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 of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 220,073, filed on 9 July 2021, which is incorporated herein by reference in its entirety.

[0002] This disclosure generally relates to a pyrolysis process for producing high-yield biocarbon compositions, and to biocarbon compositions produced therefrom. [Background technology]

[0003] Carbon is a platform element in a wide variety of industries, with a vast array of chemical, materials, and fuel applications. Carbon is used as a fuel to generate energy, including electricity. Carbon also has chemical value for various commodities and advanced materials, including metals, metal alloys, composites, carbon fibers, electrodes, and catalyst supports. For metal production, carbon is useful as a reactant to reduce 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. Carbonaceous materials 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 wastes. Due to the rising economic, environmental, and social costs associated with fossil resources, it is preferable to produce carbon-based reagents using renewable biomass. [Overview of the project]

[0005] The disclosed technology addresses the aforementioned needs in the field of this technology.

[0006] Some variations are processes for producing biocarbon pellets, and the process is (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bio-reagent and pyrolysis vapor, (b) Introducing pyrolysis steam into a separation unit to generate a pyrolysis precipitate, which is in the form of a liquid, solid, or slurry. (c) Contacting a first bioreagent with a thermal decomposition precipitate to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the thermal decomposition precipitate. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas (off-gas), wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. Thermogravimetric analysis reveals that the oxygen reactivity of the second bioreagent is lower than that of the first bioreagent. The thermogravimetric analysis is performed in the presence of pure oxygen, using a temperature gradient of 40°C / min from 25°C to 950°C.

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

[0008] In some embodiments, the TGA graph shows a first carbon oxidation regime related to the oxidation of volatile carbon, which is succeeded by a second carbon oxidation regime related to the oxidation of fixed carbon.

[0009] In some embodiments, the volatile carbon oxidation time is defined as the time 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 bioreagent may be at least 25% or at least 50% greater than the mass loss of the second bioreagent.

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

[0011] In some embodiments, thermogravimetric analysis shows that the first bioreagent has an average mass loss rate at least 10% higher in the first carbon oxidation regime compared to the second carbon oxidation regime.

[0012] In some embodiments, thermogravimetric analysis shows a first derivative curve peak for the second bioreagent within the first carbon oxidation regime at temperatures above 500°C, and thermogravimetric analysis shows a first derivative curve peak for the first bioreagent within the first carbon oxidation regime at temperatures between 200°C and 500°C.

[0013] Biomass-containing raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, and fruit You may choose from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination 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 among the multiple stages. The pyrolysis precipitate may be a condensation product of another condenser stage among 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 dust collection unit, or a combination thereof.

[0016] In some embodiments, the intermediate material includes a pyrolysis precipitate adsorbed onto the surface of the first bioreagent. Alternatively or additionally, the intermediate material may include a pyrolysis precipitate absorbed into the bulk phase of the first bioreagent.

[0017] The pyrolysis precipitate may be in liquid form, solid form, or slurry form (a 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, cross-linked 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 powder, 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, their derivatives, or any combination of the above. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0020] In some embodiments, the external binder is not introduced into the intermediate material during pelletization. Note that the pyrolysis precipitate (from the process) itself can function as an in-situ binder. An in-situ binder is not an external binder.

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

[0022] In some embodiments, the first bioreagent is ground using a first mechanical processing device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

[0023] In some embodiments, the intermediate material is crushed using a second mechanical processing device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

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

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

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

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

[0028] Step (f) can be performed at a second thermal decomposition temperature selected, for example, from approximately 300°C to approximately 1250°C. Step (f) can be performed over a second thermal decomposition time selected, for example, from approximately 1 minute to approximately 4 hours.

[0029] In some embodiments, a pyrolysis nonprecipitate is generated in a separation unit, the pyrolysis nonprecipitate is optionally recovered and at least partially oxidized to generate heat, and the heat is optionally used in the process.

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

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

[0032] The pyrolysis flue gas is optionally transported to a separation unit. Alternatively or additionally, the pyrolysis flue gas may be transported to a second separation unit (different from the separation unit of step (b)) operating under effective precipitation conditions for generating a second pyrolysis precipitate, which is in the form of a liquid, solid, or slurry. The process may further include contacting the second pyrolysis precipitate with the first or second bioreagent.

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

[0034] Biocarbon pellets may contain up to 10% by weight of ash. In various embodiments, biocarbon pellets may contain up to 5% by weight of ash or up to 1% by weight of ash.

[0035] The pyrolysis precipitate itself may contain up to 1% by weight of ash, up to 0.1% by weight of ash, or may contain essentially no ash. Low-ash pyrolysis precipitates are beneficial because ash is not added to the first bioreagent, resulting in a low-ash final product.

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

[0037] In some embodiments, at least 10% by weight of carbon in the pyrolysis precipitate is converted into fixed carbon in the biocarbon pellets. In various embodiments, at least 20% by weight or at least 50% of the carbon in the pyrolysis precipitate is converted into fixed carbon in the biocarbon pellets. In a particular embodiment, 30% to 90% by weight of carbon in the pyrolysis precipitate is converted into fixed carbon in the biocarbon pellets.

[0038] In some embodiments, 1% to 50% by weight of the fixed carbon in the biocarbon pellets originates from pyrolysis precipitates. In certain embodiments, 10% to 40% by weight of the fixed carbon in the biocarbon pellets originates from pyrolysis precipitates.

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

[0040] In step (c), less than or all of the first bioreagent can be brought into contact with the pyrolysis precipitate.

[0041] In some embodiments, the total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 14C isotope ratio, it is determined that at least 50% is renewable. The total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 14C isotope ratio, it is possible that at least 90% is renewable. The total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 1C isotope ratio, it may be possible to reproduce it completely.

[0042] Biocarbon pellets can be characterized, for example, by a hard-glob pulverability index of at least 30.

[0043] Biochar pellets can be characterized, for example, by a bulk density of at least about 20 lb / ft 3 on a dry basis.

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

[0045] Biochar pellets can have a pellet effective diameter within 10% or within 5% of the effective pellet diameter of the intermediate pellets. In other embodiments, the biochar pellets have an effective pellet diameter that is more than 110% or less than 90% of the effective pellet diameter of the intermediate pellets.

[0046] Biochar pellets can have a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, columnar, rod-shaped, pillow-shaped, lens bean-shaped, random granular, or combinations thereof.

[0047] Biochar pellets can be characterized, for example, by a pellet compressive strength at 25°C of at least about 100 lb f / in 2 or at least about 150 lb f / in 2 .

[0048] Biochar pellets can be characterized by a water uptake at 25°C of a maximum of 20 wt% after 24 hours of immersion in water.

[0049] Biochar pellets can be characterized as non-self-heating when subjected to a self-heating test in accordance with Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: ‘‘Test method for self-heating substances’’.

[0050] The process may further include introducing additives during the process. Additives may be selected from acids, bases, or salts thereof. Alternatively or additionally, additives may be selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In some embodiments, additives may 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

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

[0052] Additives can be selected to adjust the pH of the biocarbon pellet filtrate. The filtrate pH is measured by combining 20 grams of biocarbon pellets or their powder form 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] Additives can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent. 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, additives are added to the second bioreagent to lower the filtrate pH of the second bioreagent. In other embodiments, additives are 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 biocarbon pellets as a percentage of the carbon contained in the biomass-containing raw material. 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, biocarbon pellets are mechanically processed to produce biocarbon powder. Alternatively or additionally, biocarbon pellets can be combined with another amount of a second bioreagent to produce a biocarbon material. The other amount of the second bioreagent may, for example, be in pellet form or in powder form.

[0057] Another variant is a process for manufacturing biocarbon pellets, where the process is (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry. (c) Contacting a first bioreagent with a carbon-containing condensate material to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the carbon-containing condensate material. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. The second bioreagent provides a process in which the oxygen reactivity of the first bioreagent is lower than that of the first bioreagent, as determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen.

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

[0059] In some embodiments, the TGA graph shows a first carbon oxidation regime related to the oxidation of volatile carbon, which is succeeded by a second carbon oxidation regime related to the oxidation of fixed carbon.

[0060] In some embodiments, the volatile carbon oxidation time is defined as the period 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 bioreagent may have a mass loss of at least 25% or at least 50% compared to the second bioreagent.

[0061] In some embodiments, thermogravimetric analysis shows that the first bioreagent 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 bioreagent in the first carbon oxidation regime.

[0062] In some embodiments, thermogravimetric analysis shows that the first bioreagent has an average mass loss rate at least 10% higher in the first carbon oxidation regime compared to the second carbon oxidation regime.

[0063] In some embodiments, thermogravimetric analysis shows a first derivative curve peak for the second bioreagent within the first carbon oxidation regime at temperatures above 500°C, and thermogravimetric analysis shows a first derivative curve peak for the first bioreagent within the first carbon oxidation regime at temperatures between 200°C and 500°C.

[0064] Biomass-containing raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, and fruit You may choose from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

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

[0066] In some embodiments, the carbon-containing condensate material includes aromatic species. For example, the carbon-containing condensate material may be off-spec or waste aromatic flow. In certain embodiments, the carbon-containing condensate material includes lignin.

[0067] In some embodiments, the carbon-containing condensate includes sugars or sugar decomposition products.

[0068] In some embodiments, the carbon-containing condensate material includes a polymer or polymer decomposition products.

[0069] In some embodiments, the carbon-containing condensate material comprises a liquid product generated by a chemical reaction of synthesis gas, the synthesis gas being optionally obtained from pyrolysis vapor or pyrolysis exhaust gas.

[0070] In some embodiments, the carbon-containing condensate material is 14 C / 12 Determined from measurements of 14C isotope ratios, it contains at least 50%, at least 90%, or 100% (completely) renewable carbon.

[0071] In some embodiments, the intermediate material comprises a carbon-containing condensate material adsorbed onto the surface of the first bioreagent. Alternatively or additionally, the intermediate material may comprise a carbon-containing condensate material absorbed into the bulk phase of the first bioreagent.

[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, cross-linked 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 powder, 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, their derivatives, or any combination of the above. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0074] In some embodiments, the external binder is not introduced into the intermediate material during pelletization. Note that the pyrolysis precipitate (from the process) itself can function as an in-situ binder. An in-situ binder is not an external binder.

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

[0076] In some embodiments, the first bioreagent is ground using a first mechanical processing device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

[0077] In some embodiments, the intermediate material is crushed using a second mechanical processing device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

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

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

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

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

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

[0083] In some embodiments, the pyrolysis vapor is at least partially oxidized to generate heat, which is then optionally used within the process.

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

[0085] In some embodiments, the pyrolysis exhaust gas is transported to a separation unit operating under effective precipitation conditions for generating a second pyrolysis precipitate, which is in liquid or solid form. In certain embodiments, the process further includes contacting a first bioreagent with the second pyrolysis precipitate. In certain embodiments, the process further includes contacting a second bioreagent with the second pyrolysis precipitate.

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

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

[0088] In some embodiments, the biocarbon pellets contain up to 20% by weight of total volatile matter, for example, up to 10% by weight of total volatile matter.

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

[0090] In some embodiments, 1% to 50% by weight of the fixed carbon in the biocarbon pellets originates from the carbon-containing condensate material. In certain embodiments, 10% to 40% by weight of the fixed carbon in the biocarbon pellets originates from the carbon-containing condensate material.

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

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

[0093] In some embodiments, the total carbon in the biocarbon pellet is the total carbon 14 C / 12 Determined from the measurement of the 1C isotope ratio, at least 50% is renewable. In one embodiment, the total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 1C isotope ratio, it is determined that at least 90% is regenerative, or that it is completely regenerative.

[0094] In some embodiments, the biocarbon pellets are characterized by a hard-glob pulverability index of at least 30.

[0095] In some embodiments, the biocarbon pellets are at least about 20 lbs / 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 approximately 1 mm to approximately 10 cm, which is calculated as the effective diameter of the biocarbon pellet.

[0097] The biocarbon pellets may have an effective pellet diameter of 10% or 5% of the effective pellet diameter of the intermediate pellets. In other embodiments, the biocarbon pellets have an effective pellet diameter of more 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, columnar, rod-shaped, pillow-shaped, lentil-shaped, random granular, or a combination thereof.

[0099] In some embodiments, the biocarbon pellets are at least about 100 lb f / in 2 It is characterized by the pellet compressive strength at 25°C.

[0100] In some embodiments, the biocarbon pellets are at least about 150 lb f / in 2 It is characterized by the pellet 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 24 hours of immersion in water.

[0102] In some embodiments, 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 includes introducing an additive during the process. The additive can be selected from acids, bases, or salts thereof. The additive can be selected from metals, metal oxides, metal hydroxides, metal halides, or combinations 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

[0104] Additives can be selected to adjust the pH of the biocarbon pellet filtrate. The filtrate pH is measured by combining 20 grams of biocarbon pellets or their powder form 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] Additives can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent. 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. Additives can also be added to the second bioreagent to lower the filtrate pH of the second bioreagent. Alternatively, additives can be added to the second bioreagent to increase the filtrate pH of the second bioreagent. If additives are added for reasons other than pH adjustment, the additives added to the second bioreagent may not cause a change in the filtrate pH of the second bioreagent.

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

[0107] In some embodiments, the process provides a total carbon yield of at least 50%, calculated as the carbon contained in the biocarbon pellet as a percentage of the sum of the carbon in the biomass-containing raw material and the carbon in the carbon-containing condensate 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] Selectively, biocarbon pellets are formed and then mechanically processed to produce biocarbon powder.

[0110] The biocarbon pellet is optionally combined with another amount of a second bioreagent to produce a biocarbon object.

[0111] Several variations provide biocarbon pellets containing fixed carbon having a fixed carbon content of at least 60 wt%. The biocarbon pellets are characterized by thermogravimetric analysis to measure the oxygen reactivity of the biocarbon pellets, where the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature gradient of 40°C / min from 25°C to 950°C, and according to a thermogravimetric analysis graph of weight loss versus time ("TGA graph"), the biocarbon pellets require at least 240 minutes to reach 99% carbon oxidation.

[0112] In some embodiments of biocarbon pellets, according to a TGA graph of weight loss versus time from thermogravimetric analysis performed using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen, the biocarbon 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, and the anthracite control sample requires a control time to reach 99% carbon oxidation, while the time required for the biocarbon pellet to reach 99% carbon oxidation is approximately 85% to 100% of the control time. In various embodiments, the time required for the biocarbon pellet to reach 99% carbon oxidation is approximately 90% to 100% of the control time, for example, approximately 95% to 98%.

[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, which is succeeded by a second carbon oxidation regime associated with the oxidation of fixed carbon. In certain embodiments, thermogravimetric analysis shows a first derivative curve peak within the first carbon oxidation regime for the biocarbon pellets at temperatures above 500°C.

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

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

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

[0118] In some embodiments, the biocarbon pellets include a binder. The binder can be selected from starch, thermoplastic starch, cross-linked 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 granules, 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 thereof. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0119] In some embodiments, the biocarbon pellets do not contain a binder. In some embodiments, the biocarbon pellets do not contain a binder other than a pyrolysis precipitate.

[0120] In some embodiments, the biocarbon pellets include additives. The additives can be selected from acids, bases, or salts thereof. The additives can be selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In various embodiments, the additives 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

[0121] In some embodiments, the total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 14C isotope ratio, it is determined to be at least 50%, at least 90%, or completely recyclable.

[0122] In some embodiments, the biocarbon pellets are characterized by a hard-glob pulverability index of at least 30.

[0123] In some embodiments, the biocarbon pellets are at least about 20 lbs / 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 approximately 1 mm to approximately 10 cm, which is calculated as the effective diameter of the biocarbon pellet.

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

[0126] In some embodiments, the biocarbon pellets are at least about 100 lb f / in 2 Or at least about 150 lb f / in 2 It is characterized by the pellet 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 24 hours of immersion in water.

[0128] In some embodiments, 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) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) Introducing pyrolysis steam into a separation unit to generate a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a liquid, solid, or slurry. (c) Contacting a first bioreagent with a thermal decomposition precipitate to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the thermal decomposition precipitate. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. Thermogravimetric analysis revealed that the oxygen reactivity of the second bioreagent was lower than that of the first bioreagent, and that it could be produced by a process in which thermogravimetric analysis was performed in the presence of pure oxygen, using a temperature gradient of 40°C / min from 25°C to 950°C.

[0130] Biocarbon pellets, (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry. (c) Contacting a first bioreagent with a carbon-containing condensate material to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the carbon-containing condensate material. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. A second bioreagent can be produced by a process that exhibits lower oxygen reactivity than the first bioreagent, as determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen.

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

[0132] A biocarbon composition (e.g., powder) (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) Introducing pyrolysis steam into a separation unit to generate a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a liquid, solid, or slurry. (c) Contacting a first bioreagent with a thermal decomposition precipitate to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the thermal decomposition precipitate. (d) Separately from step (a), the intermediate material is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (e) recovering the second bioreagent as a biocarbon composition, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. Thermogravimetric analysis revealed that the oxygen reactivity of the second bioreagent was lower than that of the first bioreagent, and that it could be produced by a process in which thermogravimetric analysis was performed in the presence of pure oxygen, using a temperature gradient of 40°C / min from 25°C to 950°C.

[0133] A biocarbon composition (e.g., powder) (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry. (c) Contacting a first bioreagent with a carbon-containing condensate material to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the carbon-containing condensate material. (d) Separately from step (a), the intermediate material is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (e) recovering the second bioreagent as a biocarbon composition, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. A second bioreagent can be produced by a process that exhibits lower oxygen reactivity than the first bioreagent, as determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen. [Brief explanation of the drawing]

[0134] [Figure 1]An exemplary block flow diagram of a process and system for pyrolysis of biomass in a first pyrolysis reactor to produce bioreagents and pyrolysis vapors is shown. The pyrolysis vapors are sent to a separation unit that produces pyrolysis precipitates and pyrolysis non-precipitates. The pyrolysis precipitates are supplied to an optional mixing unit, to which the bioreagents are also supplied. The combined materials are sent to a pelletizing unit to produce intermediate pellets. Alternatively, there is no mixing unit, and the pyrolysis precipitates and bioreagents are supplied directly to the pelletizing unit. A binder is optionally added to the pelletizing unit. The pellets are then supplied to a second pyrolysis reactor that produces biocarbon products. The second pyrolysis reactor also produces pyrolysis exhaust gases, which can be recycled (e.g., returned to the separation unit) or treated in another way (e.g., burned). Dotted boxes and lines indicate optional units and flows, respectively.

[0135] [Figure 2] An exemplary block flow diagram of a process and system for pyrolysis of biomass in a first pyrolysis reactor to produce bioreagents and pyrolysis vapors is shown. Carbon-containing condensate material is supplied to an optional mixing unit, to which the bioreagents are also supplied. The combined material is sent to a pelletizing unit to produce intermediate pellets. Alternatively, there is no mixing unit, and the carbon-containing condensate material and bioreagents are supplied directly to the pelletizing unit. A binder is optionally added to the pelletizing unit. The pellets are then supplied to a second pyrolysis reactor to produce biocarbon products. Dotted boxes and lines represent optional units and flows, respectively.

[0136] [Figure 3] The TGA results for the biocarbon pellets of Example 1, which included pyrolysis tar carbonization, are shown, compared to the profile of biocarbon pellets without pyrolysis tar carbonization.

[0137] [Figure 4]The TGA results for the samples of Example 2 are shown to characterize their oxygen reactivity compared to anthracite control samples. [Modes for carrying out the invention]

[0138] Several variations are based on the discovery that pelletizing bioreagents and simultaneously or sequentially adding pyrolysis precipitates derived from pyrolysis vapors enhances the reaction that forms fixed carbon in the pelletized solid, thereby significantly increasing the yield of fixed carbon. Furthermore, the manufactured biocarbon pellets 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 biomaterials. The chemical energy contained in biomass comes from solar energy, which is used in the natural process of photosynthesis. Photosynthesis is the process by which plants take in carbon dioxide and water from their surroundings and use energy from sunlight to convert these into sugars, starch, cellulose, hemicellulose, and lignin. Of all renewable energy sources, biomass is unique in that it is effectively stored solar energy. Furthermore, biomass is the only renewable carbon source.

[0140] Various conversion technologies exist for transforming biomass raw materials into high-carbon materials. Pyrolysis is a process for thermally converting solid materials in the complete absence of an oxidizing agent (air or oxygen) and with a limited supply such that oxidation does not occur to a noticeable degree. Depending on the process conditions and additives, biomass pyrolysis can be controlled to produce a wide range of gases, liquids, and solids. Lower process temperatures and longer vapor residence times are favorable for solid production. Higher temperatures and longer residence times increase the conversion of biomass to synthesis gas, while moderate temperatures and short vapor residence times are generally optimal for producing liquids. Historically, the slow pyrolysis of wood has been carried out in large piles in simple batch processes without emission control. Traditional charcoal production techniques are not only energy inefficient but also highly polluting.

[0141] In particular, improved or optimized processes for producing biocarbon compositions are desired with respect to carbon yield and biocarbon properties, such as reactivity.

[0142] This description will enable those skilled in the art to construct and use the present invention and will describe several embodiments, adaptations, variations, alternatives, and uses of the present invention. These and other embodiments, features, and advantages of the present invention will become more apparent to those skilled in the art upon further detailed description of this disclosure in conjunction with the accompanying drawings.

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

[0144] definition As used herein and in the appended claims, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0145] Unless otherwise indicated, all figures used in this specification and the claims, such as reaction conditions, stoichiometry, and component concentrations, should be understood in all cases to be modified by the term "approximately." Therefore, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending at least on the specific analytical technique.

[0146] As used herein, the term “approximately” means ±20% of the indicated range, value, or structure unless otherwise indicated.

[0147] Where used herein, any concentration range, percentage range, ratio range, or integer range should be understood, unless otherwise indicated, to include any integer values ​​within the listed range and, where appropriate, fractions thereof (such as one-tenth and one-hundredth of an integer). Similarly, any range of numbers listed herein should be understood, unless otherwise indicated, to include any integers within the listed range.

[0148] As used herein, “a range from or between about X, Y, or Z” includes “at least X to a maximum of Z.”

[0149] The term "comprising," which is synonymous with "including," "containing," or "characterized by," is comprehensive or open-ended and does not exclude additional unlisted elements or method steps. "Comprising" is a technical term used in claim language to mean that a specified claim element is essential, but other claim elements can be added and still form components within the scope of the claim.

[0150] As used herein, "consisting of" excludes any element, step, or component not specified in the claim. If the phrase "consists of" (or a variation thereof) appears in a section of the claim rather than immediately following the preamble, the phrase limits only the elements described in that section and does not exclude other elements as a whole from the claim. As used herein, the phrase "consisting essentially of" limits the scope of the claim to the specified element or method step, in addition to any other elements that do not substantially affect the basis of the claimed subject matter or novel features.

[0151] With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” if any of these three terms is used herein, the subject matter disclosed and claimed herein may include the use of any of the other two terms. Accordingly, in some embodiments not expressly enumerated elsewhere, any instance of “comprising” may be replaced by “consisting of,” or alternatively by “consisting essentially of.”

[0152] Where used herein, unless expressly stated otherwise, “or” refers to an inclusive “or” and not an exclusive “or.” Unless the word “or” is expressly limited to meaning only one item that is exclusive to the other items in a list of two or more items, the use of “or” in such a list should be interpreted as including (a) any one item in the list, (b) all items in the list, or (c) any combination of items in the list. Where used herein, the phrase “and / or” such as “A and / or B” refers to A alone, B alone, or A and B together. Where the context allows, singular or plural terms may also include plural or singular terms, respectively.

[0153] As used herein, “biological” refers to materials (raw materials, products, or intermediates) containing elements such as carbon that are renewable on a timescale of months, years, or decades. Non-biological materials may be non-renewable or renewable on a timescale of centuries, millennia, millions of years, or even longer geological timescales. For example, conventional fuel sources such as coal and petroleum are non-renewable and non-biological. Biological materials may essentially be derived from biological sources. It will be understood by those skilled in the art that biological materials as or derived from natural sources may contain trace amounts of non-biological materials. Furthermore, the processes disclosed herein may be used with non-biological materials, although the beneficial environmental impact may not be significant.

[0154] The three natural isotopes of carbon, 12 C, 13 C, and 14 C exists. 12 C and 13 C is stable and occurs naturally in a ratio of approximately 93:1. 14 C is produced by thermal neutrons from cosmic radiation in the upper atmosphere, transported to Earth, and absorbed by living biological materials. Isotopeically, 14Although C constitutes a negligible portion, it is detectable by radiometric measurements because it is radioactive with a half-life of 5,700 years. Dead tissue, 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 It takes in C. Then, when an animal consumes a plant, or consumes another animal that consumes a plant, 14 They take in C into their bodies. Therefore, living plants and animals take in the same CO2 as in the atmosphere. 14 C vs 12 It has a C ratio. When an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer... 14 It does not take in C. Next, radioactive decay occurs in living organisms. 14 It gradually depletes the amount of carbon. This effect is the basis for radiocarbon dating.

[0156] Fossil fuels such as coal are primarily made from plant material that accumulated millions of years ago. During this period, 14 Because it is equivalent to thousands of half-lives of C, it is essentially all of the fossil fuels 14 C is decaying. Also, because fossil fuels were originally formed from living organisms, they are affected by the atmosphere. 13 Carbon is depleted. Therefore, carbon from fossil fuels is less beneficial compared to biocarbon. 13 C and 14 Both C resources are depleted.

[0157] This difference between carbon isotopes from recently depleted organic materials, such as those from renewable resources, and carbon isotopes from fossil fuels such as coal, allows for the determination of the carbon source in a composition. Specifically, it determines whether the carbon in the composition originates from renewable resources or fossil fuels; in other words, whether renewable resources or fossil fuels were used in the production of the composition.

[0158] Biomass is a term used to describe biologically produced substances or biomaterials. Biomass refers to a mass of living organisms, including plants, animals, and microorganisms, or, from a biochemical standpoint, cellulose, lignin, sugars, fats, and proteins. Biomass includes both the above-ground and below-ground tissues of plants, such as leaves, twigs, branches, and trunks, as well as the roots of trees and the rhizomes of grasses. The chemical energy contained in biomass comes from solar energy, which is used in the natural process of photosynthesis. This is the process by which plants take in carbon dioxide and water from their surroundings and use the energy from sunlight to convert them into sugars, starch, cellulose, hemicellulose, and lignin. Biomass is useful in that it is effectively stored solar energy. Biomass is the only renewable carbon source.

[0159] As used herein, “total carbon” is the sum of fixed and unfixed carbon present in a volatile substance. In some embodiments, the weight percentages of components are on an absolute basis, which is assumed unless otherwise specified. In other embodiments, the weight percentages of components are on an anhydrous and ashless basis.

[0160] As used herein, “zone” refers to a region of space within a single physical unit, a physically separated unit, or any combination thereof. With respect to a continuous reactor, zone boundaries may relate to structures such as the presence of flights within the reactor or separate heating elements for providing heat to separate zones. Alternatively or additionally, zone boundaries within a continuous reactor may relate to features such as separate temperatures, fluid flow patterns, solid flow patterns, or the degree of reaction. In a single-batch reactor, “zone” is an operating regime in time, rather than space. There are not necessarily abrupt transitions from one zone to another. For example, the boundary between a preheating zone and a pyrolysis zone may be somewhat arbitrary, with some amount of pyrolysis occurring in part of the preheating zone and some amount of “preheating” continuing in the pyrolysis zone. The temperature profile within the reactor, including the zone boundaries within the reactor, is typically continuous.

[0161] For the purposes of this text, “reagent” is intended to mean a material in its broadest sense, which may include fuels, chemicals, materials, compounds, additives, blend components, solvents, etc. A reagent does not necessarily have to be a chemical agent 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 modifying the mechanical, physical, or hydrodynamic properties of a material to which the reagent may be added. For example, a reagent can be introduced into a metal to impart a particular strength property to the metal. A reagent may be a substance of sufficient purity (typically carbon purity in the current context) to be used for chemical analysis or physical testing.

[0162] As used herein, “derivative” is a compound, molecule, or ion derived from another substance by a chemical reaction. The substance from which the derivative is derived is an additive. The 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 can be produced by processes and systems as disclosed in various embodiments. Any limitations regarding carbon content or any other concentration should be attributed not from the terms themselves, but only by reference to specific embodiments and their equivalents.

[0164] Some variations are processes for producing biocarbon pellets, and the process is (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) Introducing pyrolysis steam into a separation unit to generate a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a liquid, solid, or slurry. (c) Contacting a first bioreagent with a thermal decomposition precipitate to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the thermal decomposition precipitate. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. Thermogravimetric analysis reveals that the oxygen reactivity of the second bioreagent is lower than that of the first bioreagent. The process provides to perform thermogravimetric analysis in the presence of pure oxygen, using a temperature gradient 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 a first and a second biological reagent, a sample of the first biological reagent can be collected after its preparation in step (a), while a sample of the second biological reagent 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 instrument that accommodates many samples (see, for example, Figure 4).

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

[0167] In some embodiments, the TGA graph shows a first carbon oxidation regime related to the oxidation of volatile carbon, which is succeeded by a second carbon oxidation regime related to the oxidation of fixed carbon.

[0168] In some embodiments, the volatile carbon oxidation time is defined as the time 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 bioreagent may be at least 25% or at least 50% greater than the mass loss of the second bioreagent.

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

[0170] In some embodiments, thermogravimetric analysis shows that the first bioreagent has an average mass loss rate at least 10% higher in the first carbon oxidation regime compared to the second carbon oxidation regime.

[0171] In some embodiments, thermogravimetric analysis shows a first derivative curve peak for the second bioreagent within the first carbon oxidation regime at temperatures above 500°C, and thermogravimetric analysis shows a first derivative curve peak for the first bioreagent within the first carbon oxidation regime at temperatures between 200°C and 500°C.

[0172] Biomass-containing raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, and fruit You may choose from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination 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 may be, for example, a condensation product of a first condenser stage among the multiple stages. Alternatively or additionally, the pyrolysis precipitate may be a condensation product of a second, third, or later condenser stage among the multiple stages. The pyrolysis precipitate may be a condensation product that is a combination of multiple condensation products from multiple stages, which may be equal to or less than the multiple stages present in the condensation system.

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

[0175] In various embodiments, the separation unit is a condensing 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 dust collection unit, or a combination thereof, or includes them.

[0176] If the separation unit includes a condensing unit, the condensing unit may be a single-stage condenser or a multi-stage condensing system, as discussed earlier. 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 may be a direct-contact condenser or an indirect condenser (e.g., a surface condenser such as a shell-and-tube condenser).

[0177] When 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 to cause liquid-vapor separation, especially when the centrifugal force is sufficient to outweigh the other forces. Exemplary centrifugal forces range from about 10g to about 1000g, for example, about 100 to 500g, where g is gravity.

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

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

[0180] If 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 cross-flow filters. The filtration medium can be selected to separate components by, for example, molecular weight, particle size, or viscosity.

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

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

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

[0184] If the separation unit includes a liquid-liquid extraction unit, an exemplary type of liquid-liquid extraction unit includes, for example, a mixer-setra, a centrifugal extractor, a static extraction column, a stirred extraction column, and a multi-stage backflow extraction unit. Liquid-liquid extraction can use, for example, an extraction solvent that is or contains an aromatic hydrocarbon. In some embodiments, the extraction solvent is a recovered pyrolysis precipitate. The liquid-liquid extraction unit can be operated in continuous mode or batch mode.

[0185] If the separation unit includes an electrostatic precipitator, exemplary types of electrostatic precipitators include electrostatic precipitators, electrostatic separators, electrodynamic separators, capacitor-based separators, and other means or devices that employ the principle of separation by electric force. Electrostatic precipitators can be designed to collect droplets using electric field force. Electrostatic precipitators operate by charging particles (e.g., droplets) and then collecting the charged particles in an electric field. Charging occurs through two mechanisms: diffusion charging and field charging. Diffusion charging occurs when ions in a gas bounce off particles due to Brownian motion, colliding with them and transferring their charge to the particles. Field charging occurs when particles are located within an electric field containing ions. Electrostatic precipitators use a high-voltage power supply to generate 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 droplets. A discharge electrode may be suspended in the center of the pipe and act as a high-voltage (e.g., ±10 to 100 kV DC) electrode. The high voltage applied to the electrode forms an electrostatic field between the electrode and the ground channel. This field projects a force onto particles passing through it. As the particles pass through the field, they move towards the ground wall and thus accumulate on the wall. By gravity, the collected liquid flows down the electrostatic precipitator and is collected. The electrostatic precipitator uses either a positive or negative polarity power supply.

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

[0188] In some embodiments, the intermediate material includes a pyrolysis precipitate adsorbed onto the surface of the first bioreagent. In these or other embodiments, the intermediate material may include a pyrolysis precipitate absorbed into the bulk phase of the first bioreagent.

[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 phases and one or more solid phases (e.g., a slurry). The viscosity and density of the solid phases can vary widely. For example, the solid phase, or the combined solid-liquid material, may be a gel-like material, an adhesive material, or a rubber-like material.

[0190] By varying the ratio of the pyrolysis precipitate to the first bioreagent, various properties (e.g., reactivity) of the final pellet can be achieved. Varying the ratio can be achieved by bypassing a portion of the first bioreagent and blending the remainder with the pyrolysis precipitate. Alternatively or additionally, two pyrolysis reactors can be operated in parallel, bypassing the pyrolysis precipitate collected from the first pyrolysis reactor to the second pyrolysis reactor. In one scenario, one pyrolysis reactor produces a less reactive product incorporating an additional pyrolysis of twice the amount of the pyrolysis precipitate, while the other pyrolysis reactor produces a more reactive product without additional pyrolysis of the pyrolysis precipitate.

[0191] In some embodiments, steps (c) and (d) are combined. For example, the pyrolysis precipitate can be brought into contact with the first bioreagent in a pelletizing unit.

[0192] A binder can be introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, cross-linked 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 powder, 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, their derivatives, or combinations thereof. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof.

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

[0194] In some processes, step (e) is performed for drying. Steps (d) and (e) may be combined so that drying occurs together with pelletization. Alternatively, steps (e) and (f) may be combined so that both thermal decomposition and drying of the intermediate pellet occur. In certain embodiments, steps (d), (e), and (f) are all combined.

[0195] In some embodiments, the first bioreagent is ground using a mechanical device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof. In these or other embodiments, the intermediate material can be ground using a mechanical device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof. The intermediate material can be ground in place of or in addition to the first bioreagent.

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

[0197] In some processes, the first pyrolysis reactor is different from the second pyrolysis reactor. Alternatively, the first and second pyrolysis reactors may be the same unit, performing steps (a) and (f) 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, for example, 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, for example, about 400°C to about 1000°C. The second pyrolysis temperature may be higher than the first pyrolysis temperature, but this is not required.

[0199] In some embodiments, step (a) is performed over a first thermal decomposition time selected from about 10 seconds to about 24 hours, for example, from about 1 minute to about 4 hours. In these or other embodiments, step (f) is performed over a second thermal decomposition time selected from about 10 seconds to about 24 hours, for example, from about 1 minute to about 4 hours. The second thermal decomposition time may be longer than the first thermal decomposition time, but this is not required.

[0200] In processes such as step (f), the first bioreagent can act as a catalyst or reaction matrix for the fixed carbon formation reaction of the pyrolysis precipitate.

[0201] The pyrolysis nonprecipitate is typically generated within the separation unit. The pyrolysis nonprecipitate is typically a vapor stream and can be purged from the process. The purge stream from the separation unit does not necessarily have to be a 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 containing entrained liquids or solids. In some embodiments, the pyrolysis nonprecipitate is recovered and at least partially oxidized to generate heat, which is optionally used within the process.

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

[0203] Alternatively or additionally, the pyrolysis flue gas may be transported to a second separation unit (different from the separation unit of step (b)) operating under effective precipitation conditions for generating a second pyrolysis precipitate, which may be in the form of a liquid, solid, or slurry. The process may further include contacting the second pyrolysis precipitate with the first or second bioreagent.

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

[0205] In some processes, the pyrolysis precipitate contains less than 1% by weight of ash, less than 0.1% by weight of ash, or is essentially ash-free. Low-ash pyrolysis precipitates are beneficial because ash is not added to the first bioreagent, resulting in a low-ash final product.

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

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

[0208] In some embodiments, about 1% to about 50% by weight of the fixed carbon in the biocarbon pellets comes from pyrolysis precipitates. In certain embodiments, about 10% to about 40% by weight of the fixed carbon in the biocarbon pellets comes from pyrolysis precipitates.

[0209] Optionally, the intermediate material further comprises additional pyrolysis precipitates not provided from step (b) of the process. For example, the additional pyrolysis precipitates may be provided by (i) different biomass-containing raw materials and (ii) pyrolysis processes carried out using different times or locations.

[0210] In step (c), less than or all of the first bioreagent can be brought into contact with the pyrolysis precipitate.

[0211] The total carbon in biocarbon pellets is 14 C / 12 Based on measurements of the 1C isotope ratio, it is possible that at least 50% is renewable. The total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 14C isotope ratio, it may be at least 90% or completely (about 100%) regenerative.

[0212] In some embodiments, the biocarbon pellets are characterized by a hard-globe pulverability index of at least 30 or at least 50.

[0213] In some embodiments, the biocarbon pellets are 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 of 10% or 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; instead, additional process steps are performed to increase or decrease the pellet size back to the size of the intermediate pellets, or back to 10% of that size. In other embodiments, the biocarbon pellets have an effective pellet diameter of more than 110% or less than 90% of the effective pellet diameter of the intermediate pellets. In these embodiments, pyrolysis in the second pyrolysis reactor significantly changes the pellet size; instead, 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, columnar, rod-shaped, pillow-shaped, lentil-shaped, random granular, or a combination thereof.

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

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

[0218] In some embodiments, the biochar pellets are characterized as non-self-heating when subjected to a self-heating test in accordance with Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: ‘‘Test method for self-heating substances’’.

[0219] In some embodiments, the biochar pellets are substantially characterized by oxygen reactivity, as shown in the thermogravimetric analysis of FIG. 3 or FIG. 4 (see Examples 1 and 2 below). The biochar pellets have a lower reactivity with oxygen compared to biochar pellets produced by an equivalent pyrolysis process except for no carbon capture in step (c) at a temperature of about 750 - 950°C.

[0220] Biocarbon pellets can be characterized by their CRI value, or "Coke Reactivity Index." The CRI can be determined according to ASTM D5341, Coke Reactivity Index. As coke lumps descend in a blast furnace, they are subjected to reaction with backflow CO2 and abrasion from rubbing together against the furnace walls. The process flow physically weakens and chemically reacts the coke lumps, reducing their permeability and generating excess fine powder that can lead to increased coke content and losses in molten iron production. CRI testing methods are designed to indirectly measure this behavior of coke or, alternatively, biocarbon in a blast furnace. It should be noted that the chemical reaction explicitly considered by the CRI value is not carbon oxidation, but rather the reverse Boudouar reaction (C + CO2 → 2CO). In certain embodiments, the CRI value is measured by placing a 200-gram sample with particle sizes of 19–22.5 mm into a reactor and heating it to 1100°C in an inert atmosphere. Subsequently, the carbon is isothermally degassed in a 100% CO2 gas atmosphere for 2 hours, and then cooled with nitrogen gas. After cooling, the carbon is weighed and rotated 600 times in a drum, and then the material is sieved through a screen having mesh sizes of +10 and -0.5 mm. The weight loss of 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 of at least 50%, which is calculated as the carbon contained in the biocarbon pellets as a percentage of the carbon contained in the biomass-containing raw material. 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%, which is calculated as the fixed carbon contained in the biocarbon pellet as a percentage of the total carbon contained in the biomass-containing raw material. In some embodiments, the total fixed carbon yield is at least 60%, at least 70%, or at least 80%. The fixed carbon yield cannot be higher than the carbon yield. In some embodiments, additional pyrolysis carried out in a second pyrolysis reactor results in a fixed carbon yield that is close to or even the same as the carbon yield, with most or all of the carbon being fixed carbon in the final biocarbon pellet.

[0223] In some embodiments, the process further includes introducing an additive during the process. The additive can be selected from acids, bases, or salts thereof. The additive can be selected from metals, metal oxides, metal hydroxides, metal halides, or combinations 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

[0224] Additives can be selected to adjust the pH of the biocarbon pellet filtrate. The filtrate pH is measured by combining 20 grams of biocarbon pellets or their powder form 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] Additives can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent. 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. Additives can also be added to the second bioreagent to lower the filtrate pH of the second bioreagent. Alternatively, additives can be added to the second bioreagent to increase the filtrate pH of the second bioreagent. If additives are added for reasons other than pH adjustment, the additives added to the second bioreagent may not cause a change in the filtrate pH of the second bioreagent.

[0226] In some embodiments, the oxygen reactivity of the second bioreagent is reduced by adding an additive to the second bioreagent. The additive can be added after the second bioreagent has been formed, or it can be supplied to, for example, a second pyrolysis reactor, a first pyrolysis reactor, or a pelletizing unit. The additive can be introduced at multiple positions 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 biocarbon pellet as a percentage of the sum of the carbon in the biomass-containing raw material and the carbon in the carbon-containing condensate 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, biocarbon pellets are mechanically processed after their formation to produce biocarbon powder. For example, biocarbon pellets can be manufactured and delivered to another location. At the point of use, the pellets can be powdered and supplied to a reactor for purposes such as combustion, gasification, or metal ore reduction.

[0230] Optionally, biocarbon pellets are combined with another amount of a second bioreagent to produce a biocarbon object. The other amount of the second bioreagent may be pellets, powder, or other forms. In some embodiments, multiple pellets are mechanically pressed together to form a biocarbon object, which may be structural carbon elements for metalworking furnaces, etc.

[0231] Another variant is a process for manufacturing biocarbon pellets, where the process is (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry. (c) Contacting a first bioreagent with a carbon-containing condensate material to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the carbon-containing condensate material. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. The second bioreagent provides a process in which the oxygen reactivity of the first bioreagent is lower than that of the first bioreagent, as determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen.

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

[0233] In some embodiments, the TGA graph shows a first carbon oxidation regime associated with the oxidation of volatile carbon, which is succeeded 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 bioreagent may have at least 25% or at least 50% mass loss compared to the second bioreagent.

[0235] In some embodiments, thermogravimetric analysis shows that the first bioreagent 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 bioreagent in the first carbon oxidation regime.

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

[0237] In some embodiments, thermogravimetric analysis shows a first derivative curve peak within the first carbon oxidation regime for the second bioreagent at temperatures above 500 °C, and thermogravimetric analysis shows a first derivative curve peak within the first carbon oxidation regime for the first bioreagent at temperatures between 200 °C and 500 °C.

[0238] Biomass-containing raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, and fruit You may choose from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

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

[0240] For example, toluene is a carbon-containing condensable material that is in liquid form at a pressure of 1 bar and a temperature of approximately -95°C to 111°C, and is vapor above 111°C. Therefore, toluene can be a carbon-containing condensable material in the disclosed process. In comparison, methane has a boiling point of -162°C at a pressure of 1 bar and is therefore not a preferred carbon-containing condensable material in the disclosed process.

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

[0242] The carbon-containing condensate material can be in solid or liquid form at temperatures around the temperature of the contact unit used to bring a first bioreagent into contact with the carbon-containing condensate material, which is typically either a mixing unit or a pelletizing unit. For example, if the contact unit is operated at approximately 100°C, the carbon-containing condensate material should be in a solid or liquid phase at 100°C, not just a vapor phase. Essentially, the boiling point of the carbon-containing condensate material should be the same as or higher than the temperature of the contact unit (where the boiling point is calculated using the pressure of the contact unit). If the contact unit is operated at very low temperatures (e.g., cryogenic temperatures), a vaporized carbon-containing material can usually be used if the carbon-containing material is actually in a condensate phase.

[0243] Carbon-containing condensate materials can be liquids, solids, liquid-solid slurries, gas-liquid materials (e.g., having bubbles dissolved in a liquid or vapors accompanied by droplets), gas-liquid-solid materials, gels, plastics, rubbery materials, tacky materials, or sticky materials. The phases and properties (e.g., rheological properties) of carbon-containing condensate materials depend to some extent on the type of separation unit.

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

[0245] In some embodiments, the carbon-containing condensate material includes aromatic species. For example, the carbon-containing condensate material may be off-spec or waste aromatic streams (e.g., benzene / toluene / xylene streams).

[0246] In some embodiments, the carbon-containing condensate material is or comprises lignin. The lignin may be natural lignin with a high molecular weight, such as a lignin polymer obtained from lignocellulosic biomass. Alternatively, the lignin may be depolymerized lignin with a reduced molecular weight compared to natural lignin.

[0247] In some embodiments, the carbon-containing condensate material is one or more sugars or one or more sugar decomposition products, or comprises them. The sugars are, for example, C5 sugars (e.g., xylose), C6 sugars (e.g., glucose), C 12 The sugar may be a sugar (e.g., sucrose) or a sugar oligomer (e.g., xylan). The sugar decomposition product may include, for example, furfural, hydroxymethylfurfural, levulinic acid, or formic acid. The carbon-containing condensate material may be, or may contain, biomass-derived materials other than sugars or lignin, such as acetic acid, proteins, or decomposed proteins.

[0248] In certain embodiments, the carbon-containing condensate material is or comprises 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 biocarbon pellets.

[0249] In some embodiments, the carbon-containing condensate material is one or more polymers or one or more polymer decomposition products, or comprises them. For example, the carbon-containing condensate material may be polyethylene, polyethylene terephthalate, rubber (e.g., natural rubber 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 biocarbon pellets.

[0250] In some embodiments, the carbon-containing condensate material comprises a liquid product generated by a chemical reaction of synthesis gas, the synthesis gas being optionally obtained from pyrolysis vapor or pyrolysis exhaust gas.

[0251] Carbon-containing condensed material is 14 C / 12 Based on measurements of the carbon isotope ratio, it may contain at least 50% renewable carbon. Carbon-containing condensate materials are 14 C / 12 Based on measurements of 14C isotope ratios, it may contain at least 90%, at least 95%, at least 99%, or approximately 100% renewable carbon.

[0252] The intermediate material may include a carbon-containing condensate material adsorbed onto the surface of the first bioreagent. Alternatively or additionally, the intermediate material may include a carbon-containing condensate material absorbed into the bulk phase of the first bioreagent.

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

[0254] A binder can be introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, cross-linked 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 powder, 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, their derivatives, or any combination of the above. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0255] In other processes, external binders are not introduced into the intermediate material during pelletization. Bonding can still occur. For example, carbon-containing aggregate materials themselves can function as pellet binders.

[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 a particular process, steps (d), (e), and (f) are all combined.

[0258] The first bioreagent can be ground using a mechanical device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof. Alternatively or additionally, the intermediate material can be ground using a mechanical device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

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

[0260] The first pyrolysis reactor may be different from the second pyrolysis reactor. Alternatively, the first and second pyrolysis reactors may be the same unit, with steps (a) and (f) performed at different times.

[0261] In some processes, step (a) is performed at a first pyrolysis temperature selected from approximately 250°C to approximately 1250°C, for example, approximately 300°C to approximately 700°C. In some processes, step (f) is performed at a second pyrolysis temperature selected from approximately 250°C to approximately 1250°C, for example, approximately 400°C to approximately 1000°C.

[0262] In some processes, step (a) is performed over a first pyrolysis time selected from approximately 10 seconds to approximately 24 hours, for example, from approximately 1 minute to approximately 4 hours. In some processes, step (f) is performed over a second pyrolysis time selected from approximately 10 seconds to approximately 24 hours, for example, from approximately 1 minute to approximately 4 hours.

[0263] During or potentially before step (f), the first bioreagent can act as a catalyst or reaction matrix for the fixed carbon formation reaction of the carbon-containing condensate material.

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

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

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

[0267] In some embodiments, about 1% to about 50% by weight of the fixed carbon in the biocarbon pellets comes from the carbon-containing condensate material. In certain embodiments, about 10% to about 40% by weight of the fixed carbon in the biocarbon pellets comes from the carbon-containing condensate material.

[0268] In step (c), less than the total amount of the first bioreagent is brought into contact with the carbon-containing condensate material.

[0269] The total carbon in biocarbon pellets is 14 C / 12 Based on measurements of the 1C isotope ratio, it is possible that at least 50% is renewable. The total carbon in the biocarbon pellet is the total carbon14 C / 12 Based on measurements of the 14C isotope ratio, it may be at least 90%, at least 95%, or completely (about 100%) regenerative.

[0270] Biocarbon pellets can be characterized, for example, by a hard-glob pulverability index of at least 30 or at least 50.

[0271] Biocarbon pellets have a dry basis weight of at least approximately 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 approximately 1 mm to approximately 10 cm, which is calculated as the effective diameter of the biocarbon pellet.

[0273] The biocarbon pellets may have an effective pellet diameter of 10% or 5% of the effective pellet diameter of the intermediate pellets. In other embodiments, the biocarbon pellets have an effective pellet diameter of more 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, columnar, rod-shaped, pillow-shaped, lentil-shaped, random granular, or a combination thereof.

[0275] In some embodiments, the biocarbon pellets are at least about 100 lb f / in 2 For example, at least about 150 lb f / in 2 It is characterized by the pellet compressive strength at 25°C.

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

[0277] In some embodiments, 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 includes introducing an additive during the process. The additive can be selected from acids, bases, or salts thereof. The additive can be selected from metals, metal oxides, metal hydroxides, metal halides, or combinations 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

[0279] Additives can be selected to adjust the pH of the biocarbon pellet filtrate. The filtrate pH is measured by combining 20 grams of biocarbon pellets or their powder form 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] Additives can be added to the second bioreagent to adjust the filtrate pH of the second bioreagent. 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. Additives can also be added to the second bioreagent to lower the filtrate pH of the second bioreagent. Alternatively, additives can be added to the second bioreagent to increase the filtrate pH of the second bioreagent. If additives are added for reasons other than pH adjustment, the additives added to the second bioreagent may not cause a change in the filtrate pH of the second bioreagent.

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

[0282] 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''.

[0283] In some embodiments, the process provides a total carbon yield of at least 50%, which is calculated as the carbon contained in the biocarbon pellet as a percentage of the sum of the carbon in the biomass-containing raw material and the carbon in the carbon-containing condensate material. The total carbon yield may be at least 60%, at least 70%, or at least 80%.

[0284] This technology also provides biocarbon pellets produced by any of the disclosed processes.

[0285] Several variants provide biocarbon pellets containing fixed carbon having a fixed carbon content of at least 60 wt%. The biocarbon pellets are characterized by thermogravimetric analysis to measure the oxygen reactivity of the biocarbon pellets, where the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature gradient of 40°C / min from 25°C to 950°C, and according to a TGA graph of weight loss versus time from the thermogravimetric analysis, the biocarbon pellets require at least 240 minutes to reach 99% carbon oxidation.

[0286] In some embodiments of biocarbon pellets, according to a TGA graph of weight loss versus time from thermogravimetric analysis performed using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen, the biocarbon 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, and the anthracite control sample requires a control time to reach 99% carbon oxidation, while the time required for the biocarbon pellet to reach 99% carbon oxidation is approximately 85% to 100% of the control time. In various embodiments, the time required for the biocarbon pellet to reach 99% carbon oxidation is approximately 90% to 100% of the control time, for example, approximately 95% to 98%.

[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, which is succeeded by a second carbon oxidation regime associated with the oxidation of fixed carbon. In certain embodiments, thermogravimetric analysis shows a first derivative curve peak within the first carbon oxidation regime for the biocarbon pellets at temperatures above 500°C.

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

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

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

[0292] In some embodiments, the biocarbon pellets include a binder. The binder can be selected from starch, thermoplastic starch, cross-linked 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 granules, 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 thereof. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0293] In some embodiments, the biocarbon pellets do not contain a binder. In some embodiments, the biocarbon pellets do not contain a binder other than a pyrolysis precipitate.

[0294] In some embodiments, the biocarbon pellets include additives. The additives can be selected from acids, bases, or salts thereof. The additives can be selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In various embodiments, the additives 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or combinations thereof.

[0295] In some embodiments, the total carbon in the biocarbon pellet is the total carbon 14 C / 12 Based on measurements of the 14C isotope ratio, it is determined to be at least 50%, at least 90%, or completely recyclable.

[0296] In some embodiments, the biocarbon pellets are characterized by a hard-glob pulverability index of at least 30.

[0297] In some embodiments, the biocarbon pellets are at least about 20 lbs / 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 approximately 1 mm to approximately 10 cm, which is calculated as the effective diameter of the biocarbon pellet.

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

[0300] In some embodiments, the biocarbon pellets are at least about 100 lb f / in 2 Or at least about 150 lb f / in 2 It is characterized by the pellet 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 24 hours of immersion in water.

[0302] In some embodiments, 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) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) Introducing pyrolysis steam into a separation unit to generate a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a liquid, solid, or slurry. (c) Contacting a first bioreagent with a thermal decomposition precipitate to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the thermal decomposition precipitate. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. Thermogravimetric analysis revealed that the oxygen reactivity of the second bioreagent was lower than that of the first bioreagent, and that it could be produced by a process in which thermogravimetric analysis was performed in the presence of pure oxygen, using a temperature gradient of 40°C / min from 25°C to 950°C.

[0304] Biocarbon pellets, (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry. (c) Contacting a first bioreagent with a carbon-containing condensate material to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the carbon-containing condensate material. (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets, (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (g) recovering the second biological reagent as a biocarbon pellet, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. A second bioreagent can be produced by a process that exhibits lower oxygen reactivity than the first bioreagent, as determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen.

[0305] Some variations assume the recognition that while biocarbon pellets are beneficial in a broad range of embodiments, there are other embodiments in which the final biocarbon composition is not in pellet form, but rather in another form such as powder or film.

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

[0307] Biocarbon composition, (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) Introducing pyrolysis steam into a separation unit to generate a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a liquid, solid, or slurry. (c) Contacting a first bioreagent with a thermal decomposition precipitate to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the thermal decomposition precipitate. (d) Separately from step (a), the intermediate material is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (e) recovering the second bioreagent as a biocarbon composition, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. Thermogravimetric analysis revealed that the oxygen reactivity of the second bioreagent was lower than that of the first bioreagent, and that it could be produced by a process in which thermogravimetric analysis was performed in the presence of pure oxygen, using a temperature gradient of 40°C / min from 25°C to 950°C.

[0308] Biocarbon composition, (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to generate a first bioreagent and pyrolysis vapor, (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry. (c) Contacting a first bioreagent with a carbon-containing condensate material to produce an intermediate material, wherein the intermediate material comprises the first bioreagent and the carbon-containing condensate material. (d) Separately from step (a), the intermediate material is thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors. (e) recovering the second bioreagent as a biocarbon composition, The fixed carbon content of the second bioreagent is greater than that of the first bioreagent. A second bioreagent can be produced by a process that exhibits lower oxygen reactivity than the first bioreagent, as determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen.

[0309] A particular embodiment is a process for producing a biocarbon composition, wherein the process is (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to produce a first bioreagent and a first pyrolysis vapor, (b) Introducing at least a portion of the first pyrolysis vapor into a condensing system to generate a condenser liquid and a condenser vapor, (c) Contacting at least a portion of the first bioreagent with the condenser liquid to generate an intermediate material containing the first bioreagent and the condenser liquid, (d) Optionally, pelletizing the intermediate material, (e) Optionally, separately from step (a), the intermediate material is further thermally decomposed in a second thermal decomposition reactor to produce a second bioreagent and a second thermal decomposition vapor, (f) Optionally, drying the second biological reagent, (g) A process is provided which includes recovering a second bioreagent as a biocarbon composition.

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

[0311] If step (d) is performed, at least a portion of the intermediate material is pelletized. Optionally, the first bioreagent is pelletized either before or after contact with the condenser liquid.

[0312] In some embodiments of pelletizing the intermediate material, a binder is introduced into the intermediate material. The binder can be selected from starch, thermoplastic starch, cross-linked 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 powder, 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, their derivatives, or any combination thereof. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0313] In other embodiments of pelletizing the intermediate material, an external binder is not introduced into the intermediate material during pelletizing. In these cases, the condenser liquid can act as a binder for the pellet.

[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 may be configured, for example, to form a coating of condenser liquid on the pellet.

[0315] In some processes that use step (e), steps (c) and (e) are integrated.

[0316] The condensation system may include multiple condenser stages. In some embodiments, the condenser liquid is the condensation product of the 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 transported to the condensation system.

[0318] The intermediate material may include condenser liquid adsorbed onto the surface of the first bioreagent. Alternatively or additionally, the intermediate material may include condenser liquid absorbed into the bulk phase of the first bioreagent.

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

[0320] The first biological reagent can act as a catalyst or reaction matrix for the fixed carbon formation 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 into fixed carbon in the second bioreagent. In various embodiments, about, at least about, or up to about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% by weight (including the entire intervening range) of the total carbon contained in the condenser liquid is converted into fixed carbon in the second bioreagent.

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

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

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

[0325] In some embodiments, some or all of the condenser vapor is 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 vapor is at least partially oxidized (together with or separately from the condenser vapor) to generate heat, which is optionally used in the process.

[0326] In certain embodiments, pyrolysis exhaust gas or condenser vapor is at least partially oxidized to produce a reducing gas containing hydrogen or carbon monoxide. Such partial oxidation still generates useful heat, but also produces a reducing gas that can be converted to other chemical substances (e.g., methanol or Fischer-Tropsch hydrocarbons) if desired.

[0327] In some embodiments, the first bioreagent is ground using a mechanical device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof. In these or other embodiments, the intermediate material can be ground using a mechanical device selected from a hammer mill, extruder, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

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

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

[0330] In some embodiments, the biocarbon composition is in the form of a powder. In some embodiments, the biocarbon composition is in the form of pellets. In some embodiments, the biocarbon composition is in the form of a film or coating.

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

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

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

[0334] When incorporating a condenser liquid having relatively low ash into the material in the second pyrolysis reactor, the ash content of the biocarbon composition is beneficial (i.e., lower). In some embodiments, the first condenser liquid contains less than 1 wt% ash, less than 0.1 wt% ash, or is essentially ash-free. 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 wt% ash, including all intervening ranges.

[0335] The total carbon in the biocarbon composition 14 C / 12 can be determined from the measurement of the C / 14 C isotope ratio and can be at least 50% renewable. In some embodiments, the total carbon in the biocarbon composition can be determined from the measurement of the C / 12 C isotope ratio and is at least 90% renewable. The total carbon in the biocarbon composition can be determined from the measurement of the C / 14 C / 12 C isotope ratio and can be completely renewable.

[0336] In some processes, the second bioreagent is pelletized during step (f), during step (g), or after step (g). Therefore, the final biocarbon composition may be in the form of pellets.

[0337] In some processes, the biocarbon composition is characterized by a hard globe pulverability index of at least 30 or at least 50. In various embodiments, the biocarbon composition is characterized by a hard globe pulverability 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, encompassing the entire intervening range.

[0338] In some processes, the biocarbon composition is at least about 35 lbs / ft on a dry basis. 3 Or at least about 45 lbs / ft on a dry basis 3 It is characterized by its bulk density. In various embodiments, the bulk density of the biocarbon composition is about or at least about 25, 30, 35, 40, 45, or 50 lb / ft on a dry basis, encompassing the entire intervening range. 3 That is the case.

[0339] In some processes, the biocarbon composition is characterized as hydrophobic biocarbon or partially hydrophobic biocarbon.

[0340] In some processes, biocarbon compositions 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''.

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

[0342] Several variations provide a method for producing a highly fixed carbon material, which includes: pyrolysis of biomass to produce an intermediate solid and pyrolysis vapor; condensation of a portion of the pyrolysis vapor to produce a pyrolysis liquid; introduction of the pyrolysis liquid into the intermediate solid to produce a solid-liquid mixture; optionally, pelletization to produce pellets containing the solid-liquid mixture; and optionally, further pyrolysis of the solid-liquid mixture to produce a highly fixed carbon material with high yield.

[0343] In some methods, the method involves pelletizing to produce pellets containing a solid-liquid mixture. In some embodiments, pelletizing does not utilize a binder other than the pyrolysis liquid. In other embodiments, pelletizing utilizes a binder other than the pyrolysis liquid. The step of further pyrolysis of the solid-liquid mixture can be enhanced by pelletizing, for example, when the carbon contained in the solid-liquid mixture acts as a catalyst or reaction matrix for forming 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] Several variations provide a high fixed carbon material produced by a process that includes a method for producing a high fixed carbon material, which includes: pyrolysis of biomass to produce an intermediate solid and pyrolysis vapor; condensation of a portion of the pyrolysis vapor to produce a pyrolysis liquid; introduction of the pyrolysis liquid into the intermediate solid to produce a solid-liquid mixture; optionally, pelletization to produce pellets containing the solid-liquid mixture; and optionally, further pyrolysis of the solid-liquid mixture to produce a high-yield high fixed carbon material.

[0346] Other variations include a process for producing a biocarbon composition, where the process is (a) In a first pyrolysis reactor, a biomass-containing raw material is pyrolyzed to produce a first pyrolysis solid and a first pyrolysis vapor, (b) Introducing at least a portion of the first pyrolysis vapor into a condensing system to generate a condenser liquid and a condenser vapor, (c) Separately from step (a), the condenser liquid is thermally decomposed in a second thermal decomposition reactor to produce a second thermal decomposition solid and a second thermal decomposition vapor, (d) Blending the first pyrolysis solid with the second pyrolysis solid to produce a bioreagent, (e) Selectively pelletizing the bioreagents, (f) Optionally, drying or heat-treating the bioreagent, (g) A process is provided that includes recovering a bioreagent as a biocarbon composition.

[0347] In some processes, biomass-containing raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beets, sugar beet pulp, sunflowers, sorghum, canola, algae, pampas grass, alfalfa, switchgrass, fruits, and fruit shells. Selected from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

[0348] In some processes, step (e) is performed so that the bioreagent is pelletized. 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, cross-linked 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 powder, 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, their derivatives, or any combination thereof. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0350] In some embodiments using step (e), the external binder is not introduced into the bioreagent during pelletization.

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

[0352] In some embodiments, at least a portion of the second pyrolysis vapor is also transported 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; that is, they are physically different units. In some embodiments, the first and second pyrolysis reactors are the same unit, and steps (a) and (c) are performed at different times.

[0354] In some processes, at least 25% by weight of the total carbon contained in the condenser liquid is converted into fixed carbon in the second pyrolysis solid. In certain processes, at least 50% by weight of the total carbon contained in the condenser liquid is converted into fixed carbon in the second pyrolysis solid. 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 into fixed carbon in the second pyrolysis solid.

[0355] In some processes that incorporate blending 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, approximately 10% to 80% by weight of the fixed carbon in the bioreagent originates from the condenser liquid. In certain processes, approximately 20% to 60% by weight of the fixed carbon in the bioreagent originates from the condenser liquid. In various embodiments, approximately, at least, or up to approximately 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 originates from the condenser liquid.

[0357] Step (a) can be performed at a first pyrolysis temperature selected from approximately 250°C to approximately 1250°C. Optionally, the first pyrolysis temperature can be selected from approximately 300°C to approximately 700°C. Step (c) can be performed independently at a second pyrolysis temperature selected from approximately 250°C to approximately 1250°C. Optionally, the second pyrolysis temperature can be lower or higher than the first pyrolysis temperature, or they can potentially be the same.

[0358] Step (a) can be performed over a first thermal decomposition time selected from approximately 10 seconds to approximately 24 hours. Step (c) can be performed independently over a second thermal decomposition time selected from approximately 10 seconds to approximately 24 hours. The second thermal decomposition time may be shorter or longer than the first thermal decomposition time, or they may be potentially the same.

[0359] In some processes, condenser vapor is at least partially oxidized to generate heat, which is then optionally used within the process. In these or other processes, a second pyrolysis vapor is at least partially oxidized to generate heat, which is then optionally used within the process.

[0360] Bioreagents can be ground using mechanical processing equipment selected from, for example, hammer mills, extruders, attrition mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof.

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

[0362] The biocarbon composition may be in the form of a powder, pellets, or other geometric shapes.

[0363] The biocarbon composition may contain at least 50% by weight of fixed carbon, at least 60% by weight of fixed carbon, at least 70% by weight of fixed carbon, at least 80% by weight of fixed carbon, or at least 90% by weight of fixed carbon. Other fixed carbon content is as described above and applies to these process embodiments (and other processes disclosed herein).

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

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

[0366] In some processes, the total carbon in the biocarbon composition is determined from the measurement of the 14 C / 12 C isotope ratio of total carbon and is at least 50% renewable. The total carbon in the biocarbon composition is determined from the measurement of the 14 C / 12 C isotope ratio of total carbon and can be at least 90% renewable. The total carbon in the biocarbon composition is determined from the measurement of the 14 C / 12 C isotope ratio of total carbon and can be completely renewable.

[0367] Some variations are processes for manufacturing a biocarbon composition, the process comprising (a) pyrolyzing a biomass-containing feedstock in a pyrolysis reactor to produce a bioreagent and pyrolysis vapor; (b) introducing at least a portion of the pyrolysis vapor into a condensation system to produce a condenser liquid and 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; (d) optionally, pelletizing the bioreagent; (e) optionally, drying the bioreagent. (f) A process is provided which includes recovering a bioreagent as a biocarbon composition.

[0368] Starting biomass raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beets, sugar beet pulp, sunflower, sorghum, canola, algae, Japanese pampas grass, alfalfa, switchgrass, fruit, fruit shells, fruit stems, and fruit You may choose from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or a combination thereof.

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

[0370] If step (d) is performed, a binder can be introduced into the bioreagent. The binder can be selected from starch, thermoplastic starch, cross-linked 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 powder, 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, their derivatives, or any combination of the above. In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination thereof.

[0371] If step (d) is performed, an alternative is to introduce the external binder into the bioreagent during pelletization.

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

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

[0374] In some processes, at least 25% by weight of the total carbon in the condenser liquid is converted into fixed carbon in the bioreagent. In certain processes, at least 50% by weight of the total carbon in the condenser liquid is converted into fixed carbon in the bioreagent.

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

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

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

[0378] Bioreagents can be pulverized using mechanical processing equipment selected from hammer mills, extruders, attrition mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof.

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

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

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

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

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

[0384] The total carbon in the biocarbon composition is 14 C / 12 Based on measurements of the 1C isotope ratio, it is possible that at least 50% is renewable. The total carbon in the biocarbon composition is 14 C / 12 Based on measurements of the 1C isotope ratio, it is possible that at least 90% is renewable. The total carbon in the biocarbon composition is 14 C / 12 Based on measurements of the 1C isotope ratio, it may be possible to reproduce it completely.

[0385] Low-fixed carbon materials and high-fixed carbon materials may form distinct phases that do not dissolve in each other at equilibrium and relatively low temperatures. In some embodiments, low-fixed carbon materials and high-fixed carbon materials may have high equilibrium (thermodynamic) solubility in each other, but nevertheless remain kinetically frozen in the composition so that the distinct materials are observable. The distinct materials may be observable by measuring their composition, density, particle size, reactivity, or other physical or chemical properties. During the final use of the biocarbon composition, the distinction between 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 a low-fixed carbon material and a separate high-fixed carbon material, thermogravimetric analysis (TGA) of oxidation (combustion) of a test sample of the biocarbon composition is performed. In some embodiments, the resulting TGA thermal curve has two peaks characteristic of separate mass loss events correlated with the low-fixed carbon material and the high-fixed carbon material. This can be compared to a control sample of a biocarbon composition containing a single material with a known uniform fixed carbon concentration to show a TGA thermal curve with a single peak characteristic of one mass loss event of the material. In similar embodiments, the TGA thermal curve of the test sample has three or more peaks, while the TGA thermal curve of the control sample has at least one fewer peak than the test sample.

[0387] Another technique for demonstrating that a given biocarbon composition contains both low-fixed carbon material and separate high-fixed carbon material is particle size analysis. This is a feasible approach when the particle sizes associated with the low-fixed carbon material and the high-fixed carbon material are different, or when the particle size distributions associated with the low-fixed carbon material and the high-fixed carbon material are different. In some embodiments, the high-fixed carbon material tends to have smaller particles compared to the low-fixed carbon material. In some embodiments, a bimodal particle size distribution arises from the presence of both low-fixed carbon material and high-fixed carbon material, in contrast to a control sample which has a unimodal particle size distribution characteristic of a homogeneous material. In similar embodiments, the 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 also possible that each of the low-fixed carbon material and the high-fixed carbon material has a bimodal particle size distribution (with peaks centered at different sizes), and that the control sample has a bimodal particle size distribution depending on how the control sample was manufactured.

[0388] Particle size can be measured by various techniques, including dynamic light scattering, laser diffraction, image analysis, or sieving. Dynamic light scattering is a non-invasive and well-established technique typically used to measure the size and size distribution of particles in the submicron region, with modern techniques allowing measurements down to 1 nanometer. Laser diffraction is a widely used particle sizing technique for materials ranging in size from several hundred nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction devices for measuring particle size are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis for estimating particle size and distribution can be performed directly on micrographs, scanning electron microscope images, or other images. Finally, sieving is a conventional technique for separating particles by size.

[0389] Imaging techniques may be used, alternatively or additionally, to demonstrate that a given biocarbon composition contains both low-fixed carbon material and distinct high-fixed carbon material. 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 can be used to demonstrate distinct materials in a blend rather than homogeneous material. Alternatively, imaging techniques can be used to select subsamples for further analysis. Further analysis may include compositional analysis to show three-dimensional variations in fixed carbon content. Further analysis may include characterization to show three-dimensional variations in chemical or physical properties such as density, particle size, or reactivity.

[0390] Spectroscopic techniques may be used, either alternatively or additionally, to demonstrate that a given biocarbon composition contains both low-fixed carbon materials and separate high-fixed carbon materials. Spectroscopic techniques include, but are 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 contains about 10% to about 90% by weight of low-fixed carbon material. In some embodiments, the biocarbon composition contains about 10% to about 90% by weight of high-fixed carbon material. The weight ratio of low-fixed carbon material to high-fixed carbon material can be selected from about 0.1 to about 10, for example, about 0.2 to about 5, about 0.5 to about 2, or about 0.8 to about 1.2.

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

[0393] In some embodiments, the second fixed carbon concentration is, for example, about 80% to about 100% by weight, or about 70% to about 95% by weight, or 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 about 30% by weight to about 90% by weight, for example, about 40% by weight to about 80% by weight.

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

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

[0397] Highly fixed carbon materials may contain about 0 to about 50% by weight of volatile carbon on an absolute basis. In various embodiments, highly fixed carbon materials may contain about, at least about, or up to about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight of volatile carbon on an absolute basis. Highly fixed carbon materials may contain, for example, about 1% to about 20% by weight of oxygen on an absolute basis. Highly fixed carbon materials may contain, for example, about 0.1% to about 10% by weight of hydrogen on an absolute basis.

[0398] When referring to the final composition of a process, "biocarbon composition" is generally synonymous with "biocarbon product." In some embodiments, a biocarbon composition contains about 0.1% to about 20% by weight of water. In various embodiments, a biocarbon composition contains 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% by weight of water, including the entire intermediary range. Low-fixed carbon materials may contain 0 to about 50% by weight of water, including the entire intermediary range, 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% by weight of water. Independently, high-fixed-carbon materials may contain 0 to about 50% by weight of moisture, including the entire intervening range, 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% by weight of moisture. Drying can be used at one or more points in the process.

[0399] In some embodiments, the biocarbon composition contains about 0.1% to about 10% by weight of ash. In various embodiments, the biocarbon composition contains 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 ash, including the entire intermediary range. Low fixed carbon materials may contain 0 to about 25% by weight of ash, including the entire intermediary range, 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% by weight of ash. Independently, high-fixed-carbon materials may contain 0 to about 50 wt% ash, including the entire intervening range, 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.

[0400] In some embodiments, the biocarbon composition contains one or more additives in an amount of about 0.1% to about 10% by weight. In some embodiments, the biocarbon composition contains one or more additives in an amount of about 1% to about 15% by weight. In some embodiments, the biocarbon composition contains one or more additives in an amount of about 3% to about 18% by weight. In various embodiments, the biocarbon composition contains additives in an amount of 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, encompassing the entire intermediary range.

[0401] Low-fixed carbon materials may contain 0 to about 20% by weight of additives, including all intermediary ranges, 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% by weight of additives. Independently, high-fixed carbon materials may contain 0 to about 50% by weight of additives, including all intermediary ranges, 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% by weight of additives.

[0402] The additives may include organic 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 combustible.

[0403] In some embodiments, one or more additives include (or are binders). The binder can be selected from starch, thermoplastic starch, cross-linked 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 powder, 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, their derivatives, or any combination thereof.

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

[0405] One or more additives may reduce the reactivity of a biocarbon composition compared to a biocarbon composition that is equivalent except in the absence of one or more additives. Reactivity can be thermal reactivity. For example, a biocarbon composition with one or more additives may have lower self-heating properties compared to a biocarbon composition that is equivalent except in the absence of one or more additives. Alternatively or additionally, reactivity may be 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. Additives may be present in either the low-carbon or high-carbon material, or even in only one of these materials. For example, a binder may be present in 5% by weight of the total biomass composition, with 4 percentage points located in the low-carbon material and 1 percentage point located in the high-carbon material (i.e., 80% of the binder is located in the low-carbon material). In various embodiments, the percentage of total additives placed in the low-fixed-carbon material may 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 total additives placed in the high-fixed-carbon material may 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 total additives not placed in either the low-fixed-carbon or high-fixed-carbon material but elsewhere in the biocarbon composition (e.g., as separate additive phases) may be about, at least about, or up to about 0.5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

[0407] If one or more additives are present, some or all of the additives can fill pores in the low-fixed-carbon material. If one or more additives are present, some or all of the additives can fill pores in the high-fixed-carbon material. In some embodiments, one or more additives are present and fill pores inside both the low-fixed-carbon material and the high-fixed-carbon material.

[0408] Alternatively or additionally, one or more additives can be placed on the outer surface of the biocarbon composition (e.g., the outer surface of pellets or powder particles).

[0409] In some embodiments, the biocarbon 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, one or more additives may include binders for the pellets. Alternatively or additionally, the pellets may utilize the low-fixed carbon material itself as a binder within the pellets.

[0411] If one or more additives are present, the additives may be located within either the low-fixed-carbon material or the high-fixed-carbon material. Alternatively, the additives may be uniformly distributed so that they have the same average concentration within both the low-fixed-carbon and high-fixed-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'' (incorporated herein by reference).

[0413] Fixed carbon concentration is a critical parameter of biocarbon compositions. This disclosure enables maximizing, or optimizing, fixed carbon concentration in various embodiments, without necessarily maximizing it.

[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 biocarbon 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 biocarbon 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 biocarbon composition.

[0418] In some embodiments, the fixed carbon concentration and optionally the type or concentration of additives are selected to optimize the pore size ratio related to the biocarbon 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 biocarbon 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 biocarbon 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 biocarbon 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 hard-gloe pulverability index associated with the pellets.

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

[0424] The total carbon in the biocarbon composition is 14 C / 12Based on measurements of the 1C isotope ratio, it may be at least 50% renewable. In some embodiments, the total carbon is the total carbon 14 C / 12 Determined from the measurement of the 1C isotope ratio, at least 90% is renewable. In certain embodiments, the total carbon is the total carbon 14 C / 12 It can be determined from the measurement of the 1C isotope ratio and is fully reproducible.

[0425] While renewable biocarbon compositions are preferred, it is important to note that the principles of this disclosure can be applied to non-renewable materials. In certain embodiments, the biomass-containing raw material includes biomass (such as the biomass sources listed herein) as well as non-renewable raw materials such as coal. Thus, a biomass-coal mixture can be used as the biomass-containing raw material, which can be replaced, for example, with "biomass" in any of Figures 1-6. Other non-biomass raw materials that can be used in the raw material 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 utilize two or more separate pyrolysis reactors. These reactors typically operate either entirely continuously or entirely in batches, but in principle, a mixture of reaction modes can be used. Furthermore, if separate pyrolysis reactors are used, they may be located in common or separate locations.

[0427] In other embodiments, the process is carried out in a common pyrolysis reactor at different times, such as in different manufacturing campaigns. When a single pyrolysis reactor is used, it can be operated, for example, in batch mode with separate batches of low-fixed-carbon 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 over a first period, then a second material over a second period, and then the reactor can be returned to the production of the first material or something else.

[0428] In some process embodiments, a first pyrolysis reactor is operated at a first pyrolysis temperature selected from about 250°C to about 1250°C, for example, about 300°C to about 700°C. A second pyrolysis reactor can be operated at a second pyrolysis temperature selected from about 250°C to about 1250°C, for example, about 300°C to about 700°C. The second pyrolysis temperature may 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 the optimized pyrolysis of biomass with carbon recapture using the principles taught herein for generating a carbon substrate, mechanical size reduction of the carbon substrate, and the use of a binder to aggregate the carbon substrate to form biocarbon pellets. The carbon substrate may be a blend of low-fixed carbon material and high-fixed carbon material, or may consist thereof.

[0431] The Hard Grove Grindability Index ("HGI") is a measure of the grindability of materials such as biomass or coal. The HGI parameter for coal is important in power applications such as pulverized coal boilers, where coal is pulverized and burned in a suspension, and in iron production, such as pulverized coal injection, where pulverized coal is injected into a blast furnace through a lance, replacing coke and reducing iron ore to metallic iron.

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

[0433] The ability to adjust the HGI of biocarbon pellets is beneficial because downstream applications utilizing biocarbon pellets (e.g., coal replacement in boilers) have diverse HGI requirements. HGI adjustment industrially addresses well-known problems in crushing crude biomass and in crushing pellets. Furthermore, the ability to adjust the pulverability of pellets is highly advantageous, given the wide variety of downstream applications for biocarbon pellets, each with its own unique requirements. It is desirable to be able to adjust the HGI to suit specific applications such as combustion in boilers for synthesis gas production, metalworking, or gasification.

[0434] For many applications, pellets are preferred over powder (isolated biomass particles) due to advantages in distribution, storage, and safety. Ultimately, pellets may need to be reduced to powder, or at least smaller particles, at some point. Therefore, the pulverability of pellets is often a critical parameter that impacts operating and capital costs.

[0435] In some cases, such as when a boiler or gasifier utilizes a fluidized bed or a suspension of carbon particles, the pellets need to be crushed or finely ground into a powder. Another example is the injection of finely ground carbon into a blast furnace to reduce metal ore into metal. In these cases, high pellet pulverability is desirable, but not so high that the pellets collapse during delivery and handling. In other cases, it is desirable to supply the pellets themselves to a process such as a metalmaking process. In these cases, lower pulverability may be desirable, as a certain degree of pellet strength may be required to support the material bed in the reactor. Different technologies have different pellet pulverability requirements.

[0436] The Hardgrove Grindability Index (HGI) of biocarbon pellets may 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 about 30 to about 50 or about 50 to about 70. ASTM-Standard D409 / D409M relating to the "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 the Hardgrove Grindability Index or HGI in this disclosure refer to ASTM-Standard D409 / D409M.

[0437] In various embodiments, the hard globe crushability index is approximately, at least approximately, or at most approximately 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, encompassing the entire intervening range (e.g., 25-40, 30-60, etc.). The values ​​are 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, and 100.

[0438] Biocarbon pellets can be characterized by a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. Biocarbon pellets can also 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 indices 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 used as a starting material for producing smaller objects, and since "pellets" do not limit the geometric shape, they may also be called biocarbon pellets. For example, initial biocarbon pellets with an average pellet diameter of 10 mm can be produced. 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 by screening or the like. In this way, 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 larger than the average particle diameter of the initial carbon-containing particles used to produce the pellets with a binder.

[0440] When crushing biocarbon pellets to produce smaller biocarbon pellets, the crushing (and optionally screening) step can be integrated with another process step, which may include a potential industrial application. The optional step for producing smaller biocarbon pellets can utilize a grinding device selected from hammer mills, attrition mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, rock crushers, or a combination thereof.

[0441] In various process embodiments, the hard glove pulverability 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 hard glove pulverability index may be about 30 to about 50 or about 50 to about 70.

[0442] In various processes, process conditions include all intervention ranges (e.g., 30-60, 33-47, etc.), approximately, at least approximately, or at most approximately 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, 5 The system is selected and optimized to produce final biocarbon pellets with hard globe pulverability indices of 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, and 100.

[0443] In some processes, 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 pre-selecting a hard globe pulverability index, adjusting process conditions based on the pre-selected hard globe pulverability index, and achieving within ±20% of the pre-selected hard globe pulverability index for the biocarbon pellets, wherein the adjusted process conditions include adjusting one or more of the following: pyrolysis temperature, pyrolysis time, mechanical processing conditions, pelletizing conditions, binder type, binder concentration, bonding conditions, and drying. The process in a particular embodiment can achieve within ±10% or ±5% of the pre-selected hard globe pulverability index for the biocarbon pellets.

[0445] The size and geometry of biocarbon pellets may vary. As used herein, “pellets” refers to aggregated material rather than loose powder. The geometric shape of pellets is not limited to spherical or nearly spherical. Also, in this disclosure, “pellets” is synonymous with “briquettes.” The geometric shape of pellets may be spherical (circular or ball-shaped), cylindrical, cubic (square), octagonal, hexagonal, honeycomb / beehive-shaped, elliptical, egg-shaped, cylindrical, rod-shaped, pillow-shaped, random, or a combination thereof. For convenience of disclosure, the term “pellets” is generally used for any material containing powder aggregated with a binder. We also want to reiterate that this technology is by no means limited to biocarbon compositions in the form of pellets. For example, pellets can be produced using the disclosed process, then pulverized and used.

[0446] Biocarbon pellets can be characterized by an average pellet diameter, which is the true diameter in the case of spherical or cylindrical pellets, or by an equivalent diameter in the case of any other 3D geometric shape. The equivalent diameter of non-spherical pellets is the diameter of a sphere with an 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 multiple biocarbon pellets with relatively uniform sizes, such as standard deviations of less than ±100%, ±50%, ±25%, ±10%, or ±5% of the average pellet diameter. In other embodiments, there are biocarbon pellets with a wide range of sizes, as this may be advantageous in some applications.

[0448] Biocarbon pellets may contain water. The water present in biocarbon pellets may be water chemically bonded to the carbon or binder, water physically bonded (absorbed or adsorbed) to the carbon or binder, free water in the aqueous phase that is not chemically or physically bonded to the carbon or binder, or a combination thereof. If water is desired during the bonding process, it is preferable that such water is chemically or physically bonded to the carbon or binder rather than being free water.

[0449] Various moisture levels can exist. For example, biocarbon pellets may contain about 1% to about 30% by weight (e.g., 32% by weight), for example, about 5% to about 15% by weight of moisture, about 2% to about 10% by weight of moisture, or about 0.1% to about 1% by weight of moisture. In some embodiments, biocarbon pellets contain about 4 to 8% by weight of moisture. In various embodiments, 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% by weight of moisture, encompassing the entire intervening range. The moisture level of biocarbon pellets can be optimized to vary the density within the pellet.

[0450] For some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. For other market applications, such as metallurgy, lower moisture levels may be desirable (e.g., 1% by weight moisture or even lower). It should be noted that while water is present during the process of producing biocarbon pellets, these pellets are then optionally dried, meaning that the final biocarbon pellets do not necessarily contain moisture.

[0451] In some biocarbon pellets, the pellets contain about 2% to about 25% by weight of binder, about 5% to about 20% by weight of binder, or about 1% to about 5% by weight of binder. 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, 20, 25, or 30% by weight of binder, encompassing the entire intermediary range. In some embodiments, there is an inverse relationship between the water content and the binder concentration.

[0452] The binder can be used to fill the pores within the bioreagent of the biocarbon pellet. Alternatively, or additionally, the binder can be placed on the surface of the biocarbon pellet.

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

[0454] In various embodiments, the binder is selected from starch, cross-linked 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 powder, 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 thereof. The binder may be or may contain a pulverizable 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 any combination thereof. The starch may be nonionic starch, anionic starch, cationic starch, or amphoteric starch.

[0456] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and readily chemically modifiable. The cyclic structure of the starch molecule, along with strong hydrogen bonding, gives starch a rigid structure, resulting in highly ordered crystalline and granular regions. Starch in its granular state is generally unsuitable for thermoplastic treatment. To obtain thermoplastic starch, semi-crystalline starch granules can be decomposed by thermal and mechanical forces. Since the melting point of pure starch is considerably higher than its decomposition temperature, plasticizers such as water or glycol can be added. The natural crystallinity can then be destroyed by vigorous mixing (shearing) at high temperatures, resulting in thermoplastic starch. Starch can also be plasticized (decomposed) by relatively low levels of molecules that can hydrogen-bond with the 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 more 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 the starch / polyester blend, 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 by esterification or etherification, etc.

[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 under acidic or alkaline conditions after being dissolved or dispersed in an aqueous medium, for example. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to crosslink starch.

[0459] An example of a crosslinked starch is a reaction product of starch with glycerol, or another polyol such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination thereof. The reaction product can be formed from a 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 a combination thereof. Inorganic acids such as sulfuric acid can also be used to catalyze the crosslinking reaction. In some embodiments, the thermoplasticized or crosslinking 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, hydrophilic groups can be replaced with hydrophobic groups that are better resistant to water.

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

[0462] In some embodiments, the binder reduces the reactivity of the biocarbon pellets compared to biocarbon pellets that are otherwise equivalent, except for the absence of a binder. Reactivity can refer to thermal reactivity, chemical reactivity, or both.

[0463] In the case of thermal reactivity, biocarbon pellets may have lower self-heating properties compared to equivalent biocarbon pellets, except for the absence of a binder. "Self-heating properties" refer to biocarbon pellets that undergo a spontaneous exothermic reaction in the absence of any external ignition, under relatively low temperatures and an oxidizing atmosphere, in order to raise their internal temperature.

[0464] Chemical reactivity may be with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. Chemical reactivity may also be associated with reactions to CO, CO2, H2O, pyrolysis oils, and heat.

[0465] Optionally, biocarbon pellets may contain 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 raw material used in the pyrolysis process. For example, the starting biomass raw material 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 additive is 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 additive can be selected from the group consisting of (but 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, or combinations thereof. The additive may be added before, during, or after any one or more steps of the process, including adding it to the raw material itself at any point before or after the raw material is harvested.

[0467] The biocarbon pellets disclosed herein have a wide variety of downstream uses. Biocarbon pellets can be stored, sold, distributed, and converted into other products. Biocarbon pellets can be ground into a fine powder for use in boilers to burn carbon and generate electrical energy or heat. Biocarbon pellets can be ground, crushed, or milled for supply to furnaces such as blast furnaces in metal manufacturing. Biocarbon pellets can be supplied directly to furnaces such as Tecnored furnaces in metal manufacturing. Biocarbon pellets can be ground, crushed, or milled for supply to gasifiers for the purpose of producing synthesis gas from biocarbon pellets.

[0468] In many embodiments, biocarbon pellets are fed into a furnace either directly or after a step of reducing particle size by pulverization, crushing, milling, or other means. The furnace may be a blast furnace, a top gas recirculation blast furnace, a shaft furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a silenced furnace, a retort furnace, a flash furnace, a Tecnored furnace, an Ausmelt furnace, an ISASMELT furnace, a paddle 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 paddle furnace, a Bessemer furnace, a direct reducing metal furnace, or a combination or derivative thereof.

[0469] Regardless of the hard-glome pulverability index of biocarbon pellets, it should be noted that they do not necessarily undergo a subsequent pulverization process. For example, biocarbon pellets can be used directly in agricultural applications. Another example is that biocarbon pellets can be directly incorporated into engineered structures such as landscaping walls. Then, at the end of the lifespan of the structure containing the biocarbon pellets, the pellets can be reused or recycled by pulverization, combustion, gasification, or other means.

[0470] Pyrolysis process and system The following describes in more detail suitable processes and systems for the thermal decomposition of biomass raw materials or bioreagents combined with condenser liquids. In some cases, the description of the thermal decomposition reactor (or reaction) will be understood as a reference to a reactor (or reaction) for producing high-fixed-carbon materials.

[0471] "Pyrolysis" and "to pyrolyze" generally refer to the thermal decomposition of carbonaceous materials. In pyrolysis, less oxygen is present than required for the complete combustion of the material, such as 10%, 5%, 1%, 0.5%, 0.1%, or less than 0.01% of the oxygen (O2 molar basis) required for complete combustion. 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 raw material; (ii) the initiation of the primary pyrolysis reaction at this higher temperature releases volatiles and forms char; (iii) the flow of high-temperature volatiles toward lower-temperature solids results in heat transfer between the high-temperature volatiles and lower-temperature non-pyrolytic raw materials; (iv) some of the volatiles in the lower-temperature portion of the raw material condense, followed by a secondary reaction that may produce tar; (v) autocatalytic secondary pyrolysis reactions proceed while primary pyrolysis reactions occur simultaneously in competition; and (vi) further pyrolysis, reforming, water-gas shift reactions, free radical recombination, or dehydration may also occur, which are functions of residence time, temperature, and pressure profiles.

[0473] Pyrolysis can dehydrate the starting material (e.g., lignocellulosic biomass) at least partially. In various embodiments, pyrolysis removes about 50%, 75%, 90%, 95%, or more than 99% of the water from the starting material.

[0474] In some embodiments, the starting biomass raw materials include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stalks and leaves, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beets, sugar beet pulp, sunflower, sorghum, canola, algae, pampas grass, alfalfa, switchgrass, fruits, and fruit shells. The biomass materials are selected from 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, railway ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. Typically, biomass materials contain at least carbon, hydrogen, and oxygen.

[0475] The bioreagent may contain at least about 50% by weight, at least about 75% by weight, or at least about 90% by weight of total carbon. In various embodiments, the bioreagent may contain 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% by weight of carbon. Total carbon is the sum of fixed and unfixed carbon present in the volatile substance. In some embodiments, the weight percentages of components are on an absolute basis, which is assumed unless otherwise specified. In other embodiments, the weight percentages of components are on an anhydrous and ashless basis. Compositions of low-fixed-carbon and high-fixed-carbon materials are discussed in detail earlier.

[0476] The thermal decomposition conditions can vary considerably depending on the desired composition of the bioreagent and thermal decomposition exhaust gas, the starting materials, the reactor configuration, and other factors.

[0477] In some embodiments, the multiple reactor zones are designed and operated to optimize carbon yield and product quality from pyrolysis while maintaining flexibility and adjustability to raw material fluctuations and product requirements.

[0478] In some non-limiting embodiments, temperature and residence time are selected to achieve a relatively slow pyrolysis chemical reaction. A potential advantage is the substantial preservation of cell walls contained within the biomass structure, meaning the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, apparatus can be used that converts biomass particles into fine powder without mechanically destroying the cell walls or by other means. Certain such reactor configurations will be discussed in accordance with the following process description.

[0479] Additionally, if the raw material is milled or sized, such as wood chips or pellets, it may be desirable to carefully mill or size the raw material. Careful initial processing tends to preserve the strength and cell wall integrity present in the natural raw material source (e.g., wood). This may also be important if the final product should 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 supply biomass (or another carbon-containing raw material) in a manner that does not "shock" the biomass, which would rupture the cell walls and initiate the rapid decomposition of the solid phase into vapor and gas. This first zone can be thought of as gentle pyrolysis.

[0481] In some embodiments, a second zone of the pyrolysis reactor is configured as a primary reaction zone, where preheated biomass undergoes a pyrolysis chemical reaction to release gas and condensable vapors, leaving behind a considerable amount of solid material which is a high-carbon reaction intermediate. The biomass components (mainly cellulose, hemicellulose, and lignin) decompose to produce vapors, which escape by penetrating pores or by creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0482] In some embodiments, a third zone of the pyrolysis reactor is configured to receive high-carbon reaction intermediates and to cool the solid to some extent. Typically, the third zone is at a lower temperature than the second zone. In the third zone, chemical reactions and mass transfers can be surprisingly complex. Secondary reactions are thought to occur in the third zone without being limited by any particular theory or proposed mechanism. Essentially, carbon-containing components in the gas phase may decompose to form additional fixed carbon or be adsorbed onto carbon. Thus, the final carbonaceous material may not simply be a degassed residue of the solid from the processing steps, but may include additional carbon deposited from the gas phase by the decomposition of organic vapors (e.g., tar) that can form carbon.

[0483] Certain embodiments extend the concept of additional carbon formation by including a separate unit into which cooled carbon is exposed to an environment containing carbon-containing species in order to increase the carbon content of the product. If the temperature of this unit is below the thermal decomposition temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0484] Numerous options exist regarding intermediate input and output (purge or probe) flows of one or more phases present within any specific zone, various mass and energy recirculation schemes, various additives that can be introduced anywhere in the process, and the tunability of process conditions, including both reaction and separation conditions to adjust product distribution. Zone-specific input and output flows enable good process monitoring and control, such as FTIR sampling and dynamic process adjustment.

[0485] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis. Surprisingly, high-quality carbon materials, including compositions with 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 bioreagent involves the following steps: (a) A step of providing a carbon-containing raw material including biomass, (b) Optionally, the step of drying the raw material to remove at least some of the moisture contained in the raw material, (c) Optionally, the step of degassing the raw material to remove at least a portion of the interstitial oxygen contained in the raw material, if present. (d) A step of thermally decomposing the raw material for at least 10 minutes at at least one temperature selected from about 250°C to about 700°C in the presence of a substantially inert gas phase to produce a high-temperature thermal decomposition solid, a condensable vapor, and a non-condensable gas, (e) Separating at least a portion of condensable vapor and at least a portion of non-condensable gas from a high-temperature pyrolysis solid, (f) A step of cooling the high-temperature pyrolysis solid to produce a cooled pyrolysis solid, (g) The step of recovering a bioreagent containing at least a portion of the cooled pyrolysis solid.

[0487] For the purposes of this disclosure, "biomass" should be interpreted as any biological material or a mixture of biological and non-biological materials. Basically, biomass contains at least carbon, hydrogen, and oxygen. The methods and apparatus can be adapted to a wide range of materials of various types, sizes, and moisture content.

[0488] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal-derived waste, poultry-derived waste, and municipal solid waste. In various embodiments of biomass utilization, biomass raw materials may include one or more materials selected from wood harvest residues, softwood chips, hardwood chips, tree branches, tree stumps, knots, leaves, bark, sawdust, off-grade 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 cloth. Those skilled in the art will readily understand that the selection of raw materials is virtually unlimited.

[0489] This disclosure can also be used with carbon-containing raw materials 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 bio-raw material is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Raw materials may 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 raw material. Carbon-containing raw materials may be transported by any known means, such as trucks, trains, ships, barges, tractor trailers, or any other vehicle or means of transport.

[0490] The selection of one or more specific raw materials is carried out in a manner that is not considered technically important but tends to be advantageous to the economic process. Typically, regardless of the selected raw materials, screening may exist (in some embodiments) to remove undesirable substances. The raw materials may be optionally dried before processing.

[0491] The raw materials used can be provided or processed into a wide variety of particle sizes or shapes. For example, the supply material may be a fine powder or a mixture of fine and coarse particles. The supply material may be in the form of wood chips or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the supply material may include pellets or other aggregated forms of particles that are pressed together or otherwise bound together, for example, with a binder.

[0492] It should be noted that size reduction is a costly and energy-intensive process. Pyrolytically decomposed materials can be sized with significantly less energy input, i.e., it may be preferable to reduce the particle size of the product rather than the raw material. This is an option because the process does not require fine starting material and does not necessarily involve any significant particle size reduction during processing. The ability to process very large raw material pieces is a significant economic advantage. In particular, some market applications of high-carbon products actually require large sizes (e.g., on the order of centimeters), and therefore, in some embodiments, large pieces are supplied, manufactured, and sold.

[0493] In the context of this disclosure, if it is desirable to produce a final carbonaceous bioreagent having structural integrity such as a cylindrical shape, there are at least two options. 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 use a supply material that generally has the desired size or shape for the final product and to use processing steps that do not destroy the basic structure of the supply material. In some embodiments, the supply and the product have similar geometric shapes such as sphere, cylinder, or cube.

[0494] The ability to maintain the approximate size of the supply material throughout the entire process is beneficial when product strength is critical. Furthermore, it avoids the difficulties and costs associated with pelletizing high-fixed-carbon materials.

[0495] The starting feed material can be provided at a range of moisture levels, as understood. In some embodiments, the feed material may already be sufficiently dry and therefore does not need to be dried further before pyrolysis. Typically, it is desirable to utilize a commercially available source of biomass that normally contains moisture and to feed the biomass through a drying step before introducing it into the pyrolysis reactor. However, in some embodiments, dry feedstock can be utilized.

[0496] Typically, it is desirable to provide a relatively low oxygen environment in the gas phase within the pyrolysis reactor, such as O2 at approximately or up to approximately 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%. Firstly, uncontrolled combustion should be avoided in the pyrolysis reactor for safety reasons. Some total carbon oxidation to CO2 may occur, and the heat released from exothermic oxidation can assist the endothermic decomposition chemical reaction. Large amounts of carbon oxidation, including partial oxidation to synthesis gas, reduce the carbon yield to solids.

[0497] In practice, achieving a strictly oxygen-free environment within a reactor can be difficult. Approaching this limit, in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure little to no oxygen is present within the pyrolysis reactor, it may be desirable to remove air from the feed material before it is introduced into the reactor. Various methods exist for removing or reducing air from the feed material.

[0498] In some embodiments, a degassing unit is used before and after drying in which the raw material is transported in the presence of another gas that can remove adsorbed oxygen and penetrate the pores of the raw material to remove oxygen from the pores. Essentially, any gas having less than 21 volume% O2 can be used with varying effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO or CO2 is used. Mixtures such as a mixture of nitrogen and a small amount of oxygen can be used. Water vapor may be present in the degassed gas, but it should be avoided to return a significant amount of moisture to the feed. The effluent from the degassing unit can be purged (to the atmosphere or an exhaust treatment unit) or recycled.

[0499] In principle, the effluent (or a portion thereof) from the degassing unit can be introduced into the pyrolysis reactor itself because the oxygen removed from the solid is highly diluted. In this embodiment, if the reactor is operating in a counterflow configuration, it may be advantageous to introduce the degassed effluent gas into the final zone of the reactor.

[0500] Various types of degassing units can be used. If drying is to be carried out, it may be preferable to dry and then degass, as washing away soluble oxygen from the present moisture may be inefficient. In certain embodiments, the drying and degassing steps may be combined into a single unit, or some amount of degassing may be achieved during drying.

[0501] The optionally dried and optionally degassed feed material is introduced into a pyrolysis reactor or a series or parallel multiple reactor. The feed material can be introduced using any known means, including, for example, a screw feeder or a rock hopper. In some embodiments, the material feeding system incorporates an air knife.

[0502] When using a single reactor, multiple zones may exist. Multiple zones, such as two, three, four, or more, can allow for separate control of temperature, solid 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 spatial regions within a single physical unit, physically separated units, or any combination thereof. In the case of continuous reactors, zone boundaries may relate to structures such as the presence of flights within the reactor or separate heating elements for providing heat to separate zones. Alternatively or additionally, zone boundaries in continuous reactors may relate to features such as distinct temperatures, fluid flow patterns, solid flow patterns, or degrees of reaction. In single-batch reactors, “zones” are operational regimes in time, not space. Multiple-batch reactors can also be used.

[0504] It will be understood that there are not necessarily abrupt transitions from one zone to another. For example, the boundary between the preheating zone and the pyrolysis zone can be somewhat arbitrary, with some amount of pyrolysis occurring in part of the preheating zone and some amount of "preheating" continuing in the pyrolysis zone. The temperature profile within the reactor, including the zone boundaries within the reactor, is typically continuous.

[0505] Some embodiments utilize a first zone operated under preheating or mild thermal decomposition conditions. The temperature of the first zone can be selected from about 150°C to about 500°C, for example, about 300°C to about 400°C. Preferably, the temperature of the first zone is not high enough to shock the biomass material, break down the cell walls, and initiate rapid decomposition of the solid phase into vapor and gas.

[0506] All references to zone temperatures in this specification should be interpreted non-restrictively to include temperatures applicable to the bulk solid, gas phase, or reactor wall (process side) present. It will be understood that temperature gradients exist in each zone both axially and radially, as well as in time (i.e., after startup or due to transient phenomena). Thus, references to zone temperatures may refer to average temperatures or other effective temperatures that may affect the actual kinetics. Temperatures can be measured directly by thermocouples or other temperature probes, or indirectly by other means.

[0507] The second zone, or generally the primary pyrolysis zone, operates under pyrolysis or carbonization conditions. The temperature of the second zone can be selected from approximately 250°C to approximately 700°C, for example, approximately, or at least approximately, or at most approximately, 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 a considerable amount of solid material as high-carbon reaction intermediates. The biomass components (mainly cellulose, hemicellulose, and lignin) decompose to create vapors, which escape by penetrating pores or creating new pores. The preferred temperature depends at least on the residence time in the second zone, as well as the properties of the raw materials and the desired product characteristics.

[0508] A third zone, or cooling zone, is operated to cool the high-carbon reaction intermediate to a range of 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 approximately 100°C to approximately 550°C, for example, approximately 150°C to approximately 350°C.

[0509] Chemical reactions can continue to occur in the cooling zone. While not limited to any particular theory, it is thought that secondary pyrolysis reactions can be initiated in the third zone. Carbon-containing components in the gas phase can condense (due to the decrease in temperature in the third zone). However, the temperature remains high enough to facilitate reactions that can form additional fixed carbon from the condensed liquid (secondary pyrolysis), or at least reactions that can form bonds between adsorbed species and fixed carbon. One exemplary reaction that may occur is the Boudoar reaction for converting carbon monoxide into carbon dioxide and fixed carbon.

[0510] The residence time in a reactor zone can vary. There is an interaction between time and temperature, such that higher temperatures can allow for shorter reaction times for a desired amount of thermal decomposition, and vice versa. In a continuous reactor (zone), the residence time is the volume divided by the volumetric flow rate. In a batch reactor, the residence time is the batch reaction time after heating to the reaction temperature.

[0511] In multiphase reactors, it should be recognized that multiple residence times exist. In this context, each zone has residence times (and residence time distributions) for both the solid and vapor phases. For a given apparatus using multiple zones, at a given throughput, the residence times across the zones are generally coupled on the solid side, but if multiple inlet and outlet ports are used in individual zones, the residence times may not be coupled on the vapor side. The residence times of the solid and vapor phases are not coupled.

[0512] The solid residence time in the preheating zone can be selected from approximately 5 to 60 minutes, for example, 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a sufficient time is desirable to allow the biomass to reach the desired preheating temperature. The type and size of particles, the physical equipment, and the heat transfer rate, which depends on the heating parameters, determine the minimum residence time required to allow the solid to reach the desired preheating temperature. Additional time may be undesirable as it contributes to higher capital costs unless some amount of gradual pyrolysis is intended in the preheating zone.

[0513] The solid residence time in the pyrolysis zone can be selected from approximately 10 to 120 minutes, for example, 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be sufficient time for the necessary heat transfer followed by the carbonization chemical reaction. For times less than approximately 10 minutes, the temperature needs to be very high, such as above 700°C, in order to remove a large amount of non-carbon elements. This temperature promotes rapid pyrolysis and the generation of vapors and gases derived from carbon itself, but should be avoided if the intended product is solid carbon.

[0514] In a static system, there will be an equilibrium transformation that can be substantially reached at a certain time. If, as in certain embodiments, vapor flows continuously over a solid with continuous volatilization, the equilibrium constraint can be removed to allow thermal decomposition and devolatilization to continue until the reaction rate approaches zero. For longer periods, there is no substantial change to the remaining persistent solid.

[0515] The solid residence time in the cooling zone can be selected from approximately 5 to 60 minutes, for example, 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be sufficient time to cool the carbon solid to the desired temperature. The cooling rate and temperature determine the minimum residence time required to cool the carbon. Additional time may be undesirable unless some amount of secondary pyrolysis is desired.

[0516] As previously discussed, the residence time of the vapor phase can be selected and controlled separately. The vapor residence time in the preheating zone can be selected from approximately 0.1 minutes to approximately 15 minutes, for example, from approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time in the pyrolysis zone can be selected from approximately 0.1 minutes to approximately 20 minutes, for example, from approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time in the cooling zone can be selected from approximately 0.1 minutes to approximately 15 minutes, for example, from approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. Shorter vapor residence times promote the rapid removal of volatiles from the system, while longer vapor residence times promote the reaction between the components in the vapor phase and the solid phase.

[0517] The operating mode of the reactor and the entire system can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the reactor is a continuous counterflow reactor in which solids and vapors flow substantially in opposite directions. The reactor can also be operated in batch mode, but can be operated in simulated counterflow of vapor by, for example, periodically introducing and removing the gas phase from a batch vessel.

[0518] Various flow patterns may be desired or observed. In chemical reactions and simultaneous separations involving multiple phases in a multi-reactor zone, the fluid dynamics can become very complex. Typically, solid flows can approach plugged flows (well mixed in the radial dimension), while vapor flows can approach perfectly mixed flows (high-speed transport in both the radial and axial dimensions). Multiple inlet and outlet ports for vapor can contribute to the overall mixing.

[0519] The pressure in each zone can be selected and controlled independently. The pressure in each zone can be independently selected from approximately 1 kPa to approximately 3000 kPa, for example, approximately 101.3 kPa (standard atmospheric pressure). Independent zone pressure control is possible when multiple gas inlets and outlets are used, including vacuum ports for extracting gas when zone pressures below atmospheric pressure are desired.

[0520] In some embodiments, the process can be conveniently operated at atmospheric pressure. Operating at atmospheric pressure offers many advantages, ranging from mechanical simplicity to improved safety. In certain embodiments, the pyrolysis zone operates at pressures of approximately 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute pressure).

[0521] Vacuum operation (e.g., 10–100 kPa) facilitates the rapid removal of volatiles from the system. Higher pressures (e.g., 100–1000 kPa) may be useful when supplying exhaust gas to high-pressure operation. Higher pressures may also be useful to facilitate heat transfer, chemical reactions, or separation.

[0522] The step of separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the high-temperature pyrolysis solid can be carried out 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 vapor and non-condensable gas are then carried away from the zones in the sweep gas and exit the reactor.

[0523] The sweeping gas may be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweeping gas can be preheated before introduction, or cooled if it is obtained from a heating source.

[0524] Sweeping gases more completely remove volatile components by removing them from the system before they can condense or react further. Sweeping gases allow for the removal of volatiles at a higher rate than would be achieved simply by volatilization at a given process temperature. Alternatively, the use of sweeping gases allows for the use of milder temperatures to remove a particular amount of volatiles. The reason sweeping gases improve volatile removal is that the separation mechanism is not simply relative volatility, but rather a liquid / vapor phase separation assisted by the sweeping gas. Sweeping gases can reduce the mass transfer limitations of volatilization, as well as the thermodynamic limitations, by continuously depleting a given volatile species, evaporating more volatile species to achieve thermodynamic equilibrium.

[0525] Some embodiments remove gases full of volatile organic carbon from subsequent processing steps to produce products with high fixed carbon content. If not removed, the volatile carbon may be adsorbed or absorbed onto the pyrolyzed solid, thereby requiring additional energy (cost) to achieve the desired purer form of carbon. It is also hypothesized that rapidly removing the vapors can increase the porosity of the pyrolyzed solid. Higher porosity is desirable for some products.

[0526] In certain embodiments, the sweeping gas, combined with a relatively low process pressure such as atmospheric pressure, provides fast vapor removal without requiring a large amount of inert gas.

[0527] In some embodiments, the sweep gas flows countercurrently with respect to the flow direction of the raw materials. In other embodiments, the sweep gas flows parallel to the flow direction of the raw materials. In some embodiments, the solid flow pattern approaches a plugged flow, while the sweep gas and gas phase flow patterns generally approach a perfectly mixed flow in one or more zones.

[0528] Sweeping can be performed in one or more of the reactor zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted (along with the generated volatiles) from the cooling or pyrolysis zone. In some embodiments, the sweep gas is introduced into the pyrolysis zone and extracted from the pyrolysis or preheating zone. In some embodiments, the sweep gas is introduced into the preheating zone and extracted from the pyrolysis zone. In these or other embodiments, the sweep gas can be introduced into each of the preheating zone, pyrolysis zone, and cooling zone, and can also be extracted from each of the zones.

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

[0530] The sweep gas can be introduced continuously, especially when the solid flow is continuous. When 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 when the pyrolysis reaction is operated continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, using suitable valves and controls.

[0531] The volatile-containing sweep gas can exit from one or more reactor zones, and if obtained from multiple zones, it can be combined. The resulting gas stream, containing various vapors, can then be supplied to a thermal oxidation unit for control of air discharge. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are supplied to the thermal oxidation unit to reach a temperature sufficient to substantially destroy the volatiles contained therein.

[0532] The effluent of the thermal oxidation system is a high-temperature gas stream containing water, carbon dioxide, and nitrogen. This effluent can be purged directly into an air discharge if desired. Preferably, the energy content of the thermal oxidation system effluent is recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another flow (such as a sweep gas). The energy content can be utilized by directly or indirectly heating, or assisting in the heating, of units at other points in the process, such as a dryer or reactor. In some embodiments, essentially all of the thermal oxidation system effluent is used for indirect heating (utility side) of a dryer. The thermal oxidation system can use fuels other than natural gas.

[0533] The yield of carbonaceous materials can vary depending on the aforementioned factors, including the type of raw materials and process conditions. In some embodiments, the net yield of solids as a percentage of the starting materials on a dry basis is at least 25%, 30%, 35%, 40%, 45%, 50%, or higher. The remainder is divided between condensable vapors such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on the process conditions, including the presence of water.

[0534] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the raw materials is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or more. For example, in some embodiments, the carbonaceous material contains about 40% to about 70% of the carbon contained in the starting materials. The remaining carbon forms methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatic compounds, tars, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0535] In alternative embodiments, some portions 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 gaseous stream obtained from the reactor, including various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids derived from a cooling zone or separate cooling unit. These embodiments are described in more detail below.

[0536] Following the reaction and cooling within the cooling zone (if present), the carbonaceous solid can be introduced into a separate cooling unit. In some embodiments, the solid is recovered and simply cooled slowly. If the carbonaceous solid is reactive or unstable in air, it may be desirable to maintain an inert atmosphere or to rapidly cool the solid to a temperature below 40°C, for example, ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. The term "cooling unit" should be broadly interpreted to include containers, tanks, pipes, or parts thereof.

[0537] In some embodiments, the process further includes operating a cooling unit to cool the warm pyrolysis solid with steam, thereby generating a lower temperature pyrolysis solid and superheated steam, and drying is carried out at least partially using the superheated steam obtained from an external cooler. Optionally, the cooling unit can be operated to first cool the warm pyrolysis solid with steam to a first cooling unit temperature, and then cool it with air to a second cooling unit temperature, the second cooling unit temperature being lower than the first cooling unit temperature and associated with reducing the risk of combustion of the warm pyrolysis solid in the presence of air.

[0538] Following cooling to ambient conditions, the carbonaceous solid can be recovered and stored, transported to another site, shipped to another site, or otherwise disposed of, traded, or sold. The solid can be fed into a unit to reduce particle size. Various size reduction units, including pulverizers, shredders, grinders, fine grinders, jet mills, pin mills, and ball mills, are known in the art.

[0539] Several other means for screening or separation based on particle size may be included. Grinding, if present, may be upstream or downstream of grinding. Some of the screened material (e.g., large lumps) can be returned to the grinding unit. Small and large particles can be recovered for separate downstream use. In some embodiments, the cooled pyrolysis solid is ground into a fine powder such as pulverized carbon or activated carbon product.

[0540] Various additives can be introduced throughout the process before, during, or after any step disclosed herein. Additives can be broadly classified as process additives selected to improve process performance, such as carbon yield or thermal decomposition time / temperature, in order to achieve a desired carbon purity, and as process additives selected to improve one or more properties of the bioreagent or downstream product incorporating the reagent. Certain additives can provide enhanced process and product (bioreagent or product containing a bioreagent) properties.

[0541] Additives may be added before, during, or after any one or more steps of the process, including adding them to the raw materials themselves at any point before or after the harvesting of the raw materials. Additive treatment may be incorporated before, during, or after sizing, drying, or other preparation of the raw materials. Additives may be incorporated into or on raw material supply facilities, transport trucks, unloading equipment, storage bins, conveyors (including open or closed conveyors), dryers, process heaters, or any other units. Additives may be added anywhere in the pyrolysis process itself using suitable means for introducing the additives. Additives may also be added after carbonization or after grinding, if desired.

[0542] In some embodiments, the additive is selected from metals, metal oxides, metal hydroxides, or combinations thereof. For example, the additive may be selected from, but is not limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0543] In some embodiments, the additive is selected from acids, bases, or salts thereof. For example, the additive may be selected from, but is not 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 a metal and a halogen (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are generally obtained by direct bonding of a basic metal salt with a hydrohalic acid, or more generally by neutralization. In some embodiments, the additive is selected from iron chloride (FeCl2 or FeCl3), iron bromide (FeBr2 or FeBr3), or their hydrates, and any combination thereof.

[0545] Additives can result in a final product with a higher energy content (energy density). The increase in energy content may result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content may result from the removal of non-combustible materials or materials with a lower energy density than carbon. In some embodiments, additives reduce the degree of liquid formation to favor the formation of solids and gases, or to favor the formation of solids.

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

[0547] Additives can result in bioreagents having improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, modulus of elasticity, bulk modulus, or shear modulus. Additives can improve mechanical properties simply by their presence (e.g., the additive itself imparts strength to the mixture) or by some transformation occurring within the additive phase or the resulting mixture. For example, reactions such as vitrification may occur within a portion of the bioreagent containing the additive, thereby improving the final strength.

[0548] Chemical additives can be applied to wet or dry biomass raw materials. Additives can be applied as solid powders, sprays, mists, liquids, or vapors. In some embodiments, additives can be introduced by spraying a liquid solution (such as an aqueous solution or solvent) or by immersion in a tank, bottle, bag, or other container.

[0549] In certain embodiments, immersion pretreatment is used, in which the solid raw material is immersed in a bath containing the additive for a time sufficient to allow the additive to permeate the solid feed material, either in a batch or continuous manner.

[0550] In some embodiments, additives applied to the raw materials can reduce the energy required for thermal decomposition or increase the yield of the carbonaceous product. In these or other embodiments, additives applied to the raw materials can provide functionality desirable for the intended use of the carbonaceous product.

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

[0552] In some embodiments, a portion of the manufactured solid 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 processed solid may have a higher fixed carbon content. Solids, liquids, and gaseous flows generated or present in the process may be independently recycled and passed on to subsequent steps, or removed / purged from the process at any point.

[0553] In some embodiments, the pyrolyzed material is recovered and then fed into a separate unit for further pyrolysis to create a product with higher carbon purity (e.g., conversion of a low-fixed-carbon material to a high-fixed-carbon material). In some embodiments, the secondary process can be carried out in a simple container, such as a steel drum, through which a heated inert gas (such as heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas, containing volatiles, can be sent, for example, to a thermal oxidation unit or returned to the main process reactor. To cool the final product, the solid can be cooled by passing another flow of inert gas, initially at, for example, ambient temperature, through it and then returned to the inert gas preheating system.

[0554] Some variant forms are, (a) A feeder configured to introduce carbon-containing raw materials, (b) an optional dryer, which is operably connected to the supply device and configured to remove moisture contained in the carbon-containing raw material, (c) A multizone reactor operably connected to a dryer, the multizone reactor comprising at least one pyrolysis zone operably connected to a spatially separated cooling zone, and the multizone reactor being configured to have outlets for removing condensable vapors and noncondensable gases from a solid, (d) A solid cooler arranged in operable communication with a multi-zone reactor, (e) A bioreagent manufacturing system comprising a solid cooler and a bioreagent recovery unit operably connected to it.

[0555] Some variant forms are, (a) A feeder configured to introduce carbon-containing raw materials, (b) an optional dryer, which is operably connected to the supply device and configured to remove moisture contained in the carbon-containing raw material, (c) an optional preheater configured to be operably connected to the dryer and to heat or gently thermally decompose the raw material, (d) A pyrolysis reactor configured to be operably connected to a preheater and to pyrolyze the raw materials, (e) A cooler configured to be operably connected to the pyrolysis reactor and configured to cool the pyrolysis solid, (f) A bioreagent manufacturing system comprising a bioreagent recovery unit operably connected to a cooler, The system utilizes a bioreagent manufacturing system configured to include at least one gas outlet for removing condensable vapors and non-condensable gases from a solid.

[0556] The feeding device can be physically integrated with the multi-zone reactor by means of a screw feeding device or auger mechanism for introducing the feed solid into the first reaction zone.

[0557] In some embodiments, the system further comprises a preheating zone operably connected to the pyrolysis zone. Each of the pyrolysis zone, the cooling zone, and the preheating zone (if it exists) may be located within a single unit or within separate units.

[0558] Optionally, a dryer can be configured as a drying zone within a multi-zone reactor. Optionally, a solid cooler can be placed within a multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0559] The system may include 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 replaced oxygen from the system. In some embodiments, the purging means is a degasser operably arranged in communication between the dryer and the multizone reactor.

[0560] A multi-zone reactor is preferably configured to include at least a first gas inlet and a first gas outlet. The first gas inlet and the first gas outlet can be arranged to communicate with different zones or the same zone.

[0561] In some embodiments, the multizone reactor is configured to include a second gas inlet or a second gas outlet. In some embodiments, the multizone reactor is configured to include a third gas inlet or a third gas outlet. In some embodiments, the multizone reactor is configured to include a fourth gas inlet or a fourth gas outlet. In some embodiments, each zone within the multizone reactor is configured to include a gas inlet and a gas outlet.

[0562] The gas inlet and outlet not only allow for the introduction and extraction of steam, but the gas outlet (probe) in particular enables precise process monitoring and control across various stages of the process, including all stages of the process and potentially all stages of the process. Precise process monitoring is expected to lead to improvements in yield and efficiency, both dynamically and over a period of time, if process conditions can be adjusted using the operational history.

[0563] In a preferred embodiment, a reaction gas probe is positioned to be operably in communication with the pyrolysis zone. Such a reaction gas probe may be useful for extracting and analyzing gases to determine the degree of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or regulated in any number of ways, such as by adjusting the feed rate, the rate of inert gas sweep, the temperature (of one or more zones), the pressure (of one or more zones), additives, etc.

[0564] As intended herein, “monitoring and control” via a reaction gas probe should be interpreted to include any one or more sample extractions via the reaction gas probe, and optionally, if deemed necessary or desirable, to make process adjustments or equipment adjustments based on the measurements using well-known principles of process control (such as feedback, feedforward, proportional-integral-differential logic).

[0565] Reaction gas probes can be configured to extract gas samples in many ways. For example, the sampling line may have a pressure lower than the pyrolysis reactor pressure, and as a result, when the sampling line is opened, a certain amount of gas can be easily extracted from the pyrolysis zone. The sampling line may be under vacuum, for example, when the pyrolysis zone is close to atmospheric pressure. Typically, a reaction gas probe is associated with one gas output or a part of it (e.g., a line branched off from a gas output line).

[0566] In some embodiments, both the gas input and gas output are utilized as reaction gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with the process sample ("sample sweep"). Such configurations can be used in zones that do not have gas inlets / outlets for substantially inert gas for processing, or the reaction gas probes can be associated with separate gas inlets / outlets in addition to the process inlets and outlets. (In embodiments utilizing sample sweep) the sampling inert gas periodically introduced and withdrawn for sampling may differ from the process inert gas, if desired, either for reasons of analytical accuracy or for introducing an analytical tracer.

[0567] For example, the acetic acid concentration in the gas phase of the pyrolysis zone can be measured using a gas probe to extract the sample, which is then analyzed using a suitable technique (gas chromatography, GC; mass spectrometry, MS; GC-MS, or Fourier transform infrared spectroscopy, FTIR, etc.). The CO or CO2 concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity for gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity for liquid.

[0568] In some embodiments, the system further comprises at least one additional gas probe operably connected to a cooling zone, or a drying zone (if present) or a preheating zone (if present).

[0569] Gas probes for cooling zones can be useful, for example, for determining the extent of any additional chemical reactions occurring within the cooling zone. Gas probes in cooling zones can also be useful as independent temperature measurements (in addition to thermocouples placed within the cooling zone, for example). This independent measurement may be a correlation between the cooling temperature and a certain type of measured quantity. The correlation may be developed separately or established after a period of process operation.

[0570] A gas probe for the drying zone may be useful for determining the degree of drying, for example, by measuring the moisture content. A gas probe in the preheating zone may be useful for determining the degree of any mild thermal decomposition that occurs, for example.

[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 relative to the solid phase. Alternatively or additionally, the preheating zone (if present) can be configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the drying zone can be configured with a gas outlet to generate a substantially countercurrent flow.

[0572] One or more pyrolysis reactors can be selected from any suitable reactor configuration capable of carrying out the pyrolysis process. Exemplary reactor configurations include, but are not limited to, fixed-bed reactors, fluidized-bed reactors, jet-bed reactors, augers, ablation reactors, rotating cones, rotating drum kilns, calciners, roasters, moving-bed reactors, transport-bed reactors, ablation reactors, rotating cones, or microwave-assisted pyrolysis reactors.

[0573] In some embodiments where the auger is used, sand or another heat carrier can be optionally used. For example, the raw materials and sand can be supplied at one end of the screw. The screw mixes the sand and raw materials and transports them through the reactor. The screw can provide good control over the residence time of the raw materials and does not dilute the pyrolysis products with a carrier or fluidizing gas. The sand can be reheated in a separate container.

[0574] In some embodiments where the ablation process is used, the raw material is moved at high speed against the molten iron surface. Ablation of any char formed on the surface can maintain a high heat transfer rate. Such apparatus can prevent dilution of the product. Alternatively, the raw material particles can be suspended in a carrier gas and introduced at high speed through a cyclone with heated walls.

[0575] In some embodiments in which a fluidized bed reactor is used, the raw materials can be introduced into a bed of hot sand fluidized by a gas, which is typically a recirculated product gas. The term “sand” as used herein also includes similar substantially inert materials such as glass particles and recovered ash particles. The high heat transfer rate from the fluidized sand can result in rapid heating of the raw materials. Some ablation due to friction with the sand particles may occur. Heat is typically supplied by heat exchanger tubes through which the hot combustion gas flows.

[0576] A circulating fluidized bed reactor can be used in which gas, sand, and raw materials are moved together. Exemplary transport gases include recirculated product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the raw materials, 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 back into the reactor.

[0577] In some embodiments, a multizone reactor is a continuous reactor comprising a raw material inlet, a plurality of spatially separated reaction zones configured to independently control the temperature and mixing within each of the reaction zones, and a carbonaceous solid outlet, wherein one of the reaction zones is configured to have a first gas inlet for introducing a substantially inert gas into the reactor, and another of the reaction zones is configured to have a first gas outlet.

[0578] In various embodiments, the reactor includes at least two, three, four, or more reaction zones. Each reaction zone is arranged in communication with separately controllable heating means, independently selected from electric heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat transfer, or a combination thereof. In some embodiments, at least one reactor zone is heated by an effluent flow from a thermal oxidation device, if present.

[0579] The reactor can be configured to separately control the gas phase composition and gas phase residence time of at least two reaction zones, up to all reaction zones present within the reactor.

[0580] The reactor may be equipped with a second gas inlet or a second gas outlet. In some embodiments, the reactor is configured with a gas inlet in each reaction zone. In these or other embodiments, the reactor is configured with a gas outlet in each reaction zone. The reactor may be a parallel-flow or counter-flow reactor.

[0581] In some embodiments, the raw material inlet is equipped with a screw or auger feeding mechanism. In some embodiments, the carbonaceous solid outlet is equipped with a screw or auger output mechanism.

[0582] Certain embodiments utilize a rotary or oven equipped with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., rotates around its central axis. The rotational speed affects the solid flow pattern, as well as heat and mass transport. Each reaction zone is configured with flights positioned on its inner wall to provide stirring of the solids. The flights may be independently adjustable in each reaction zone.

[0583] Other means of stirring the solid, such as augers, screws, or paddle conveyors, can be used. 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 designed with the ability to maintain the approximate size of the feed material throughout the process, i.e., the ability to process biomass raw materials without destroying or significantly damaging their structure. In some embodiments, the pyrolysis zone does not include augers, screws, or rakes, which tend to significantly reduce the size of the feed material being pyrolyzed.

[0585] In some embodiments, the system further includes a thermal oxidizer operably connected to an outlet from which condensable vapors and non-condensable gases are removed. The thermal oxidizer is preferably configured to receive separate fuels (such as natural gas) and oxidizers (such as air) into a combustion chamber adapted to burn at least a portion of the fuels and condensable vapors. Certain non-condensable gases, such as CO or CH4, can also be oxidized to CO2.

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

[0587] In some embodiments, the system further comprises a carbon-enhancing unit operably connected to a solid cooler and configured to combine condensable vapor in at least a partially condensed form with the solid. The carbon-enhancing unit can increase the carbon content of the bioreagent obtained from the recovery unit.

[0588] The system may further include separate pyrolysis units adapted to further pyrolyze the bioreagent to further increase its carbon content. These separate pyrolysis units may be relatively simple containers, units, or devices such as tanks, barrels, bottles, drums, totes, sacks, or roll-offs.

[0589] The entire system may be in a fixed location or distributed across several locations. The system can be constructed using modules that can be easily replicated for actual scaling up. The system can also be constructed using the principle of economic scale, as is well known in process industries.

[0590] Next, we will describe some variations of solid carbon reinforcement. In some embodiments, the process for producing bioreagents is (a) To provide carbon-containing raw materials including biomass, (b) Optionally, drying the raw materials to remove at least some of the moisture contained in them, (c) Optionally, degas the raw material to remove at least a portion of the interstitial oxygen present in the raw material, (d) In the pyrolysis zone, in the presence of a substantially inert gas, the raw material is pyrolyzed for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce a high-temperature pyrolysis solid, a condensable vapor, and a non-condensable gas. (e) Separating at least a portion of condensable vapor and at least a portion of non-condensable gas from a high-temperature pyrolysis solid, (f) In a cooling zone, in the presence of a substantially inert gas, the high-temperature pyrolysis solid is cooled for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid, (g) Optionally, cooling a warm pyrolysis solid to produce a low-temperature pyrolysis solid, (h) Thereafter, at least a portion of the condensable vapor or at least a portion of the non-condensable gas from step (e) is passed through a warm pyrolysis solid or a low-temperature pyrolysis solid to form an enhanced pyrolysis solid with increased carbon content. (i) recovering a bioreagent containing at least a portion of the enhanced pyrolysis solid.

[0591] In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through a warm pyrolysis solid in vapor or condensed form to produce an enhanced pyrolysis solid with increased carbon content. In some embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through a warm pyrolysis solid to produce an enhanced pyrolysis solid with increased carbon content.

[0592] Alternatively or additionally, vapor or gas can be brought into contact with a low-temperature pyrolysis solid. In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through the cold pyrolysis solid in vapor or condensed form to produce an enhanced pyrolysis solid with increased carbon content. In some embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through the cold pyrolysis solid to produce an enhanced pyrolysis solid with increased carbon content.

[0593] In certain embodiments, step (h) includes passing substantially all of the condensable vapor from step (e) through a low-temperature pyrolysis solid in vapor or condensed form to produce an enhanced pyrolysis solid with increased carbon content. In certain embodiments, step (h) includes passing substantially all of the non-condensable gas from step (e) through a low-temperature pyrolysis solid to produce an enhanced pyrolysis solid with increased carbon content.

[0594] The process may include various methods for treating or separating the steam or gas before using it for carbon strengthening. For example, an 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) can be supplied to a separation unit configured to produce at least first and second output streams. In certain embodiments, the intermediate feed stream may consist of all of the condensable steam, all of the non-condensable gas, or both.

[0595] Separation techniques include, or can be used, distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separation can be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and can utilize differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to the 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 their relative volatility. For example, the separation unit may be a distillation column, a flash tank, or a condenser.

[0597] Therefore, in some embodiments, the first output stream contains condensable vapor, and the second output stream contains non-condensable gas. The condensable vapor may contain at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapor from pyrolysis may contain aromatic compounds such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic compounds such as persistent tar may be present in the vapor. The non-condensable gas may contain 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 separated based on their relative polarity. For example, the separation unit may be a stripping column, a packed bed, a chromatography column, or a membrane.

[0599] Therefore, in some embodiments, the first output stream contains a polar compound, and the second output stream contains a nonpolar compound. The polar compound may contain at least one carbon-containing molecule selected from methanol, furfural, and acetic acid. The nonpolar compound may contain at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives.

[0600] Step (h) can increase the total carbon content of the bioreagent compared to the process, which is identical except for the absence of step (h). The degree of increase in carbon content may be, in various embodiments, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or more.

[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. The volatile carbon content is the carbon due to volatile substances in the reagent. Volatile substances may be, but are not limited to, aliphatic or aromatic compounds (e.g., terpenes); oxygenated compounds including alcohols, aldehydes, or ketones; and hydrocarbons including various tars. Volatile carbon typically remains bound to or adsorbed on the solid under 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), some amount of volatile carbon can become fixed carbon (e.g., via Boudoar carbon formation from CO). Typically, the volatile substances 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 bioreagent. The increase in energy content may result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. The degree of increase in energy content may be, in various embodiments, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher.

[0604] Further separation can be used to recover one or more non-condensable gases or condensable vapors for use in the process or further treatment. For example, further treatment may be included to produce purified carbon monoxide or hydrogen.

[0605] As another example, acetic acid can be separated and then reduced to ethanol. The reduction of acetic acid can be achieved, at least partially, using hydrogen derived from the produced non-condensable gas.

[0606] Condensible vapors can be used for energy in either a process (such as thermal oxidation) or carbon enrichment to increase the carbon content of bioreagents. Certain non-condensable gases, such as CO or CH4, can be used for energy in a process or as part of a substantially inert gas for a pyrolysis step. Any combination of the aforementioned is also possible.

[0607] A potential advantage of including step (h) is that the gas stream is cleaned and the resulting gas stream is concentrated with respect to CO and CO2. The resulting gas stream can be used for energy recovery, recycled for solid carbon enrichment, or used as an inert gas in a reactor. Similarly, by separating the non-condensable gas from the condensable vapor, the CO / CO2 stream can be prepared for use, for example, as an inert gas in a reactor system or cooling system.

[0608] Other variations are based on the understanding that the principle of the carbon strengthening step can be applied to any raw material to which carbon addition is desired.

[0609] In some embodiments, a batch or continuous process for manufacturing bioreagents is, (a) To provide a solid flow containing a carbon-containing material, (b) To provide a gas stream containing 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 a gas flow through a solid flow under suitable conditions to form a carbon-containing product having an increased carbon content relative to a carbon-containing material.

[0610] In some embodiments, the starting carbon-containing material is pyrolytic biomass or roasted biomass. The gaseous flow can be obtained during an integrated process that provides the carbon-containing material. Alternatively, the gaseous flow can be obtained from separate processing of the carbon-containing material. The gaseous flow or a portion thereof can be obtained from an external source (e.g., a sawmill oven). Mixtures of gaseous flows from various sources, as well as mixtures of carbon-containing materials, are possible.

[0611] In some embodiments, the process further includes recirculating or reusing the gas stream to repeat the process and further increase the carbon or energy content of the carbon-containing product. In some embodiments, the process further includes recirculating or reusing the gas stream to carry out the process and increase the carbon or energy content of another raw material different from the carbon-containing material.

[0612] In some embodiments, the process further includes introducing a gas stream into a separation unit configured to produce at least first and second output streams, the gas stream comprising a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas. The first and second output streams can be separated based on relative volatility, relative polarity, or any other property. The gas streams can be obtained from separate treatments of carbon-containing materials.

[0613] In some embodiments, the process further includes recirculating or reusing the gas stream to repeat the process and further increase the carbon content of the carbon-containing product. In some embodiments, the process further includes recirculating or reusing the gas stream to carry out the process and increase the carbon content of another raw material.

[0614] Carbon-containing products may have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, compared to the starting carbon-containing material.

[0615] In related variant forms, the bioreagent manufacturing system is (a) A feeder configured to introduce carbon-containing raw materials, (b) an optional dryer, which is operably connected to the supply device and configured to remove moisture contained in the carbon-containing raw material, (c) A multizone reactor operably connected to a dryer, the multizone reactor comprising at least one pyrolysis zone operably connected to a spatially separated cooling zone, and the multizone reactor being configured to have outlets for removing condensable vapors and noncondensable gases from a solid, (d) A solid cooler arranged in operable communication with a multi-zone reactor, (e) A material concentration unit configured to be operably connected to a solid cooler and to pass condensable vapor or non-condensable gas through a solid to form a reinforced solid with increased carbon content, (f) A bioreagent recovery unit is provided which is operably connected to a material concentration unit.

[0616] The system may further include a preheating zone operably connected to the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within a multi-zone reactor. Each zone may be located within a single unit or separate units. A solid cooler may also be located 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 generating a substantially countercurrent flow of the gas phase relative to the solid phase. In these or other embodiments, the preheating zone or drying zone (or dryer) is configured with a gas outlet, thereby generating a substantially countercurrent flow of the gas phase relative to the solid phase.

[0618] In certain embodiments, the system incorporates a material concentration unit, and the material concentration unit is (i) A housing having an upper part and a lower part, (ii) an inlet located at the bottom of the lower part of the housing, configured to carry condensable vapor and non-condensable gas, (iii) An outlet at the top of the upper part of the housing, configured to carry a concentrated gas stream derived from condensable vapor and non-condensable gas, (iv) A defined path between the upper and lower parts of the housing, (v) A transport system following a path, the transport system being configured to transport a solid, the housing being shaped so that the solid adsorbs at least a portion of a condensable vapor or at least a portion of a non-condensable gas.

[0619] The disclosed technology can be used to produce various compositions useful as bioreagents, and products incorporating such reagents. In some variations, the bioreagent can be produced using any of the processes disclosed herein, for example, (a) A step of providing a carbon-containing raw material including biomass, (b) Optionally, the step of drying the raw material to remove at least some of the moisture contained in the raw material, (c) Optionally, the step of degassing the raw material to remove at least a portion of the interstitial oxygen contained in the raw material, if present. (d) In a pyrolysis zone, in the presence of a substantially inert gas, the raw material is pyrolyzed for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce a high-temperature pyrolysis solid, a condensable vapor, and a non-condensable gas; (e) Separating at least a portion of condensable vapor and at least a portion of non-condensable gas from a high-temperature pyrolysis solid, (f) In a cooling zone, in the presence of a substantially inert gas, the high-temperature pyrolysis solid is cooled for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) A step of cooling a warm pyrolysis solid to produce a low-temperature pyrolysis solid, (h) Produced by a process comprising the step of recovering a bioreagent containing at least a portion of a low-temperature pyrolysis solid.

[0620] In some embodiments, the reagent contains at least 70% by weight, at least 80% by weight, at least 90% by weight, or at least 95% by weight of total carbon on a dry basis. The total carbon includes at least fixed carbon and may further include carbon from volatile substances. In some embodiments, the carbon from volatile substances accounts for 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 bioreagent may contain approximately 10% by weight or less of hydrogen on a dry basis, for example, approximately 5% by weight or less. The bioreagent may contain approximately 1% by weight or less of nitrogen on a dry basis, for example, approximately 0.5% by weight or less. The bioreagent may contain approximately 0.5% by weight or less of phosphorus on a dry basis, for example, approximately 0.2% by weight or less. The bioreagent may contain approximately 0.2% by weight or less of sulfur on a dry basis, for example, approximately 0.1% by weight or less.

[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 are substantially carbon plus any ash and any moisture present, and contain little to no hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur. Accordingly, some embodiments provide bioreagents having less than 100% carbon on a dry / ashless (DAF) basis.

[0624] Generally speaking, raw materials such as biomass contain non-volatile species, including silica and various metals, that are not readily released during pyrolysis. Of course, it is also possible to use ashless raw materials, in which case substantial amounts of ash should not be present in the pyrolysis solid. Ash can be measured, for example, using ASTM D3174.

[0625] Various amounts of non-combustible materials, such as ash, may be present. The bioreagent may contain approximately 10% by weight or less of non-combustible materials on a dry basis, for example, approximately 5% by weight, approximately 2% by weight, or approximately 1% by weight or less. In certain embodiments, the reagent contains little to no ash, or essentially no ash or other non-combustible materials at all. Therefore, some embodiments provide essentially pure carbon containing 100% carbon on a dry basis.

[0626] Various amounts of water may be present. On a total mass basis, bioreagents may contain at least 1% by weight, 2% by weight, 5% by weight, 10% by weight, 15% by weight, 25% by weight, 35% by weight, 50% by weight, or more of water. Where intended herein, “water” should be interpreted to include any form of water present in the bioreagent, including absorbed water, adsorbed water molecules, chemical hydrates, and physical hydrates. Equilibrium water content may vary depending on at least local environmental factors such as relative humidity. Furthermore, water content may vary during transport, preparation for use, and other logistics. Water content can be measured, for example, using ASTM D3173.

[0627] Bioreagents can have varying energy content, which for this purpose means an energy density based on a higher calorific value associated with the total combustion of the oven-dry reagent. For example, bioreagents may have an energy content of 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 can be measured, for example, using ASTM D5865.

[0628] The bioreagent can be formed into a powder, such as a coarse powder or a fine powder. For example, in this embodiment, the reagent can 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 bioreagent is formed into a structural object containing compressed, bound, or aggregated particles. The starting material for forming these objects may be in powder form of the reagent, such as an intermediate obtained by particle size reduction. The object may be formed using mechanical pressing or other means to optionally aggregate the binder or particles together.

[0630] In some embodiments, the bioreagent is manufactured in the form of a structural object whose structure is substantially derived from the raw materials. For example, a raw material chip may produce a bioreagent product chip. Alternatively, a raw material cylinder may produce a bioreagent cylinder, which may be somewhat smaller but otherwise can maintain the basic structure and geometric shape of the starting material.

[0631] The bioreagent can 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 larger. In various embodiments, the minimum or maximum dimension may be length, width, or diameter.

[0632] Other variations relate to the incorporation of additives into the process, the product, or both. In some embodiments, the bioreagent includes at least one process additive incorporated during the process. In these or other embodiments, the reagent includes at least one product additive introduced into the reagent after the process.

[0633] In some embodiments, the bioreagent is on a dry basis. 70% by weight or more total carbon, Hydrogen at a concentration of 5% by weight or less, 1% by weight or less of nitrogen, Phosphorus of 0.5% by weight or less, Sulfur at 0.2% by weight or less, The additive comprises a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

[0634] The additives are by no means limited, but may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0635] In some embodiments, the bioreagent is on a dry basis. 70% by weight or more total carbon, Hydrogen at a concentration of 5% by weight or less, 1% by weight or less of nitrogen, Phosphorus of 0.5% by weight or less, Sulfur at a concentration of 0.2% by weight or less, It includes an additive selected from acids, bases, or salts thereof.

[0636] The additives are by no means limited, but may be selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof.

[0637] In a particular embodiment, the bioreagent is on a dry basis. 70% by weight or more total carbon, Hydrogen at a concentration of 5% by weight or less, 1% by weight or less of nitrogen, Phosphorus of 0.5% by weight or less, Sulfur at 0.2% by weight or less, A first additive selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof, A second additive selected from acids, bases, or salts thereof, The first additive is different from the second additive.

[0638] The first additive can be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, or a combination thereof, and the second additive can 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 bioreagent essentially consists, on a dry basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-flammable material, and additives selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0640] In certain embodiments, the bioreagent essentially consists, on a dry basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, a non-flammable substance, and additives selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, or combinations thereof.

[0641] The amount of additives (or total additives) can vary widely, including about 0.01% to about 25% by weight, including about 0.1% by weight, about 1% by weight, about 5% by weight, about 10% by weight, or about 20% by weight. Therefore, it will be understood that when relatively large amounts of additives, such as more than about 1% by weight, are incorporated, the energy content calculated based on the total reagent weight (including additives) will decrease. Furthermore, in various embodiments, bioreagents with additives may have an energy content of at least about 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 considerations regarding product form also apply to embodiments that incorporate additives. In fact, certain embodiments incorporate additives as binders, fluxes, or other modifiers to improve the final properties for a particular application.

[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. Certain market mechanisms (e.g., renewable carbon identification numbers, tax credits, etc.) may exist where value is derived from the renewable carbon content in the bioreagent.

[0644] In certain embodiments, fixed carbon can be classified as non-renewable carbon (e.g., coal-derived), while volatile carbon, which can be added separately, can be renewable carbon in order to increase not only the energy content but also the renewable carbon value.

[0645] The bioreagents manufactured as described herein are useful for a wide variety of carbonaceous products. These bioreagents may themselves be desirable market products. Bioreagents such as those provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including a higher renewable carbon content) compared to the current state of the art.

[0646] In a modified form, the product may include any of the bioreagents that can be obtained by the disclosed process or that are described in the compositions shown herein, or any part, combination, or derivative thereof.

[0647] Generally speaking, bioreagents can be used for various purposes: they can be combusted to generate energy (including electricity and heat); they can be partially oxidized, gasified, or steam reformed to produce synthesis gas; they can be utilized for their adsorption or absorption properties; they can be utilized for their reaction properties in metal refining (such as reduction of metal oxides) or other industrial processes; or they can be utilized for their material properties in carbon steel and various other metal alloys. Essentially, bioreagents can be used in any market application of carbon-based commodities or advanced materials, including specialized uses that should be developed.

[0648] Prior to suitability for any product application or actual use, the disclosed bioreagents can be analyzed, measured, and optionally modified (by additives, etc.) in various ways. Several potentially important properties other than chemical composition and energy content include, to name a few, density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, and basicity.

[0649] Products or materials that can incorporate these bioreagents may include, but are not limited to, carbon-based blast furnace additive products, carbon-based taconite pellet additive products, ladle-added carbon-based products, metcoke carbon-based products, coal substitute products, carbon-based coking products, carbon breeze products, carbon for casting, carbon for sintering, fluidized bed carbon-based raw materials, carbon-based furnace additive products, injectable carbon-based products, pulverized carbon-based products, stoker carbon-based products, carbon electrodes, or activated carbon products.

[0650] The use of disclosed bioreagents in metal manufacturing can reduce slag, increase overall efficiency, and mitigate lifecycle environmental impacts. Therefore, some embodiments are particularly well-suited for metal processing and metal manufacturing.

[0651] Some variations utilize bioreagents as carbon-based blast furnace adducts. A blast furnace is a type of metallurgical furnace used for smelting (but not limited to) industrial metals such as iron. Smelting is a form of extractive metallurgy, primarily used to produce metals from ore. Smelting uses heat and chemical reducing agents to break down the ore. Carbon or carbon monoxide derived from carbon removes oxygen from the ore, leaving the elemental metal.

[0652] The reducing agent may consist of or contain a bioreagent. In a blast furnace, the bioreagent, ore, and typically limestone, can be continuously supplied through the top of the furnace, while air (optionally with oxygen concentration) is blown into the bottom of the chamber, so that the chemical reaction occurs throughout the furnace as the material moves downward. The final product is usually the molten metal and slag phase removed from the bottom, as well as the flue gas exiting from the top of the furnace. The downward flow of ore in contact with the upward flow of high-temperature carbon monoxide-concentrated 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 crucial for economical blast furnace operation. Carbon decomposition varies depending on its location in the blast furnace and involves a combination of reactions with CO2, H2O, or O2, as well as abrasion between carbon particles and abrasion against other components of the input. Decomposed carbon particles can cause clogging and performance degradation.

[0654] The coke reactivity test is a highly regarded measure of the performance of carbon in a blast furnace. This test has two elements: the coke reactivity index (CRI) and the post-reaction coke strength (CSR). Carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​are preferred for better blast furnace performance. The CRI can be determined in its as-received state according to any suitable method known in the art, for example, by the ASTM method DS341.

[0655] In some embodiments, the bioreagent provides a carbon product having properties suitable for direct introduction into a blast furnace.

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

[0657] Some embodiments use one or more additives in an amount sufficient to provide a bioreagent that, when added to another carbon source (e.g., coke) having a CRI or CSR insufficient for use as a blast furnace product, provides a composite product having a CRI or CSR sufficient for use in a blast furnace. In some embodiments, one or more additives are present in an amount sufficient to provide a bioreagent having 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 bioreagent. 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 bioreagent in the blast furnace can be increased. These compounds result in stronger materials, i.e., higher CSR, which can improve blast furnace efficiency. Furthermore, additives such as alkaline earth metals, or those selected from their oxides or carbonates, can result in lower emissions (e.g., SO2).

[0659] In some embodiments, the blast furnace substitute is a bioreagent containing at least about 55 wt% carbon, less than or equal to about 0.5 wt% sulfur, less than or equal to about 8 wt% non-combustible material, and a calorific value of at least about 11,000 Btu / pound. In some embodiments, the blast furnace substitute further comprises less than or equal to about 0.035 wt% phosphorus, about 0.5 wt% to about 50 wt% volatile matter, and optionally one or more additives. In some embodiments, the blast furnace substitute contains about 2 wt% to about 15 wt% dolomite, about 2 wt% to about 15 wt% dolomite lime, about 2 wt% to about 15 wt% bentonite, or about 2 wt% to about 15 wt% calcium oxide. In some embodiments, the blast furnace substitute has dimensions substantially in the range of about 1 cm to about 10 cm.

[0660] In some embodiments, bioreagents are useful as a substitute for foundry coke. Foundry coke is generally characterized by having a carbon content of at least about 85% by weight, a sulfur content of about 0.6% by weight, volatile substances of about 1.5% by weight or less, ash of about 13% by weight or less, moisture of about 8% by weight or less, phosphorus of about 0.035% by weight, a CRI value of about 30, and dimensions in the range of about 5 cm to about 25 cm.

[0661] Some variant forms utilize bioreagents as carbon-based taconite pellet additives. The ore used in the production of iron and steel is iron oxide. The main iron oxide ores include hematite, limonite (also called brown ore), taconite, and magnetite / black ore. Taconite is a low-grade but important ore and contains both magnetite and hematite. The iron content of taconite is generally 25% to 30% by weight. Blast furnaces typically require ore containing at least 50% by weight of iron for efficient operation. Iron ore can undergo beneficiation, including crushing, screening, tumbling, flotation, and magnetic separation. The refined ore is concentrated to over 60% iron and is often 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 instance, pellets approximately 1 centimeter in diameter containing about 65% by weight of iron can be formed. The pellets are then calcined to oxidize the magnetite to hematite. The pellets are durable and remain porous enough for the blast furnace charge to pass heated gas through and react with the pelletized ore.

[0663] Taconite pellets can be supplied to a blast furnace to produce iron, as described above with respect to blast furnace additives. In some embodiments, bioreagents are introduced into the blast furnace. In these or other embodiments, the bioreagents are incorporated into the taconite pellets themselves. For example, beneficiated taconite ore powder can be mixed with bioreagents and binders, rolled into small objects, and then calcined until hardened. In such embodiments, taconite-carbon pellets with a suitable composition can be conveniently introduced into the blast furnace without requiring a separate carbon source.

[0664] Some variations utilize bioreagents as ladle-added carbon products. A ladle is a container used to transport and pour molten metal. A casting ladle is used to pour molten metal into a mold to produce a casting. A transfer ladle is used to transfer large quantities of molten metal from one process to another. A processing ladle is used for processes that occur within the ladle to alter several aspects 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 bioreagent can be introduced into any type of ladle, but typically, carbon is added to the processing ladle in a suitable amount based on the target carbon content. The carbon injected into the ladle may be in the form of a fine powder for good material transport of carbon to the final composition. In some embodiments, when the bioreagent is used as a ladle addition product, it has a minimum dimension of about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or larger.

[0666] In some embodiments, high-carbon bioreagents are useful as ladle carbon additives in basic oxygen furnace or electric arc furnace facilities where ladle carbon addition is used (for example, by adding it to ladle carbon during steelmaking).

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

[0668] Directly reduced iron (DRI), also known as sponge iron, is produced from the direct reduction of iron ore (in the form of lumps, pellets, or powder) using reducing gases conventionally produced from natural gas or coal. The reducing gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide acting as reducing agents. The bioreagents provided herein can be converted into a CO-containing gas stream to act as reducing agents and produce directly 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 to no gangue (slag) and low levels of metallic residue. They are a high-grade pig iron product with excellent deliverable and handling properties. The carbon contained in the iron nuggets or any part thereof may be the bioreagents provided herein. Iron nuggets can be produced by reducing iron ore in a rotary hearth furnace using the bioreagents as a reducing agent and energy source.

[0670] Several variants utilize metallurgical coke carbon products as bioreagents. Metallurgical coke, also known as "m...

Claims

1. A process for producing biocarbon pellets, wherein the process is (a) The pyrolysis of a biomass-containing raw material in a first pyrolysis reactor to generate a first bioreagent and pyrolysis vapor, wherein the first bioreagent contains at least 70% by weight of total carbon on a dry basis. (b) Introducing the pyrolysis steam into the separation unit, thereby generating a pyrolysis precipitate, wherein the pyrolysis precipitate is in the form of a solid or slurry, (c) Contacting the first bioreagent with the pyrolysis precipitate to produce an intermediate material, wherein the intermediate material includes the first bioreagent and the pyrolysis precipitate, (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets. (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce further carbonized bioreagents and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors, and (g) recovering the further carbonized bioreagent as a biocarbon pellet, wherein, The fixed carbon content of the further carbonized bioreagent is greater than the fixed carbon content of the first bioreagent, and Thermogravimetric analysis reveals that the oxygen reactivity of the further carbonized bioreagent is lower than that of the first bioreagent, wherein the thermogravimetric analysis is performed in the presence of pure oxygen using a temperature gradient of 40°C / min from 25°C to 950°C.

2. The separation unit optionally includes a condensation system: The condensation system has multiple stages, or The process according to claim 1, wherein the pyrolysis precipitate is a condensation product of the first condenser step among the plurality of steps.

3. The process according to claim 1, wherein the separation unit includes 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, or an electrostatic dust collection unit.

4. The process according to claim 1, wherein the intermediate material includes the pyrolysis precipitate adsorbed onto the surface of the first bioreagent.

5. The process according to claim 1, wherein the intermediate material comprises the pyrolysis precipitate absorbed into the bulk phase of the first bioreagent, and optionally the pyrolysis precipitate is in solid or slurry form.

6. A binder is introduced into the intermediate material, optionally the binder being starch, thermoplastic starch, cross-linked 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 powder, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, The process according to claim 1, wherein the binder is selected from 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 thereof, and preferably the binder is selected from starch, thermoplastic starch, cross-linked starch, starch polymer, derivatives thereof, or any combination thereof.

7. The process according to claim 1, wherein the first bioreagent acts as a catalyst or reaction matrix for the fixed carbon formation reaction of the pyrolysis precipitate.

8. Step (a) The process is carried out at a first thermal decomposition temperature of at least 250°C to a maximum of 700°C, or This is carried out over a first thermal decomposition time of at least 1 minute to a maximum of 4 hours. The process according to claim 1.

9. Step (f) The process is carried out at a second thermal decomposition temperature of at least 300°C to a maximum of 1250°C, or This is carried out over a second thermal decomposition time of at least 1 minute to a maximum of 4 hours. The process according to claim 1.

10. Further comprising generating a thermally decomposed nonprecipitate within the separation unit, The process according to claim 1, optionally recovering the pyrolysis nonprecipitate and at least partially oxidizing it to generate heat, preferably using the heat within the process.

11. The aforementioned pyrolysis exhaust gas To transport to the separation unit, or The process further includes transporting to a second separation unit, wherein the second separation unit operates under effective precipitation conditions for producing a second pyrolysis precipitate, and the second pyrolysis precipitate is optionally in the form of a solid or slurry: The method further comprises contacting the first bioreagent with the second pyrolysis precipitate, or The process according to claim 1, further comprising contacting the further carbonized bioreagent with the second pyrolysis precipitate.

12. The process according to claim 1, wherein the pyrolysis precipitate contains up to 1% by weight or up to 0.1% by weight of ash, or is essentially free of ash.

13. The process according to claim 1, further comprising converting at least 10% by weight, at least 20% by weight, or at least 50% by weight of carbon contained in the pyrolysis precipitate into fixed carbon in the biocarbon pellets.

14. The process according to claim 1, further comprising converting at least 30% to a maximum of 90% by weight of carbon contained in the pyrolysis precipitate into fixed carbon in the biocarbon pellets.

15. The process according to claim 1, wherein at least 1% to a maximum of 50% by weight or at least 10% to a maximum of 40% by weight of the fixed carbon in the biocarbon pellets is derived from the pyrolysis precipitate.

16. The process according to claim 1, wherein the intermediate material further comprises additional pyrolysis precipitates not provided from step (b) of the process.

17. Step (c) is Contacting less than all of the first bioreagent with the pyrolysis precipitate, or Bring less than the entire amount of the thermal decomposition precipitate into contact with the first biological reagent. The process according to any one of claims 1 to 16, including the process described in any one of claims 1 to 16.

18. The process according to claim 1, wherein the biocarbon pellets, 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 No. 4: 'Test method for self-heating substances'", are optionally characterized as non-self-heating, and the oxygen reactivity of the further carbonized bioreagent is reduced by adding an additive to the further carbonized bioreagent.

19. The process according to claim 1, wherein the process provides a total carbon yield of at least 50%, which is calculated as the carbon contained in the biocarbon pellets as a percentage of the carbon contained in the biomass-containing raw material, and preferably the total carbon yield is at least 60%, at least 70%, or at least 80%.

20. A process for producing biocarbon pellets, wherein the process is (a) The pyrolysis of a biomass-containing raw material in a first pyrolysis reactor to generate a first bioreagent and pyrolysis vapor, wherein the first bioreagent contains at least 70% by weight of total carbon on a dry basis. (b) To provide a carbon-containing condensate material, wherein the carbon-containing condensate material is a liquid, solid, or slurry, (c) Contacting the first bioreagent with the carbon-containing condensate material to produce an intermediate material, wherein the intermediate material includes the first bioreagent and the carbon-containing condensate material, (d) Pelleting the intermediate material to produce intermediate pellets, (e) Optionally, drying the intermediate pellets. (f) Separately from step (a), the intermediate pellet is thermally decomposed in a second thermal decomposition reactor to produce further carbonized bioreagents and thermal decomposition exhaust gas, wherein the first thermal decomposition reactor and the second thermal decomposition reactor are the same reactor or different reactors, and (g) recovering the further carbonized bioreagent as a biocarbon pellet, wherein, The fixed carbon content of the further carbonized bioreagent is greater than the fixed carbon content of the first bioreagent, and The process wherein the further carbonized bioreagent has oxygen reactivity determined by thermogravimetric analysis using a temperature gradient of 40°C / min from 25°C to 950°C in the presence of pure oxygen, which is lower than that of the first bioreagent.

21. The process according to claim 1 or 20, wherein, according to the TGA graph of weight loss over time from the thermogravimetric analysis, the further carbonized bioreagent requires at least 5% or at least 10% longer time to reach 99% oxidation compared to the first bioreagent.

22. The TGA graph from the aforementioned thermogravimetric analysis shows a first carbon oxidation regime related to the oxidation of volatile carbon, which is succeeded by a second carbon oxidation regime related to the oxidation of fixed carbon, optionally: The volatile carbon oxidation time is defined as the time from the start of the first carbon oxidation regime to the start of the second carbon oxidation regime, wherein during the volatile carbon oxidation time, the mass loss of the first bioreagent is at least 25% or at least 50% greater than the mass loss of the further carbonized bioreagent. The thermogravimetric analysis shows that the first bioreagent 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 further carbonized bioreagent in the first carbon oxidation regime. The thermogravimetric analysis shows that the first bioreagent has an average mass loss rate at least 10% higher than that of the second carbon oxidation regime, or The process according to claim 1 or 20, wherein the thermogravimetric analysis shows a first derivative curve peak for the further carbonized bioreagent within the first carbon oxidation regime at temperatures above 500°C, where the thermogravimetric analysis shows a first derivative curve peak for the first bioreagent within the first carbon oxidation regime at temperatures of at least 200°C to a maximum of 500°C.

23. The carbon-containing condensed material is The thermal decomposition precipitate is derived from the aforementioned thermal decomposition vapor. It is a pyrolysis precipitate provided externally from a different process, or Contains aromatic species (wherein preferably, the carbon-containing condensate material is off-spec or waste aromatic flow), It includes lignin, sugars or sugar decomposition products, polymers or polymer decomposition products, or liquid products produced by chemical reactions of synthesis gas (wherein optionally, the synthesis gas includes the pyrolysis vapor or the pyrolysis exhaust gas), or １４ C / １２ Based on measurements of the carbon isotope ratio, it contains at least 50%, at least 90%, or essentially all, renewable carbon. The process according to claim 20.

24. The aforementioned intermediate material is The carbon-containing condensed material adsorbed on the surface of the first bioreagent, or The carbon-containing condensate material is absorbed into the bulk phase of the first bioreagent, The process according to claim 20.

25. The process according to claim 1 or 20, wherein steps (c) and (d) are integrated.

26. The process according to claim 20, wherein a binder is introduced into the intermediate material.

27. The process according to claim 1 or 20, wherein an external binder is not introduced into the intermediate material during pelletization.

28. Perform the drying step (e) described above, optionally: Steps (d) and (e) are integrated, or The process according to claim 1 or 20, wherein steps (e) and (f) are integrated.

29. The process according to claim 1 or 20, wherein the first pyrolysis reactor is different from the second pyrolysis reactor.

30. The process according to claim 1 or 20, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same unit, and steps (a) and (f) are performed at different times.

31. The process according to claim 20, wherein the first bioreagent acts as a catalyst or reaction matrix for the fixed carbon formation reaction of the carbon-containing condensate material.

32. Step (a) The process is carried out at a first thermal decomposition temperature of at least 250°C to a maximum of 700°C, or This is carried out over a first thermal decomposition time of at least 1 minute to a maximum of 4 hours. The process according to claim 1 or 20.

33. Step (f) The process is carried out at a second thermal decomposition temperature of at least 300°C to a maximum of 1250°C, or This is carried out over a second thermal decomposition time of at least 1 minute to a maximum of 4 hours. The process according to claim 1 or 20.

34. The process according to claim 1 or 20, further comprising at least partially oxidizing the pyrolysis vapor or pyrolysis exhaust gas to generate heat, and optionally further comprising using the heat in the process.

35. The present invention further comprises transporting the pyrolysis exhaust gas to a separation unit operating under effective precipitation conditions to produce a second pyrolysis precipitate, wherein the second pyrolysis precipitate is in solid form, and herein optionally: Contacting the first bioreagent with the second thermal decomposition precipitate, or The process according to claim 20, further comprising contacting the further carbonized bioreagent with the second pyrolysis precipitate.

36. The biocarbon pellets Containing at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 85% by weight, or at least 90% by weight of fixed carbon, Contains up to 10% by weight, up to 5% by weight, or up to 1% by weight of ash, The process according to claim 1 or 20, comprising up to 20% by weight or up to 10% by weight of total volatile substances.

37. The process according to claim 20, wherein at least 25% by weight, at least 50% by weight, or at least 75% by weight of the carbon in the carbon-containing condensate material is converted into fixed carbon in the biocarbon pellets.

38. The process according to claim 20, wherein at least 1% to a maximum of 50% by weight or at least 10% to a maximum of 40% by weight of the fixed carbon in the biocarbon pellets is derived from the carbon-containing condensate material.

39. Step (c) is Contacting less than all of the first bioreagent with the carbon-containing condensate material, or Contacting less than the total amount of the carbon-containing condensed material with the first bioreagent, The process according to claim 20, further comprising:

40. The total carbon in the biocarbon pellet is １４ C / １２ The process according to claim 1 or 20, which is renewable by at least 50% or at least 90% or essentially completely, as determined from measurements of the 13C isotope ratio.

41. The biocarbon pellets Characterized by a hard glove crushing index of at least 30, At least 20 lb / ft on a dry basis ３ Characterized by bulk density, The biocarbon pellets have the characteristic of having an average pellet size of at least 1 mm to a maximum of 10 cm, which is calculated as the effective diameter of the biocarbon pellets. It has the characteristics of a pellet shape selected from spherical, cylindrical, cubic, octagonal, hexagonal, honeycomb, elliptical, columnar, rod-shaped, pillow-shaped, lentil-shaped, random granular, or a combination thereof. At least 100 lb ｆ / in ２ or at least 150 lb ｆ / in ２ characterized by the pellet compression strength at 25 °C of Characterized by a maximum water absorption of 20% by weight after immersion in water at 25°C for 24 hours, If a substance undergoes a self-heating test in accordance with the "Test and Judgment Criteria Manual, Revised 7th Edition, 2019, published by the United Nations, p. 375, 33.4.6 Test No. 4 'Test Method for Self-Heatening Substances'", it is characterized as non-self-heating, or Characterized by an effective pellet diameter of no more than 10% of the effective pellet diameter of the intermediate pellet, The process according to claim 1 or 20.

42. The process further includes introducing an additive, wherein the additive is optionally: Selected from acids, bases, or salts thereof, Selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. 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, dolomite lime, fluorite, fluorospar, bentonite, calcium oxide, lime, titanium dioxide, or a combination thereof, The pH of the filtrate of the biocarbon pellets is adjusted, where the pH of the filtrate is measured by combining 20 grams of the biocarbon pellets or their powder form (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. The pH of the filtrate of the further carbonized bioreagent is adjusted by adding the further carbonized bioreagent to the bioreagent, where the pH of the filtrate is measured by combining 20 grams of the further carbonized 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. By being added to the further carbonized bioreagent, the pH of the filtrate of the further carbonized bioreagent is reduced. By adding to the further carbonized bioreagent, the pH of the filtrate of the further carbonized bioreagent is increased, or By being added to the further carbonized bioreagent, the oxygen reactivity of the further carbonized bioreagent is reduced. The process according to claim 1 or 20.

43. The process according to claim 20, which provides a total carbon yield of at least 50%, at least 60%, at least 70%, or at least 80%, calculated as the carbon contained in the biocarbon pellets as a percentage of the total carbon in the biomass-containing raw material and the carbon-containing condensate material.

44. The process according to claim 1 or 20, wherein the process is continuous or semi-continuous.

45. The process according to claim 1 or 20, further comprising mechanically processing the biocarbon pellets to produce biocarbon powder.

46. The process according to claim 1 or 20, further comprising generating a biocarbon object by combining the biocarbon pellets with an additional amount of the further carbonized bioreagent.

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