor stream and can be purged from the process. The purge stream from the separation unit does not necessarily have to be in the vapor phase, depending on the choice of separation unit. For example, the purge stream can be a liquid stream, such as a liquid-liquid extraction solvent, or a vapor stream with entrained liquids or solids. In some embodiments, the pyrolysis non-precipitates are collected and at least partially oxidized to generate heat, which is optionally used in the process.

[0202] In some embodiments, the pyrolysis tail gas (from the second pyrolysis reactor) is at least partially oxidized to generate heat, which is optionally used in the process. Optionally, at least a portion of the pyrolysis tail gas is conveyed back to the separation unit. Recycling the pyrolysis tail gas in this manner can provide carbon atoms (in the pyrolysis tail gas) with the potential to reach the final biocarbon pellets as fixed carbon.

[0203] Alternatively or additionally, the pyrolysis exhaust gas can be conveyed to a second separation unit (different from the separation unit of step (b)) operated under precipitation conditions effective to produce a second pyrolysis precipitate, the second pyrolysis precipitate being in the form of a liquid, solid or slurry. The process can further comprise contacting the second pyrolysis precipitate with the first bio-reagent or the second bio-reagent.

[0204] The biocarbon pellets recovered in step (g) can contain, for example, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, at least 85% by weight fixed carbon, or at least 90% by weight fixed carbon. The biocarbon pellets can contain, for example, less than 10% by weight ash, less than 5% by weight ash, or less than 1% by weight ash.

[0205] In some processes, the pyrolysis precipitate contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash. A low ash pyrolysis precipitate is beneficial because no ash is added to the first bio-reagent, resulting in a low ash final product.

[0206] In some embodiments, the biocarbon pellets contain less than 20% total volatiles by weight, or less than 10% total volatiles by weight.

[0207] In some embodiments, at least 10% by weight of the carbon in the pyrolysis precipitate is converted to fixed carbon in the bio-carbon pellets. In various embodiments, at least 20%, at least 30%, at least 40%, at least 50%, or between 30% and 90% by weight of the carbon in the pyrolysis precipitate is converted to fixed carbon in the bio-carbon pellets.

[0208] In some embodiments, about 1% to about 50% by weight of the fixed carbon in the biocarbon pellets is derived from the pyrolytic precipitation. In certain embodiments, about 10% to about 40% by weight of the fixed carbon in the biocarbon pellets is derived from the pyrolytic precipitation.

[0209] Optionally, the intermediate material further comprises additional pyrolysis precipitate not provided from step (b) of the process. For example, the additional pyrolysis precipitate can be provided by a pyrolysis process conducted using (i) a different biomass-containing feedstock and (ii) a different time or location.

[0210] In step (c), less than all or all of the first bio-reagent can be contacted with the pyrolysis precipitate.In step (c), less than all or all of the pyrolysis precipitate can be contacted with the first bio-reagent.

[0211] The total carbon in biocarbon pellets is 14 C / 12 The total carbon in the biocarbon pellets is at least 50% renewable, as determined by C isotope ratio measurements. 14 C / 12 It may be at least 90% or completely (about 100%) renewable, as determined from C isotope ratio measurements.

[0212] In some embodiments, the biocarbon pellets are characterized by a Hardgrove Crushability Index of at least 30 or at least 50.

[0213] In some embodiments, the biocarbon pellets have a molecular weight of at least about 25 lb / ft on a dry basis. 3 , at least about 30 lb / ft 3 , at least about 35 lb / ft 3 , at least about 40 lb / ft 3 , or at least about 45 lb / ft 3 It is characterized by its bulk density.

[0214] The biocarbon pellets may have an effective pellet diameter within 10% or within 5% of the effective pellet diameter of the intermediate pellets. In these embodiments, pyrolysis in the second pyrolysis reactor does not significantly change the pellet size, and alternatively, additional process steps are performed to increase or decrease the pellet size back to the size of the intermediate pellets, or back to within 10% of that size. In other embodiments, the biocarbon pellets have an effective pellet diameter that is greater than 110% or less than 90% of the effective pellet diameter of the intermediate pellets. In these embodiments, pyrolysis in the second pyrolysis reactor does significantly change the pellet size, and alternatively, additional process steps are performed to increase or decrease the pellet size.

[0215] In some embodiments, the biocarbon pellets have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, cylinder-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

[0216] In some embodiments, the biocarbon pellets are at least about 100 lbs. f / in 2 In certain embodiments, the biocarbon pellets have a pellet compressive strength of at least about 150 lb at 25° C. f / in 2 In various embodiments, the biocarbon pellets have a pellet compression strength of about or at least about 25, 50, 75, 100, 125, 150, 175, or 200 lbs, including any intervening range. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0217] In some embodiments, the bio-carbon pellets are hydrophobic. In some embodiments, the bio-carbon pellets are characterized by a water uptake of up to 20% by weight at 25° C. after 24 hours of immersion in water. In certain embodiments, the bio-carbon pellets are characterized by a water uptake of up to 15%, 10%, or 5% by weight at 25° C. after 24 hours of immersion in water.

[0218] In some embodiments, the biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to the 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”.

[0219] In some embodiments, the bio-carbon pellets are substantially characterized by their oxygen reactivity as shown in the thermogravimetric analysis of Figure 3 or Figure 4 (see Examples 1 and 2 below). The bio-carbon pellets are less reactive with oxygen at temperatures between about 750-950°C compared to bio-carbon pellets produced by an otherwise equivalent pyrolysis process without carbon recapture in step (c).

[0220] Biocarbon pellets can be characterized by a "coke reactivity index" or CRI value. CRI can be determined according to ASTM D5341, Coke Reactivity Index. As the coke lump descends in the blast furnace, it is reacted with the backflow CO 2The coke mass is subjected to reactions with CO and undergoes abrasion from the lumps rubbing together against the furnace walls. The process streams physically weaken and chemically react the coke mass, reducing permeability and producing excess fines which can result in increased coke rates and loss of hot metal production. The CRI test method is designed to indirectly measure this behavior of coke or alternatively biocarbon in the blast furnace. Note that the chemical reaction explicitly taken into account by the CRI value is not carbon oxidation, but rather the reverse Boudouard reaction (C+CO 2 In one particular embodiment, the CRI value is measured by placing 200 grams of a sample having a particle size of 19-22.5 mm in a reactor and heating it to 1100° C. in an inert atmosphere. The carbon is then mixed with 100% CO 2 The pellets are degassed isothermally in a gas atmosphere for 2 hours and then cooled with nitrogen gas. After cooling, the carbon is weighed and spun in an I-drum for 600 revolutions, followed by sieving the material through screens with mesh sizes of +10 and -0.5 mm. The weight loss of the carbon represents the coke reactivity index CRI, and the remaining carbon on the +10 mm sieve represents the coke strength CSR after reaction. In some embodiments, the CRI of the biocarbon pellets is about 20% to about 80%, for example, about or up to about 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%.

[0221] The process can provide a total carbon yield, calculated as the carbon contained in the bio-carbon pellets as a percentage of the carbon contained in the biomass-containing feedstock, of at least 50%. In some embodiments, the total carbon yield is at least 60%, at least 70%, or at least 80%.

[0222] The process can provide a total fixed carbon yield of at least 50%, calculated as the fixed carbon contained in the biocarbon pellets as a percentage of the total carbon contained in the biomass-containing feedstock. In some embodiments, the total fixed carbon yield is at least 60%, at least 70%, or at least 80%. The fixed carbon yield may not be at least about the carbon yield. In some embodiments, additional pyrolysis performed in a second pyrolysis reactor results in a fixed carbon yield that is close to or even approximately the same as the carbon yield, with most or all of the carbon being fixed carbon in the final biocarbon pellets.

[0223] In some embodiments, the process further comprises introducing an additive into the process. The additive can be selected from an acid, a base, or a salt thereof. The additive can be selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. For example, the additive can be selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof.

[0224] The additives can be selected to adjust the filtrate pH of the biocarbon pellets, which is measured by combining 20 grams of the biocarbon pellets, or a powder form thereof, on a dry basis, with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter.

[0225] An additive can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent, and the filtrate pH is measured by combining 20 grams of the second bioreagent on a dry basis with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter. An additive can be added to the second bioreagent to decrease the filtrate pH of the second bioreagent. Alternatively, an additive can be added to the second bioreagent to increase the filtrate pH of the second bioreagent. If the additive is added for a reason other than pH adjustment, the additive added to the second bioreagent may not result in a change in the filtrate pH of the second bioreagent.

[0226] In some embodiments, the oxygen reactivity of the second bio-reagent is reduced by adding an additive to the second bio-reagent. The additive can be added to the second bio-reagent after it is formed, or the additive can be fed, for example, to the second pyrolysis reactor, the first pyrolysis reactor, or the pelletization unit. The additive can be introduced at multiple locations in the process.

[0227] In some embodiments, the process provides a total carbon yield of at least 50%, calculated as the carbon contained in the bio-carbon pellets as a percentage of the sum of the carbon in the biomass-containing feedstock and the carbon in the carbon-containing condensable matter material. In certain embodiments, the total carbon yield is at least 60%, at least 70%, or at least 80%.

[0228] The process can be continuous or semi-continuous.

[0229] Optionally, the bio-carbon pellets are mechanically processed after they are formed to produce a bio-carbon powder. For example, the bio-carbon pellets can be manufactured and shipped to another location. At the site of use, the pellets can be pulverized and fed to a reactor, for example, for combustion, gasification, metal ore reduction, etc.

[0230] Optionally, the bio-carbon pellets are combined with another amount of a second bio-reagent to produce a bio-carbon object. The other amount of the second bio-reagent may be in pellet, powder, or other form. In some embodiments, multiple pellets are mechanically pressed together to form a bio-carbon object, which may be, for example, a structural carbon element for a metal fabrication furnace.

[0231] Another variation is a process for producing bio-carbon pellets, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensable matter material, the carbon-containing condensable matter material being a liquid, a solid, or a slurry; (c) contacting a first biological reagent with a carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; The process provides a method for determining whether a second bio-reagent has a lower oxygen reactivity than the first bio-reagent by thermogravimetric analysis using a temperature ramp of 40° C. / min from 25° C. to 950° C. in the presence of pure oxygen.

[0232] In some embodiments, the second bioreagent requires at least 5% or at least 10% more time to reach 99% oxidation compared to the first bioreagent, according to a TGA graph of weight loss versus time from thermogravimetric analysis.

[0233] In some embodiments, the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon followed by a second carbon oxidation regime associated with the oxidation of fixed carbon.

[0234] In some embodiments, the volatile carbon oxidation time is defined as from the start of the first carbon oxidation regime to the start of the second carbon oxidation regime. During the volatile carbon oxidation time, the first biological reagent may have a mass loss of at least 25% or at least 50% compared to the second biological reagent.

[0235] In some embodiments, thermogravimetric analysis indicates that the first biological reagent has a mass loss rate in the first carbon oxidation regime that is at least 25% or at least 50% higher than the mass loss rate of the second biological reagent in the first carbon oxidation regime.

[0236] In some embodiments, thermogravimetric analysis indicates that the first biological reagent has an average mass loss rate that is at least 10% higher during the first carbon oxidation regime compared to the second carbon oxidation regime.

[0237] In some embodiments, the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the second biological reagent at a temperature of at least about 500°C, and the thermogravimetric analysis exhibits a first derivative curve peak in the first carbon oxidation regime for the first biological reagent at a temperature between 200°C and 500°C.

[0238] Biomass-containing feedstocks 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 sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit husks, fruit stem ... The waste stream may be selected from peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0239] "Carbon-containing condensed matter material" refers to a material that includes at least one phase of condensed matter that includes carbon. As used herein, the condensed matter phase is solid, liquid, or a combination thereof (not a pure vapor or plasma state of matter) at a temperature of 25° C. and a pressure of 1 bar. In various embodiments, the carbon-containing condensed matter material is in solid or liquid form at temperatures of about 25° C. or less, about 50° C. or less, about 75° C. or less, about 100° C. or less, about 125° C. or less, about 150° C. or less, about 175° C. or less, about 200° C. or less, about 225° C. or less, about 250° C. or less, about 275° C. or less, or about 300° C. or less, all of which temperatures refer to the form of the condensed matter material at atmospheric pressure of 1 bar.

[0240] By way of example, toluene is a carbon-containing condensable material that is in liquid form at temperatures between about -95°C and 111°C at 1 bar pressure, and vapor above 111°C. Thus, toluene may be a carbon-containing condensable material in the disclosed process. As a comparative example, methane has a boiling point of -162°C at 1 bar pressure, and is therefore not a preferred carbon-containing condensable material in the disclosed process.

[0241] Any carbon-containing condensable material will generally vaporize at some point, i.e., at a high enough temperature (and under the influence of pressure). The fact that a carbon-containing material may be present in the process in a vapor phase does not disqualify its use as a carbon-containing condensable material, as long as the material is ultimately condensed to a liquid (or solid). In some embodiments, the carbon-containing material condenses to a liquid (or solid) during mixing with the first biological reagent in step (c).

[0242] The carbon-containing condensable material may be in solid or liquid form at temperatures around the temperature of the contacting unit used to contact the first biological reagent with the carbon-containing condensable material, typically either a mixing unit or a pelleting unit. For example, if the contacting unit is operated at about 100° C., the carbon-containing condensable material should be in solid or liquid phase at 100° C., not just vapor phase. Essentially, the boiling point of the carbon-containing condensable material should be the same as or higher than the temperature of the contacting unit (boiling point here is calculated at the pressure of the contacting unit). If the contacting unit is operated at very low temperatures (e.g., cryogenic), typically vapor carbon-containing material can be used where the carbon-containing material is actually in the condensed matter phase.

[0243] The carbon-containing condensable matter material may be a liquid, a solid, a slurry of liquid and solid, a gas-liquid material (e.g., having gas bubbles dissolved in a liquid or having vapor entrained with liquid droplets), a gas-liquid-solid material, a gel, a plastic, a rubbery material, a sticky material, or a sticky material. The phase and properties (e.g., rheological properties) of the carbon-containing condensable matter material will depend to some extent on the type of separation unit.

[0244] In some embodiments, the carbon-containing condensable material is a pyrolytic precipitate derived from pyrolytic vapors. In other embodiments, the carbon-containing condensable material is a pyrolytic precipitate provided externally from a different process. In some embodiments, the carbon-containing condensable material is not a pyrolytic precipitate, but rather some other liquid or solid material.

[0245] In some embodiments, the carbon-containing condensable matter material comprises an aromatic species. For example, the carbon-containing condensable matter material can be an off-spec or waste aromatic stream (e.g., a benzene / toluene / xylene stream).

[0246] In some embodiments, the carbon-containing condensed matter material is or includes lignin. The lignin can be a native lignin having a high molecular weight, such as a lignin polymer obtained from lignocellulosic biomass. Alternatively, the lignin can be a depolymerized lignin having a reduced molecular weight compared to the native lignin.

[0247] In some embodiments, the carbon-containing condensed matter material is or includes one or more sugars or one or more sugar degradation products. Sugars can be, for example, C 5 Sugars (e.g., xylose), C 6 Sugar (e.g., glucose), C 12 The sugar degradation products may be, for example, furfural, hydroxymethylfurfural, levulinic acid, or formic acid. The carbon-containing condensed matter material may be or include a biomass-derived material other than sugar or lignin, such as, for example, acetic acid, protein, or decomposed protein.

[0248] In certain embodiments, the carbon-containing condensate material is or includes non-biological materials such as coal tar, coal liquefaction products, petroleum tar, or crude oil, however, such non-biological materials reduce the renewable carbon content of the final bio-carbon pellets.

[0249] In some embodiments, the carbon-containing condensable matter material is or includes one or more polymers or one or more polymer decomposition products. For example, the carbon-containing condensable matter material can be polyethylene, polyethylene terephthalate, rubber (e.g., natural or synthetic rubber in recycled tires), or heat-treated forms thereof. In the case of recycled tires, carbon from polyisoprene or styrene butadiene rubber, as well as carbon from carbon black, can be incorporated into the bio-carbon pellets.

[0250] In some embodiments, the carbon-containing condensable matter material comprises a liquid product produced by chemical reaction of a syngas, the syngas optionally being derived from pyrolysis steam or pyrolysis exhaust gas.

[0251] Carbon-containing condensed matter materials include 14 C / 12 The carbon-containing condensed matter material may contain at least 50% renewable carbon as determined from C isotope ratio measurements. 14 C / 12 It may contain at least 90%, at least 95%, at least 99%, or about 100% renewable carbon as determined from C isotope ratio measurements.

[0252] The intermediate material may include a carbon-containing condensed matter material adsorbed onto a surface of the first biological reagent. Alternatively or additionally, the intermediate material may include a carbon-containing condensed matter material absorbed within a bulk phase of the first biological reagent.

[0253] In some processes utilizing carbon-containing condensed matter materials, steps (c) and (d) are combined.

[0254] A binder can be introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, 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 any combination of the foregoing.

[0255] In other processes, no external binder is introduced to the intermediate material during pelletization. Bonding can still occur. For example, the carbon-containing aggregate material itself can function as the pellet binder.

[0256] In some embodiments where drying is desired, step (e) is performed.

[0257] In some processes, steps (d) and (e) are combined. In some processes, steps (e) and (f) are combined. In one particular process, steps (d), (e), and (f) are all combined.

[0258] The first bio-reagent can be comminuted using a mechanical processing device selected from 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. Alternatively or additionally, the intermediate material can be comminuted using a mechanical processing device selected from 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.

[0259] In some processes, step (d) utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0260] The first pyrolysis reactor can be different from the second pyrolysis reactor. Alternatively, the first pyrolysis reactor and the second pyrolysis reactor can be the same unit, and steps (a) and (f) are carried out at different times.

[0261] In some processes, step (a) is carried out at a first pyrolysis temperature selected from about 250° C. to about 1250° C., e.g., from about 300° C. to about 700° C. In some processes, step (f) is carried out at a second pyrolysis temperature selected from about 250° C. to about 1250° C., e.g., from about 400° C. to about 1000° C.

[0262] In some processes, step (a) is carried out for a first pyrolysis time selected from about 10 seconds to about 24 hours, e.g., from about 1 minute to about 4 hours. In some processes, step (f) is carried out for a second pyrolysis time selected from about 10 seconds to about 24 hours, e.g., from about 1 minute to about 4 hours.

[0263] During step (f) or potentially prior to this step, the first biological reagent may act as a catalyst or reaction matrix for the fixed carbon formation reaction of the carbon-containing condensed matter material.

[0264] In some embodiments, the pyrolysis vapors are at least partially oxidized to generate heat, which is optionally used in the process. In these or other embodiments, the pyrolysis exhaust gas is at least partially oxidized to generate heat, which is optionally used in the process.

[0265] The biocarbon pellets may contain at least 60%, at least 70%, at least 80%, at least 85%, or at least 90% fixed carbon by weight. The biocarbon pellets may contain less than 10%, less than 5%, or less than 1% ash by weight. The biocarbon pellets may contain less than 20% or less than 10% total volatile matter by weight.

[0266] In some processes, at least 25% by weight of the carbon in the carbon-containing condensable matter material is converted to fixed carbon in the bio-carbon pellets. In certain processes, at least 50% by weight of the carbon in the carbon-containing condensable matter material is converted to fixed carbon in the bio-carbon pellets. In certain processes, at least 75% by weight of the carbon in the carbon-containing condensable matter material is converted to fixed carbon in the bio-carbon pellets.

[0267] In some embodiments, between about 1% and about 50% by weight of the fixed carbon in the biocarbon pellets is derived from the carbon-containing condensable matter material. In certain embodiments, between about 10% and about 40% by weight of the fixed carbon in the biocarbon pellets is derived from the carbon-containing condensable matter material.

[0268] In step (c), less than all of the first biological reagent is contacted with the carbon-containing condensed matter material.In step (c), less than all of the carbon-containing condensed matter material is contacted with the first biological reagent.

[0269] The total carbon in biocarbon pellets is 14 C / 12 The total carbon in the biocarbon pellets is at least 50% renewable, as determined by C isotope ratio measurements.14 C / 12 It may be at least 90%, at least 95%, or completely (about 100%) renewable, as determined from C isotope ratio measurements.

[0270] The biocarbon pellets can be characterized by a Hardgrove Crushability Index of at least 30, or at least 50, for example.

[0271] The biocarbon pellets have a dry weight of at least about 25, 30, 35, 40, or 45 lb / ft 3 It can be characterized by its bulk density.

[0272] In some embodiments, the biocarbon pellets have an average pellet size selected from about 1 mm to about 10 cm, calculated as the effective diameter of the biocarbon pellets.

[0273] The biocarbon pellets may have an effective pellet diameter within 10% or within 5% of the effective pellet diameter of the intermediate pellets. In other embodiments, the biocarbon pellets have an effective pellet diameter that is greater than 110% or less than 90% of the effective pellet diameter of the intermediate pellets.

[0274] In some embodiments, the biocarbon pellets have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, cylinder-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

[0275] In some embodiments, the biocarbon pellets are at least about 100 lbs. f / in 2 , for example at least about 150 lbs. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0276] The bio-carbon pellets can be hydrophobic or partially hydrophobic. In some embodiments, the bio-carbon pellets are characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0277] In some embodiments, the biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to the 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”.

[0278] In some embodiments, the process further comprises introducing an additive into the process. The additive can be selected from an acid, a base, or a salt thereof. The additive can be selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. For example, the additive can be selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof.

[0279] The additives can be selected to adjust the filtrate pH of the biocarbon pellets, which is measured by combining 20 grams of the biocarbon pellets, or a powder form thereof, on a dry basis, with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter.

[0280] An additive can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent, and the filtrate pH is measured by combining 20 grams of the second bioreagent on a dry basis with 100 milliliters of distilled water to form a mixture, filtering the mixture through filter paper, and measuring the pH of the filtrate with a pH meter. An additive can be added to the second bioreagent to decrease the filtrate pH of the second bioreagent. Alternatively, an additive can be added to the second bioreagent to increase the filtrate pH of the second bioreagent. If the additive is added for a reason other than pH adjustment, the additive added to the second bioreagent may not result in a change in the filtrate pH of the second bioreagent.

[0281] In some embodiments, the oxygen reactivity of the second biological reagent is reduced by adding an additive to the second biological reagent.

[0282] Biocarbon pellets are characterized as non-self-heating when subjected to the self-heating test in accordance with the 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”.

[0283] In some embodiments, the process provides a total carbon yield of at least 50%, calculated as the carbon contained in the bio-carbon pellets as a percentage of the sum of the carbon in the biomass-containing feedstock and the carbon in the carbon-containing condensable matter material. The total carbon yield can be at least 60%, at least 70%, or at least 80%.

[0284] The present technology also provides bio-carbon pellets produced by any of the disclosed processes.

[0285] Some variations provide biocarbon pellets comprising fixed carbon having a fixed carbon content of at least 60% by weight, wherein the biocarbon pellets are characterized by a thermogravimetric analysis measuring the oxygen reactivity of the biocarbon pellets, the thermogravimetric analysis being performed in the presence of pure oxygen from 25° C. to 950° C. using a temperature ramp of 40° C. / min, and wherein the biocarbon pellets require at least 240 minutes to reach 99% carbon oxidation according to a TGA graph of weight loss versus time from the thermogravimetric analysis.

[0286] In some embodiments of the bio-carbon pellets, according to TGA graphs of weight loss versus time from thermogravimetric analysis performed in the presence of pure oxygen from 25° C. to 950° C. using a temperature ramp of 40° C. / min, the bio-carbon pellets require at least 250 minutes, 260 minutes, 270 minutes, 280 minutes, 290 minutes, 300 minutes, 310 minutes, or 320 minutes to reach 99% carbon oxidation.

[0287] In some embodiments, thermogravimetric analysis is performed on an anthracite control sample, which requires a control time to reach 99% carbon oxidation, and the time required for the biocarbon pellets to reach 99% carbon oxidation is about 85% to about 100% of the control time. In various embodiments, the time required for the biocarbon pellets to reach 99% carbon oxidation is about 90% to about 100%, e.g., about 95% to about 98%, of the control time.

[0288] In some embodiments, the biocarbon pellets contain volatile carbon and the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon followed by a second carbon oxidation regime associated with the oxidation of fixed carbon. In certain embodiments, the thermogravimetric analysis shows a first derivative curve peak within the first carbon oxidation regime for the biocarbon pellets at a temperature of at least about 500° C.

[0289] In some embodiments, the biocarbon pellets contain at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, at least 85% by weight fixed carbon, or at least 90% by weight fixed carbon.

[0290] In some embodiments, the biocarbon pellets include up to 10% ash by weight, up to 5% ash by weight, or up to 1% ash by weight.

[0291] In some embodiments, the biocarbon pellets contain up to 20% total volatile matter by weight, or up to 10% total volatile matter by weight.

[0292] In some embodiments, the biocarbon pellets include a binder, which can be selected from starch, thermoplastic 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, 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 any combination of the foregoing.

[0293] In some embodiments, the bio-carbon pellets do not include a binder. In some embodiments, the bio-carbon pellets do not include a binder other than the pyrolytic precipitate.

[0294] In some embodiments, the biocarbon pellets include an additive. The additive can be selected from an acid, a base, or a salt thereof. The additive can be selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. In various embodiments, the additive is selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof.

[0295] In some embodiments, the total carbon in the biocarbon pellets is 14 C / 12 At least 50%, at least 90%, or completely renewable, as determined from C isotope ratio measurements.

[0296] In some embodiments, the biocarbon pellets are characterized by a Hardgrove Crushability Index of at least 30.

[0297] In some embodiments, the biocarbon pellets have a density of at least about 20 lb / ft on a dry basis. 3 It is characterized by its bulk density.

[0298] In some embodiments, the biocarbon pellets have an average pellet size selected from about 1 mm to about 10 cm, calculated as the effective diameter of the biocarbon pellets.

[0299] In some embodiments, the biocarbon pellets have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, cylinder-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

[0300] In some embodiments, the biocarbon pellets are at least about 100 lbs. f / in 2 Or at least about 150 lbs. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0301] In some embodiments, the biocarbon pellets are characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0302] In some embodiments, the biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to the 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”.

[0303] Biocarbon pellets, (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, the pyrolysis precipitate being in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolytic precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolytic precipitate; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; Thermogravimetric analysis shows that the second bio-reagent has a lower oxygen reactivity than the first bio-reagent, and the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

[0304] Biocarbon pellets, (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensable matter material, the carbon-containing condensable matter material being a liquid, a solid, or a slurry; (c) contacting a first biological reagent with a carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as a bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; A second bio-reagent can be produced by the process, which has a lower oxygen reactivity than the first bio-reagent by thermogravimetric analysis using a temperature ramp of 40 °C / min from 25 °C to 950 °C in the presence of pure oxygen.

[0305] Some variations are premised on the recognition that while bio-carbon pellets are beneficial in a wide range of embodiments, other embodiments exist in which the final bio-carbon composition is not in pellet form, but rather in another form such as a powder or film.

[0306] Some variations provide a biocarbon composition comprising fixed carbon having a fixed carbon content of at least 60% by weight, the biocarbon composition being characterized by thermogravimetric analysis measuring the oxygen reactivity of the biocarbon pellets, the thermogravimetric analysis being performed in the presence of pure oxygen from 25° C. to 950° C. using a temperature ramp of 40° C. / min, and the biocarbon pellets requiring at least 240 minutes to reach 99% carbon oxidation according to a TGA graph of weight loss versus time from the thermogravimetric analysis.

[0307] The biocarbon composition is (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, the pyrolysis precipitate being in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolytic precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolytic precipitate; (d) separately from step (a), pyrolyzing the intermediate material in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (e) recovering the second bio-reagent as a bio-carbon composition; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; Thermogravimetric analysis shows that the second bio-reagent has a lower oxygen reactivity than the first bio-reagent, and the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

[0308] The biocarbon composition is (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensable matter material, the carbon-containing condensable matter material being a liquid, a solid, or a slurry; (c) contacting a first biological reagent with a carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; (d) separately from step (a), pyrolyzing the intermediate material in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (e) recovering the second bio-reagent as a bio-carbon composition; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; A second bio-reagent can be produced by the process, which has a lower oxygen reactivity than the first bio-reagent by thermogravimetric analysis using a temperature ramp of 40 °C / min from 25 °C to 950 °C in the presence of pure oxygen.

[0309] Certain embodiments are directed to a process for producing a bio-carbon composition, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor to produce a first bio-reagent and a first pyrolysis vapor; (b) directing at least a portion of the first pyrolysis vapor into a condensation system to produce a condenser liquid and a condenser vapor; (c) contacting at least a portion of the first biological reagent with a condenser liquid, thereby producing an intermediate material comprising the first biological reagent and the condenser liquid; (d) optionally pelletizing the intermediate material; (e) optionally, separately from step (a), further pyrolyzing the intermediate material in a second pyrolysis reactor to produce a second bio-reagent and a second pyrolysis vapor; (f) optionally drying the second biological reagent; (g) recovering the second bio-reagent as a bio-carbon composition.

[0310] In some embodiments using step (d), steps (c) and (d) are integrated. In some embodiments, step (d) is performed in a pelletizing unit and step (c) is also performed in the pelletizing unit. In other embodiments using step (d), step (d) follows step (c).

[0311] When step (d) is performed, at least a portion of the intermediate material is pelletized. Optionally, the first biological reagent is pelletized before or after contacting it with the condenser liquid.

[0312] In some embodiments where the intermediate material is pelletized, a binder is introduced into the intermediate material. The binder may be selected from starch, thermoplastic 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, 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 any combination of the foregoing.

[0313] In other embodiments where the intermediate material is pelletized, no external binder is introduced to the intermediate material during pelletization, in these cases the condenser liquid can act as a binder for the pellets.

[0314] In some embodiments, the carbon recapture unit is located upstream of the second pyrolysis reactor. In other embodiments, the carbon recapture unit is the first stage of the second pyrolysis reactor. The carbon recapture unit can be configured, for example, to form a coating of condenser liquid on the pellets.

[0315] In some processes using step (e), steps (c) and (e) are combined.

[0316] The condensation system may include multiple condenser stages. In some embodiments, the condenser liquid is the condensation product of a first stage of a condensation system having multiple condenser stages.

[0317] In some embodiments, at least a portion of the second pyrolysis vapor is also conveyed to a condensation system.

[0318] The intermediate material may comprise a condenser liquid adsorbed onto a surface of the first bio-reagent. Alternatively or additionally, the intermediate material may comprise a condenser liquid absorbed within a bulk phase of the first bio-reagent.

[0319] In some embodiments involving step (e), the first pyrolysis reactor is different from the second pyrolysis reactor, while in other embodiments the first pyrolysis reactor and the second pyrolysis reactor are the same unit and steps (a) and (e) are carried out at different times.

[0320] The first biological reagent can act as a catalyst or reaction matrix for the fixed carbon forming reaction of the condenser liquid.

[0321] In some embodiments, at least 25% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the second bio-reagent, and in various embodiments, about, at least about, or up to about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% by weight (including all intervening ranges) of the total carbon contained in the condenser liquid is converted to fixed carbon in the second bio-reagent.

[0322] In some embodiments, about 10% to about 80% by weight of the fixed carbon in the second bio-reagent is derived from the first condenser liquid. In certain embodiments, about 20% to about 60% by weight of the fixed carbon in the second bio-reagent is derived from the first condenser liquid. In various embodiments, about, at least about, or up to about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 75%, or 80% by weight (including all intervening ranges) of the fixed carbon in the second bio-reagent is derived from the first bio-reagent.

[0323] In some processes, step (a) is carried out at a first pyrolysis temperature selected from about 250°C to about 1250°C, e.g., about 300°C to about 700°C. In these or other processes, step (e) is carried out at a second pyrolysis temperature selected from about 300°C to about 1350°C, e.g., about 350°C to about 800°C. The first pyrolysis temperature can be less than, equal to, or greater than the second pyrolysis temperature. In some embodiments, the second pyrolysis temperature is at least about the first pyrolysis temperature to allow for effective pyrolysis of compounds that did not form fixed carbon in the first pyrolysis reactor. In such embodiments, the second pyrolysis temperature can be, for example, at least about 5°C, 10°C, 25°C, 50°C, 100°C, 150°C, or 200°C of the first pyrolysis temperature.

[0324] In some processes, step (a) is carried out for a first pyrolysis time selected from about 10 seconds to about 24 hours, e.g., about 10 minutes to about 4 hours. In these or other processes, step (e) is carried out for a second pyrolysis time selected from about 10 seconds to about 24 hours, e.g., about 15 minutes to about 5 hours. The first pyrolysis time can be less than, equal to, or greater than the second pyrolysis time. In some embodiments, the second pyrolysis time is longer than the first pyrolysis time to allow for effective pyrolysis of compounds that did not form fixed carbon in the first pyrolysis reactor. In such embodiments, the second pyrolysis time can be, for example, about 5, 10, 15, 20, 30, 40, 50, 60, 90, or 120 minutes longer than the first pyrolysis time.

[0325] In some embodiments, some or all of the condenser vapors are at least partially oxidized to generate heat, which is optionally used in the process. In these or other embodiments, some or all of the second pyrolysis vapors are at least partially oxidized (with or without the condenser vapors) to generate heat, which is optionally used in the process.

[0326] In certain embodiments, pyrolysis exhaust gas or condenser vapors are at least partially oxidized to produce reduced gases including hydrogen or carbon monoxide. Such partial oxidation still produces useful heat, but also produces reduced gases that can be converted to other chemicals (e.g., methanol or Fischer-Tropsch hydrocarbons) if desired.

[0327] In some embodiments, the first bio-reagent is ground using a mechanical processing device selected from 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 these or other embodiments, the intermediate material can be ground using a mechanical processing device selected from 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.

[0328] In embodiments using step (d), step (d) may utilize a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0329] In some processes, carbon-containing fines are produced in a second pyrolysis reactor. Optionally, the carbon-containing fines are recycled to step (c). If step (d) is performed, the carbon-containing fines produced in the second pyrolysis reactor can be recycled to step (d) instead of or in addition to being recycled to step (c). Alternatively or additionally, the carbon-containing fines can be combusted to generate energy or used for other purposes.

[0330] In some embodiments, the bio-carbon composition is in the form of a powder. In some embodiments, the bio-carbon composition is in the form of a pellet. In some embodiments, the bio-carbon composition is in the form of a film or coating.

[0331] The biocarbon composition may comprise at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 75% by weight fixed carbon, at least 80% by weight fixed carbon, at least 85% by weight fixed carbon, or at least 90% by weight fixed carbon. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 55, 60, 65, 70, 75, 80, 85, or 90% by weight fixed carbon.

[0332] The biocarbon composition may comprise at least 55% by weight total carbon, at least 60% by weight total carbon, at least 70% by weight total carbon, at least 75% by weight total carbon, at least 80% by weight total carbon, at least 85% by weight total carbon, at least 90% by weight total carbon, or at least 95% by weight total carbon. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 60, 65, 70, 75, 80, 85, 90, or 95% by weight total carbon, including all intervening ranges.

[0333] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, less than 2% ash by weight, or less than 1% ash by weight. In various embodiments, the biocarbon composition comprises about or up to about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.2, or 0.1% ash by weight, including all intervening ranges.

[0334] The ash content of the biocarbon composition is beneficial (i.e., lower) when a condenser liquid having a relatively low ash is incorporated into the material in the second pyrolysis reactor. In some embodiments, the first condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or essentially no ash. In various embodiments, the first condenser liquid contains about or up to about 5, 4, 3, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02, or 0.01% ash by weight, including all intervening ranges.

[0335] The total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition may be at least 50% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition may be at least 50% renewable as determined from C isotope ratio measurements. 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0336] In some processes, the second bio-reagent is pelleted during step (f), during step (g), or after step (g), and thus the final bio-carbon composition may be in the form of a pellet.

[0337] In some processes, the biocarbon composition is characterized by a Hardgrove Crushability Index of at least 30 or at least 50. In various embodiments, the biocarbon composition is characterized by a Hardgrove Crushability 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.

[0338] In some processes, the biocarbon composition has a dry content of at least about 35 lb / ft 3 or at least about 45 lb / ft on a dry basis 3 In various embodiments, the biocarbon 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 It is.

[0339] In some processes, the bio-carbon composition is characterized as a hydrophobic bio-carbon or a partially hydrophobic bio-carbon.

[0340] In some processes, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with the 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”.

[0341] In some processes, the biocarbon composition is characterized by a lack of odor generation at 25° C. for 24 hours. In some embodiments, the biocarbon composition is characterized by a lack of odor generation at 50° C. for 24 hours. In some embodiments, the biocarbon composition is characterized by a lack of odor generation at 25° C. for 48 hours. Odor generation in this context refers to organic molecules that have evaporated from the biocarbon composition, such organic molecules being typically detectable by humans. Examples include formaldehyde, acetic acid, ethanol, methanol, or mercaptans.

[0342] Some variations provide methods of making high fixed carbon materials that include pyrolyzing biomass to produce intermediate solids and pyrolysis vapors, condensing a portion of the pyrolysis vapors to produce pyrolysis liquids, introducing the pyrolysis liquids to the intermediate solids to produce a solid-liquid mixture, optionally pelletizing to produce pellets comprising the solid-liquid mixture, and optionally further pyrolyzing the solid-liquid mixture to produce a high yield of high fixed carbon materials.

[0343] In some methods, the method includes pelletizing to produce pellets comprising the solid-liquid mixture. In some embodiments, the pelletizing does not utilize a binder other than the pyrolysis liquid. In other embodiments, the pelletizing utilizes a binder other than the pyrolysis liquid. Further pyrolysis of the solid-liquid mixture can be enhanced by pelletizing, such as when carbon contained in the solid-liquid mixture acts as a catalyst or reactive matrix for the formation of additional fixed carbon.

[0344] In some methods, at least 60% by weight of the total carbon contained in the biomass forms fixed carbon in the high fixed carbon material, in certain methods, at least 70%, at least 80%, at least 90%, or at least 95% by weight of the total carbon contained in the biomass forms fixed carbon in the high fixed carbon material.

[0345] Some variations provide high fix carbon materials produced by a process that includes a method of making a high fix carbon material that includes pyrolyzing biomass to produce intermediate solids and pyrolysis vapors, condensing a portion of the pyrolysis vapors to produce pyrolysis liquids, introducing the pyrolysis liquids to the intermediate solids to produce a solid-liquid mixture, optionally pelletizing to produce pellets comprising the solid-liquid mixture, and optionally further pyrolyzing the solid-liquid mixture to produce a high yield of the high fix carbon material.

[0346] Another variation is a process for producing a bio-carbon composition, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor to produce a first pyrolysis solid and a first pyrolysis vapor; (b) directing at least a portion of the first pyrolysis vapor into a condensation system to produce a condenser liquid and a condenser vapor; (c) separately from step (a), pyrolyzing the condenser liquid in a second pyrolysis reactor to produce a second pyrolysis solid and a second pyrolysis vapor; (d) blending the first pyrolysis solid with the second pyrolysis solid, thereby producing a bio-reagent; (e) optionally pelleting the biological reagent; (f) optionally drying or heat treating the biological reagent; (g) recovering the bio-reagent as a bio-carbon composition.

[0347] In some processes, biomass-containing feedstocks 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 sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit husks. , 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.

[0348] In some processes, step (e) is performed such that the biological reagents are pelleted. Step (e) may be integrated with step (d), step (f), or both of these steps.

[0349] In some embodiments using step (e), a binder is introduced into the bioreagent. The binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, 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 any combination of the foregoing.

[0350] In some embodiments using step (e), no external binder is introduced to the bioreagent during pelleting.

[0351] In some processes, the condensation system includes multiple condenser stages. The condenser liquid may be a condensation product of a first of the multiple condenser stages.

[0352] In some embodiments, at least a portion of the second pyrolysis vapor is also conveyed to the same condensation system that condenses the first pyrolysis vapor, or to a separate condensation system.

[0353] The first pyrolysis reactor is typically different from the second pyrolysis reactor, i.e., they are physically different units. In some embodiments, the first pyrolysis reactor and the second pyrolysis reactor are the same unit and steps (a) and (c) are carried out at different times.

[0354] In some processes, at least 25% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the second pyrolysis solids. In certain processes, at least 50% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the second pyrolysis solids. In various embodiments, about, at least about, or up to about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by weight (including all intervening ranges) of the total carbon contained in the condenser liquid is converted to fixed carbon in the second pyrolysis solids.

[0355] In some processes incorporating blending of a first pyrolysis solid and a second pyrolysis solid, the second pyrolysis solid forms at least 5% by weight of the bioreagent on an absolute basis, in certain processes the second pyrolysis solid forms at least 10% or at least 20% by weight of the bioreagent on an absolute basis.

[0356] In some processes, about 10% to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In certain processes, about 20% to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In various embodiments, about, at least about, or up to about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by weight (including all intervening ranges) of the fixed carbon in the bioreagent is derived from the condenser liquid.

[0357] Step (a) can be carried out at a first pyrolysis temperature selected from about 250° C. to about 1250° C. Optionally, the first pyrolysis temperature is selected from about 300° C. to about 700° C. Step (c) can be independently carried out at a second pyrolysis temperature selected from about 250° C. to about 1250° C. Optionally, the second pyrolysis temperature is selected from about 300° C. to about 700° C. The second pyrolysis temperature can be lower than the first pyrolysis temperature, or can be at least about the first pyrolysis temperature, or they can potentially be the same.

[0358] Step (a) can be carried out for a first pyrolysis time selected from about 10 seconds to about 24 hours. Step (c) can be independently carried out for a second pyrolysis time selected from about 10 seconds to about 24 hours. The second pyrolysis time can be shorter or longer than the first pyrolysis time, or they can potentially be the same.

[0359] In some processes, the condenser vapors are at least partially oxidized to generate heat that is optionally used in the process. In these or other processes, the second pyrolysis vapors are at least partially oxidized to generate heat that is optionally used in the process.

[0360] The bioreagent can be pulverized using mechanical processing equipment selected from, 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 combinations thereof.

[0361] If step (e) is performed, it can utilize a pelletizing device selected from, for example, an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquette, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0362] The biocarbon composition can be in the form of a powder, pellets, or another geometric shape.

[0363] The biocarbon composition may comprise at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, or at least 90% by weight fixed carbon. Other fixed carbon contents are discussed above and apply to these process embodiments (as well as other processes disclosed herein).

[0364] The biocarbon composition may contain less than 10% by weight ash, less than 5% by weight ash, less than 2% by weight ash, or less than 1% by weight ash. Other ash contents are discussed above and apply to these process embodiments (as well as other processes disclosed herein).

[0365] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash. The low ash content of the condenser liquid reduces the final ash content of the biocarbon composition. Other condenser liquid ash contents are described above and apply to these process embodiments (as well as other processes disclosed herein).

[0366] In some processes, the total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 50% renewable, as determined by C isotope ratio measurements. 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0367] Some variations are processes for producing a bio-carbon composition, the process comprising: (a) pyrolyzing a biomass-containing feedstock in a pyrolysis reactor to produce a bio-reagent and a pyrolysis vapor; (b) directing at least a portion of the pyrolysis vapor into a condensation system to produce a condenser liquid and a condenser vapor; (c) contacting the starting biomass feedstock with at least a portion of the condenser liquid, thereby producing a biomass-containing feedstock comprising the starting biomass feedstock and at least a portion of the condenser liquid; and (d) optionally pelleting the biological reagent; (e) optionally drying the biological reagent; (f) recovering the bio-reagent as a bio-carbon composition.

[0368] The starting biomass feedstocks are 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 shells, fruit stems, fruit husks, fruit stem ... The waste stream may be selected from peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0369] In some embodiments, step (c) utilizes spraying at least a portion of the condenser liquid onto the starting biomass feedstock. The biomass-containing feedstock may include the condenser liquid adsorbed onto a surface of the starting biomass feedstock. Alternatively or additionally, the biomass-containing feedstock includes the condenser liquid absorbed within a bulk phase of the starting biomass feedstock.

[0370] When performing step (d), a binder can be introduced into the bioreagent. The binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, 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 any combination of the foregoing.

[0371] If step (d) is performed, alternatively, an external binder is introduced into the bioreagent during pelleting.

[0372] In some processes, steps (c) and (d) are integrated and both occur within the pelletizing unit. In some processes, steps (d) and (e) are both performed and integrated.

[0373] The condensation system may include multiple condenser stages. The condenser liquid may be the condensation product of an individual stage (e.g., the first stage) of the multiple condenser stages.

[0374] In some processes, at least 25% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the bio-reagent. In certain processes, at least 50% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the bio-reagent.

[0375] In some processes, about 10% to about 80% by weight of the fixed carbon in the bioreagent comes from the condenser liquid. In certain processes, about 20% to about 60% by weight of the fixed carbon in the bioreagent comes from the condenser liquid.

[0376] Step (a) can be carried out at a pyrolysis temperature selected from about 250° C. to about 1250° C., for example, from about 300° C. to about 700° C. Step (a) can be carried out for a first pyrolysis time selected from about 10 seconds to about 24 hours.

[0377] In some processes, some or all of the condenser vapor is at least partially oxidized to produce heat, which is optionally used in the process.

[0378] The bioreagent can be pulverized utilizing mechanical processing equipment selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or combinations thereof.

[0379] In processes using step (d), this step can utilize a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0380] The final biocarbon composition may be in the form of, for example, a powder or pellets.

[0381] In some embodiments, the biocarbon composition comprises at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, or at least 90% by weight fixed carbon.

[0382] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, less than 2% ash by weight, or less than 1% ash by weight.

[0383] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0384] The total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 50% renewable, as determined from measurements of the C isotope ratio. 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0385] The low and high set carbon materials may form separate phases that are insoluble in one another at equilibrium and relatively low temperatures. In some embodiments, the low and high set carbon materials may have high equilibrium (thermodynamic) solubility in one another, but nevertheless remain kinetically frozen in the composition such that separate materials are observable. The separate materials may be observable by measuring composition, density, particle size, reactivity, or other physical or chemical properties. During the end use of the biocarbon composition, the distinction of the materials may be lost (e.g., at high temperatures or during carbon oxidation).

[0386] In one technique to demonstrate that a given biocarbon composition contains both low and distinct high fixed carbon materials, a thermogravimetric analysis (TGA) of the oxidation (combustion) of a biocarbon composition test sample is performed. In some embodiments, the resulting TGA heat curve has two peaks characteristic of distinct mass loss events that correlate with the low and high fixed carbon materials. This can be compared to a control sample of a biocarbon composition that contains a single material with a known uniform fixed carbon concentration, showing a TGA heat curve with a single peak characteristic of one mass loss event of the material. In similar embodiments, the TGA heat curve of the test sample has three or more peaks, while the TGA heat curve of the control sample has at least one less peak than the test sample.

[0387] Another technique to demonstrate that a given biocarbon composition contains both low and distinct high set carbon materials is particle size analysis. This is a viable approach when the particle sizes associated with the low and high set carbon materials are different, or when the particle size distributions associated with the low and high set carbon materials are different. In some embodiments, the high set carbon materials tend to have smaller particles compared to the low set carbon materials. In some embodiments, a bimodal particle size distribution results from the presence of both low and high set carbon materials, as opposed to a control sample having a unimodal particle size distribution characteristic of a homogenous material. In similar embodiments, a test sample may have a particle size distribution with at least one more mode than the particle size distribution of the control sample. For example, it is possible that the low and high set carbon materials each have a bimodal particle size distribution (peaks centered at different sizes) and that the control sample has a bimodal particle size distribution depending on how the control sample was produced.

[0388] Particle size can be measured by a variety of techniques, including, for example, dynamic light scattering, laser diffraction, image analysis, or sieve separation. Dynamic light scattering is a non-invasive, well-established technique for measuring particle size and size distribution, typically in the submicron range, with the latest techniques measuring down to one nanometer. Laser diffraction is a widely used particle sizing technique for materials with sizes ranging 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 conventional technique for separating particles by size.

[0389] Alternatively or additionally, imaging techniques may be utilized to demonstrate that a given biocarbon composition contains both low and distinct high fixed carbon materials. Imaging techniques include, but are not limited to, optical microscopy, dark field microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray tomography (XRT). For example, imaging techniques may be used to demonstrate distinct materials in a blend rather than a homogenous material. Or, imaging techniques may be used to select subsamples for further analysis. Further analysis may be compositional analysis to show three-dimensional variations in fixed carbon content. Further analysis may be property analysis to show three-dimensional variations in chemical or physical properties such as density, particle size, or reactivity.

[0390] Spectroscopic techniques may alternatively or additionally be utilized to demonstrate that a given biocarbon composition contains both low-fixation carbon materials and distinct high-fixation carbon materials, including, but not limited to, energy dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.

[0391] In some embodiments, the biocarbon composition comprises about 10% to about 90% by weight of the low fixation carbon material. In some embodiments, the biocarbon composition comprises about 10% to about 90% by weight of the high fixation carbon material. The weight ratio of the low fixation carbon material to the high fixation carbon material can be selected from about 0.1 to about 10, e.g., from about 0.2 to about 5, from about 0.5 to about 2, or from about 0.8 to about 1.2.

[0392] In some embodiments, the first fixed carbon concentration is, for example, from about 20% to about 40% by weight, or from about 25% to about 50% by weight, or from about 30% to about 55% by weight.

[0393] In some embodiments, the second fixed carbon concentration is, for example, from about 80% to about 100% by weight, or from about 70% to about 95% by weight, or from about 60% to about 90% by weight.

[0394] In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is from about 30% to about 90% by weight, such as from about 40% to about 80% by weight.

[0395] The biocarbon composition may comprise a total fixed carbon concentration of about 25% to about 95% by weight on an absolute basis. In some embodiments, the biocarbon composition comprises a total fixed carbon concentration of about 35% to about 85% by weight on an absolute basis.

[0396] The low-set carbon material may comprise from about 45% to about 80% volatile carbon by weight on an absolute basis (i.e., including ash and moisture). In various embodiments, the low-set carbon material may comprise about, at least about, or up to about 45, 50, 55, 60, 65, 70, 75, or 80% volatile carbon by weight on an absolute basis. The low-set carbon material may comprise, for example, from about 1% to about 20% oxygen by weight on an absolute basis. The low-set carbon material may comprise, for example, from about 0.1% to about 10% hydrogen by weight on an absolute basis.

[0397] The high-fixed carbon material may comprise from about 0 to about 50% volatile carbon by weight on an absolute basis. In various embodiments, the high-fixed carbon material may comprise about, at least about, or up to about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% volatile carbon by weight on an absolute basis. The high-fixed carbon material may comprise, for example, from about 1% to about 20% oxygen by weight on an absolute basis. The high-fixed carbon material may comprise, for example, from about 0.1% to about 10% hydrogen by weight on an absolute basis.

[0398] "Bio-carbon composition" is generally synonymous with "bio-carbon product" when referring to the final composition of the process. In some embodiments, the bio-carbon composition comprises about 0.1% to about 20% moisture by weight. In various embodiments, the bio-carbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, including all intervening ranges. The low fixed carbon material may comprise 0 to about 50% moisture by weight, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, including all intervening ranges. Independently, the high fixed carbon material can contain from 0 to about 50% moisture by weight, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, including all intervening ranges. Drying can be used at one or more points in the process.

[0399] In some embodiments, the biocarbon composition comprises about 0.1% to about 10% ash by weight. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% ash by weight, including all intervening ranges. The low fixed carbon material can comprise 0 to about 25% ash by weight, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% ash by weight, including all intervening ranges. Independently, the high fixed carbon material can contain from 0 to about 50 wt.% ash, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 wt.% ash, inclusive of all intervening ranges.

[0400] In some embodiments, the bio-carbon composition comprises about 0.1% to about 10% by weight of one or more additives. In some embodiments, the bio-carbon composition comprises about 1% to about 15% by weight of one or more additives. In some embodiments, the bio-carbon composition comprises about 3% to about 18% by weight of one or more additives. In various embodiments, the bio-carbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight of the additive, including all intervening ranges.

[0401] The low set carbon material can include 0 to about 20 weight percent additive, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 weight percent additive, inclusive of all intervening ranges. Independently, the high set carbon material can include 0 to about 50 weight percent additive, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 weight percent additive, inclusive of all intervening ranges.

[0402] The additives may include organic additives or inorganic additives. In some embodiments, one or more additives include renewable materials. In some embodiments, one or more additives include materials that can be partially oxidized or combusted.

[0403] In some embodiments, the one or more additives include (or are) a binder. The binder may be selected from starch, thermoplastic 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or any combination of the foregoing.

[0404] In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination of the foregoing. The binder may be an optionally crosslinked thermoplastic starch. The thermoplastic starch may be a reaction product of starch and a polyol, which may be selected from ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination thereof. The reaction product may be formed from a reaction catalyzed by an acid, which may be selected from formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof. Alternatively, the reaction product may be formed from a reaction catalyzed by a base.

[0405] The one or more additives may reduce the reactivity of the biocarbon composition compared to an otherwise equivalent biocarbon composition without the one or more additives. The reactivity may be thermal reactivity. For example, a biocarbon composition with one or more additives may have a lower self-heating tendency compared to an otherwise equivalent biocarbon composition without the one or more additives. Alternatively or additionally, the reactivity is chemical reactivity with oxygen, water, hydrogen, carbon monoxide, or metals (e.g., iron).

[0406] When additives are used, they do not need to be uniformly distributed throughout the biomass composition. The additives may be present in either the low-fixed carbon material or the high-fixed carbon material, or even only in one of these materials. For example, the binder may be present at 5% by weight in the total biomass composition, but 4 percentage points of that amount are located in the low-fixed carbon material and 1 percentage point is located in the high-fixed carbon material (i.e., 80% of the binder is located in the low-fixed carbon material). In various embodiments, the percentage of the total additive that is disposed within the low fixation carbon material can be about, at least about, or up to about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; the percentage of the total additive that is disposed within the high fixation carbon material can be about, at least about, or up to about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; and the percentage of the total additive that is not disposed within either the low fixation carbon material or the high fixation carbon material but elsewhere within the bio-carbon composition (e.g., as a separate additive phase) can be about, at least about, or up to about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

[0407] When one or more additives are present, some or all of the additives may be pore-filling within the low fixation carbon material. When one or more additives are present, some or all of the additives may be pore-filling within the high fixation carbon material. In some embodiments, one or more additives are present and pore-filling within both the low fixation carbon material and the high fixation carbon material.

[0408] Alternatively, or additionally, one or more additives can be disposed on an outer surface of the biocarbon composition (eg, an outer surface of a pellet or powder particle).

[0409] In some embodiments, the bio-carbon composition is in the form of a powder.

[0410] In some embodiments, the biocarbon composition is in the form of pellets. When the form is pellets, the one or more additives 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.

[0411] When one or more additives are present, the additives may be located within one of the low fixity carbon materials or the high fixity carbon materials, or alternatively, the additives may be uniformly distributed such that the additives have the same average concentration within the low fixity carbon materials and the high fixity carbon materials.

[0412] In some embodiments, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with the 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", which is incorporated herein by reference.

[0413] Fixed carbon concentration is an important parameter of a biocarbon composition. The present disclosure allows for maximizing or optimizing, but not necessarily maximizing, the fixed carbon concentration in various embodiments.

[0414] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the energy content associated with the biocarbon composition.

[0415] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the bulk density associated with the bio-carbon composition.

[0416] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the hydrophobicity associated with the bio-carbon composition.

[0417] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the pore size associated with the bio-carbon composition.

[0418] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the ratio of pore sizes associated with the bio-carbon composition.

[0419] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the surface area associated with the bio-carbon composition.

[0420] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the reactivity associated with the bio-carbon composition.

[0421] In some embodiments, the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the ion exchange capacity associated with the bio-carbon composition.

[0422] In some embodiments, the biocarbon composition 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 Crushability Index associated with the pellets.

[0423] In some embodiments, the bio-carbon composition is in the form of a pellet, and the fixed carbon concentration, and optionally the type or concentration of additives, are selected to optimize the pellet durability index associated with the pellet.

[0424] The total carbon in the biocarbon composition is 14 C / 12In some embodiments, the total carbon can be at least 50% renewable as determined from a measurement of the C isotope ratio. 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.

[0425] Although renewable biocarbon compositions are preferred, it is important to note that the principles of the present disclosure 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 any of Figures 1-6, for example. 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 combinations thereof.

[0426] Some processes use two or more separate pyrolysis reactors, which are typically all continuous or all batch, although in principle a mixture of reaction modes can be used, and when separate pyrolysis reactors are used, they can be at a common location or at different locations.

[0427] In other embodiments, the processes are carried out in a common pyrolysis reactor at different times, such as different 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 materials, or using different pyrolysis conditions. Alternatively, a single pyrolysis reactor can be operated continuously or semi-continuously to produce a first material for a first period of time, then a second material for a second period of time, after which the reactor can be returned to the production of the first material or something else.

[0428] In some process embodiments, the first pyrolysis reactor is operated at a first pyrolysis temperature selected from about 250° C. to about 1250° C., e.g., from about 300° C. to about 700° C. The second pyrolysis reactor can be operated at a second pyrolysis temperature selected from about 250° C. to about 1250° C., e.g., from about 300° C. to about 700° C. The second pyrolysis temperature can be the same as or different from the first pyrolysis temperature.

[0429] In some embodiments, the first pyrolysis reactor is operated for a first pyrolysis time selected from about 10 seconds to about 24 hours. In these or other embodiments, the second pyrolysis reactor is operated for a second pyrolysis time selected from about 10 seconds to about 24 hours. The second pyrolysis time may be the same as or different from the first pyrolysis time.

[0430] 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 be or may include a blend of low and high fixed carbon materials.

[0431] 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, where it can replace coke and reduce iron ore to metallic iron.

[0432] In some embodiments, varying the fixed carbon content allows for optimization of the HGI. The incorporation of binders or other additives may also allow for HGI tunability.

[0433] The ability to adjust the HGI of biocarbon pellets is beneficial because downstream applications utilizing biocarbon pellets (e.g., replacing coal in a boiler) have different HGI requirements. HGI adjustability addresses the well-known problems industrially of the difficulty in grinding crude biomass and the difficulty in grinding pellets. Furthermore, there are numerous downstream uses of biocarbon pellets, each with its own requirements, so being able to adjust the grindability of the pellets 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, metals production, or gasification.

[0434] In many applications, pellets are preferred over powders (isolated biomass particles) based on delivery, storage, and safety advantages. Ultimately, pellets may need to be reconstituted into powder, or at least smaller bodies, at some point. Thus, pellet grindability is often a critical parameter that impacts operational and capital costs.

[0435] In some cases, 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 ores to metals. In these cases, high pellet grindability is desirable, but not too high that the pellets fall apart during delivery and handling. In other cases, it is desirable to feed the pellets themselves to a process, such as a metal making process. In these cases, lower grindability may be desirable, since some pellet strength may be required to support the bed of material in the reactor. Different technologies have different pellet grindability requirements.

[0436] The Hardgrove Grindability Index of the biocarbon pellets can be at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 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.

[0437] 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, 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, 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, 134, 135, 136, 13 , 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.

[0438] The bio-carbon pellets may be characterized by a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. The bio-carbon pellets may be characterized by a pellet durability index of less than 99%, less than 95%, less than 90%, less than 85%, or less than 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.

[0439] In some embodiments, biocarbon pellets are utilized as starting materials for making smaller objects, and "pellets" may also be referred to as biocarbon pellets, since "pellets" does not limit the geometric shape. For example, initial biocarbon pellets with an average pellet diameter of 10 mm can be made. These initial biocarbon 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 biocarbon pellets can be produced, for example, having an average pellet diameter of 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. In certain embodiments, the average pellet diameter of the smaller biocarbon pellets is preferably greater than the average particle diameter of the initial carbon-containing particles used to make the pellets with the binder.

[0440] When the bio-carbon pellets are crushed to produce smaller bio-carbon pellets, the crushing (and optionally screening) step can be integrated with another process step, potentially including the point of industrial use. The optional step to produce smaller bio-carbon pellets can utilize a crushing device selected from a hammer mill, attrition mill, disk mill, pin mill, ball mill, cone crusher, jaw crusher, rock crusher, or combinations thereof.

[0441] In various process embodiments, the Hardgrove Crushability Index is at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. For example, the Hardgrove Crushability Index can be from about 30 to about 50, or from about 50 to about 70.

[0442] 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, 109, 109, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1081, 1092, 1094, 1096, 1098, 1098, 1099, 1000, 1001, 1002, 10 8, 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.

[0443] In some processes, the biocarbon pellets are characterized by a pellet durability index of at least 80%, at least 90%, or at least 95%.

[0444] In some embodiments, the process includes preselecting a hardgrove grindability index, adjusting process conditions based on the preselected hardgrove grindability index, and achieving within ±20% of the preselected hardgrove grindability index for the biocarbon 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, and drying. The process of certain embodiments can achieve within ±10%, or within ±5%, of the preselected hardgrove grindability index for the biocarbon pellets.

[0445] The size and geometry of the biocarbon pellets may vary. As used herein, "pellets" refers to aggregated bodies, not loose powder. The geometry of the pellets is not limited to spherical or nearly spherical. Also, in this disclosure, "pellets" is synonymous with "briquettes." The geometry of the pellets may be spherical (round or ball shaped), cylindrical, cubic (square), octagonal, hexagonal, honeycomb / honeycomb shaped, elliptical, ovoid, cylindrical, rod shaped, pillow shaped, random, or combinations thereof. For convenience of disclosure, the term "pellets" is used generally for any body comprising powder aggregated using a binder. Also, it is reiterated that this technology is in no way limited to biocarbon compositions in the form of pellets. For example, after pellets are produced using the disclosed process, the pellets can be powdered and then used.

[0446] Biocarbon pellets can be characterized by an average pellet diameter, which is the true diameter in the case of a sphere or cylinder, or an 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, including 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, including all intervening ranges.

[0447] In some embodiments, there are a plurality of bio-carbon pellets that are relatively uniform in size, such as a standard deviation of less than ±100%, less than ±50%, less than ±25%, less than ±10%, or less than ±5% of the average pellet diameter. In other embodiments, there are a wide range of sizes of bio-carbon pellets, as this may be advantageous in some applications.

[0448] The biocarbon pellets may contain moisture. The moisture present in the biocarbon pellets may be water that is chemically bound to the carbon or binder, water that is 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 is preferred that such moisture is chemically or physically bound to the carbon or binder, rather than being free water.

[0449] Various moisture levels can be present. For example, the biocarbon pellets can contain about 1% to about 30% (e.g., 32%) by weight, such as about 5% to about 15% moisture, about 2% to about 10% moisture, or about 0.1% to about 1% moisture. In some embodiments, the biocarbon pellets contain about 4-8% moisture. In various embodiments, the biocarbon 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% moisture, including all intervening ranges. The moisture level of the biocarbon pellets can be optimized to vary the density within the pellets.

[0450] 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 is present in the process of making biocarbon pellets, but these pellets are then optionally dried, which means that the final biocarbon pellets do not necessarily contain moisture.

[0451] In some biocarbon pellets, the biocarbon pellets include about 2% to about 25% binder by weight, about 5% to about 20% binder by weight, or about 1% to about 5% binder by weight. In various embodiments, the biocarbon pellets include 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% binder by weight, including all intervening ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0452] The binder may be pore-filled within the bio-reagent of the bio-carbon pellet. Alternatively or additionally, the binder may be disposed on the surface of the bio-carbon pellet.

[0453] The binder may be an organic binder or an inorganic binder. In some embodiments, the binder is or includes a renewable material. In some embodiments, the binder is or includes a biodegradable material. In some embodiments, the binder may be partially oxidized or combusted.

[0454] In various embodiments, the binder is selected from 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or any combination of the foregoing. The binder may be or may include a grindable plasticizer.

[0455] In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), derivatives thereof, or combinations of any of the foregoing. The starch can be a nonionic starch, anionic starch, cationic starch, or zwitterionic starch.

[0456] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and can be easily chemically modified. The ring structure of starch molecules, together with the strong hydrogen bonds, give 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. Plasticizers such as water or glycols can be added, since the melting point of pure starch is considerably at least about its decomposition temperature. The native crystallinity can then be destroyed by vigorous mixing (shear) at high temperatures, resulting in thermoplastic starch. Starch can be plasticized (destroyed) by relatively low levels of molecules that can hydrogen bond with starch hydroxyl groups, such as water, glycerol, or sorbitol.

[0457] 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 and 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.

[0458] In some embodiments, the starch-containing binder is or comprises crosslinked starch. Various methods for crosslinking starch are known in the art. Starch materials can be crosslinked, for example, under acidic or alkaline conditions after dissolving or dispersing in an aqueous medium. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to crosslink starch.

[0459] An example of a crosslinked 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 combinations thereof. The reaction product can be formed from a crosslinking 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 combinations thereof. Inorganic acids, such as sulfuric acid, can also be utilized to catalyze the crosslinking reaction. In some embodiments, the thermoplasticized or crosslinked reaction product can instead be formed from a crosslinking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0460] 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.

[0461] In some embodiments, the binder serves other purposes such as (but not limited to) moisture retention within the biocarbon pellets and as a food source for microorganisms.

[0462] In some embodiments, the binder reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the binder, which can refer to thermal or chemical reactivity (or both).

[0463] In the case of thermal reactivity, the biocarbon pellets may have a reduced self-heating tendency compared to otherwise comparable biocarbon pellets without the binder. "Self-heating" refers to the biocarbon pellets undergoing a spontaneous exothermic reaction in the absence of any external ignition, at relatively low temperatures and in an oxidizing atmosphere, to increase the internal temperature of the biocarbon pellets.

[0464] The chemical reactivity can be with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. Chemical reactivity can be, for example, with CO, CO 2 , H 2 O, pyrolysis oils, and reactions to heat.

[0465] Optionally, the biocarbon pellets include one or more 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.

[0466] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additives are selected from acids, bases, or salts thereof. In some embodiments, at least one additive is selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. For example, the additives can be selected from the group consisting of (but are not limited to) 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof. The additives can be added before, during, or after any one or more steps of the process, including adding to the feedstock itself at any time before or after the feedstock is harvested.

[0467] The biocarbon 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 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 production. They can be pulverized, crushed, or milled for feeding into gasifiers for the purpose of making syngas from the biocarbon pellets.

[0468] In many embodiments, the biocarbon pellets are fed into a furnace, either directly or after a step of pulverizing, crushing, milling, or otherwise reducing the particle size. The furnace can be a blast furnace, a top gas recirculating 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.

[0469] It should be noted that despite the Hardgrove Crushability Index of biocarbon pellets, they do not necessarily undergo a subsequent grinding process. For example, biocarbon pellets can be used directly in agricultural applications. As another example, biocarbon pellets can be directly incorporated into engineered structures, such as landscape walls. Then, at the end of the life of the structure containing the biocarbon pellets, the pellets can be crushed, combusted, gasified, or otherwise reused or recycled.

[0470] Pyrolysis Processes and Systems Suitable processes and systems for pyrolyzing biomass feedstock or bioreagents together with condenser liquid will now be described in more detail. Descriptions of pyrolysis reactors (or reactions) will in some cases be understood as references to reactors (or reactions) for producing high fixed carbon materials.

[0471] "Pyrolysis" and "pyrolyzing" generally refer to the thermal decomposition of carbonaceous materials. Pyrolysis requires the use of oxygen (O 2 Less oxygen is present than is required for complete combustion of the material, such as less than 10%, 5%, 1%, 0.5%, 0.1%, or 0.01% (on a molar basis). In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0472] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a 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 and subsequently undergo secondary reactions to produce tars; (v) autocatalytic secondary pyrolysis reactions proceed while competing primary pyrolysis reactions occur simultaneously; and (vi) further pyrolysis, reforming, water-gas shift reactions, free-radical recombination, or dehydration may also occur, which are a function of residence time, temperature, and pressure profiles.

[0473] 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.

[0474] In some embodiments, the starting biomass feedstock is 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, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit husks. , 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. It is noted that typically the biomass feedstock comprises at least carbon, hydrogen, and oxygen.

[0475] 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 comprises 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 and non-fixed carbon present in the volatile materials. In some embodiments, the weight percentages of the components are on an absolute basis, which is assumed unless otherwise stated. In other embodiments, the component weight percentages are on a water-free and ash-free basis. The compositions of low and high fixed carbon materials are discussed in detail above.

[0476] Pyrolysis conditions can vary widely depending on the desired composition of the bioreagents and pyrolysis exhaust gas, the starting materials, the reactor configuration, and other factors.

[0477] 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.

[0478] 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, equipment can be used that does not mechanically disrupt the cell walls or otherwise convert the biomass particles into small fines. Certain such reactor configurations are discussed in accordance with the process description below.

[0479] 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.

[0480] 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.

[0481] In some embodiments, the second zone of the pyrolysis reactor is configured as a primary reaction zone, where the 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 (mainly cellulose, hemicellulose, and lignin) decompose to create vapors that escape by penetrating pores or creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0482] In some embodiments, the third zone of the pyrolysis reactor is configured to receive the high carbon reaction intermediates and to cool the solids to some extent. Typically, the third zone is at a lower temperature than the second zone. In the third zone, the 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, the final carbonaceous material may not simply be the solid degassed residue of the processing step, but may include additional carbon deposited from the gas phase, such as by decomposition of organic vapors (e.g., tars) that can form carbon.

[0483] 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.

[0484] 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 adjustments.

[0485] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis.Surprisingly, high quality carbon materials, including compositions having a very high percentage of fixed carbon, can be obtained from the disclosed processes and systems.

[0486] 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 raw material to remove at least a portion of the moisture contained in the raw material; (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 solids.

[0487] "Biomass" for the purposes of this disclosure should be construed as any living material or mixture of living and non-living materials. Essentially, biomass contains at least carbon, hydrogen, and oxygen. The methods and apparatus can accommodate a wide range of materials of different types, sizes, and moisture contents.

[0488] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal waste, poultry waste, and municipal solid waste. In various embodiments utilizing biomass, the biomass feedstock may include one or more materials selected from wood harvest residues, softwood chips, hardwood chips, tree branches, tree stumps, knots, leaves, bark, sawdust, off-spec paper pulp, cellulose, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal waste, municipal sewage, commercial waste, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, carbohydrates, plastics, and fabrics. Those skilled in the art will readily appreciate that the options for feedstock are virtually limitless.

[0489] The present disclosure 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 waste 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 trucks, trains, ships, barges, tractor trailers, or any other vehicle or conveyance.

[0490] The selection of the particular raw material(s) is not considered technically critical, but is done 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 be optionally dried prior to processing.

[0491] 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, such as with a binder.

[0492] It should be noted that size reduction is a costly and energy intensive process. Pyrolyzed material 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 since 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. In particular, some market applications of high carbon products actually require large sizes (e.g., on the order of centimeters), so in some embodiments, large pieces are supplied, manufactured and sold.

[0493] 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 this disclosure. 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 the product have similar geometric shapes, such as spheres, cylinders, or cubes.

[0494] 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.

[0495] The starting feedstock may be provided with 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 required. Typically, it is desirable to utilize commercial sources of biomass that are normally moist, and to feed the biomass through a drying step prior to introduction into the pyrolysis reactor. However, in some embodiments, dry feedstock may be utilized.

[0496] Typically, in the pyrolysis reactor, 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 is present in the gas phase. 2 It is desirable to provide a relatively low oxygen environment, such as low CO. First, uncontrolled combustion should be avoided in the pyrolysis reactor for safety reasons. 2 Some amount of total carbon oxidation to solids may occur, and the heat released from the exothermic oxidation may support the endothermic decomposition chemical reactions. Large amounts of carbon oxidation, including partial oxidation to syngas, will reduce the carbon yield to solids.

[0497] In practice, it can be difficult to achieve a strictly oxygen-free environment in the reactor. This limit can be approached, and in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that there is little or no oxygen 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 to remove or reduce air in the feed.

[0498] In some embodiments, before or after drying, a degassing unit is utilized in which the feedstock is conveyed in the presence of another gas that can remove adsorbed oxygen and permeate the feedstock pores to remove oxygen from the pores. Essentially, less than 21% by volume O 2 Any gas having a nitrogen content may be used with varying effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO or CO 2 can be used. Mixtures such as a mixture of nitrogen and small amounts of oxygen can be used. Water vapor may be present in the degassed 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 to an emissions treatment unit) or recycled.

[0499] 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.

[0500] 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.

[0501] The optionally dried and optionally degassed feedstock is introduced into the 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 feed system incorporates an air knife.

[0502] When a single reactor is used, there can be multiple zones, such as two, three, four or more zones, which can allow separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, or pressure to adjust the overall process performance.

[0503] References to "zones" should 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, the boundaries of zones may relate to structures such as the presence of flights within the reactor or separate heating elements to provide heat to separate zones. Alternatively or additionally, the boundaries of zones 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.

[0504] 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, some amount of pyrolysis may occur in a portion of the preheat zone, and some amount of "preheat" may continue to occur in the pyrolysis zone. The temperature profile within the reactor is typically continuous, including at the zone boundaries within the reactor.

[0505] 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., for example, from about 300° C. to about 400° C. The temperature of the first zone is preferably not so high as to bombard the biomass material and rupture the cell walls and initiate rapid decomposition of the solid phase into vapors and gases.

[0506] All references to zone temperatures herein should be interpreted without limitation to include temperatures that may be applied to the bulk solids present, or the gas phase, or the reactor walls (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 references 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.

[0507] 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, for example, about, or as low as about, 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 (mainly cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or by creating new pores. The preferred temperature depends at least on the residence time of the second zone, as well as the nature of the feedstock and the desired product properties.

[0508] The third zone, or cooling zone, is operated to cool the high carbon reaction intermediates 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.

[0509] 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 reduction 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 Boudouard reaction to convert carbon monoxide to carbon dioxide and fixed carbon.

[0510] 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.

[0511] It should be recognized that in a multiphase reactor, there are multiple residence times. In the present context, there are residence times (and residence time distributions) for both 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 combined on the solid side, but if multiple inlet and outlet ports are utilized in the individual zones, the residence times may not be combined on the vapor side. The residence times of the solids and vapor are not combined.

[0512] The solids residence time in the preheat 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 temperature, a sufficient time is desirable to allow the biomass to reach the desired preheat temperature. The heat transfer rate, which depends on the particle type and size, physical equipment, and heating parameters, dictates the minimum residence time required to allow the solids to reach the desired preheat temperature. Additional time may not be desirable unless some amount of mild pyrolysis is intended in the preheat zone, as it contributes to higher capital costs.

[0513] 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 enough time for the necessary heat transfer to occur followed by the chemical reaction of carbonization. For times less than about 10 minutes, the temperature needs to be very high, such as above 700° C., to remove a large amount of non-carbon elements. This temperature promotes fast pyrolysis and its production of steam and gases derived from the carbon itself, but should be avoided if the intended product is solid carbon.

[0514] In a static system, there will be an equilibrium conversion that can be substantially reached at a certain time. When steam is continuously flowing over the solids with continuous devolatilization, as in certain embodiments, the equilibrium constraint can be removed to allow pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times do not tend to substantially change the remaining refractory solids.

[0515] 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 enough time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature dictate the minimum residence time necessary to allow the carbon to cool. Additional time may not be desirable unless some amount of secondary pyrolysis is desired.

[0516] As discussed above, the residence times of the vapor phases can be selected and controlled separately. The vapor residence time of the preheat zone can be selected from about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time of the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time of the cooling zone can be selected from about 0.1 minutes to about 15 minutes, for example, 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.

[0517] 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, with solids and vapor flowing 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 gas phase from the batch vessel.

[0518] 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, the flow of solids can approach plug flow (well mixed in the radial dimension), while the flow of vapor can approach perfectly mixed flow (high velocity transport in both radial and axial dimensions). Multiple inlet and outlet ports for the vapor can contribute to the overall mixing.

[0519] 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.

[0520] The process may be conveniently operated at atmospheric pressure in some embodiments. 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).

[0521] Vacuum operation (e.g., 10-100 kPa) promotes rapid clearing of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) may be useful when feeding exhaust gas to high pressure operation. Higher pressures may also be useful to promote heat transfer, chemical reactions, or separations.

[0522] 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.

[0523] The sweep gas is, for example, N 2 , Ar, CO, CO 2 , H 2 , H 2 O, C.H. 4 , other light hydrocarbons, or combinations thereof. The sweep gas may be first preheated before introduction, or may be cooled if obtained from a heated source.

[0524] The sweep gas removes volatile components more completely 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 simply volatilization at a given process temperature. Alternatively, the use of a sweep gas allows a more gentle temperature 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 limitations of volatilization as well as the thermodynamic limitations by continuously depleting a given volatile species to allow more volatile species to evaporate and achieve thermodynamic equilibrium.

[0525] Some embodiments remove gases full of volatile organic carbon from subsequent processing steps 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 the rapid removal of steam can increase porosity in the pyrolyzed solids. Higher porosity is desirable for some products.

[0526] 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.

[0527] In some embodiments, the sweep gas flows countercurrent to the feed flow direction. In other embodiments, the sweep gas flows cocurrent to the feed flow direction. In some embodiments, the flow patterns of the solids approach plug flow, while the flow patterns of the sweep gas and vapor phase generally approach perfectly mixed flow in one or more zones.

[0528] The sweep may 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 may be introduced into each of the preheating zone, pyrolysis zone, and cooling zone, and may also be extracted from each of the zones.

[0529] In some embodiments, the zone or zones in which the separation is carried out are units physically separated from the reactor. Separation units or zones can be located between reactor zones, if desired. For example, a separation unit can be installed between a pyrolysis unit and a cooling unit.

[0530] The sweep gas can be introduced continuously, especially if 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, with suitable valves and controls.

[0531] The volatiles-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.

[0532] 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 an 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 (utility side) the dryer. The thermal oxidizer can use fuels other than natural gas.

[0533] The yield of carbonaceous materials may 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 split 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 the process conditions, including the water present.

[0534] 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 comprises from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon forms methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0535] 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 resulting gas stream from the reactor, including various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids originating from a cooling zone or a separate cooling unit. These embodiments are described in more detail below.

[0536] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids may 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, e.g., to a temperature below 40° C., such as 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.

[0537] In some embodiments, the process further comprises operating a cooling unit to cool the warm pyrolyzed solids with steam, thereby producing low temperature pyrolyzed solids and superheated steam, and drying is performed at least in part with the superheated steam obtained from the 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.

[0538] 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.

[0539] Some other means for screening or separation based on particle size may be included. Grinding, if present, may be upstream or downstream of 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 finely divided carbon or activated carbon product.

[0540] Various additives can be introduced throughout the process before, during, or after any of the steps 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 of downstream products incorporating the reagent. Certain additives can provide enhanced process and product (bioreagent or products containing bioreagent) properties.

[0541] The additives can be added before, during, or after any one or more steps of the process, including adding 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, landing equipment, storage bin, conveyor (including open or closed conveyor), 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 additives. If desired, the additives can be added after carbonization, or even after pulverization.

[0542] In some embodiments, the additive is selected from a metal, a metal oxide, a metal hydroxide, or a combination thereof. For example, the additive can 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, or a combination thereof.

[0543] 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.

[0544] 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 basic metal salts with hydrohalic acids, or more commonly by neutralization. In some embodiments, the additive is ferric chloride (FeCl 2 or FeCl3 ), iron bromide (FeBr 2 or FeBr 3 ), or a hydrate thereof, and any combination thereof.

[0545] 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 extent of liquid formation in favor of the formation of solids and gases, or in favor of the formation of solids.

[0546] Without being limited to any particular hypothesis, the additives can chemically modify the starting biomass, or the treated biomass prior to pyrolysis, to reduce cell wall fracture for greater strength / integrity. In some embodiments, the additives can increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0547] The additives may result in the bioreagent having improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. The additives may improve mechanical properties by simply being present (e.g., the additive itself imparts strength to the mixture) or by some transformation occurring within the additive phase or the resulting mixture. For example, a reaction such as vitrification may occur within a portion of the bioreagent that contains the additive, thereby improving the final strength.

[0548] 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 of a liquid solution (such as in an aqueous solution or solvent) or by immersion in a tank, bin, bag, or other container.

[0549] 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.

[0550] In some embodiments, the 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, the additives applied to the feedstock can provide desirable functionality for the intended use of the carbonaceous product.

[0551] Throughput or process capacity can vary widely from small laboratory scale units to full scale operations, including any pilot, demonstration, or semi-commercial scale. In various embodiments, the process capacity (of feedstock, product, or both) is at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day, or more.

[0552] 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 a subsequent step, or removed / purged from the process at any point.

[0553] In some embodiments, the pyrolyzed material is recovered and then fed to a separate unit for further pyrolysis to create products with higher carbon purity (e.g., conversion of low fixed carbon materials to high fixed carbon materials). In some embodiments, a secondary process is performed using heated inert gas (heated N 2This can be done in a simple vessel such as a steel drum through which a secondary sweep gas (such as hexane, hexanediamine, hexanediaminetetraacetate ...

[0554] Some variations include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; and (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solid-state cooler disposed in operative communication with the multi-zone reactor; and (e) a biological reagent production system comprising a biological reagent recovery unit disposed in operative communication with the solid-state cooler.

[0555] Some variations include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; and (c) an optional preheater disposed in operative communication with the dryer and configured to heat or gently pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operative communication with the preheater and configured to pyrolyze the feedstock; (e) a cooler disposed in operative communication with the pyrolysis reactor and configured to cool the pyrolysis solids; and (f) a biological reagent retrieval unit disposed in operative communication with the cooler, A bioreagent production system is utilized, the system being configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0556] The feed system can be physically integrated with the multi-zone reactor, such as through the use of a screw feeder or auger mechanism to introduce the feed solids into the first reaction zone.

[0557] In some embodiments, the system further comprises a pre-heating zone disposed in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and pre-heating zone (if present) may be located in a single unit or may be located in separate units.

[0558] 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).

[0559] The system may include a purging means for removing oxygen from the system. For example, the purging means may include 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.

[0560] The multi-zone reactor is preferably configured with at least a first gas inlet and a first gas outlet, which may be arranged in communication with different zones or the same zone.

[0561] 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.

[0562] The 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 efficiency, both dynamically and over time, when operating history can be utilized to adjust process conditions.

[0563] In a preferred embodiment, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe may be useful for extracting gases and analyzing them 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, temperature (in one or more zones), pressure (in one or more zones), additives, etc.

[0564] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more samplings via the reactive gas probe, and, optionally, making process or equipment adjustments based on the measurements, if deemed necessary or desirable, using well-known principles of process control (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0565] 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 branched off from the gas output line).

[0566] 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 ("sample sweep"). Such configurations 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) may be different from the process inert gas, if desired, either for reasons of analytical accuracy or to introduce an analytical tracer.

[0567] For example, the concentration of acetic acid 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.). 2 The concentration can be measured and used, for example, as an indicator of pyrolysis selectivity towards gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity towards liquids.

[0568] 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 pre-heating zone (if present).

[0569] A gas probe for the cooling zone may 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 may also be useful as an independent measurement of temperature (e.g., in addition to a thermocouple located in the cooling zone). This independent measurement may be a correlation between cooling temperature and a measured quantity of a particular species. The correlation may be developed separately or may be established after a period of process operation.

[0570] A gas probe for the drying zone can be useful to determine the degree of drying, for example by measuring the moisture content. A gas probe in the preheat zone can be useful, for example, to determine the extent of any mild pyrolysis that occurs.

[0571] 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 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 to the solid phase. Alternatively or additionally, the drying zone can be configured with a gas outlet to generate a substantially countercurrent flow.

[0572] The pyrolysis reactor or reactors can 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 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.

[0573] 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 a 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.

[0574] 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 formed 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.

[0575] 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" are intended to include similar substantially inert materials such as glass particles, recovered ash particles, and the like. The high rate of heat transfer from the fluidized sand may result in rapid heating of the feedstock. There may be some ablation due to friction with the sand particles. Heat is typically provided by heat exchanger tubes through which the hot combustion gases flow.

[0576] A circulating fluidized bed reactor can be used where 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.

[0577] In some embodiments, a multi-zone reactor is a continuous reactor comprising a feed inlet, a plurality of spatially separated reaction zones configured to separately control 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.

[0578] In various embodiments, the reactor comprises at least two, three, four, or more reaction zones, each of which is disposed in communication with a separately adjustable heating means independently selected from electrical heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste 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.

[0579] 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.

[0580] 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.

[0581] In some embodiments, the feedstock inlet comprises a screw or auger feed mechanism. In some embodiments, the carbonaceous solids outlet comprises a screw or auger output mechanism.

[0582] Certain embodiments utilize a rotary calciner 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 the solids flow patterns, as well as heat and mass transport. Each of the reaction zones can be configured with flights disposed on the interior walls to provide agitation of the solids. The flights can be separately adjustable in each of the reaction zones.

[0583] Other means of agitating the solids can be used, such as an auger, screw, or paddle conveyor. In some embodiments, the reactor includes a single continuous auger positioned throughout each of the reaction zones. In other embodiments, the reactor includes twin screws positioned throughout each of the reaction zones.

[0584] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., to process the biomass feedstock without destroying or significantly damaging its structure, hi some embodiments, the pyrolysis zone does not include augers, screws, or rakes, which would tend to significantly reduce the size of the feedstock being pyrolyzed.

[0585] In some embodiments, the system further includes a thermal oxidizer disposed in operative communication with the outlet through which the condensable vapors and non-condensable gases are removed. The thermal oxidizer is preferably configured to receive a separate fuel (such as natural gas) and an oxidant (such as air) into a combustion chamber adapted to combust at least a portion of the fuel and condensable vapors. 4 It also oxidizes certain non-condensable gases such as CO 2 It can be.

[0586] When a thermal oxidizer is used, the system may include a heat exchanger disposed between the thermal oxidizer and the dryer configured to utilize at least a portion of the heat of combustion for the dryer. This embodiment may contribute significantly to the overall energy efficiency of the process.

[0587] 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 vapors 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.

[0588] 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.

[0589] The entire system may be at a fixed location or may be distributed over several locations. The system may be built using modules that can be easily replicated for practical scale-up. The system may also be built using economy of scale principles, as is well known in the process industries.

[0590] Several 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 raw material to remove at least a portion of the moisture contained in the raw material; (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 and 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 solids to produce cooler pyrolysis solids; (h) thereafter, 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 pyrolytic solid to form an enhanced pyrolytic solid having an increased carbon content; (i) recovering the biological reagent comprising at least a portion of the enhanced pyrolysis solids.

[0591] In some embodiments, step (h) comprises passing at least a portion of the condensable vapors from step (e), in vapor or condensed form, through the 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 the warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content.

[0592] Alternatively or additionally, the steam or gas may be contacted with the cold pyrolytic solid. In some embodiments, step (h) comprises passing at least a portion of the condensable steam from step (e), in steam or condensed form, through the cold 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 cold pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0593] 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.

[0594] 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 consisting 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 a first and a second output stream. In certain embodiments, the intermediate feed stream includes all of the condensable steam, all of the non-condensable gas, or both.

[0595] Separation techniques may include or use distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separation may be primarily based on, for example, distillation, absorption, adsorption, or diffusion and may exploit differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to a stationary phase, and any combination thereof.

[0596] 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.

[0597] 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 xylenes. 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, and methane.

[0598] 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.

[0599] 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, and acetic acid. The non-polar compounds may comprise at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives.

[0600] Step (h) may increase the total carbon content of the bioreagent relative to an otherwise identical process without step (h). The degree of increase in carbon content may be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more in various embodiments.

[0601] 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 that is 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.

[0602] Depending on the conditions associated with step (h), it is possible for some amount of the volatile carbon to become fixed carbon (e.g., via Boudouard carbon formation from CO). Typically, the 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.

[0603] 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.

[0604] 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.

[0605] As another example, separation of acetic acid can be performed followed by reduction of the acetic acid to ethanol, which can be accomplished, at least in part, using hydrogen derived from the produced non-condensable gases.

[0606] The condensable vapors can be used either for energy in processes (such as by thermal oxidation) or for carbon enrichment to increase the carbon content of the bioreagent. 4 Certain non-condensable gases such as may be utilized for energy in the process or as part of the substantially inert gas for the pyrolysis step, as well as any combination of the foregoing.

[0607] A potential advantage of including step (h) is that the gas stream is scrubbed and the resulting gas stream is free of CO and CO. 2 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, the separation of non-condensable gases from condensable vapors allows for a CO / CO ratio. 2 The stream is prepared for use, for example, as an inert gas in a reactor system or a cooling system.

[0608] 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.

[0609] In some embodiments, a batch or continuous process for producing 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 solids stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0610] In some embodiments, the starting carbon-containing material is a pyrolyzed or torrefied biomass. The gas stream can be obtained during an integrated process to provide the carbon-containing material. Or, 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.

[0611] 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.

[0612] 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 including 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.

[0613] 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.

[0614] 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.

[0615] In a related variation, the bioreagent production system comprises: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; and (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solid-state cooler disposed in operative communication with the multi-zone reactor; and (e) a material enrichment unit disposed in operative 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 operative communication with the material concentrating unit.

[0616] The system may further comprise a preheat zone disposed in operative 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. A solids cooler may also be disposed within the multi-zone reactor.

[0617] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet, thereby producing a substantially countercurrent flow of the gas phase to the solid phase. In these or other embodiments, the preheating zone or drying zone (or dryer) is configured with a gas outlet, thereby producing a substantially countercurrent flow of the gas phase to the solid phase.

[0618] In certain embodiments, the system incorporates an ingredient enrichment unit, the ingredient enrichment unit comprising: (i) a housing having an upper portion and a lower portion; (ii) an inlet at a 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; and (v) a transport system following the pathway, the transport system configured to transport the solid, the housing being shaped such that the solid adsorbs at least a portion of the condensable vapor or at least a portion of the non-condensable gas.

[0619] The disclosed technology 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 raw material to remove at least a portion of the moisture contained in the raw material; (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 and 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 solids.

[0620] In some embodiments, the reagent comprises about at least 70%, at least 80%, at least 90%, or at least 95% total carbon by weight on a dry basis. Total carbon includes at least fixed carbon and may further include carbon from volatile matter. In some embodiments, carbon from volatile matter 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.

[0621] The biological reagent may include about 10% or less by weight, e.g., about 5% or less by weight, hydrogen on a dry basis. The biological reagent may include about 1% or less by weight, e.g., about 0.5% or less by weight, nitrogen on a dry basis. The biological reagent may include about 0.5% or less by weight, e.g., about 0.2% or less by weight, phosphorus on a dry basis. The biological reagent may include about 0.2% or less by weight, e.g., about 0.1% or less by weight, sulfur on a dry basis.

[0622] 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.

[0623] Certain embodiments provide reagents that contain little or essentially no hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture present. Thus, some embodiments provide bioreagents that have 100% or less carbon on a dry / ash-free (DAF) basis.

[0624] 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 not be a substantial amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0625] 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 includes little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon that includes 100% carbon on a dry basis.

[0626] Various 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 moisture by weight. As intended herein, "moisture" should be interpreted as including 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 at least on the local environment, such as relative humidity. Moisture may also vary during transportation, preparation for use, and other logistics. Moisture may be measured, for example, using ASTM D3173.

[0627] The bioreagent may have a variety of energy contents, which for the present purposes means an energy density based on the higher calorific value associated with the total combustion of the bone dry reagent. For example, the bioreagent may 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. The energy content may be measured, for example, using ASTM D5865.

[0628] 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.

[0629] In some embodiments, the biological reagents are formed into structural objects comprising compressed, bound, or aggregated particles. The starting material for forming these objects may be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The objects may be formed by mechanical pressing or other forces, optionally with binders or other means of agglomerating the particles together.

[0630] In some embodiments, the bio-reagent is manufactured in the form of a structural object whose structure is substantially derived from the source material. For example, a source tip may produce a product tip of the bio-reagent. Or, a source cylinder may produce a bio-reagent cylinder, which may be somewhat smaller but otherwise maintain the basic structure and geometry of the starting material.

[0631] The bioreagent may be produced or formed into an object 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 may be a length, width, or diameter.

[0632] Other variations 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.

[0633] In some embodiments, the biological reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight 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.

[0634] 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, or combinations thereof.

[0635] In some embodiments, the biological reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight 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.

[0636] 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.

[0637] In certain embodiments, the biological reagents are, on a dry basis, 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight 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.

[0638] 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, or a combination 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 a combination thereof.

[0639] In certain embodiments, the bio-reagent, on a dry basis, consists essentially 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.

[0640] In certain embodiments, the biological reagent consists essentially of, on a dry basis, 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.

[0641] 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 at least about 1% by weight, is incorporated, the energy content calculated based on the total reagent weight (including additives) will be reduced. Further, in various embodiments, the 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.

[0642] 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 enhance final properties for particular applications.

[0643] In preferred 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.) whereby value is attributed to the renewable carbon content in the bioreagent.

[0644] 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.

[0645] 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.

[0646] In variations, the article of manufacture 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.

[0647] 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 steels 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.

[0648] 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 properties of potential importance 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.

[0649] The products or materials into which these bio-reagents may be incorporated may 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, carbon-based coking products, carbon breeze products, foundry carbon, sintering carbon, fluidized bed carbon-based feedstock, carbon-based furnace additive products, injectable carbon-based products, pulverized carbon-based products, stoker carbon-based products, carbon electrodes, or activated carbon products.

[0650] Use of the disclosed bio-reagents in metal production can reduce slag, increase overall efficiency, and reduce life cycle environmental impacts. Thus, some embodiments are particularly well suited for metal processing and manufacturing.

[0651] Some variations utilize bio-reagents as carbon-based blast furnace additive products. A blast furnace is a type of metallurgical furnace used in smelting to produce industrial metals such as (but not limited to) iron. Smelting is a form of extractive metallurgy whose primary use is to produce metals from their ores. Smelting uses heat and chemical reducing agents to break down the ore. Carbon, or carbon monoxide derived from the carbon, removes the oxygen from the ore, leaving behind the elemental metal.

[0652] The reducing agent may consist of or include a bioreagent. In a blast furnace, the bioreagent, ore, and typically limestone, may be continuously fed through the top of the furnace, while air (optionally with oxygen enrichment) is blown into the bottom of the chamber, so that chemical reactions occur throughout the furnace as the material moves downward. The end products are usually molten metal and slag phases removed from the bottom, and flue gases exiting the top of the furnace. The downward flow of the ore in contact with the upward flow of hot carbon monoxide enriched gas is a countercurrent process.

[0653] The quality of carbon in a blast furnace is measured by its resistance to degradation. The role of carbon as a permeable medium is important in economical blast furnace operation. The degradation of carbon varies with position in the blast furnace and is related to the degradation of CO. 2 , H 2 O or O 2 Degraded carbon particles can cause clogging and reduced performance.

[0654] Coke reactivity test is a highly regarded measure of the performance of carbon in a blast furnace. This test has two components: Coke Reactivity Index (CRI) and Reacted Coke Strength (CSR). Carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​are preferred for better blast furnace performance. CRI can be determined as received according to any suitable method known in the art, for example, by ASTM method DS341.

[0655] In some embodiments, the bio-reagent provides a carbon product with properties suitable for direct introduction into a blast furnace.

[0656] The strength of the bio-reagent can be determined by any suitable method known in the art, for example, by drop splash test or CSR test. In some embodiments, the bio-reagent, when optionally blended with another carbon source, provides a final carbon product with a CSR of at least about 50%, 60%, or 70%. The combination product can also provide a final coke product with a suitable reactivity for combustion in a blast furnace. In some embodiments, the product has a CRI such that the bio-reagent is suitable for use as an additive or replacement for met-coal, met-coke, coke breeze, foundry coke, sinter carbon, or injectable coal.

[0657] Some embodiments employ one or more additives in an amount sufficient to provide a bio-reagent that, when added to another carbon source (e.g., coke) that has insufficient CRI or CSR for use as a blast furnace product, provides a composite product with sufficient CRI or CSR for use in a blast furnace. In some embodiments, the one or more additives are present in an amount sufficient to provide a bio-reagent with a CRI of about 40%, 30%, or 20% or less.

[0658] In some embodiments, one or more additives selected from alkaline earth metals, or their oxides or carbonates, are introduced during or after the process of producing the bio-reagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate can be introduced as additives. By adding these compounds before, during, or after pyrolysis, the reactivity of the bio-reagent in the blast furnace can be increased. These compounds can result in stronger materials, i.e., higher CSR, thereby improving blast furnace efficiency. Furthermore, additives such as those selected from alkaline earth metals, or their oxides or carbonates, can result in lower emissions (e.g., SO 2 ) can be obtained.

[0659] In some embodiments, the blast furnace replacement product is a bioreagent comprising at least about 55% carbon, about 0.5% or less sulfur, about 8% or less non-combustible materials, and a calorific value of at least about 11,000 Btu / lb. In some embodiments, the blast furnace replacement product further comprises about 0.035% or less phosphorus, about 0.5% to about 50% volatile materials, and optionally one or more additives. In some embodiments, the blast furnace replacement product comprises about 2% to about 15% dolomite, about 2% to about 15% dolomitic lime, about 2% to about 15% bentonite, or about 2% to about 15% calcium oxide by weight. In some embodiments, the blast furnace replacement product has a dimension substantially in the range of about 1 cm to about 10 cm.

[0660] In some embodiments, the bio-reagent is useful as a foundry coke replacement product. Foundry coke is generally characterized as having a carbon content of at least about 85% by weight, a sulfur content of about 0.6% by weight, no more than about 1.5% by weight volatile matter, no more than about 13% by weight ash, no more than about 8% by weight moisture, no more than about 0.035% by weight phosphorus, a CRI value of about 30, and dimensions ranging from about 5 cm to about 25 cm.

[0661] Some variations utilize bioreagents as carbon-based taconite pellet additive products. The ores used in making iron and steel are iron oxides. The main iron oxide ores include hematite, limonite (also called brown ore), taconite, and magnetite, a black ore. Taconite is a low-grade but important ore that contains both magnetite and hematite. The iron content of taconite is generally 25% to 30% by weight. Blast furnaces typically require at least 50% iron-containing ore by weight for efficient operation. Iron ore can undergo beneficiation, including crushing, screening, tumbling, flotation, and magnetic separation. Refined ore is often concentrated to over 60% iron and formed into pellets before delivery.

[0662] For example, taconite can be ground into a fine powder and combined with a binder such as bentonite clay and limestone. For example, pellets about one centimeter in diameter containing about 65% iron by weight can be formed. The pellets are calcined to oxidize the magnetite to hematite. The pellets are durable and ensure that the blast furnace charge remains porous enough to allow heated gases to pass through and react with the pelletized ore.

[0663] The taconite pellets can be fed into a blast furnace to produce iron, as described above with respect to blast furnace additive products. In some embodiments, bio-reagents are introduced into the blast furnace. In these or other embodiments, the bio-reagents are incorporated into the taconite pellets themselves. For example, beneficiated taconite ore powder can be mixed with bio-reagents and binders, rolled into small bodies, and then baked until hard. In such embodiments, taconite-carbon pellets having the appropriate composition can be conveniently introduced into a blast furnace without the need for a separate carbon source.

[0664] Some variations utilize bio-reagents as ladle-added carbon-based products. A ladle is a vessel used to transport and pour out molten metal. Casting ladles are used to pour molten metal into molds to produce castings. Transfer ladles are used to transfer large volumes of molten metal from one process to another. Processing ladles are used for processes that occur in the ladle to change some aspect of the molten metal, such as the conversion of cast iron to ductile iron by the addition of various elements to the ladle.

[0665] The bio-reagent can be introduced into any type of ladle, but typically, carbon is added to the treatment ladle in a suitable amount based on the target carbon content. The carbon injected into the ladle can be in the form of a fine powder for good mass transfer of the carbon to the final composition. In some embodiments, the bio-reagent, when used as a ladle-added product, has a minimum dimension of about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or greater.

[0666] In some embodiments, the high carbon bio-reagent is useful as a ladle added carbon additive, for example, in basic oxygen furnace or electric arc furnace facilities where ladle addition of carbon is used (e.g., added to ladle carbon during steel production).

[0667] In some embodiments, the ladle-added carbon additive further comprises up to about 5% by weight manganese, up to about 5% by weight calcium oxide, or up to about 5% by weight dolomitic lime.

[0668] Direct reduced iron (DRI), also called sponge iron, is produced from the direct reduction of iron ore (in lump, pellet, or fine form) with reducing gases traditionally produced from natural gas or coal. The reducing gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide that act as reducing agents. The bio-reagents provided herein can be converted into a gas stream containing CO to act as a reducing agent to produce direct reduced iron.

[0669] Iron nuggets are a high quality steelmaking and iron casting feed material. Iron nuggets are essentially all iron and carbon with little gangue (slag) and low levels of metallic residuals. They are a premium grade pig iron product with excellent shipping and handling characteristics. The carbon contained in the iron nuggets or any portion thereof can be a bio-reagent as provided herein. Iron nuggets can be produced by reducing iron ore in a rotary hearth furnace using the bio-reagent as a reducing agent and energy source.

[0670] Some variations utilize bioreagents as metallurgical coke carbon-based products. Metallurgical coke, also known as "meth" coke, is a carbonaceous material typically produced by destructive distillation of various blends of bituminous coal. The final solid is unmelted carbon, called metallurgical coke. As a result of the loss of volatile gases and partial melting, metcoke has an open-porous morphology. Metcoke has a very low volatile content. However, ash components that were part of the original bituminous coal feedstock remain encapsulated in the resulting coke. Metcoke feedstock is available in a wide range of sizes, from fine powder to basketball-sized chunks. Typical purity ranges from 86-92% fixed carbon by weight.

[0671] Metallurgical coke is used wherever high quality, tough, resilient wear carbon is required. Applications include, but are not limited to, conductive flooring, friction materials (e.g., carbon linings), foundry coatings, foundry carbon risers, corrosion materials, drilling applications, reducing agents, heat treating agents, ceramic packing media, electrolytic processes, and oxygen scavenging.

[0672] Metcoke can be characterized as having a heating value of about 10,000-14,000 Btu / lb and an ash con...

Claims

1. 1. A biocarbon pellet composition, wherein the biocarbon pellet comprises at least 60% by weight fixed carbon content, the biocarbon pellet requires at least 240 minutes to reach 99% carbon oxidation as determined from thermogravimetric analysis, and a thermogravimetric graph of weight loss versus time from a thermogravimetric analysis measuring the oxygen reactivity of the biocarbon pellet is recorded, the thermogravimetric analysis being performed in the presence of pure oxygen using a temperature ramp of 40°C / minute from 25°C to 950°C.

2. 10. The bio-carbon pellet of claim 1, wherein the bio-carbon pellet requires at least 270 minutes to reach 99% carbon oxidation according to a TGA graph of weight loss versus time from the thermogravimetric analysis.

3. 10. The bio-carbon pellet of claim 1, wherein the TGA graph of weight loss versus time from the thermogravimetric analysis indicates that the bio-carbon pellet requires at least 300 minutes to reach 99% carbon oxidation.

4. 10. The biocarbon pellet of claim 1, wherein a thermogravimetric analysis is performed on an anthracite control sample, the anthracite control sample requires a control time to reach 99% carbon oxidation, and the time required for the biocarbon pellet to reach 99% carbon oxidation is about 85% to about 100% of the control time.

5. 10. The bio-carbon pellet of claim 1, wherein the bio-carbon pellet comprises volatile carbon and the TGA graph exhibits a first carbon oxidation regime associated with the oxidation of volatile carbon, followed by a second carbon oxidation regime associated with the oxidation of fixed carbon.

6. 6. The biocarbon pellet of claim 5, wherein the thermogravimetric analysis exhibits a first derivative curve peak within the first carbon oxidation regime for the biocarbon pellet at a temperature of at least about 500°C.

7. 10. The bio-carbon pellet of claim 1, wherein the bio-carbon pellet comprises at least 60% by weight of fixed carbon.

8. 8. The bio-carbon pellet of claim 7, wherein the bio-carbon pellet comprises at least 70% by weight of fixed carbon.

9. 8. The bio-carbon pellet of claim 7, wherein the bio-carbon pellet comprises at least 80% by weight of fixed carbon.

10. 8. The bio-carbon pellet of claim 7, wherein the bio-carbon pellet comprises at least 85% by weight of fixed carbon.

11. 8. The bio-carbon pellet of claim 7, wherein the bio-carbon pellet comprises at least 90% by weight of fixed carbon.

12. 10. The bio-carbon pellet of claim 1, wherein the bio-carbon pellet comprises up to 10% by weight of ash.

13. 13. The bio-carbon pellet of claim 12, wherein the bio-carbon pellet comprises up to 5% by weight of ash.

14. 13. The bio-carbon pellet of claim 12, wherein the bio-carbon pellet comprises up to 1% by weight of ash.

15. 10. The bio-carbon pellet of claim 1, wherein the bio-carbon pellet comprises up to 20% by weight of total volatile matter.

16. 16. The biocarbon pellet of claim 15, wherein the biocarbon pellet comprises up to 10% by weight of total volatile matter.

17. The bio-carbon pellet of claim 1 , wherein the bio-carbon pellet includes a binder.

18. 18. The biocarbon pellets of claim 17, wherein the binder is selected from starch, thermoplastic 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, 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, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or any combination of the foregoing.

19. 18. The biocarbon pellet of claim 17, wherein the binder is selected from starch, thermoplastic starch, cross-linked starch, starch polymers, derivatives thereof, or any combination of the foregoing.

20. The bio-carbon pellet of claim 1 , wherein the bio-carbon pellet is binder-free.

21. The bio-carbon pellet of claim 1 , wherein the bio-carbon pellet comprises an additive.

22. 22. The biocarbon pellet of claim 21, wherein the additive is selected from an acid, a base, or a salt thereof.

23. 22. The biocarbon pellet of claim 21, wherein the additive is selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

24. 22. The biocarbon pellet of claim 21, wherein the additive is selected from 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 halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

25. The total carbon in the biocarbon pellets is １４ C / １２ 10. The biocarbon pellets of claim 1, which are at least 50% renewable as determined from C isotope ratio measurements.

26. The total carbon in the biocarbon pellets is １４ C / １２ 26. The biocarbon pellet of claim 25, which is at least 90% renewable as determined from C isotope ratio measurements.

27. The total carbon in the biocarbon pellets is １４ C / １２ 26. The biocarbon pellet of claim 25, which is fully renewable as determined from measurements of C isotope ratios.

28. 10. The biocarbon pellets of claim 1, wherein the biocarbon pellets are characterized by a Hardgrove Crushability Index of at least 30.

29. The biocarbon pellets have a dry weight of at least about 20 lb / ft. ３ 2. The biocarbon pellet of claim 1, characterized by a bulk density of

30. 10. The biocarbon pellets of claim 1, wherein the biocarbon pellets have an average pellet size selected from about 1 mm to about 10 cm, calculated as the effective diameter of the biocarbon pellets.

31. 10. The biocarbon pellets of claim 1, wherein the biocarbon pellets have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, pillar-shaped, rod-shaped, pillow-shaped, lentil-shaped, random granular, or combinations thereof.

32. The biocarbon pellets are at least about 100 lbs. ｆ / in ２ 2. The biocarbon pellet of claim 1, characterized by a pellet compressive strength at 25°C of

33. The biocarbon pellets are at least about 150 lbs. ｆ / in ２ 33. The biocarbon pellet of claim 32, characterized by a pellet compressive strength at 25°C of

34. 10. The biocarbon pellets of claim 1, wherein the biocarbon pellets are characterized by a water uptake of up to 20% by weight after immersion in water at 25°C for 24 hours.

35. 2. The biocarbon pellet of claim 1, wherein the biocarbon pellet is characterized as non-self-heating when subjected to a self-heating test according to 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."

36. The biocarbon pellets (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) introducing the pyrolysis vapor into a separation unit, thereby producing a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the pyrolysis precipitate, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the pyrolysis precipitate; (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as the bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; 36. The biocarbon pellet of any one of claims 1 to 35, produced by a process wherein the second bio-reagent has a lower oxygen reactivity than the first bio-reagent according to thermogravimetric analysis, the thermogravimetric analysis being carried out in the presence of pure oxygen using a temperature ramp of 40°C / min from 25°C to 950°C.

37. The biocarbon pellets (a) pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor, thereby producing a first bio-reagent and pyrolysis vapors; (b) providing a carbon-containing condensed matter material, wherein the carbon-containing condensed matter material is a liquid, a solid, or a slurry; (c) contacting the first biological reagent with the carbon-containing condensed matter material, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the carbon-containing condensed matter material; and (d) pelletizing the intermediate material, thereby producing intermediate pellets; (e) optionally drying the intermediate pellets; (f) separately from step (a), pyrolyzing the intermediate pellets in a second pyrolysis reactor, thereby producing a second bio-reagent and a pyrolysis exhaust gas, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same reactor or different reactors; (g) recovering the second bio-reagent as the bio-carbon pellet; the fixed carbon content of the second biological reagent is greater than the fixed carbon content of the first biological reagent; 36. The biocarbon pellet of any one of claims 1 to 35, produced by a process wherein the second bio-reagent has a lower oxygen reactivity than the first bio-reagent according to thermogravimetric analysis using a temperature ramp of 40°C / min from 25°C to 950°C in the presence of pure oxygen.

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