Process and system for recapturing carbon from biomass pyrolysis liquids - Patents.com

Abstract

The present disclosure provides a method of making a high fixed carbon material, including pyrolyzing a biomass to produce intermediate solids and pyrolysis vapors, condensing the pyrolysis vapors to produce a pyrolysis liquid, blending the pyrolysis liquid with the intermediate solids to produce a mixture, and further pyrolyzing the mixture to produce a high fixed carbon material. The process may include pyrolyzing a biomass-containing feedstock in a first pyrolysis reactor to produce a first bio-reagent and a first pyrolysis vapor, introducing the first pyrolysis vapor into a condensation system to produce a condenser liquid, contacting the first bio-reagent with the condenser liquid, thereby producing an intermediate material, further pyrolyzing the intermediate material in a second pyrolysis reactor to produce a second bio-reagent and a second pyrolysis vapor, and recovering the second bio-reagent as a high yield bio-carbon composition. The process may further include pelletizing the intermediate material. A number of process and system configurations are disclosed.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority benefit of U.S. Provisional Patent Application No. 63 / 228,536, filed August 2, 2021, which is incorporated by reference in its entirety.

[0002] The present technology relates generally to pyrolysis processes that utilize the recapture of carbon from pyrolysis oils to create high yield biocarbon compositions. [Background technology]

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

[0004] Carbon can in principle be produced from virtually any carbonaceous material. 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 waste materials. Due to the rising economic, environmental, and social costs associated with fossil resources, it is preferable to utilize renewable biomass to produce carbon-based reagents.

[0005] Biomass is a term used to describe biologically produced or living matter. The chemical energy contained in biomass comes from solar energy using the natural process of photosynthesis. Photosynthesis is the process by which plants take carbon dioxide and water from their surroundings and convert them into sugars, starch, cellulose, hemicellulose, and lignin using energy from sunlight. Of all renewable energy sources, biomass is unique in that it is effectively stored solar energy. Furthermore, biomass is the only renewable source of carbon.

[0006] Various conversion technologies exist for biomass feedstocks to carbonaceous materials. Pyrolysis is a process for thermal conversion of solid materials in the complete absence of oxidizing agents (air or oxygen) and with limited supply such that oxidation does not occur appreciably. Depending on process conditions and additives, biomass pyrolysis can be adjusted to produce widely varying amounts of gas, liquids, and solids. Lower process temperatures and longer steam residence times favor the production of solids. High temperatures and longer residence times increase biomass conversion to syngas, while moderate temperatures and short steam residence times are generally optimal for producing liquids. Historically, slow pyrolysis of wood has been carried out in large piles, in simple batch processes, and without emissions controls. Traditional charcoal production techniques are not only energy inefficient, but also highly polluting.

[0007] Improved or optimized processes for producing bio-carbon compositions are desirable, especially with regard to carbon yield and bio-carbon properties. Summary of the Invention

[0008] overview Some variations are processes for producing a bio-carbon composition, the process comprising: pyrolyzing a feedstock in a first pyrolysis reactor, the feedstock comprising biomass, thereby producing a first bio-reagent and a first pyrolysis vapor; introducing the first pyrolysis vapor into a condensation system, thereby generating a condenser liquid and a condenser vapor; contacting a first biological reagent with a condenser liquid, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the condenser liquid; heat treating the intermediate material in a heat treatment unit, thereby producing a second bio-reagent and an exhaust gas; recovering the second bio-reagent as a bio-carbon composition.

[0009] In some embodiments, the feedstock is softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems. , fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0010] In some embodiments, the process further includes pelleting the first bio-reagent. In these or other embodiments, the process may further include pelleting the intermediate material. In certain embodiments, pelleting the intermediate material is integrated with contacting the first bio-reagent with the condenser liquid. In other embodiments, pelleting the intermediate material occurs after contacting the first bio-reagent with the condenser liquid.

[0011] Pelletizing the intermediate material, if performed, may include introducing a binder into the intermediate material. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing.

[0012] In some embodiments, pelletizing the intermediate material does not include introducing an external binder to the intermediate material.

[0013] In some processes, the carbon recapture unit is located upstream of the thermal treatment unit. In certain processes, the carbon recapture unit is the first stage of the thermal treatment unit. The carbon recapture unit may be a mixing unit that contacts the first biological reagent with the condenser liquid. Alternatively or additionally, the carbon recapture unit may be separate from the mixing unit. The carbon recovery unit may be supplied with a carbon source different from the condenser liquid, such as an external carbon source or a waste carbon-containing stream from the process.

[0014] In some embodiments, the condensation system includes multiple condenser stages. The condenser liquid can be, for example, a condensation product of a first stage of the multiple condenser stages. In some embodiments, the condenser liquid is a condensation product of multiple stages of the multiple condenser stages. In certain embodiments, the multiple stages do not include the last stage of the multiple condenser stages, especially when the last stage is configured or operated such that the final condenser product contains a high concentration of water.

[0015] In some embodiments, the intermediate material comprises a condenser liquid adsorbed onto a surface of the first bio-reagent. Alternatively or additionally, the intermediate material may comprise a condenser liquid absorbed within the bulk phase of the first bio-reagent.

[0016] In some embodiments, the thermal treatment unit is a second pyrolysis reactor operated at a temperature of at least about 250° C., the second pyrolysis reactor configured to pyrolyze the intermediate material. In other embodiments, the thermal treatment unit is operated at a relatively low temperature selected from, for example, about 80° C. to about 250° C.

[0017] The thermal treatment unit may include an internal oxygen-free environment, or at least a low-oxygen environment. In some embodiments, an inert gas is introduced into the thermal treatment unit. In certain embodiments, the thermal treatment unit is operated under vacuum.

[0018] In some embodiments, the process further includes introducing the exhaust gas from the thermal treatment unit into a condensation system. These embodiments may be desirable when the exhaust gas contains high concentrations of carbon.

[0019] In some embodiments, the thermal-treatment unit is configured to dry the second biological reagent. In these embodiments, the exhaust gas from the thermal-treatment unit comprises or consists essentially of water vapor.

[0020] The process may further include drying the bio-carbon composition after heat treatment in the heat treatment unit.

[0021] In a typical embodiment, the first pyrolysis reactor is separate from the second pyrolysis reactor, in other embodiments the first and second pyrolysis reactors are the same physical unit but perform the pyrolysis and heat treatment at different times.

[0022] In some embodiments, the process includes performing a fixed carbon formation reaction on the condenser liquid. The fixed carbon formation reaction can utilize the first bio-reagent as a catalyst. Alternatively or additionally, the fixed carbon formation reaction can utilize the first bio-reagent as a reaction matrix.

[0023] In some processes, the process includes converting at least 25%, at least 50%, or at least 75% by weight of the total carbon contained in the condenser liquid to fixed carbon contained in the second bio-reagent.

[0024] In some embodiments, at least about 10% and up to about 80% by weight of the fixed carbon in the second bio-reagent is derived from the condenser liquid, in certain embodiments, at least about 20% and up to about 60% by weight of the fixed carbon in the second bio-reagent is derived from the condenser liquid.

[0025] In some processes, all of the condenser liquid is contacted with the first bio-reagent. In other processes, less than all of the condenser liquid is contacted with the first bio-reagent. In this disclosure, references to "condenser liquid" can relate to either a portion of the condenser liquid formed in the process or all of the condenser liquid formed in the process, unless otherwise specified.

[0026] In some processes, the condenser liquid is contacted with the first biological reagent without any intermediate chemical treatment. In other processes, the condenser liquid is chemically treated before contact with the first biological reagent. There are various types of chemical treatments that can be performed on the condenser liquid, and generally speaking, chemical treatment refers to the introduction or removal of mass or energy from the condenser liquid. Exemplary types of chemical treatments include separating certain components (e.g., water or acetic acid) from the condenser liquid, or chemically reacting the condenser liquid with reactants (e.g., CO and / or H2).

[0027] In some embodiments, the condenser liquid is subjected to a purification step prior to contact with the first biological reagent. In these or other embodiments, the condenser liquid is subjected to a reaction step prior to contact with the first biological reagent. In certain embodiments, there is a reaction and purification step that not only initially removes undesired impurities in the condenser liquid, but also removes undesired chemical reaction by-products in the intermediate material.

[0028] In some embodiments, pyrolyzing the feedstock (in the first pyrolysis reactor) is performed at a first pyrolysis temperature of at least about 250° C. and up to about 1250° C. In certain embodiments, the first pyrolysis temperature is at least about 300° C. and up to about 700° C. In some embodiments, pyrolyzing the feedstock (in the first pyrolysis reactor) is performed for a first pyrolysis time of at least about 10 seconds and up to about 24 hours.

[0029] In some embodiments where the heat treatment is at a pyrolysis temperature, pyrolyzing the intermediate material is carried out at a second pyrolysis temperature of at least about 250° C. and up to about 1250° C. In certain embodiments, the second pyrolysis temperature is at least about 300° C. and up to about 700° C. In some embodiments, pyrolyzing the intermediate material is carried out for a second pyrolysis time of at least about 10 seconds and up to about 24 hours.

[0030] The process may further include oxidizing the condenser vapors, thereby generating heat. Additionally or alternatively, the process may further include oxidizing the tail gas (from the thermal treatment unit), thereby generating heat. Heat generated from the oxidation of the condenser vapors and / or tail gas may be recycled in the process, for example to provide heat to the first pyrolysis reactor.

[0031] In some embodiments, the process further comprises grinding the first bio-reagent using a mechanical treatment device, the mechanical treatment device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0032] In some embodiments, the process further comprises grinding the intermediate material using a mechanical treatment device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0033] In some embodiments employing pelletizing the intermediate material, the pelletizing may utilize a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0034] In some embodiments, the process further includes generating a fine powder comprising carbon in the thermal treatment unit and further includes recirculating the fine powder to the step of contacting the first biological reagent with the condenser liquid.

[0035] In some embodiments, the process further comprises generating a fine powder comprising carbon in the heat treatment unit, and further comprises recycling the fine powder to the step of recovering the second bio-reagent.

[0036] In various processes, the biocarbon composition is in the form of a powder.

[0037] In various processes, the biocarbon composition is in the form of pellets. After the pellets are formed, the process may further include pulverizing the pellets to form a powder again.

[0038] In some embodiments, the process includes drying the second bio-reagent and further includes pelleting the second bio-reagent to produce a pellet, where pelleting the second bio-reagent occurs during drying, after drying, or after recovery.

[0039] In some embodiments, the biocarbon composition comprises at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, or at least 90% by weight fixed carbon.

[0040] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, or less than 1% ash by weight.

[0041] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0042] The total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 50% renewable, as determined from measurements of the C isotope ratio. 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0043] In some embodiments, the biocarbon composition has a dry basis of at least about 5 lb / ft 3 , at least about 10 lb / ft 3 , or at least about 20 lb / ft 3 It is characterized by its bulk density.

[0044] In some embodiments, the biocarbon composition is hydrophobic and thus characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0045] In some embodiments, the biocarbon composition is 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”.

[0046] When the biocarbon composition is in the form of pellets, the pellets can, for example, have a mass per unit area of ​​at least about 10 lb / ft on a dry basis. 3 , at least about 25 lb / ft 3 , or at least about 35 lb / ft 3 It can be characterized by its bulk density.

[0047] When the biocarbon composition is in the form of pellets, the pellets can be characterized by a Hardgrove Crushability Index of at least 30, at least 50, or at least 70, for example.

[0048] When the biocarbon composition is in the form of pellets, the pellets are at least about 100 lb. f / in 2 Or at least about 150 lbs. f / in 2 The composition can be characterized by its pellet compressive strength at 25°C.

[0049] Another variation is a system for producing a bio-carbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a feedstock comprising biomass to produce a first bio-reagent and a first pyrolysis vapor; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the first pyrolysis vapor to generate a condenser liquid and a condenser vapor; a mixing unit in fluid communication with the first biological reagent and the condensation system, the mixing unit configured to contact the first biological reagent with the condenser liquid to generate an intermediate material; a thermal treatment unit in fluid communication with the mixing unit, the thermal treatment unit configured to thermally treat the intermediate material to generate a second bio-reagent and an exhaust gas; A system is provided comprising: a system output disposed within or in fluid communication with the thermal treatment unit, the system output configured to recover a second bio-reagent as a bio-carbon composition.

[0050] In some systems, the mixing unit is a pelletizing unit. In other systems, the system includes a pelletizing unit that is separate from the mixing unit, and the pelletizing unit is located between the mixing unit and the heat treatment unit.

[0051] In some systems, the condensation system includes multiple condenser stages, for example, 2, 3, 4, or more condenser stages.

[0052] In some systems, the recirculation line is configured to recirculate exhaust gas from the heat treatment unit to the condensation system when there is exhaust gas from the heat treatment unit.

[0053] In some systems, the thermal treatment unit is a second pyrolysis reactor. In other systems, the thermal treatment unit is a dryer. In still other systems, there is a first thermal treatment unit that is a dryer and a second thermal treatment unit that is a second pyrolysis reactor, arranged in any order.

[0054] Some systems include a mechanical processing device configured to pulverize the first bio-reagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0055] Some systems include a mechanical processing device configured to pulverize the intermediate material, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0056] Some systems further include a pelletizing device configured to pelletize the intermediate material, the pelletizing device being selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0057] Another variation is a process for producing a bio-carbon composition, the process comprising: pyrolyzing a feedstock in a first pyrolysis reactor, the feedstock comprising biomass, thereby producing a first pyrolysis solid and a first pyrolysis vapor; introducing the first pyrolysis vapor into a condensation system, thereby producing a condenser liquid and a condenser vapor; thermally treating the condenser liquid in a second reactor, thereby producing a solid or semi-solid material; blending the first pyrolysis solid with a solid or semi-solid material, thereby producing a bio-reagent; and recovering the bio-reagent as a bio-carbon composition.

[0058] Feedstocks include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit pulps ... The waste material may be selected from seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0059] In some embodiments, the process further comprises drying or heat treating the bio-reagent.

[0060] In some embodiments, the process further comprises pelleting the biological reagent.

[0061] In certain embodiments, the process further comprises drying or heat treating the bio-reagent and further comprises pelleting the bio-reagent, wherein the pelleting and drying or heat treating are integrated.

[0062] In embodiments in which pellets are formed, pelletizing may be integrated with blending the first pyrolysis solid with a solid or semi-solid material.

[0063] In embodiments where a pellet is formed, the process may include introducing a binder to the bioreagent. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing.

[0064] In certain embodiments where a pellet is formed, no external binder is introduced to the bioreagent during pelleting.

[0065] In some processes, the condensation system includes multiple condenser stages. The condenser liquid can be a condensation product of a first stage of the multiple condenser stages. The condenser liquid can be a condensation product of multiple stages of the multiple condenser stages. In certain embodiments, the multiple stages do not include a final stage of the multiple condenser stages.

[0066] In some embodiments, the second reactor is a non-pyrolytic thermal reactor or a non-pyrolytic catalytic reactor.

[0067] In some embodiments, the second reactor is a second pyrolysis reactor that produces solid or semi-solid material and pyrolysis tail gas. In certain embodiments, the process may further include conveying the pyrolysis tail gas to a condensation system. The second pyrolysis reactor may be separate from the first pyrolysis reactor. Alternatively, the first and second pyrolysis reactors are the same unit, and pyrolysis of the feedstock and thermal treatment of the condenser liquid occur at different times.

[0068] In some processes, at least 25%, at least 50%, or at least 75% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in solid or semi-solid materials.

[0069] In some processes, the solid or semi-solid material forms at least 5%, at least 10%, or at least 20% by weight of the bioreagent on an absolute basis.

[0070] In some embodiments, at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid, in certain embodiments, at least about 20% and up to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid.

[0071] In some processes, all of the condenser liquid is heat treated in the second reactor. In other processes, less than all of the condenser liquid is heat treated in the second reactor.

[0072] In some processes, the condenser liquid is thermally treated in the second reactor without any intermediate chemical treatment between the condensation system and the second reactor.

[0073] In some processes, the condenser liquid is chemically treated prior to thermal treatment in the second reactor. In certain processes, the condenser liquid is subjected to a purification step prior to thermal treatment in the second reactor. In certain processes, the condenser liquid is subjected to a reaction step prior to thermal treatment in the second reactor. In some specific processes, the condenser liquid is subjected to a reaction step and a purification step (in either order) prior to thermal treatment in the second reactor.

[0074] In some embodiments, pyrolysis of the feedstock (in the first pyrolysis reactor) is carried out at a first pyrolysis temperature of at least about 250°C and up to about 1250°C, e.g., at least about 300°C and up to about 700°C.

[0075] In some embodiments, the second reactor is a second pyrolysis reactor operated at a second pyrolysis temperature, the second pyrolysis temperature being at least about 250°C and up to about 1250°C, e.g., at least about 300°C and up to about 700°C.

[0076] In other embodiments, the second reactor is operated at a temperature selected from about 80°C to about 250°C.

[0077] The process may further include oxidizing the condenser vapor, thereby producing heat. Additionally or alternatively, the process may further include oxidizing the reactor exhaust gas, thereby producing heat.

[0078] Some processes further include grinding the bioreagent using a mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0079] In some processes that employ pelleting the bioreagent, the pelleting utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0080] In various embodiments, the biocarbon composition comprises at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight fixed carbon.

[0081] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, or less than 1% ash by weight.

[0082] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0083] The total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 50% renewable, as determined from measurements of the C isotope ratio. 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0084] In some embodiments, the biocarbon composition has a dry basis of at least about 5 lb / ft 3 , at least about 10 lb / ft 3 , or at least about 20 lb / ft 3 It is characterized by its bulk density.

[0085] In some embodiments, the biocarbon composition is characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0086] In some embodiments, the biocarbon composition is 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”.

[0087] In some embodiments, the biocarbon composition is in the form of pellets. The pellets have a dry weight of at least about 10 lb / ft 3 , at least about 25 lb / ft 3 , or at least about 35 lb / ft 3 The pellets may be characterized by a bulk density of at least about 100 lb. The pellets may be characterized by a Hardgrove Crushability Index of at least 30, at least 50, or at least 70. The pellets may be characterized by a bulk density of at least about 100 lb. f / in 2 Or at least about 150 lbs. f / in 2 The composition can be characterized by its pellet compressive strength at 25°C.

[0088] Another variation is a system for producing a bio-carbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a feedstock comprising biomass to produce a first pyrolysis solid and a first pyrolysis vapor; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the first pyrolysis vapor to generate a condenser liquid and a condenser vapor; a second reactor in fluid communication with the condensation system, the second reactor configured to thermally treat the condenser liquid to produce a solid or semi-solid material; a mixing unit in fluid communication with the first pyrolysis reactor and the second reactor, the mixing unit configured to blend the first pyrolysis solid with a solid or semi-solid material to generate a bio-reagent; A system is provided comprising: a system output in fluid communication with the mixing unit, the system output configured to recover the bio-reagent as a bio-carbon composition.

[0089] In some systems, the mixing unit is a pelletizing unit. In some systems, the system includes a pelletizing unit that is separate from the mixing unit, the pelletizing unit being located between the mixing unit and the system output.

[0090] In some systems, the condensation system includes multiple condenser stages.

[0091] In some systems, the second reactor is a second pyrolysis reactor. The system may further include a recycle line configured to recycle the pyrolysis exhaust gas to the condensation system.

[0092] In some systems, the second reactor is a non-pyrolytic thermal reactor or a non-pyrolytic catalytic reactor.

[0093] The system may further comprise a mechanical processing device configured to pulverize the bioreagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0094] The system may further comprise a pelletizing device configured to pelletize the bioreagent, the pelletizing device being selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0095] Yet another variation is a process for producing a bio-carbon composition, the process comprising: pyrolyzing a first feedstock in a first pyrolysis reactor, thereby producing a bio-reagent and a pyrolysis vapor; introducing the pyrolysis vapor into a condensation system, thereby producing a condenser liquid and a condenser vapor; contacting a second feedstock with a condenser liquid, the second feedstock comprising biomass, thereby producing a first feedstock, the first feedstock comprising the second feedstock and the condenser liquid; and recovering the bio-reagent as a bio-carbon composition.

[0096] Biomass includes softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit In one embodiment, the waste stream may be selected from plant 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 and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0097] Some processes further include pelleting the bio-reagent. Pelleting the bio-reagent may include introducing a binder to the bio-reagent. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing. Optionally, pelleting the bio-reagent can be done without introducing an external binder to the bio-reagent.

[0098] In some embodiments, the condensation system includes multiple condenser stages. The condenser liquid can be a condensation product of a first stage of the multiple condenser stages. In certain embodiments, the condenser liquid is a condensation product of multiple stages of the multiple condenser stages, optionally not including a final stage of the multiple condenser stages.

[0099] In some processes, the step of contacting the second feedstock with the condenser liquid includes spraying the condenser liquid onto the biomass. Other means of contacting the second feedstock with the condenser liquid can be used, including (but not limited to) submerging the biomass in the condenser liquid, coating particles of the biomass with a film of the condenser liquid, or other techniques.

[0100] In some processes, the first feedstock comprises condenser liquid adsorbed onto the surface of the biomass. Alternatively or additionally, the first feedstock may comprise condenser liquid absorbed within the bulk phase of the biomass.

[0101] In some processes involving contacting biomass with condenser liquid, the process further comprises heat treating the bioreagent in a heat treatment unit. If the bioreagent is subjected to pelleting, the heat treatment can be before, during or after pelleting.

[0102] In some processes using a thermal treatment unit, the thermal treatment unit is a second pyrolysis reactor operated at a second pyrolysis temperature of at least about 250° C. The second pyrolysis reactor is configured to pyrolyze the bioreagent. The second pyrolysis reactor is typically separate (i.e., physically different) from the first pyrolysis reactor. Alternatively, the first and second pyrolysis reactors can be the same unit, with pelletizing and heat treatment occurring at different times.

[0103] In some embodiments, waste gases can be generated by pyrolysis of the biological reagents in the thermal treatment unit, which can be recycled to the condensation system.

[0104] In other processes using a thermal treatment unit, the thermal treatment unit is operated at a temperature selected from about 80°C to about 250°C.

[0105] In some embodiments using a thermal treatment unit, the thermal treatment unit includes an internal oxygen-free environment. An inert gas can be introduced into the thermal treatment unit. The thermal treatment unit can be operated under a vacuum.

[0106] The thermal treatment unit may be configured to dry the bio-reagent. Alternatively or additionally, the process may further comprise drying the bio-carbon composition after thermal treatment in the optional thermal treatment unit.

[0107] Some processes include converting at least 25%, at least 50%, or at least 75% by weight of the total carbon contained in the condenser liquid to fixed carbon contained in the bio-reagent.

[0108] In some processes, at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In certain processes, at least about 20% and up to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid.

[0109] All of the condenser liquid can be contacted with the second feed, or alternatively, less than all of the condenser liquid is contacted with the second feed.

[0110] In some processes, the condenser liquid is contacted with the second feed without any intermediate chemical treatment. In other processes, the condenser liquid is chemically treated prior to contact with the second feed. For example, the condenser liquid may be subjected to purification and / or reaction steps prior to contact with the second feed.

[0111] In some embodiments involving contacting the biomass with condenser liquid, a portion of the condenser liquid is added to the bioreagent rather than contacting it with the biomass.

[0112] Pyrolysis of the first feedstock in the first pyrolysis reactor can be carried out at a first pyrolysis temperature of at least about 250° C. to a maximum of about 1250° C., such as at least about 300° C. to a maximum of about 700° C. The first pyrolysis time in the first pyrolysis reactor can be at least about 10 seconds to a maximum of about 24 hours.

[0113] When there is a heat treatment unit configured as a second pyrolysis reactor, the second pyrolysis temperature can be at least about 250° C. and up to about 1250° C., for example, at least about 300° C. and up to about 700° C. The second pyrolysis time can be at least about 10 seconds and up to about 24 hours.

[0114] In some embodiments, the process further comprises oxidizing the condenser vapor, thereby producing heat. In these or other embodiments, the process further comprises oxidizing the exhaust gas from the thermal treatment unit, thereby producing heat. The heat can be used within the process for a variety of purposes.

[0115] Some processes further include grinding the bioreagent using a mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0116] If the process employs pelleting the bioreagent, the pelletizing equipment can be selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquette, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0117] Some processes further include drying the bio-reagent and further include pelleting the bio-reagent to form a pellet. Pelleting the bio-reagent can be before, during, or after drying.

[0118] In some processes, the biocarbon composition comprises at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% fixed carbon by weight.

[0119] In some processes, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, or less than 1% ash by weight.

[0120] In some processes, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0121] In some embodiments, the total carbon in the biocarbon composition is14 C / 12 It may be at least 50%, at least 90%, or 100% (fully) renewable, as determined from measurements of C isotope ratios.

[0122] In some processes, the biocarbon composition has a dry mass of at least about 5 lb / ft 3 , at least about 10 lb / ft 3 , or at least about 20 lb / ft 3 It is characterized by its bulk density.

[0123] In some processes, the biocarbon composition is characterized by a water uptake of up to 20% by weight at 25° C. after immersion in water for 24 hours.

[0124] In some processes, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: “Test method for self-heating substances”.

[0125] In some processes, the biocarbon composition is in the form of pellets. The pellets have a mass of at least about 10 lb / ft on a dry basis. 3 , at least about 25 lb / ft 3 , or at least about 35 lb / ft 3 The pellets may be characterized by a bulk density of at least about 100 lb. The pellets may be characterized by a Hardgrove Crushability Index of at least 30, at least 50, or at least 70. The pellets may be characterized by a bulk density of at least about 100 lb. f / in 2 Or at least about 150 lbs. f / in 2 The composition can be characterized by its pellet compressive strength at 25°C.

[0126] One particular variation is a system for producing a bio-carbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a first feedstock to produce a bio-reagent and a pyrolysis vapor; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the pyrolysis vapors to generate a condenser liquid and a condenser vapor; a mixing unit in fluid communication with the condensation system, the mixing unit configured to contact a second feedstock comprising biomass with the condenser liquid to produce the first feedstock; A system is provided comprising: a system output in fluid communication with the first pyrolysis reactor, the system output configured to recover the bio-reagent as a bio-carbon composition.

[0127] Some systems further include a pelleting unit in fluid communication with the first pyrolysis reactor, the pelleting unit configured to pelletize the bio-reagent to produce a pellet.

[0128] Some systems further comprise a heat treatment unit in fluid communication with the pelleting unit (if present) or in fluid communication with the first pyrolysis reactor. In certain systems, the heat treatment unit is disposed downstream of the pelleting unit, the heat treatment unit configured to receive the pellets. In certain systems, the heat treatment unit is disposed between the first pyrolysis reactor and the pelleting unit, the pelleting unit configured to receive the heat-treated bioreagent.

[0129] In some systems, the thermal treatment unit is a second pyrolysis reactor operated at a second pyrolysis temperature of at least about 250° C., the second pyrolysis reactor configured to pyrolyze the bio-reagent. The system can include a recirculation line configured to recirculate the pyrolysis exhaust gas from the second pyrolysis reactor to the condensation system.

[0130] In one particular system, the thermal processing unit is operated at a temperature selected from about 80°C to about 250°C.

[0131] In some systems, the condensation system includes multiple condenser stages, for example, 2, 3, 4, 5, or more stages.

[0132] In some systems, the mixing unit is configured to spray condenser liquid onto the biomass.

[0133] The system may further comprise a mechanical processing device configured to pulverize the bioreagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0134] The system may further comprise a pelletizing unit selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof. [Brief description of the drawings]

[0135] In Figures 1-8, dotted boxes and lines indicate optional units and flows, respectively.

[0136] [Figure 1] 1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser having at least one condensation stage. The condenser produces condenser vapors and condenser liquid. The condenser liquid is fed to a mixing unit, which also feeds bio-reagents. The combined material is optionally sent to a pelletizing unit to produce pellets. The pellets are then fed to a thermal treatment unit to produce a bio-carbon product.

[0137] [Diagram 2] 1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser having at least one condensation stage. The condenser produces condenser vapors and a condenser liquid. The condenser liquid is optionally fed to a pelletizing unit, where the bio-reagents are also fed, to produce pellets. The pellets (or the condenser liquid + bio-reagents) are fed to a thermal treatment unit, which produces a bio-carbon product.

[0138] [Diagram 3] 1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser having at least one condensation stage. The condenser produces condenser vapors and condenser liquid. The bio-reagents are fed to a pelletizing unit to produce pellets. The pellets and condenser liquid (or one of the condenser liquids if there are multiple fractions) are fed to a carbon recapture unit to produce an intermediate material. The intermediate material is then fed to a thermal treatment unit to produce a bio-carbon product.

[0139] [Figure 4] 1 depicts an exemplary block flow diagram of a process and system in which biomass is pyrolyzed in a first pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser having at least one condensation stage. The condenser produces condenser vapors and condenser liquid. The bio-reagents and condenser liquid (or one of the condenser liquids, if there are multiple fractions) are fed to a carbon recapture unit to produce an intermediate material. The intermediate material is then fed to a thermal treatment unit to produce a bio-carbon product.

[0140] [Diagram 5]1 depicts an exemplary block flow diagram of a process and system in which biomass is pyrolyzed in a first pyrolysis reactor to produce a first pyrolysis solid and a pyrolysis vapor. The pyrolysis vapor is sent to a condenser including at least one condensation stage. The condenser produces a condenser vapor and a condenser liquid. The condenser liquid (or one of the condenser liquids, if there are multiple fractions) is fed to a second pyrolysis reactor to produce a second pyrolysis solid and a pyrolysis tail gas. The first and second pyrolysis solids can be combined. The blended material can be pelletized. Whether or not the blended material is pelletized, the blended material can be dried or heat treated to produce a final biocarbon product.

[0141] [Figure 6] 1 depicts an exemplary block flow diagram of a process and system in which biomass is pyrolyzed in a first pyrolysis reactor to produce a first pyrolysis solid and a pyrolysis vapor. The pyrolysis vapor is sent to a condenser including at least one condensation stage. The condenser produces a condenser vapor and a condenser liquid. The condenser liquid (or one of the condenser liquids, if there are multiple fractions) is fed to a second reactor to produce a solid or semi-solid material and a reactor tail gas. The first and second pyrolysis solids can be combined. The blended material can be pelletized. Whether or not the blended material is pelletized, the blended material can be dried or heat treated to produce a final biocarbon product.

[0142] [Figure 7]1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass impregnated with condenser liquid in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser that includes at least one condensation stage. The condenser produces condenser vapors and condenser liquid. The condenser liquid (or one of the condenser liquids, if there are multiple fractions) is fed to a mixing unit with the incoming biomass to produce a feedstock (biomass + condenser liquid). In some embodiments, the bio-reagents from the pyrolysis reactor are pelletized. Whether or not the bio-reagents are pelletized, they can be dried or heat treated to produce a final bio-carbon product.

[0143] [Figure 8] 1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass impregnated with condenser liquid in a first pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser including at least one condensation stage. The condenser produces condenser vapors and condenser liquid. The condenser liquid (or one of the condenser liquids if there are multiple fractions) is fed to a mixing unit with the incoming biomass to produce a feedstock (biomass + condenser liquid). In some embodiments, the bio-reagents from the first pyrolysis reactor are pelletized. Whether or not the bio-reagents are pelletized, they can be sent to a second pyrolysis reactor to produce a final bio-carbon product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0144] Detailed Description This description enables one skilled in the art to make and use the disclosed technology and describes several embodiments, adaptations, variations, alternatives, and uses of the technology. These and other embodiments, features, and advantages of the present disclosure will become more apparent to those skilled in the art upon reference to the following detailed description in conjunction with the accompanying drawings.

[0145] As used herein, when the indefinite article "a" or "an" is used in connection with a statement or description of the presence of a step in a process disclosed herein, the use of such an indefinite article does not limit the presence of the step in the process to one, unless the statement or description explicitly provides to the contrary. As used herein, when an amount, concentration, or other value or parameter is given as a range or list of upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range or value and any lower range or value, regardless of whether the ranges are individually disclosed.

[0146] Where a range of numerical values ​​is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. The scope of the present disclosure is not intended to be limited to the specific values ​​recited when defining a range.

[0147] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or "containing," or other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, mixture, process, method, article, or device that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or device.

[0148] Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not an exclusive or. Unless the word "or" is expressly limited in relation to a list of two or more items to mean only one item exclusively from the other items, the use of "or" in such a list should be interpreted to include (a) any one item in the list, (b) all items in the list, or (c) any combination of items in the list. As used herein, the phrase "and / or," such as in "A and / or B," refers to A alone, B alone, and both A and B. Where the context permits, singular or plural terms may also include the plural or singular terms, respectively.

[0149] As used herein, the term "about" refers to variations in a reported numerical quantity that may occur. The term "about" means within 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% of the reported numerical value.

[0150] Reference herein to "any intervening range" in a list of values ​​means that the parameter may, in some embodiments, be selected from a subrange beginning with one of those values ​​and ending with another higher value in the list. For example, if the temperature may be 150°C, 200°C, 250°C, or 300°C, including any intervening ranges, the temperature may be selected from the subranges of 150-200°C, 150-250°C, 150-300°C, 200-250°C, 200-300°C, or 250-300°C.

[0151] As used herein, the term "substantially" refers to the complete or nearly complete extent or degree of an action, feature, characteristic, state, structure, item, or result. For example, an object that is "substantially" enclosed would mean that the object is completely enclosed or nearly completely enclosed. The exact acceptable degree of deviation from absolute completeness may depend on the particular context, in some cases. Generally speaking, however, approximating completeness would be such as to have the same overall result as if absolute and total completeness had been obtained. The use of "substantially" is equally applicable when used in a negative sense to refer to a complete or nearly complete lack of an action, feature, characteristic, state, structure, item, or result.

[0152] To the extent that any material incorporated by reference herein conflicts with the present disclosure, the present disclosure shall control.

[0153] For the present purposes, "biological" is intended to mean a material (either a feedstock, product, or intermediate) that contains elements such as carbon that are renewable on time scales of months, years, or decades. Non-biological materials may be non-renewable or may be renewable on time scales of centuries, millennia, millions of years, or even longer geological time scales. Biological materials may include a mixture of biological and non-biological sources.

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

[0155] Plants fix atmospheric carbon through photosynthesis. 14 C. The animals then, when they consume the plant, or consume other animals that consume the plant, 14 C into their bodies. Thus, living plants and animals absorb the same amount of CO2 as there is in the atmosphere. 14 C vs. 12 C ratio. When an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer produces new 14 C is not incorporated. Radioactive decay then occurs in living organisms. 14 It gradually depletes C. This effect is the basis of radiocarbon dating.

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

[0157] This difference between the carbon isotopes of recently depleted organic matter, such as from renewable sources, and the carbon isotopes of fossil fuels, such as coal, allows for the determination of the source of carbon in the composition, specifically, whether the carbon in the composition is derived from a renewable resource or from a fossil fuel, in other words, whether a renewable resource or a fossil fuel was used in the production of the composition.

[0158] Carbon 14 C / 12 The C isotope ratio can be measured using ASTM D6866.

[0159] Carbon14 C / 12 Measuring C isotope ratios (in solid carbon or in vapor forms such as CO, CO2, or CH4) is a proven technique. Similar concepts can be applied to hydrogen, 2 H / 1 H isotope ratios are measured ( 2 H is also known as deuterium D). Fossil sources tend to be depleted in deuterium compared to biomass. See Schiegl et al., "Deuterium content of organic matter", Earth and Planetary Science Letters, Volume 7, Issue 4, 1970, Pages 307-313, and Hayes, "Fractionation of the Isotopes of Carbon and Hydrogen in Biosynthetic Processes", Mineralogical Society of America, National Meeting of the Geological Society of America, Boston, MA, 2001 (incorporated herein by reference).

[0160] For the present purposes, "reagent" is intended to mean a material in its broadest sense, and a reagent may be a fuel, a chemical, a material, a compound, an additive, a blend component, a solvent, etc. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. A reagent may be, but is not necessarily, a chemical reactant that is consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in adjusting the mechanical, physical, or hydrodynamic properties of a material to which it may be added. For example, a reagent may be introduced into a metal to impart certain strength properties to the metal. A reagent may be a substance of sufficient purity (in the present context, typically carbon purity) to be used in chemical analysis or physical testing.

[0161] The terms "low fixed carbon" and "high fixed carbon" are used herein for practical purposes to describe materials that may be produced, in various embodiments, by the processes and systems as disclosed. Any limitations on carbon content or any other concentration should be implied only by reference to specific embodiments and their equivalents, and not from the terms themselves.

[0162] In this disclosure, references to "condenser liquid" may relate to either a portion of the condenser liquid formed in the process or all of the condenser liquid formed in the process, unless otherwise specified.

[0163] Some variations are processes for producing a bio-carbon composition, the process comprising: pyrolyzing a feedstock in a first pyrolysis reactor, the feedstock comprising biomass, thereby producing a first bio-reagent and a first pyrolysis vapor; introducing the first pyrolysis vapor into a condensation system, thereby producing a condenser liquid and a condenser vapor; contacting a first biological reagent with a condenser liquid, thereby producing an intermediate material, the intermediate material comprising the first biological reagent and the condenser liquid; heat-treating the intermediate material in a heat-treating unit, thereby producing a second bio-reagent and an exhaust gas; and recovering the second bio-reagent as a bio-carbon composition.

[0164] In some embodiments, the feedstock is softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems. , fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0165] In some embodiments, the process further includes pelleting the first bio-reagent. In these or other embodiments, the process may further include pelleting the intermediate material. In certain embodiments, pelleting the intermediate material is integrated with contacting the first bio-reagent with the condenser liquid. In other embodiments, pelleting the intermediate material occurs after contacting the first bio-reagent with the condenser liquid.

[0166] Pelletizing the intermediate material, if performed, may include introducing a binder into the intermediate material. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing.

[0167] In some embodiments, pelletizing the intermediate material does not include introducing an external binder into the intermediate material. In these cases, the condenser liquid can act as a binder for the pellets.

[0168] In some processes (see, e.g., FIG. 3 or 4), the carbon recapture unit is located upstream of the thermal treatment unit. In certain processes, the carbon recapture unit is the first stage of the thermal treatment unit. The carbon recapture unit can be a mixing unit that contacts the first biological reagent with the condenser liquid. Alternatively or additionally, the carbon recapture unit can be separate from the mixing unit. In some embodiments, the carbon recapture unit is located upstream of the second pyrolysis reactor. In other embodiments, the carbon recapture unit is the first stage of the second pyrolysis reactor. The carbon recapture unit can be configured, for example, to form a coating of condenser liquid on the pellets. The carbon recovery unit can provide a carbon source different from the condenser liquid, such as an external carbon source or a waste carbon-containing stream from the process.

[0169] In some embodiments, the condensation system includes multiple condenser stages. The condenser liquid can be, for example, a condensation product of a first stage of the multiple condenser stages. In some embodiments, the condenser liquid is a condensation product of multiple stages of the multiple condenser stages. In certain embodiments, the multiple stages do not include the last stage of the multiple condenser stages, especially when the last stage is configured or operated such that the final condenser product contains a high concentration of water.

[0170] In some embodiments, the intermediate material comprises a condenser liquid adsorbed onto a surface of the first bio-reagent. Alternatively or additionally, the intermediate material may comprise a condenser liquid absorbed within the bulk phase of the first bio-reagent.

[0171] In some embodiments, the thermal treatment unit is a second pyrolysis reactor operated at a temperature of at least about 250° C., the second pyrolysis reactor configured to pyrolyze the intermediate material. Pyrolysis conditions are described in more detail later in this specification.

[0172] In other embodiments, the thermal treatment unit is operated at a relatively low temperature, for example, selected from about 80° C. to about 250° C. In various embodiments, the thermal treatment unit is operated at a temperature of about, at least about, or up to about 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., or 250° C., including any intervening range.

[0173] The thermal treatment unit preferably includes an internal anoxic environment, or at least a low-oxygen environment. In various embodiments, the internal environment of the thermal treatment unit is up to about 5% O2 by volume, 4% O2 by volume, 3% O2 ​​by volume, 2% O2 by volume, 1% O2 by volume, 0.5% O2 by volume, 0.2% O2 by volume, 0.1% O2 by volume, 0.05% O2 by volume, 0.02% O2 by volume, or 0.01% O2 by volume, including any intervening range. The internal environment of the thermal treatment unit can be measured using a gas phase sample probe and an oxygen sensor, such as an ultrasonic oxygen sensor or a tunable diode laser.

[0174] In some embodiments, an inert gas is introduced into the heat treatment unit, which can be nitrogen, argon, carbon dioxide, or a mixture thereof.

[0175] In certain embodiments, the thermal treatment unit is operated under superatmospheric pressure. The absolute pressure in the thermal treatment unit can be from about 1 bar to about 10 bar, for example from about 1 bar to about 5 bar, or from about 1 bar to about 2 bar.

[0176] In certain embodiments, the thermal treatment unit is operated under vacuum. The absolute pressure in the thermal treatment vacuum unit can be, for example, about or up to about 0.99 bar, 0.9 bar, 0.8 bar, 0.7 bar, 0.6 bar, 0.5 bar, 0.4 bar, 0.3 bar, 0.2 bar, or 0.1 bar, including any intervening ranges.

[0177] In some embodiments, the process further includes introducing the exhaust gas from the thermal treatment unit into a condensation system. These embodiments may be desirable when the exhaust gas contains high concentrations of carbon.

[0178] In some embodiments, the thermal treatment unit is configured to dry the second biological reagent. In these embodiments, the exhaust gas from the thermal treatment unit comprises or consists essentially of water vapor.

[0179] The process may further include drying the biocarbon composition after heat treatment in the heat treatment unit. Drying toward the end of the process may be desirable because heat treatment may result in chemical reactions that form water, i.e., reactive water that was not present with the feedstock or prior to the chemical formation of water.

[0180] In a typical embodiment, the first pyrolysis reactor is separate from the second pyrolysis reactor, in other embodiments the first and second pyrolysis reactors are the same physical unit but perform the pyrolysis and heat treatment at different times.

[0181] In some embodiments, the process includes performing a fixed carbon formation reaction on the condenser liquid. The fixed carbon formation reaction can utilize the first bio-reagent as a catalyst. Alternatively or additionally, the fixed carbon formation reaction can utilize the first bio-reagent as a reaction matrix.

[0182] In some processes, the process comprises converting at least 25%, at least 50%, or at least 75% by weight of the total carbon contained in the condenser liquid to fixed carbon contained in the second bio-reagent, hi various embodiments, the process comprises converting about or at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight (including any intervening ranges) of the total carbon contained in the condenser liquid to fixed carbon contained in the second bio-reagent.

[0183] In some embodiments, at least about 10% and up to about 80% by weight of the fixed carbon in the second bio-reagent is derived from the condenser liquid. In certain embodiments, at least about 20% and up to about 60% by weight of the fixed carbon in the second bio-reagent is derived from the condenser liquid. In various embodiments, the percentage of fixed carbon in the second bio-reagent that is derived from the condenser liquid is about, at least about, or up to about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, including any intervening ranges.

[0184] In some processes, all of the condenser liquid is contacted with the first bio-reagent. In other processes, less than all of the condenser liquid is contacted with the first bio-reagent. In various embodiments, the percentage of the condenser liquid that is contacted with the first bio-reagent is about, at least about, or up to about 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%, including any intervening ranges.

[0185] In some processes, the condenser liquid is contacted with the first biological reagent without any intermediate chemical treatment. In other processes, the condenser liquid is chemically treated before contact with the first biological reagent. There are various types of chemical treatments that can be performed on the condenser liquid, and generally speaking, chemical treatment refers to the introduction or removal of mass or energy from the condenser liquid. Exemplary types of chemical treatments include separating certain components (e.g., water or acetic acid) from the condenser liquid, or chemically reacting the condenser liquid with reactants (e.g., CO and / or H2).

[0186] In some embodiments, the condenser liquid is subjected to a purification step prior to contact with the first biological reagent. In these or other embodiments, the condenser liquid is subjected to a reaction step prior to contact with the first biological reagent. In certain embodiments, there is a reaction and purification step that not only initially removes undesired impurities in the condenser liquid, but also removes undesired chemical reaction by-products in the intermediate material.

[0187] In some embodiments, pyrolysis of the feedstock (in the first pyrolysis reactor) is carried out at a first pyrolysis temperature of at least about 250° C. and up to about 1250° C. In certain embodiments, the first pyrolysis temperature is at least about 300° C. and up to about 700° C. In some embodiments, pyrolysis of the feedstock (in the first pyrolysis reactor) is carried out at a first pyrolysis time of at least about 10 seconds and up to about 24 hours. In various embodiments, pyrolysis conditions that can be used in the first pyrolysis reactor are described in detail later herein. The conditions in the first pyrolysis reactor can be any of the pyrolysis conditions described later herein (see the section entitled "Pyrolysis Processes and Systems").

[0188] In some embodiments where the thermal treatment is at a pyrolysis temperature, pyrolysis of the intermediate material is carried out at a second pyrolysis temperature of at least about 250° C. and up to about 1250° C. In certain embodiments, the second pyrolysis temperature is at least about 300° C. and up to about 700° C. In some embodiments, pyrolysis of the intermediate material is carried out at a second pyrolysis time of at least about 10 seconds and up to about 24 hours. The second pyrolysis temperature may be lower or higher than the first pyrolysis temperature, or they may potentially be the same. The second pyrolysis time may be shorter or longer than the first pyrolysis time, or they may potentially be the same. In various embodiments, pyrolysis conditions that may be used for the second pyrolysis reactor are described in detail later herein. The conditions of the second pyrolysis reactor may be any of the pyrolysis conditions described later herein (see the section entitled "Pyrolysis Processes and Systems").

[0189] The process may further include oxidizing the condenser vapors, thereby generating heat. Additionally or alternatively, the process may further include oxidizing the tail gas (from the thermal treatment unit), thereby generating heat. Heat generated from the oxidation of the condenser vapors and / or tail gas may be recycled in the process, for example to provide heat to the first pyrolysis reactor.

[0190] In some embodiments, the process further comprises grinding the first bio-reagent using a mechanical treatment device, the mechanical treatment device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0191] In some embodiments, the process further comprises grinding the intermediate material using a mechanical treatment device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0192] In some embodiments employing pelletizing the intermediate material, the pelletizing may utilize a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0193] In some embodiments, the process further includes generating a fine powder comprising carbon in the thermal treatment unit and further includes recirculating the fine powder to the step of contacting the first biological reagent with the condenser liquid.

[0194] In some embodiments, the process further comprises generating a fine powder comprising carbon in the thermal treatment unit and further comprises recycling some or all of the fine powder to the step of recovering the second biological reagent.

[0195] In various processes, the biocarbon composition is in the form of a powder. The powder particle size can vary widely, as described elsewhere herein.

[0196] In various processes, the biocarbon composition is in the form of pellets. Pellet size and shape can vary widely, as described elsewhere herein.

[0197] After the pellets are formed, the process may further include pulverizing the pellets to reform a powder. The modified powder may, for example, be similar to the initial powder (before the pellets were formed) or may have a different particle size.

[0198] In some embodiments, the process includes drying the second bio-reagent and further includes pelleting the second bio-reagent to produce a pellet, where pelleting the second bio-reagent occurs during drying, after drying, or after recovery.

[0199] In some embodiments, the biocarbon composition comprises at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, or at least 90% by weight fixed carbon.

[0200] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, or less than 1% ash by weight.

[0201] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0202] The total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 50% renewable, as determined from measurements of the C isotope ratio. 14 C / 12The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0203] In some embodiments, the biocarbon composition has a dry basis of at least about 5 lb / ft 3 , at least about 10 lb / ft 3 , or at least about 20 lb / ft 3 In various embodiments, the biocarbon composition is characterized by a bulk density of about, at least about, or up to about 5, 10, 15, 20, 25, or 30 lb / ft, including any intervening range. 3 Bulk density is the apparent density according to ASTM D 1895B, which is incorporated herein by reference. Bulk density is not corrected for porosity and is an extrinsic material property.

[0204] Another measure of density is the intrinsic material density, which is the density of a material in the absence of any porosity (porous interstices). Intrinsic material density is also called packed density or solid density. In some embodiments, the biocarbon composition has a density of at least about 50 lb / ft on a dry basis. 3 , at least about 75 lb / ft 3 , at least about 100 lb / ft 3 , or at least about 125 lb / ft 3 In various embodiments, the biocarbon composition has a specific material density of about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, or 140 lb / ft, including any intervening range. 3 When the biocarbon composition is in the form of a powder, i.e., multiple particles, there are voids between the particles and there may be micropores within the volume of each particle. The intrinsic material density is the density of only the continuous solid material within the particle and between any pores within that particle.

[0205] In some embodiments, the biocarbon composition is hydrophobic and thus characterized by a water uptake of up to 20% by weight after 24 hours of immersion in water at 25° C. In various embodiments, the biocarbon composition is characterized by a water uptake of up to 20, 15, 10, 5, or 2% by weight after 24 hours of immersion in water at 25° C.

[0206] In some embodiments, the biocarbon composition is 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”.

[0207] When the biocarbon composition is in the form of pellets, the pellets can, for example, have a mass per unit area of ​​at least about 10 lb / ft on a dry basis. 3 , at least about 25 lb / ft 3 , or at least about 35 lb / ft 3 In various embodiments, the biocarbon pellets can be characterized by a bulk density of about, at least about, or up to about 10, 15, 20, 25, 30, 35, or 40 lb / ft, including any intervening range. 3 It is characterized by its bulk density.

[0208] When the biocarbon composition is in the form of pellets, the pellets can be characterized, for example, by a Hardgrove Crushability Index of at least 30, at least 50, or at least 70. In various embodiments, the pellets are characterized by a Hardgrove Crushability Index of about, at least about, or up to about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, including any intervening ranges.

[0209] When the biocarbon composition is in the form of pellets, the pellets are at least about 100 lb. f / in 2 Or at least about 150 lbs. f / in 2 The pellets can be characterized by a pellet compression strength at 25° C. of about or at least about 50, 75, 100, 125, 150, 175, or 200 lb, including any intervening range. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0210] Another variation is a system for producing a bio-carbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a feedstock comprising biomass to produce a first bio-reagent and a first pyrolysis vapor; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the first pyrolysis vapor to generate a condenser liquid and a condenser vapor; a mixing unit in fluid communication with the first biological reagent and the condensation system, the mixing unit configured to contact the first biological reagent with the condenser liquid to generate an intermediate material; a thermal treatment unit in fluid communication with the mixing unit, the thermal treatment unit configured to thermally treat the intermediate material to generate a second bio-reagent and an exhaust gas; A system is provided comprising: a system output disposed within or in fluid communication with the thermal treatment unit, the system output configured to recover a second bio-reagent as a bio-carbon composition.

[0211] In some systems, the mixing unit is a pelletizing unit. In other systems, the system includes a pelletizing unit that is separate from the mixing unit, and the pelletizing unit is located between the mixing unit and the heat treatment unit.

[0212] The condensation system may be designed according to known principles of a condenser configured to condense at least a portion of the pyrolysis vapors according to vapor-liquid thermodynamics.

[0213] When the pyrolysis vapors enter the condensation system operated at a selected temperature and pressure, a portion of the pyrolysis vapor typically condenses to form a condenser liquid. The remaining portion of the pyrolysis vapor that does not condense at the selected temperature and pressure is called the condenser vapor. In order to utilize only the condenser liquid for downstream processing, there is a vapor-liquid separation, which is a complete separation of the vapor and liquid produced in the condensation system. Complete separation of the vapor and liquid at the selected temperature and pressure is equivalent to one equilibrium stage of separation.

[0214] The condensation system may be configured to achieve one separation equilibrium stage, less than one separation equilibrium stage, or more than one separation equilibrium stage. The condensation system may be configured to achieve at least one separation equilibrium stage. If the condensation system is a multi-stage condensation system, generally speaking, the number of separation equilibrium stages will be greater than one.

[0215] In certain embodiments for certain feedstocks and process conditions (e.g., low pyrolysis temperatures are applied to dry feedstocks with high volatile carbon content), only pyrolysis liquids and no pyrolysis vapors are formed in the condensation system. In these embodiments, there is no vapor-liquid separation as such, since there is no condenser vapor, i.e., all pyrolysis vapors are condensed into pyrolysis liquids.

[0216] Exemplary condensation system configurations include double tube, shell and tube, shell and coil, or combinations thereof. Exemplary condensation system equipment includes horizontal in-shell condenser, vertical in-shell condenser, horizontal in-tube condenser, vertical in-tube condenser, tank, distillation column, or combinations thereof.

[0217] Condensation systems in the form of columns can be operated horizontally, vertically or at an angle and can be operated upflow (against gravity), downflow (with gravity), parallel to gravity or at an angle to gravity.

[0218] The condensation system may be operated continuously or semi-continuously, such as with a continuous input of pyrolysis vapors and a continuous output of both condenser vapor and condenser liquid. A semi-continuous condensation system means that there is an intermittent input of pyrolysis vapors and / or an intermittent output of at least one of the condenser vapor and condenser liquid.

[0219] Other embodiments utilize a batch condensation system in which a quantity of pyrolysis vapors is introduced into a batch vessel (e.g., a tank) for condensation. After a batch condensation period, the condenser vapors are withdrawn and the condenser liquid remains in the batch vessel. Or, after a batch condensation period, the condenser liquid is withdrawn and the condenser vapors remain in the batch vessel.

[0220] The condensation system may be air-cooled, gas-cooled (other than by air), water-cooled, liquid-cooled (other than by water, such as using a liquid coolant), or a combination thereof. Heat transfer for condensation may be achieved by natural convection, forced convection, conduction, or a combination thereof.

[0221] In some embodiments, the primary heat transfer in a condensation system occurs by direct liquid contact, such as liquid atomization. The liquid atomized by the steam can be water or another liquid, such as an external liquid (e.g., biodiesel), an internal liquid (e.g., condenser liquid), or a combination thereof. Typically, in embodiments employing direct liquid contact, the liquid atomized by the steam becomes part of the condenser liquid. In certain embodiments, the liquid atomized by the steam is itself a carbon-containing liquid, and some or all of the carbon contained in the liquid ultimately becomes carbon in the biocarbon composition.

[0222] In some embodiments, the condensation system includes a unit operation to separate liquid (e.g., aerosol droplets) from vapor. For example, there may be an electrostatic precipitator, a filter, an inertial impaction collection surface, or a combination thereof, after condensing the vapor to a liquid or after combining with the vapor condensation.

[0223] In some embodiments, the condensation system includes not only one or more condensers, but also a separation stage that is not based on vapor-liquid equilibrium separation due to differences in boiling points. Rather, the additional separation stage may be based, for example, on polarity, molecular size, affinity with another phase, or ionic binding potential. In various embodiments, the condensation system further includes a means for filtration, scrubbing, membrane separation, activated carbon adsorption, chromatography, ion exchange, liquid-liquid extraction, chemical precipitation, and / or electrostatic precipitator.

[0224] In various embodiments, the condensation system includes a condensation subsystem and another subsystem selected from a liquid-vapor cyclone separator, a demister, a distillation unit, a filtration unit, a membrane unit, a scrubbing unit (also called a scrubber), a chemical precipitation unit, a liquid-liquid extraction unit, an electrostatic precipitator unit, or a combination thereof.

[0225] This specification is incorporated by reference in its teachings of condenser equipment design. thEd., McGraw-Hill, 2019, pages 11-1 to 11-12.

[0226] In some systems, the condensation system includes multiple condenser stages, e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more condenser stages. When there are multiple condenser stages operating at different temperatures and / or pressures, the liquid and vapor composition generally varies from stage to stage. This configuration allows for a tailored composition profile across the stages, allowing the ability to recover and utilize fractions with desirable high carbon content, or other properties (e.g., low water content). The condenser liquid contacted with the bioreagent can be optimized, e.g., may include some, but not all, of the condensates of the individual condenser stages. As an example, in some embodiments, the last stage of a multi-stage condenser system produces a water-rich condensate. If a high fixed carbon product is desired, it may not be desirable to add the water-rich condensate to the bioreagent. In this scenario, the water-rich condensate can instead be recycled for other plant purposes.

[0227] In certain embodiments, the composition of the liquid from a particular stage, or from multiple stages, is compositionally analyzed to determine its suitability for use in combination with a bio-reagent to increase the carbon content. For example, if the liquid contains too much water or organic acids, the liquid can be used for other purposes, while if the liquid contains high organics, phenolics, aromatics, etc., the liquid can be added to the bio-reagent for thermal treatment (e.g., secondary pyrolysis).

[0228] In some systems, the recycle line is configured to recycle exhaust gas, if any, from the heat treatment unit back to the condensation system.

[0229] In some systems, the thermal treatment unit is a second pyrolysis reactor. In other systems, the thermal treatment unit is a dryer. In still other systems, there is a first thermal treatment unit that is a dryer and a second thermal treatment unit that is a second pyrolysis reactor, arranged in any order.

[0230] Some systems include a mechanical processing device configured to pulverize the first bio-reagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0231] Some systems include a mechanical processing device configured to pulverize the intermediate material, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0232] Some systems further include a pelletizing device configured to pelletize the intermediate material, the pelletizing device being selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0233] Other variations of this technology are predicated on the thermal treatment of the condenser liquid to create a solid or semi-solid material that can be blended with the solid bio-reagent. These variations are processes for producing bio-carbon compositions, the process comprising: pyrolyzing a feedstock in a first pyrolysis reactor, the feedstock comprising biomass, thereby producing a first pyrolysis solid and a first pyrolysis vapor; introducing the first pyrolysis vapor into a condensation system, thereby producing a condenser liquid and a condenser vapor; thermally treating the condenser liquid in a second reactor, thereby producing a solid or semi-solid material; blending the first pyrolysis solid with a solid or semi-solid material, thereby producing a bio-reagent; and recovering the bio-reagent as a bio-carbon composition.

[0234] Feedstocks include softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit pulps ... The waste material may be selected from seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0235] In some embodiments, the process further comprises drying or heat treating the bio-reagent.

[0236] In some embodiments, the process further comprises pelleting the biological reagent.

[0237] In certain embodiments, the process further comprises drying or heat treating the bio-reagent and further comprises pelleting the bio-reagent, wherein the pelleting and drying or heat treating are integrated.

[0238] In embodiments in which pellets are formed, pelletizing may be integrated with blending the first pyrolysis solid with a solid or semi-solid material.

[0239] In embodiments where a pellet is formed, the process may include introducing a binder to the bioreagent. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing.

[0240] In certain embodiments where pellets are formed, no external binder is introduced to the bioreagent during pelleting, in these cases the condenser liquid can act as a binder for the pellets.

[0241] In some processes, the condensation system includes multiple condenser stages. The condenser liquid can be a condensation product of a first stage of the multiple condenser stages. The condenser liquid can be a condensation product of multiple stages of the multiple condenser stages. In certain embodiments, the multiple stages do not include a final stage of the multiple condenser stages.

[0242] In some embodiments, the second reactor is a non-pyrolytic thermal reactor or a non-pyrolytic catalytic reactor.

[0243] In some embodiments, the second reactor is a second pyrolysis reactor that produces solid or semi-solid material and pyrolysis tail gas. In certain embodiments, the process may further include conveying the pyrolysis tail gas to a condensation system. The second pyrolysis reactor may be separate from the first pyrolysis reactor. Alternatively, the first and second pyrolysis reactors are the same unit, and pyrolysis of the feedstock and thermal treatment of the condenser liquid occur at different times.

[0244] In some processes, at least 25%, at least 50%, or at least 75% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the solid or semi-solid material. In various embodiments, the percentage of the total carbon contained in the condenser liquid that is converted to fixed carbon in the solid or semi-solid material is about, at least about, or up to about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight, including any intervening ranges.

[0245] In some processes, the solid or semi-solid material forms at least 5%, at least 10%, or at least 20% by weight of the bioreagent on an absolute basis. In various embodiments, the percentage of the bioreagent that is solid or semi-solid material is about, at least about, or up to about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight, including any intervening ranges.

[0246] The solid or semi-solid material is optionally further processed, e.g., chemically treated, prior to blending with the first pyrolysis solid. For example, the solid or semi-solid material can be separated by particle size. The solid or semi-solid material can be reacted with one or more reactants.

[0247] In some embodiments, at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In certain embodiments, at least about 20% and up to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In various embodiments, the percentage of fixed carbon in the bioreagent derived from the condenser liquid is about, at least about, or up to about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight, including any intervening ranges.

[0248] In some processes, all of the condenser liquid is heat treated in the second reactor. In other processes, less than all of the condenser liquid is heat treated in the second reactor. In various embodiments, the percentage of the condenser liquid that is heat treated in the second reactor is about, at least about, or up to about 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%, including any intervening ranges.

[0249] In some processes, the condenser liquid is thermally treated in the second reactor without any intermediate chemical treatment between the condensation system and the second reactor.

[0250] In some processes, the condenser liquid is chemically treated prior to thermal treatment in the second reactor. In certain processes, the condenser liquid is subjected to a purification step prior to thermal treatment in the second reactor. In certain processes, the condenser liquid is subjected to a reaction step prior to thermal treatment in the second reactor. In some specific processes, the condenser liquid is subjected to a reaction step and a purification step (in either order) prior to thermal treatment in the second reactor.

[0251] In some embodiments, pyrolysis of the feedstock (in the first pyrolysis reactor) is carried out at a first pyrolysis temperature of at least about 250° C. and up to about 1250° C., such as at least about 300° C. and up to about 700° C. The conditions in the first pyrolysis reactor can be any of the pyrolysis conditions described later herein (see the section entitled "Pyrolysis Processes and Systems").

[0252] In some embodiments, the second reactor is a second pyrolysis reactor operated at a second pyrolysis temperature, the second pyrolysis temperature being at least about 250° C. and up to about 1250° C., for example, at least about 300° C. and up to about 700° C. The conditions in the second pyrolysis reactor can be any of the pyrolysis conditions described later herein (see the section entitled "Pyrolysis Processes and Systems").

[0253] In other embodiments, the second reactor is operated at a temperature selected from about 80° C. to about 250° C. In various embodiments, the second reactor is operated at a temperature of about, at least about, or up to about 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., or 250° C., including any intervening ranges. At these temperatures (below about 250° C.), no thermal decomposition is expected, although at long residence times a very small amount of thermal decomposition may occur.

[0254] The process may further include oxidizing the condenser vapor, thereby producing heat. Additionally or alternatively, the process may further include oxidizing the reactor exhaust gas, thereby producing heat.

[0255] Some processes further include grinding the bioreagent using a mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0256] In some processes that employ pelleting the bioreagent, the pelleting utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0257] In various embodiments, the biocarbon composition comprises at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 90% by weight fixed carbon.

[0258] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, or less than 1% ash by weight.

[0259] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0260] The total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 50% renewable, as determined from measurements of the C isotope ratio. 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined by C isotope ratio measurements. 14 C / 12 In various embodiments, the carbon content of the total carbon in the biocarbon composition can be fully renewable, as determined from measurements of the C isotope ratio. 14 C / 12 The percentage of renewable carbon by C isotope ratio is about or at least about 50%, 60%, 70%, 80%, 90%, 95%, 99%, 99.5%, 99.9%, or 100%, including any intervening ranges.

[0261] In some embodiments, the biocarbon composition has a dry basis of at least about 5 lb / ft 3 , at least about 10 lb / ft3 , or at least about 20 lb / ft 3 In various embodiments, the biocarbon composition is characterized by a bulk density of about, at least about, or up to about 5, 10, 15, 20, 25, or 30 lb / ft, including any intervening range. 3 It is characterized by its bulk density.

[0262] In some embodiments, the biocarbon composition has a dry basis of at least about 50 lb / ft 3 , at least about 75 lb / ft 3 , at least about 100 lb / ft 3 , or at least about 125 lb / ft 3 In various embodiments, the biocarbon composition has a specific material density of about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, or 140 lb / ft, including any intervening range. 3 is characterized by a specific material density of

[0263] In some embodiments, the biocarbon composition is hydrophobic and thus characterized by a water uptake of up to 20% by weight after 24 hours of immersion in water at 25° C. In various embodiments, the biocarbon composition is characterized by a water uptake of up to 20, 15, 10, 5, or 2% by weight after 24 hours of immersion in water at 25° C.

[0264] In some embodiments, the biocarbon composition is 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”.

[0265] When the biocarbon composition is in the form of pellets, the pellets can, for example, have a mass per unit area of ​​at least about 10 lb / ft on a dry basis. 3 , at least about 25 lb / ft 3 , or at least about 35 lb / ft 3 In various embodiments, the biocarbon pellets can be characterized by a bulk density of about, at least about, or up to about 10, 15, 20, 25, 30, 35, or 40 lb / ft, including any intervening range. 3 It is characterized by its bulk density.

[0266] When the biocarbon composition is in the form of pellets, the pellets can be characterized, for example, by a Hardgrove Crushability Index of at least 30, at least 50, or at least 70. In various embodiments, the pellets are characterized by a Hardgrove Crushability Index of about, at least about, or up to about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, including any intervening ranges.

[0267] When the biocarbon composition is in the form of pellets, the pellets are at least about 100 lb. f / in 2 Or at least about 150 lbs. f / in 2 The pellets can be characterized by a pellet compression strength at 25° C. of about or at least about 50, 75, 100, 125, 150, 175, or 200 lb, including any intervening range. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0268] Another variation is a system for producing a bio-carbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a feedstock comprising biomass to produce a first pyrolysis solid and a first pyrolysis vapor; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the first pyrolysis vapor to generate a condenser liquid and a condenser vapor; a second reactor in fluid communication with the condensation system, the second reactor configured to thermally treat the condenser liquid to produce a solid or semi-solid material; a mixing unit in fluid communication with the first pyrolysis reactor and the second reactor, the mixing unit configured to blend the first pyrolysis solid with a solid or semi-solid material to generate a bio-reagent; A system is provided comprising: a system output in fluid communication with the mixing unit, the system output configured to recover the bio-reagent as a bio-carbon composition.

[0269] In some systems, the mixing unit is a pelletizing unit. In some systems, the system includes a pelletizing unit that is separate from the mixing unit, the pelletizing unit being located between the mixing unit and the system output.

[0270] The condensation system may be designed according to known principles of a condenser configured to condense at least a portion of the pyrolysis vapors according to vapor-liquid thermodynamics.

[0271] The condensation system may be configured to achieve one separation equilibrium stage, less than one separation equilibrium stage, or more than one separation equilibrium stage. The condensation system may be configured to achieve at least one separation equilibrium stage. If the condensation system is a multi-stage condensation system, generally speaking, the number of separation equilibrium stages will be greater than one.

[0272] Exemplary condensation system configurations include double tube, shell and tube, shell and coil, or combinations thereof. Exemplary condensation system equipment includes horizontal in-shell condenser, vertical in-shell condenser, horizontal in-tube condenser, vertical in-tube condenser, tank, distillation column, or combinations thereof.

[0273] Condensation systems in the form of columns can be operated horizontally, vertically or at an angle and can be operated upflow (against gravity), downflow (with gravity), parallel to gravity or at an angle to gravity.

[0274] The condensation system may be operated continuously or semi-continuously, such as with a continuous input of pyrolysis vapors and a continuous output of both condenser vapor and condenser liquid. A semi-continuous condensation system means that there is an intermittent input of pyrolysis vapors and / or an intermittent output of at least one of the condenser vapor and condenser liquid.

[0275] Other embodiments utilize a batch condensation system in which a quantity of pyrolysis vapors is introduced into a batch vessel (e.g., a tank) for condensation. After a batch condensation period, the condenser vapors are withdrawn and the condenser liquid remains in the batch vessel. Or, after a batch condensation period, the condenser liquid is withdrawn and the condenser vapors remain in the batch vessel.

[0276] The condensation system may be air-cooled, gas-cooled (other than by air), water-cooled, liquid-cooled (other than by water, such as using a liquid coolant), or a combination thereof. Heat transfer for condensation may be achieved by natural convection, forced convection, conduction, or a combination thereof.

[0277] In some embodiments, the primary heat transfer in a condensation system occurs by direct liquid contact, such as liquid atomization. The liquid atomized by the steam can be water or another liquid, such as an external liquid (e.g., biodiesel), an internal liquid (e.g., condenser liquid), or a combination thereof. Typically, in embodiments employing direct liquid contact, the liquid atomized by the steam becomes part of the condenser liquid. In certain embodiments, the liquid atomized by the steam is itself a carbon-containing liquid, and some or all of the carbon contained in the liquid ultimately becomes carbon in the biocarbon composition.

[0278] In some embodiments, the condensation system includes a unit operation for separating liquid (e.g., aerosol droplets) from vapor. For example, there may be an electrostatic precipitator, a filter, an inertial impaction collection surface, or a combination thereof, after condensing the vapor to a liquid or after integration with vapor condensation. In some embodiments, the condensation system includes not only one or more condensers, but also a separation stage that is not based on vapor-liquid equilibrium separation due to differences in boiling points. Rather, the additional separation stage may be based, for example, on polarity, molecular size, affinity with another phase, or ionic binding potential. In various embodiments, the condensation system further includes a means for filtration, scrubbing, membrane separation, activated carbon adsorption, chromatography, ion exchange, liquid-liquid extraction, chemical precipitation, and / or electrostatic precipitator.

[0279] In various embodiments, the condensation system includes a condensation subsystem and another subsystem selected from a liquid-vapor cyclone separator, a demister, a distillation unit, a filtration unit, a membrane unit, a scrubbing unit, a chemical precipitation unit, a liquid-liquid extraction unit, an electrostatic precipitator unit, or a combination thereof.

[0280] In some systems, the condensation system includes multiple condenser stages, for example 2, 3, 4, 5, 6, 7, 8, 9, 10, or more condenser stages.

[0281] In some systems, the second reactor is a second pyrolysis reactor. The system may further include a recycle line configured to recycle the pyrolysis exhaust gas to the condensation system.

[0282] In some systems, the second reactor is a non-pyrolytic thermal reactor or a non-pyrolytic catalytic reactor.

[0283] The system may further comprise a mechanical processing device configured to pulverize the bioreagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0284] The system may further comprise a pelletizing device configured to pelletize the bioreagent, the pelletizing device being selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0285] Yet other variations assume the addition of condenser liquid to the starting biomass (feed to the pyrolysis reactor) rather than the solids created during pyrolysis. These variations are processes for producing biocarbon compositions, the process comprising: pyrolyzing a first feedstock in a first pyrolysis reactor, thereby producing a bio-reagent and a pyrolysis vapor; introducing the pyrolysis vapor into a condensation system, thereby producing a condenser liquid and a condenser vapor; contacting a second feedstock with a condenser liquid, the second feedstock comprising biomass, thereby producing a first feedstock, the first feedstock comprising the second feedstock and the condenser liquid; and recovering the bio-reagent as a bio-carbon composition.

[0286] Biomass includes softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit In one embodiment, the waste stream may be selected from plant 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 and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0287] Some processes further include pelleting the bio-reagent. Pelleting the bio-reagent may include introducing a binder to the bio-reagent. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing. Optionally, the bio-reagents can be pelletized without introducing an external binder to the bio-reagents, in which case the condenser liquid can act as a binder for the pellets.

[0288] In some embodiments, the condensation system includes multiple condenser stages. The condenser liquid can be a condensation product of a first stage of the multiple condenser stages. In certain embodiments, the condenser liquid is a condensation product of multiple stages of the multiple condenser stages, optionally not including a final stage of the multiple condenser stages.

[0289] In some processes, the step of contacting the second feedstock with the condenser liquid includes spraying the condenser liquid onto the biomass. Other means of contacting the second feedstock with the condenser liquid can be used, including (but not limited to) submerging the biomass in the condenser liquid, coating particles of the biomass with a film of the condenser liquid, or other techniques.

[0290] In some processes, the first feedstock comprises condenser liquid adsorbed onto the surface of the biomass. Alternatively or additionally, the first feedstock may comprise condenser liquid absorbed within the bulk phase of the biomass.

[0291] In some processes involving contacting biomass with condenser liquid, the process further comprises heat treating the bioreagent in a heat treatment unit. If the bioreagent is subjected to pelleting, the heat treatment can be before, during or after pelleting.

[0292] In some processes using a thermal treatment unit, the thermal treatment unit is a second pyrolysis reactor operated at a second pyrolysis temperature of at least about 250° C. The second pyrolysis reactor is configured to (further) pyrolyze the bioreagent. The second pyrolysis reactor is typically separate (i.e., physically different) from the first pyrolysis reactor. Alternatively, the first and second pyrolysis reactors can be the same unit, with pelletizing and heat treatment occurring at different times.

[0293] In some embodiments, waste gases can be generated by pyrolysis of the biological reagents in the thermal treatment unit, which can be recycled to the condensation system.

[0294] In other processes using a thermal treatment unit, the thermal treatment unit is operated at a temperature selected from about 80°C to about 250°C, e.g., about 90°C to about 200°C, about 100°C to about 250°C, or about 125°C to about 225°C.

[0295] In some embodiments using a thermal treatment unit, the thermal treatment unit includes an internal oxygen-free environment. An inert gas can be introduced into the thermal treatment unit. The thermal treatment unit can be operated under a vacuum.

[0296] The thermal treatment unit may be configured to dry the bio-reagent. Alternatively or additionally, the process may further comprise drying the bio-carbon composition after thermal treatment in the optional thermal treatment unit.

[0297] Some processes include converting at least 25%, at least 50%, or at least 75% by weight of the total carbon contained in the condenser liquid to fixed carbon contained in the bio-reagent. In various embodiments, the process includes converting about or at least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight (including any intervening ranges) of the total carbon contained in the condenser liquid to fixed carbon contained in the bio-reagent.

[0298] In some embodiments, at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In certain embodiments, at least about 20% and up to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In various embodiments, the percentage of fixed carbon in the bioreagent derived from the condenser liquid is about, at least about, or up to about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, including any intervening ranges.

[0299] In some processes, all of the condenser liquid is contacted with the second feed. In other processes, less than all of the condenser liquid is contacted with the second feed. In various embodiments, the percentage of the condenser liquid that is contacted with the second feed is about, at least about, or up to about 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%, including any intervening ranges.

[0300] In some processes, the condenser liquid is contacted with the second feed without any intermediate chemical treatment. In other processes, the condenser liquid is chemically treated prior to contact with the second feed. For example, the condenser liquid may be subjected to purification and / or reaction steps prior to contact with the second feed.

[0301] In some embodiments involving contacting the biomass with condenser liquid, a portion of the condenser liquid is added to the bioreagent rather than contacting it with the biomass.

[0302] Pyrolysis of the first feedstock in the first pyrolysis reactor can be carried out at a first pyrolysis temperature of at least about 250° C. to a maximum of about 1250° C., such as at least about 300° C. to a maximum of about 700° C. The first pyrolysis time in the first pyrolysis reactor can be at least about 10 seconds to a maximum of about 24 hours. The conditions in the first pyrolysis reactor can be any of the pyrolysis conditions described later herein (see the section entitled "Pyrolysis Processes and Systems").

[0303] If there is a thermal treatment unit configured as a second pyrolysis reactor, the second pyrolysis temperature can be at least about 250° C. and up to about 1250° C., such as at least about 300° C. and up to about 700° C. The second pyrolysis time can be at least about 10 seconds and up to about 24 hours. The second pyrolysis reactor conditions can be any of the pyrolysis conditions described later herein (see the section entitled "Pyrolysis Processes and Systems").

[0304] In some embodiments, the process further comprises oxidizing the condenser vapor, thereby producing heat. In these or other embodiments, the process further comprises oxidizing the exhaust gas from the thermal treatment unit, thereby producing heat. The heat can be used within the process for a variety of purposes.

[0305] Some processes further include grinding the bioreagent using a mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0306] If the process employs pelleting the bioreagent, the pelletizing equipment can be selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquette, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

[0307] Some processes further include drying the bio-reagent and further include pelleting the bio-reagent to form a pellet. Pelleting the bio-reagent can be before, during, or after drying.

[0308] In some processes, the biocarbon composition comprises at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% fixed carbon by weight.

[0309] In some processes, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, or less than 1% ash by weight.

[0310] In some processes, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0311] In some embodiments, the total carbon in the biocarbon composition is 14 C / 12 As determined from measurements of C isotope ratios, the carbon content of the biocarbon composition may be at least 50%, at least 90%, or 100% (fully) renewable. 14 C / 12 The percentage of renewable carbon by C isotope ratio is about or at least about 50%, 60%, 70%, 80%, 90%, 95%, 99%, 99.5%, 99.9%, or 100%, including any intervening ranges.

[0312] In some embodiments, the biocarbon composition has a dry basis of at least about 5 lb / ft 3 , at least about 10 lb / ft 3 , or at least about 20 lb / ft 3 In various embodiments, the biocarbon composition is characterized by a bulk density of about, at least about, or up to about 5, 10, 15, 20, 25, or 30 lb / ft, including any intervening range. 3 It is characterized by its bulk density.

[0313] In some embodiments, the biocarbon composition has a dry basis of at least about 50 lb / ft 3 , at least about 75 lb / ft 3 , at least about 100 lb / ft 3 , or at least about 125 lb / ft 3 In various embodiments, the biocarbon composition has a specific material density of about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, or 140 lb / ft, including any intervening range. 3 is characterized by a specific material density of

[0314] In some embodiments, the biocarbon composition is hydrophobic and thus characterized by a water uptake of up to 20% by weight after 24 hours of immersion in water at 25° C. In various embodiments, the biocarbon composition is characterized by a water uptake of up to 20, 15, 10, 5, or 2% by weight after 24 hours of immersion in water at 25° C.

[0315] In some embodiments, the biocarbon composition is 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”.

[0316] When the biocarbon composition is in the form of pellets, the pellets can, for example, have a mass per unit area of ​​at least about 10 lb / ft on a dry basis. 3 , at least about 25 lb / ft 3 , or at least about 35 lb / ft 3In various embodiments, the biocarbon pellets can be characterized by a bulk density of about, at least about, or up to about 10, 15, 20, 25, 30, 35, or 40 lb / ft, including any intervening range. 3 It is characterized by its bulk density.

[0317] When the biocarbon composition is in the form of pellets, the pellets can be characterized, for example, by a Hardgrove Crushability Index of at least 30, at least 50, or at least 70. In various embodiments, the pellets are characterized by a Hardgrove Crushability Index of about, at least about, or up to about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, including any intervening ranges.

[0318] When the biocarbon composition is in the form of pellets, the pellets are at least about 100 lb. f / in 2 Or at least about 150 lbs. f / in 2 The pellets can be characterized by a pellet compression strength at 25° C. of about or at least about 50, 75, 100, 125, 150, 175, or 200 lb, including any intervening range. f / in 2 The pellets are characterized by their compressive strength at 25°C.

[0319] One particular variation is a system for producing a bio-carbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a first feedstock to produce a bio-reagent and a pyrolysis vapor; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the pyrolysis vapors to generate a condenser liquid and a condenser vapor; a mixing unit in fluid communication with the condensation system, the mixing unit configured to contact a second feedstock comprising biomass with the condenser liquid to produce the first feedstock; A system is provided comprising: a system output in fluid communication with the first pyrolysis reactor, the system output configured to recover the bio-reagent as a bio-carbon composition.

[0320] Some systems further include a pelleting unit in fluid communication with the first pyrolysis reactor, the pelleting unit configured to pelletize the bio-reagent to produce a pellet.

[0321] Some systems further comprise a heat treatment unit in fluid communication with the pelleting unit (if present) or in fluid communication with the first pyrolysis reactor. In certain systems, the heat treatment unit is disposed downstream of the pelleting unit, the heat treatment unit configured to receive the pellets. In certain systems, the heat treatment unit is disposed between the first pyrolysis reactor and the pelleting unit, the pelleting unit configured to receive the heat-treated bioreagent.

[0322] In some systems, the thermal treatment unit is a second pyrolysis reactor operated at a second pyrolysis temperature of at least about 250° C., the second pyrolysis reactor configured to pyrolyze the bio-reagent. The conditions of the second pyrolysis reactor can be any of the pyrolysis conditions described later herein (see the section entitled “Pyrolysis Processes and Systems”). The system can include a recycle line configured to recycle the pyrolysis exhaust gas from the second pyrolysis reactor to the condensation system.

[0323] In certain systems, the thermal treatment unit is operated at a temperature selected from about 80° C. to about 250° C. In various embodiments, the thermal treatment unit is operated at a temperature of about, at least about, or up to about 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., or 250° C., including any intervening ranges.

[0324] The condensation system may be designed according to known principles of a condenser configured to condense at least a portion of the pyrolysis vapors according to vapor-liquid thermodynamics.

[0325] The condensation system may be configured to achieve one separation equilibrium stage, less than one separation equilibrium stage, or more than one separation equilibrium stage. The condensation system may be configured to achieve at least one separation equilibrium stage. If the condensation system is a multi-stage condensation system, generally speaking, the number of separation equilibrium stages will be greater than one.

[0326] Exemplary condensation system configurations include double tube, shell and tube, shell and coil, or combinations thereof. Exemplary condensation system equipment includes horizontal in-shell condenser, vertical in-shell condenser, horizontal in-tube condenser, vertical in-tube condenser, tank, distillation column, or combinations thereof.

[0327] Condensation systems in the form of columns can be operated horizontally, vertically or at an angle and can be operated upflow (against gravity), downflow (with gravity), parallel to gravity or at an angle to gravity.

[0328] The condensation system may be operated continuously or semi-continuously, such as with a continuous input of pyrolysis vapors and a continuous output of both condenser vapor and condenser liquid. A semi-continuous condensation system means that there is an intermittent input of pyrolysis vapors and / or an intermittent output of at least one of the condenser vapor and condenser liquid.

[0329] Other embodiments utilize a batch condensation system in which a quantity of pyrolysis vapors is introduced into a batch vessel (e.g., a tank) for condensation. After a batch condensation period, the condenser vapors are withdrawn and the condenser liquid remains in the batch vessel. Or, after a batch condensation period, the condenser liquid is withdrawn and the condenser vapors remain in the batch vessel.

[0330] The condensation system may be air-cooled, gas-cooled (other than by air), water-cooled, liquid-cooled (other than by water, such as using a liquid coolant), or a combination thereof. Heat transfer for condensation may be achieved by natural convection, forced convection, conduction, or a combination thereof.

[0331] In some embodiments, the primary heat transfer in a condensation system occurs by direct liquid contact, such as liquid atomization. The liquid atomized by the steam can be water or another liquid, such as an external liquid (e.g., biodiesel), an internal liquid (e.g., condenser liquid), or a combination thereof. Typically, in embodiments employing direct liquid contact, the liquid atomized by the steam becomes part of the condenser liquid. In certain embodiments, the liquid atomized by the steam is itself a carbon-containing liquid, and some or all of the carbon contained in the liquid ultimately becomes carbon in the biocarbon composition.

[0332] In some embodiments, the condensation system includes a unit operation to separate liquid (e.g., aerosol droplets) from vapor. For example, there may be an electrostatic precipitator, a filter, an inertial impaction collection surface, or a combination thereof, after condensing the vapor to a liquid or after combining with the vapor condensation.

[0333] In some embodiments, the condensation system includes not only one or more condensers, but also a separation stage that is not based on vapor-liquid equilibrium separation due to differences in boiling points. Rather, the additional separation stage may be based, for example, on polarity, molecular size, affinity with another phase, or ionic binding potential. In various embodiments, the condensation system further includes a means for filtration, scrubbing, membrane separation, activated carbon adsorption, chromatography, ion exchange, liquid-liquid extraction, chemical precipitation, and / or electrostatic precipitator.

[0334] In various embodiments, the condensation system includes a condensation subsystem and another subsystem selected from a liquid-vapor cyclone separator, a demister, a distillation unit, a filtration unit, a membrane unit, a scrubbing unit, a chemical precipitation unit, a liquid-liquid extraction unit, an electrostatic precipitator unit, or a combination thereof.

[0335] In some systems, the condensation system includes multiple condenser stages, e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more condenser stages. The multiple condenser stages can be stages of a single unit, e.g., stages defined by trays in a distillation column, or physically separate units, e.g., arranged in series.

[0336] In some systems, the mixing unit is configured to spray the condenser liquid onto the biomass, while in other systems the mixing unit is configured to submerge the biomass in the condenser liquid.

[0337] The system may further comprise a mechanical processing device configured to pulverize the bioreagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0338] The system may further comprise a pelletizing unit selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0339] In various embodiments where the condenser liquid is chemically treated prior to contact with another material (e.g., biomass reagent or second feedstock), the chemical treatment can be purification that may involve another separation step besides condensation. For example, chromatography or another type of separation based on polarity can be performed to remove oxygen-containing molecules such as water, organic acids, and / or alcohols. The chemical treatment can be purification that involves, for example, filtration or membrane separation followed by the addition of a purification agent such as a flocculant or filter aid. The chemical treatment can be purification based on liquid-liquid extraction, such as with an organic aromatic solvent to target the extraction of aromatic molecules that may later be beneficial for fixed carbon formation.

[0340] In various embodiments where the condenser liquid is chemically treated prior to contact with another material, the chemical treatment can be a reaction. The reaction can be catalyzed or uncatalyzed. If a catalyst is used, the catalyst can be a homogeneous catalyst (e.g., an inorganic acid such as sulfuric acid) or a heterogeneous catalyst (e.g., an aluminosilicate). The chemical reaction of the condenser liquid may or may not involve another reactant. That is, the chemical reaction may only involve reactants already present in the condenser liquid, such as acids, esters, alcohols, aldehydes, ketones, furans, and phenolic compounds.

[0341] Alternatively or additionally, an external reactant can be added to the condenser liquid. The external reactant can be a gas, such as H2 or CO, a liquid, such as methanol or ethanol, or a solid, such as sugar or cellulose. Reaction with H2 or CO can be useful, for example, to form new bonds in the condenser liquid or to rearrange bonds. Reaction with methanol or ethanol (or larger alcohols) can be useful, for example, to stabilize the condenser liquid by converting carboxylic acids and reactive carbonyl compounds to esters, ethers, and acetals. Reaction with sugar or cellulose can be useful, for example, to form longer polymers in the condenser liquid that can assist in later carbonization.

[0342] Just as the initial condensation to create the condenser liquid can be performed in a multi-stage condensation system, chemical processing can be performed in multiple stages. The multiple stages can be purification or reaction stages in various orders. It may be desirable to use a temperature profile of increasing temperature with inter-stage removal of one phase (e.g., vapor or water) to support a chemical reaction in a later stage. For example, if the formation of carbon-carbon bonds (single, double, triple, and / or aromatic bonds) is desired, it may be useful to separate small molecules such as water to promote reaction equilibrium to the desired product.

[0343] It should be noted that in the variants where the condenser liquid is thermally treated to form a solid or semi-solid material, the condenser liquid is chemically treated to a completely solid or semi-solid state. There are many embodiments where the condenser liquid is chemically treated but not completely solid or semi-solid, rather the condenser liquid remains in a liquid state when added to the bioreagent or second ingredient. Of course, many combinations are possible. For example, a portion of the condenser liquid can be converted to a solid or semi-solid material, while another portion is chemically treated and then combined with the bioreagent and further pyrolyzed, and the resulting solid is added to the solid or semi-solid material.

[0344] In some embodiments, at least 25% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the second bio-reagent, in various embodiments, about, at least about, or up to about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% by weight (including all intervening ranges) of the total carbon contained in the condenser liquid is converted to fixed carbon in the second bio-reagent.

[0345] In some embodiments, at least about 10% to up to about 80% by weight of the fixed carbon in the second bio-reagent is derived from the first condenser liquid. In certain embodiments, at least about 20% to up to about 60% by weight of the fixed carbon in the second bio-reagent is derived from the first condenser liquid. In various embodiments, about, at least about, or up to about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 75%, or 80% by weight (including any intervening ranges) of the fixed carbon in the second bio-reagent is derived from the first bio-reagent.

[0346] In some processes, step (a) is performed at a first pyrolysis temperature selected from at least about 250°C to at most about 1250°C, e.g., at least about 300°C to at most about 700°C. In these or other processes, step (e) is performed at a second pyrolysis temperature selected from at least about 300°C to at most about 1350°C, e.g., at least about 350°C to at most 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 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.

[0347] In some processes, step (a) is carried out for a first pyrolysis time selected from at least about 10 seconds up to about 24 hours, e.g., at least about 10 minutes up to about 4 hours. In these or other processes, step (e) is carried out for a second pyrolysis time selected from at least about 10 seconds up to about 24 hours, e.g., at least about 15 minutes up to about 5 hours. The first pyrolysis time may be less than, equal to, or greater than the second pyrolysis time. In some embodiments, the second pyrolysis time is longer than the first pyrolysis time to allow for effective pyrolysis of compounds that did not form fixed carbon in the first pyrolysis reactor. In such embodiments, the second pyrolysis time may be, for example, about 5, 10, 15, 20, 30, 40, 50, 60, 90, or 120 minutes longer than the first pyrolysis time.

[0348] In some embodiments, some or all of the condenser vapors are at least partially oxidized to generate heat that can be used in the process. In these or other embodiments, some or all of the second pyrolysis vapors are at least partially oxidized (with or separately from the condenser vapors) to generate heat that can be used in the process.

[0349] In certain embodiments, pyrolysis exhaust gas or condenser vapors are at least partially oxidized to produce reduced gases including hydrogen and / or carbon monoxide. Such partial oxidation still produces useful heat, but also produces reduced gases that can be converted to other chemicals (e.g., methanol or Fischer-Tropsch hydrocarbons) if desired.

[0350] In some embodiments, the first bio-reagent is ground using a mechanical processing device selected from the group including, for example, a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof. In these or other embodiments, the intermediate material can be ground using a mechanical processing device selected from the group including, for example, a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0351] In embodiments employing step (d), step (d) can utilize a pelletizing device selected from the group including, for example, an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0352] In some processes, carbonaceous fines are produced in a second pyrolysis reactor. In some embodiments, the carbonaceous fines are recycled to step (c). If step (d) is performed, the carbonaceous fines produced in the second pyrolysis reactor can be recycled to step (d) instead of or in addition to being recycled to step (c). Alternatively or additionally, the carbonaceous fines can be combusted to generate energy or used for other purposes.

[0353] In some embodiments, the bio-carbon composition is in the form of a powder. In some embodiments, the bio-carbon composition is in the form of a pellet.

[0354] The biocarbon composition may comprise at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 75% by weight fixed carbon, at least 80% by weight fixed carbon, at least 85% by weight fixed carbon, or at least 90% by weight fixed carbon. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 55, 60, 65, 70, 75, 80, 85, or 90% by weight fixed carbon.

[0355] The biocarbon composition may comprise at least 55% by weight total carbon, at least 60% by weight total carbon, at least 70% by weight total carbon, at least 75% by weight total carbon, at least 80% by weight total carbon, at least 85% by weight total carbon, at least 90% by weight total carbon, or at least 95% by weight total carbon. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 60, 65, 70, 75, 80, 85, 90, or 95% by weight total carbon, including all intervening ranges.

[0356] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, less than 2% ash by weight, or less than 1% ash by weight. In various embodiments, the biocarbon composition comprises about or up to about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.2, or 0.1% ash by weight, including all intervening ranges.

[0357] The ash content of the biocarbon composition is beneficial (i.e., lower) when a condenser liquid having low ash is incorporated into the material in the second pyrolysis reactor. In some embodiments, the first condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or essentially no ash. In various embodiments, the first condenser liquid contains about or up to about 5, 4, 3, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.02, or 0.01% ash by weight, including all intervening ranges.

[0358] In some embodiments, the total carbon in the biocarbon composition is 14 C / 12 At least 50% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition is at least 50% renewable as determined from C isotope ratio measurements. 14 C / 12 At least 90% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition is at least 90% renewable as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0359] In some processes, the second bio-reagent is pelleted during step (f), during step (g), or after step (g), and thus the final bio-carbon composition may be in the form of a pellet.

[0360] In some processes, the biocarbon composition is characterized by a Hardgrove Crushability Index of at least 30 or at least 50. In various embodiments, the biocarbon composition is characterized by a Hardgrove Crushability Index of about, at least about, or up to about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, including all intervening ranges.

[0361] In some processes, the biocarbon composition has a dry content of at least about 35 lb / ft 3 or at least about 45 lb / ft on a dry basis 3 In various embodiments, the biocarbon composition has a bulk density of about or at least about 25, 30, 35, 40, 45, or 50 lb / ft on a dry basis, including all intervening ranges. 3 It is.

[0362] In some processes, the bio-carbon composition is characterized as a hydrophobic bio-carbon or a partially hydrophobic bio-carbon.

[0363] In some processes, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: “Test method for self-heating substances”.

[0364] In some processes, the biocarbon composition is characterized by a lack of odor generation at 25° C. for 24 hours. In some embodiments, the biocarbon composition is characterized by a lack of odor generation at 50° C. for 24 hours. In some embodiments, the biocarbon composition is characterized by a lack of odor generation at 25° C. for 48 hours. Odor generation in this context refers to organic molecules that have evaporated from the biocarbon composition, such organic molecules being typically detectable by humans. Examples include formaldehyde, acetic acid, ethanol, methanol, or mercaptans.

[0365] Some variations provide a method of making a high fixed carbon material that includes pyrolyzing biomass to produce intermediate solids and pyrolysis vapors, condensing the pyrolysis vapors to produce pyrolysis liquids, and introducing the pyrolysis liquids to the intermediate solids to produce a solid-liquid mixture. In some embodiments, the method also includes pelletizing to produce pellets comprising the solid-liquid mixture. In some embodiments, the method further includes further pyrolyzing the solid-liquid mixture to produce a high yield of the high fixed carbon material.

[0366] In some methods, the method includes pelletizing to produce pellets comprising the solid-liquid mixture. In some embodiments, the pelletizing does not utilize a binder other than the pyrolysis liquid. In other embodiments, the pelletizing utilizes a binder other than the pyrolysis liquid. Further pyrolysis of the solid-liquid mixture can be enhanced by pelletizing, such as when carbon contained in the solid-liquid mixture acts as a catalyst or reactive matrix for the formation of additional fixed carbon.

[0367] 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.

[0368] Some variations provide high fixed carbon materials produced by a process that includes a method of making a high fixed carbon material including pyrolyzing biomass to produce intermediate solids and pyrolysis vapors, condensing the pyrolysis vapors to produce pyrolysis liquids, and introducing the pyrolysis liquids to the intermediate solids to produce a solid-liquid mixture. In some embodiments, the method also includes pelletizing to produce pellets containing the solid-liquid mixture. In some embodiments, the method further includes further pyrolyzing the solid-liquid mixture to produce a high yield of the high fixed carbon material.

[0369] In some processes (e.g., FIG. 5) incorporating blending of a first pyrolysis solid and a second pyrolysis solid, the second pyrolysis solid forms at least 5% by weight of the bioreagent on an absolute basis. In certain processes, the second pyrolysis solid forms at least 10% or at least 20% by weight of the bioreagent on an absolute basis.

[0370] In some processes, at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In certain processes, at least about 20% and up to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In various embodiments, about, at least about, or up to about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by weight (including all intervening ranges) of the fixed carbon in the bioreagent is derived from the condenser liquid.

[0371] The biocarbon composition may comprise at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, or at least 90% by weight fixed carbon. Other fixed carbon contents are discussed above and apply to these process embodiments (as well as other processes disclosed herein).

[0372] The biocarbon composition may contain less than 10% by weight ash, less than 5% by weight ash, less than 2% by weight ash, or less than 1% by weight ash. Other ash contents are discussed above and apply to these process embodiments (as well as other processes disclosed herein).

[0373] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash. The low ash content of the condenser liquid reduces the final ash content of the biocarbon composition. Other condenser liquid ash contents are described above and apply to these process embodiments (as well as other processes disclosed herein).

[0374] In some processes, the total carbon in the biocarbon composition is 14 C / 12 At least 50% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition is at least 50% renewable as determined from C isotope ratio measurements. 14 C / 12At least 90% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition is at least 90% renewable as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0375] Some variations are processes for producing a bio-carbon composition, the process comprising: (a) pyrolyzing a first feedstock (also referred to as a "biomass-containing feedstock") in a pyrolysis reactor to produce a bio-reagent and pyrolysis vapor; (b) introducing the pyrolysis vapor into a condensation system to produce a condenser liquid and a condenser vapor; (c) contacting a second feedstock (also described as a "starting biomass feedstock") with the condenser liquid, thereby producing a first feedstock containing the second feedstock and the condenser liquid; (d) recovering the bio-reagent as a bio-carbon composition.

[0376] In some embodiments, the process further comprises pelleting the bio-reagent and / or drying the bio-reagent.

[0377] The starting biomass feedstocks are softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit In one embodiment, the waste stream may be selected from the group comprising: plant 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 and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0378] In some embodiments, step (c) utilizes spraying at least the condenser liquid onto the starting biomass feedstock. The biomass-containing feedstock may include the condenser liquid adsorbed onto a surface of the starting biomass feedstock. Alternatively or additionally, the biomass-containing feedstock includes the condenser liquid absorbed within the bulk phase of the starting biomass feedstock.

[0379] When performing step (d), a binder can be introduced into the bioreagent. The binder can be selected from the group including starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations thereof. In certain embodiments, the binder is selected from the group including starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof.

[0380] When step (d) is performed, in some embodiments, an external binder is introduced to the bioreagent during pelleting.

[0381] In some processes, steps (c) and (d) are integrated and both occur within the pelletizing unit. In some processes, steps (d) and (e) are both performed and integrated.

[0382] The condensation system may include multiple condenser stages. The condenser liquid may be the condensation product of an individual stage (e.g., the first stage) of the multiple condenser stages.

[0383] In some processes, at least 25% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the bio-reagent. In certain processes, at least 50% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the bio-reagent.

[0384] In some processes, at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid. In certain processes, at least about 20% and up to about 60% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid.

[0385] Step (a) can be carried out at a pyrolysis temperature selected from at least about 250° C. to a maximum of about 1250° C., such as at least about 300° C. to a maximum of about 700° C. Step (a) can be carried out for a first pyrolysis time selected from at least about 10 seconds to a maximum of about 24 hours.

[0386] In some processes, some or all of the condenser vapor may be at least partially oxidized to produce heat that can be used in the process.

[0387] The bioreagent may be pulverized utilizing a mechanical processing device selected from the group including a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0388] In processes using step (d), this step may utilize a pelletizing device selected from the group including an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0389] The final biocarbon composition may be in the form of, for example, a powder or pellets.

[0390] In some embodiments, the biocarbon composition comprises at least 50% by weight fixed carbon, at least 60% by weight fixed carbon, at least 70% by weight fixed carbon, at least 80% by weight fixed carbon, or at least 90% by weight fixed carbon.

[0391] In some embodiments, the biocarbon composition comprises less than 10% ash by weight, less than 5% ash by weight, less than 2% ash by weight, or less than 1% ash by weight.

[0392] In some embodiments, the condenser liquid contains less than 1% ash by weight, less than 0.1% ash by weight, or is essentially free of ash.

[0393] In some embodiments, the total carbon in the biocarbon composition is 14 C / 12 At least 50% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition is at least 50% renewable as determined from C isotope ratio measurements. 14 C / 12 At least 90% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon composition is at least 90% renewable as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0394] The present disclosure provides bio-carbon compositions produced by any of the disclosed processes.The present disclosure provides systems configured to carry out any of the disclosed processes.

[0395] Some embodiments will now be described with reference to the accompanying drawings, Figures 1-8, which illustrate various processes and systems. In the block flow diagrams, dotted boxes and lines indicate optional units and flows, respectively.

[0396] FIG. 1 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser having at least one condensation stage. The condenser produces condenser vapor and condenser liquid. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The condenser liquid is fed to a mixing unit, to which the bio-reagents are also fed, to produce an intermediate material. The intermediate material is optionally sent to a pelletizing unit, optionally with the addition of an external binder, to produce pellets. The pellets or intermediate material are then fed to a thermal treatment unit, which produces a bio-carbon product. The thermal treatment unit also produces exhaust gases, which can be fed to the condenser shown in FIG. 1, or to a different condenser, or can be treated in another way (e.g., combusted).

[0397] FIG. 2 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser having at least one condensation stage. The condenser produces condenser vapors and condenser liquids. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The condenser liquid is optionally fed to a pelletizing unit, optionally with the addition of an external binder, to which the bio-reagents are also fed, to produce pellets. The pellets (or intermediate material including the bio-reagents and the condenser liquid) are then fed to a thermal treatment unit to produce a bio-carbon product. The thermal treatment unit also produces exhaust gases, which can be fed to the condenser shown in FIG. 2, or to a different condenser, or can be otherwise treated (e.g., combusted).

[0398] FIG. 3 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bioreagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser that includes at least one condensation stage. The condenser produces condenser vapors and condenser liquids. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The bioreagents are fed to a pelleting unit to produce pellets. In some embodiments, a binder is added to the pelleting unit. The pellets and condenser liquid (or one of the condenser liquids if there are multiple fractions) are fed to a carbon recapture unit to produce intermediate material. The intermediate material is then optionally fed to a thermal treatment unit that produces a biocarbon product. The thermal treatment unit also produces exhaust gases, which can be fed to the condenser shown in FIG. 3, or to a different condenser, or can be otherwise treated (e.g., combusted).

[0399] FIG. 4 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a pyrolysis reactor to produce bioreagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser that includes at least one condensation stage. The condenser produces condenser vapors and condenser liquids. If there are multiple condenser stages, there will be multiple condenser vapors and multiple condenser liquids. The bioreagents and condenser liquids (or one of the condenser liquids if there are multiple fractions) are fed to a carbon recapture unit to produce intermediate materials. The intermediate materials are then fed to a thermal treatment unit that produces biocarbon products. The thermal treatment unit also produces exhaust gases, which can be fed to the condenser shown in FIG. 4, or to a different condenser, or can be otherwise treated (e.g., combusted).

[0400] FIG. 5 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a first pyrolysis reactor to produce a first pyrolysis solid and pyrolysis vapor. The pyrolysis vapor is sent to a condenser that includes at least one condensation stage. The condenser produces a condenser vapor and a condenser liquid. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The condenser liquid (or one of the condenser liquids if there are multiple fractions) is fed to a second pyrolysis reactor to produce a second pyrolysis solid and a pyrolysis tail gas. The second pyrolysis reactor can be a coking reactor for coking or carbonizing condenser liquid. The pyrolysis tail gas can be recycled back to the condenser or can be otherwise treated (e.g., can be combusted). The first and second pyrolysis solids can be combined to produce a biocarbon product. In some embodiments, the first pyrolysis solids and / or the second pyrolysis solids are recovered as a product without being combined with the other of the second pyrolysis solids or the first pyrolysis solids. The blended material can be pelletized. Whether or not the blended material is pelletized, the blended material can be dried or heat treated to produce the final biocarbon product.

[0401] FIG. 6 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass in a first pyrolysis reactor to produce a first pyrolysis solid and pyrolysis vapor. The pyrolysis vapor is sent to a condenser that includes at least one condensation stage. The condenser produces a condenser vapor and a condenser liquid. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The condenser liquid (or one of the condenser liquids if there are multiple fractions) is fed to a second reactor to produce solid or semi-solid material and a reactor tail gas. The second reactor can be a coking reactor for coking or carbonizing condenser liquid, or the second reactor can be a reactor operated at a temperature lower than the pyrolysis temperature. The reactor tail gas can be recycled back to the condenser or can be otherwise treated (e.g., combusted). The first and second pyrolysis solids can be combined to produce a biocarbon product. In some embodiments, the first pyrolysis solids and / or the second pyrolysis solids are recovered as a product without being combined with the other of the second pyrolysis solids or the first pyrolysis solids. The blended material can be pelletized. Whether or not the blended material is pelletized, the blended material can be dried or heat treated to produce the final biocarbon product.

[0402] FIG. 7 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass impregnated with condenser liquid in a pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser that includes at least one condensation stage. The condenser produces condenser vapors and condenser liquids. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The condenser liquid (or one of the condenser liquids if there are multiple fractions) is fed to a mixing unit with the incoming biomass to produce a feedstock (biomass + condenser liquid). The feedstock is what is fed to the pyrolysis reactor. In some embodiments, the bio-reagents from the pyrolysis reactor are pelletized. Whether or not the bio-reagents are pelletized, they can be dried or heat treated to produce the final bio-carbon product.

[0403] FIG. 8 depicts an exemplary block flow diagram of a process and system for pyrolyzing biomass impregnated with condenser liquid in a first pyrolysis reactor to produce bio-reagents and pyrolysis vapors. The pyrolysis vapors are sent to a condenser that includes at least one condensation stage. The condenser produces condenser vapors and condenser liquids. If there are multiple condenser stages, there are multiple condenser vapors and multiple condenser liquids. The condenser liquid (or one of the condenser liquids if there are multiple fractions) is fed to a mixing unit with the incoming biomass to produce a feedstock (biomass + condenser liquid). The feedstock is what is fed to the first pyrolysis reactor. In some embodiments, the bio-reagents from the first pyrolysis reactor are pelletized. Whether or not the bio-reagents are pelletized, they can be sent to a second pyrolysis reactor to produce the final bio-carbon product. The pyrolysis exhaust gas from the optional second pyrolysis reactor can be recycled back to the condenser, or can be fed to a different condenser, or can be otherwise treated (e.g., can be combusted).

[0404] A variation of Figures 5 and 6 is that the pyrolysis vapors can be coked directly rather than coking the condensed fraction of the pyrolysis vapors, however this reduces the coking efficiency due to the presence of non-condensable gases (e.g., CO2) that may be difficult to convert to solid carbon.

[0405] In another variation, the condenser of Figures 5 or 6 is replaced by a different separation unit, such as a liquid-vapor cyclone separator.

[0406] In another variation, the principles of Figures 5 and 7 are both used. For example, the condenser liquid can be mixed with the incoming biomass (such as that shown in Figure 7), while the condenser liquid can be coked in a second pyrolysis reactor (such as that shown in Figure 5). This selectivity applies to all process configurations. For example, in Figure 1, instead of all the condenser liquid being fed to the mixing unit, a portion of the condenser liquid can be mixed with the incoming biomass or coked separately, or both of these options.

[0407] In some embodiments relating to the configurations of Figure 5 or Figure 6, the first pyrolysis solid forms a high fixed carbon material while the second pyrolysis solid (Figure 5) or solid or semi-solid material (Figure 6) forms a low fixed carbon material. In these embodiments, generally speaking, a relatively high temperature in the first pyrolysis reactor is useful.

[0408] In other embodiments related to the configurations of Figure 5 or Figure 6, the first pyrolysis solid forms a low fixed carbon material, while the second pyrolysis solid (Figure 5) or solid or semi-solid material (Figure 6) forms a high fixed carbon material. In these embodiments, generally speaking, a relatively high temperature in the second reactor (e.g., second pyrolysis reactor) is useful.

[0409] In some embodiments, the biocarbon product (composition) comprises: (a) a low fixed carbon material having a first fixed carbon concentration of at least about 20% to at most about 55% by weight of fixed carbon on an absolute basis, (b) a high fixed carbon material having a second fixed carbon concentration of at least about 50% to about 100% by weight of fixed carbon on an absolute basis, the second fixed carbon concentration being greater than the first fixed carbon concentration; (c) 0 to a maximum of about 30% by weight moisture; (d) 0 to a maximum of about 15% by weight ash; and (e) 0 up to about 20 weight percent of one or more additives.

[0410] In some embodiments, the low fixed carbon material and the high fixed carbon material are present in the biocarbon composition as a homogenous physical blend. The first fixed carbon concentration can be uniform throughout the biocarbon composition. The second fixed carbon concentration can be uniform throughout the biocarbon composition. In certain embodiments, both the first fixed carbon concentration and the second fixed carbon concentration are uniform throughout the biocarbon composition.

[0411] In other embodiments, the low set carbon material and the high set carbon material are present in the biocarbon composition as a heterogeneous physical blend. For example, the low set carbon material and the high set carbon material may be present in the biocarbon composition as separate layers. The low set carbon material may be included in a shell or coating around a core that includes the high set carbon material. Or, the high set carbon material may be included in a shell or coating around a core that includes the low set carbon material. In some embodiments, the high set carbon material is in the form of particulates in a continuous phase of the low set carbon material. In other embodiments, the low set carbon material is in the form of particulates in a continuous phase of the high set carbon material.

[0412] The low and high set carbon materials may form separate phases that are insoluble in each other at equilibrium and low temperatures. In some embodiments, the low and high set carbon materials may have high equilibrium (thermodynamic) solubility in each other, but nevertheless remain kinetically frozen in the composition such that separate materials are observable. The separate materials may be observable by measuring composition, density, particle size, reactivity, or other physical or chemical properties. During the end use of the biocarbon composition, the distinction of the materials may be lost (e.g., at high temperatures or during carbon oxidation).

[0413] In one technique to demonstrate that a given biocarbon composition contains both low and distinct high fixed carbon materials, a thermogravimetric analysis (TGA) of the combustion of a biocarbon composition test sample is performed. In some embodiments, the resulting TGA heat curve contains two peaks characteristic of distinct mass loss events that correlate with the low and high fixed carbon materials. This can be compared to a control sample of a biocarbon composition that contains a single material with a uniform fixed carbon concentration, which shows a TGA heat curve with a single peak characteristic of one mass loss event of the material. In similar embodiments, the TGA heat curve of the test sample contains three or more peaks, while the TGA heat curve of the control sample contains at least one less peak than the test sample.

[0414] Another technique to demonstrate that a given biocarbon composition contains both low and distinct high set carbon materials is particle size analysis. This is a viable approach when the particle sizes associated with the low and high set carbon materials are different, or when the particle size distributions associated with the low and high set carbon materials are different. In some embodiments, the high set carbon material tends to contain smaller particles compared to the low set carbon material. In some embodiments, a bimodal particle size distribution results from the presence of both low and high set carbon materials, as opposed to a control sample that contains a unimodal particle size distribution characteristic of a homogenous material. In similar embodiments, the test sample may contain a particle size distribution with at least one more mode than the particle size distribution of the control sample. For example, it is possible that the low and high set carbon materials each contain a bimodal particle size distribution (peaks centered at different sizes) and that the control sample contains a bimodal particle size distribution depending on how the control sample was produced.

[0415] Particle size can be measured by a variety of techniques, including, for example, dynamic light scattering, laser diffraction, image analysis, or sieve separation. Dynamic light scattering is a non-invasive, well-established technique for measuring particle size and size distribution, typically in the submicron range, with the latest techniques measuring down to one nanometer. Laser diffraction is a widely used particle sizing technique for materials with sizes ranging from hundreds of nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction instruments for measuring particle size are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis to estimate particle size and distribution can be performed directly on photomicrographs, scanning electron photomicrographs, or other images. Finally, sieving is a conventional technique for separating particles by size.

[0416] Alternatively or additionally, imaging techniques can be utilized to demonstrate that a given biocarbon composition contains both low and distinct high fixed carbon materials. Imaging techniques include, but are not limited to, optical microscopy, dark field microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray tomography (XRT). For example, imaging techniques can be used to demonstrate distinct materials in a blend rather than a homogenous material. Or, imaging techniques can be used to select subsamples for further analysis. Further analysis can be compositional analysis to show three-dimensional variations in fixed carbon content. Further analysis can be property analysis to show three-dimensional variations in chemical or physical properties such as density, particle size, or reactivity.

[0417] Spectroscopic techniques may alternatively or additionally be utilized to demonstrate that a given biocarbon composition contains both low-fixation carbon materials and distinct high-fixation carbon materials, including, but not limited to, energy dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.

[0418] In some embodiments, such as (but not limited to) those related to Figure 6, the bio-carbon composition comprises at least about 10% to at most about 90% by weight of the low set carbon material. In some embodiments, the bio-carbon composition comprises at least about 10% to at most about 90% by weight of the high set carbon material. The weight ratio of the low set carbon material to the high set carbon material can be selected from at least about 0.1 to at most about 10, e.g., at least about 0.2 to at most about 5, at least about 0.5 to at most about 2, or at least about 0.8 to at most about 1.2.

[0419] In some embodiments, the first fixed carbon concentration is, for example, at least about 20% by weight and up to about 40% by weight, or at least about 25% by weight and up to about 50% by weight, or at least about 30% by weight and up to about 55% by weight.

[0420] In some embodiments, the second fixed carbon concentration is, for example, at least about 80% by weight and up to about 100% by weight, or at least about 70% by weight and up to about 95% by weight, or at least about 60% by weight and up to about 90% by weight.

[0421] In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30% by weight and up to about 90% by weight, such as at least about 40% by weight and up to about 80% by weight.

[0422] The biocarbon composition may comprise a total fixed carbon concentration of at least about 25% and up to about 95% by weight on an absolute basis. In some embodiments, the biocarbon composition comprises a total fixed carbon concentration of at least about 35% and up to about 85% by weight on an absolute basis.

[0423] The low-set carbon material may comprise at least about 45% and up to about 80% volatile carbon by weight on an absolute basis (i.e., including ash and moisture). In various embodiments, the low-set carbon material may comprise about, at least about, or up to about 45, 50, 55, 60, 65, 70, 75, or 80% volatile carbon by weight on an absolute basis. The low-set carbon material may, for example, comprise at least about 1% and up to about 20% oxygen by weight on an absolute basis. The low-set carbon material may, for example, comprise at least about 0.1% and up to about 10% hydrogen by weight on an absolute basis.

[0424] The high-set carbon material may comprise at least about 0 and up to about 50% volatile carbon by weight on an absolute basis. In various embodiments, the high-set carbon material may comprise about, at least about, or up to about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% volatile carbon by weight on an absolute basis. The high-set carbon material may, for example, comprise at least about 1% and up to about 20% oxygen by weight on an absolute basis. The high-set carbon material may, for example, comprise at least about 0.1% and up to about 10% hydrogen by weight on an absolute basis.

[0425] "Biocarbon composition" is generally synonymous with "biocarbon product" when referring to the final composition of the process. In some embodiments, the biocarbon composition comprises at least about 0.1% and up to about 20% moisture by weight. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, including all intervening ranges. The low set carbon material can contain 0 to up to about 50% moisture by weight, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, inclusive of all intervening ranges. Independently, the high set carbon material can contain 0 to up to about 50% moisture by weight, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, inclusive of all intervening ranges. Drying can be used at one or more points in the process.

[0426] In some embodiments, the biocarbon composition comprises at least about 0.1% to up to about 10% ash by weight. In various embodiments, the biocarbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% ash by weight, including all intervening ranges. The low fixed carbon material can comprise 0 to up to about 25% ash by weight, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% ash by weight, including all intervening ranges. Independently, the high fixed carbon material can comprise from 0 to up to about 50% ash by weight, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% ash by weight, inclusive of all intervening ranges.

[0427] In some embodiments, the bio-carbon composition comprises at least about 0.1% and up to about 10% by weight of one or more additives. In some embodiments, the bio-carbon composition comprises at least about 1% and up to about 15% by weight of one or more additives. In some embodiments, the bio-carbon composition comprises at least about 3% and up to about 18% by weight of one or more additives. In various embodiments, the bio-carbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight of additives, including all intervening ranges.

[0428] The low set carbon material can include from 0 to up to about 20 weight percent additive, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 weight percent additive, inclusive of all intervening ranges. Independently, the high set carbon material can include from 0 to up to about 50 weight percent additive, e.g., about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 weight percent additive, inclusive of all intervening ranges.

[0429] The additives may include organic additives and / 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 and / or combusted.

[0430] In some embodiments, the one or more additives include (or are) a binder. The binder may be selected from the group comprising starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations thereof.

[0431] In certain embodiments, the binder is selected from the group including starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof. The binder may be a thermoplastic starch. In some embodiments, the thermoplastic starch is crosslinked. The thermoplastic starch may be a reaction product of starch and a polyol, which may be selected from the group including 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 may be selected from the group including 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.

[0432] The one or more additives may reduce the reactivity of the biocarbon composition compared to an otherwise equivalent biocarbon composition without the one or more additives. The reactivity may be thermal reactivity. For example, a biocarbon composition having one or more additives may include a lower self-heating tendency compared to an otherwise equivalent biocarbon composition without the one or more additives. Alternatively or additionally, the reactivity is chemical reactivity with oxygen, water, hydrogen, carbon monoxide, and / or metals (e.g., iron).

[0433] When additives are used, they do not need to be uniformly distributed throughout the biomass composition. The additives may be present in either the low-fixed carbon material or the high-fixed carbon material, or even only in one of these materials. For example, the binder may be present at 5% by weight in the total biomass composition, but 4 percentage points of that amount are located in the low-fixed carbon material and 1 percentage point is located in the high-fixed carbon material (i.e., 80% of the binder is located in the low-fixed carbon material). In various embodiments, the percentage of the total additive that is disposed within the low fixation carbon material can be about, at least about, or up to about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; the percentage of the total additive that is disposed within the high fixation carbon material can be about, at least about, or up to about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; and the percentage of the total additive that is not disposed within either the low fixation carbon material or the high fixation carbon material but elsewhere within the bio-carbon composition (e.g., as a separate additive phase) can be about, at least about, or up to about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

[0434] When one or more additives are present, some or all of the additives may be pore-filling within the low fixation carbon material. When one or more additives are present, some or all of the additives may be pore-filling within the high fixation carbon material. In some embodiments, one or more additives are present and pore-filling within both the low fixation carbon material and the high fixation carbon material.

[0435] Alternatively, or additionally, one or more additives can be disposed on an outer surface of the biocarbon composition (eg, an outer surface of a pellet or powder particle).

[0436] In some embodiments, the bio-carbon composition is in the form of a powder.

[0437] In some embodiments, the biocarbon composition is in the form of pellets. When the form is pellets, the one or more additives may include a binder for the pellets. Alternatively or additionally, the pellets may utilize the low fixed carbon material itself as a binder within the pellets.

[0438] When one or more additives are present, the additives may be located within one of the low fixity carbon materials or the high fixity carbon materials, or alternatively, the additives may be uniformly distributed such that the additives have the same average concentration within the low fixity carbon materials and the high fixity carbon materials.

[0439] In some embodiments, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with the Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances", which is incorporated herein by reference.

[0440] Fixed carbon concentration is an important parameter of a biocarbon composition. The present disclosure allows for maximizing or optimizing, but not necessarily maximizing, the fixed carbon concentration in various embodiments.

[0441] In some embodiments, the fixed carbon concentration is selected to optimize the energy content associated with the biocarbon composition. In some embodiments, the fixed carbon concentration and the type and / or concentration of additives are selected to optimize the energy content associated with the biocarbon composition.

[0442] In some embodiments, the fixed carbon concentration is selected to optimize the bulk density associated with the biocarbon composition. In some embodiments, the fixed carbon concentration and the type and / or concentration of additives are selected to optimize the bulk density associated with the biocarbon composition.

[0443] In some embodiments, the fixed carbon concentration is selected to optimize the hydrophobicity associated with the bio-carbon composition. In some embodiments, the fixed carbon concentration and the type and / or concentration of additives are selected to optimize the hydrophobicity associated with the bio-carbon composition.

[0444] In some embodiments, the fixed carbon concentration is selected to optimize the pore size associated with the bio-carbon composition. In some embodiments, the fixed carbon concentration and additive type and / or concentration are selected to optimize the pore size associated with the bio-carbon composition.

[0445] In some embodiments, the fixed carbon concentration is selected to optimize the ratio of pore sizes associated with the bio-carbon composition. In some embodiments, the fixed carbon concentration and additive type and / or concentration are selected to optimize the ratio of pore sizes associated with the bio-carbon composition.

[0446] In some embodiments, the fixed carbon concentration optimizes the surface area associated with the biocarbon composition. In some embodiments, the fixed carbon concentration and the type and / or concentration of additives are selected to optimize the surface area associated with the biocarbon composition.

[0447] In some embodiments, the fixed carbon concentration is selected to optimize the reactivity associated with the bio-carbon composition. In some embodiments, the fixed carbon concentration and the type and / or concentration of additives are selected to optimize the reactivity associated with the bio-carbon composition.

[0448] In some embodiments, the fixed carbon concentration is selected to optimize the ion exchange capacity associated with the biocarbon composition. In some embodiments, the fixed carbon concentration and the type and / or concentration of additives are selected to optimize the ion exchange capacity associated with the biocarbon composition.

[0449] In some embodiments, the bio-carbon composition is in the form of pellets and the fixed carbon concentration is selected to optimize the Hardgrove Crushability Index associated with the pellets. In some embodiments, the bio-carbon composition is in the form of pellets and the fixed carbon concentration and additive types and / or concentrations are selected to optimize the Hardgrove Crushability Index associated with the pellets.

[0450] In some embodiments, the bio-carbon composition is in the form of pellets and the fixed carbon concentration is selected to optimize a pellet durability index associated with the pellets. In some embodiments, the bio-carbon composition is in the form of pellets and the fixed carbon concentration and additive type and / or concentration are selected to optimize a pellet durability index associated with the pellets.

[0451] In some embodiments, the total carbon in the biocarbon composition is 14 C / 12 In some embodiments, the total carbon is at least 50% renewable as determined from a measurement of the C isotope ratio. 14 C / 12 In certain embodiments, the total carbon is at least 90% renewable as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0452] Although renewable biocarbon compositions are preferred, it is important to note that the principles disclosed can be applied to non-renewable materials. In certain embodiments, the biomass-containing feedstock includes biomass (such as the biomass sources listed herein), as well as non-renewable feedstocks such as coal. Thus, a biomass-coal mixture can be utilized as the biomass-containing feedstock, which can be substituted for "biomass" in any of Figures 1-6, for example. Other non-biomass feedstocks that can be used in the feedstock mixture include, for example, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0453] Some processes use two or more separate pyrolysis reactors, which are typically all continuous or all batch, although in principle a mixture of reaction modes can be used, and when separate pyrolysis reactors are used, they can be at a common location or at different locations.

[0454] In other embodiments, the processes are carried out in a common pyrolysis reactor at different times, such as separate production campaigns. If a single pyrolysis reactor is used, it can be operated in batch mode, for example with separate batches of low and high fixed carbon materials, or using different pyrolysis conditions. Alternatively, a single pyrolysis reactor can be operated continuously or semi-continuously to produce a first material for a first period of time, then a second material for a second period of time, after which the reactor can be returned to the production of the first material or something else.

[0455] In some process embodiments, the first pyrolysis reactor is operated at a first pyrolysis temperature selected from at least about 250° C. up to about 1250° C., e.g., at least about 300° C. up to about 700° C. The second pyrolysis reactor can be operated at a second pyrolysis temperature selected from at least about 250° C. up to about 1250° C., e.g., at least about 300° C. up to about 700° C. The second pyrolysis temperature can be the same as or different from the first pyrolysis temperature.

[0456] In some embodiments, the first pyrolysis reactor is operated for a first pyrolysis time selected from at least about 10 seconds up to about 24 hours. In these or other embodiments, the second pyrolysis reactor is operated for a second pyrolysis time selected from at least about 10 seconds up to about 24 hours. The second pyrolysis time may be the same as or different from the first pyrolysis time.

[0457] Some embodiments are based on optimized pyrolysis of biomass with carbon recapture using the principles taught herein to produce a carbon substrate, mechanical size reduction of the carbon substrate, and the use of a binder to agglomerate the carbon substrate to form bio-carbon pellets. The carbon substrate may be or may include a blend of low and high fixed carbon materials.

[0458] The Hardgrove Grindability Index ("HGI") is a measure of the grindability of a material such as biomass or coal. The HGI parameter for coal is important in power applications such as pulverized coal boilers, where the coal is pulverized and burned in suspension, and in steelmaking, such as pulverized coal injection, where the pulverized coal is injected into a blast furnace through a lance, where it can replace coke and reduce iron ore to metallic iron.

[0459] In some embodiments, varying the fixed carbon content allows for optimization of the HGI. The incorporation of binders or other additives may also allow for HGI tunability.

[0460] The ability to adjust the HGI of biocarbon pellets is beneficial because downstream applications utilizing biocarbon pellets (e.g., replacing coal in a boiler) include various HGI requirements. HGI adjustability addresses the well-known problems industrially of the difficulty in grinding crude biomass and the difficulty in grinding pellets. Furthermore, because there are so many downstream uses of biocarbon pellets, each with its own requirements, being able to adjust the grindability of the pellets is highly advantageous. It is desirable to be able to adjust the HGI to suit a particular application, such as combustion in a boiler to make syngas, metals production, or gasification.

[0461] In many applications, pellets are preferred over powders (isolated biomass particles) based on delivery, storage, and safety advantages. Ultimately, pellets may need to be reconstituted into powder, or at least smaller bodies, at some point. Thus, pellet grindability is often a critical parameter that impacts operational and capital costs.

[0462] In some cases, the pellets need to be crushed or pulverized into a powder, such as when a boiler or gasifier utilizes a fluidized bed or a suspension of carbon particles. Another example is pulverized carbon injection into a blast furnace to reduce metal ores to metals. In these cases, high pellet grindability is desirable, but not too high that the pellets break down during delivery and handling. In other cases, it is desirable to feed the pellets themselves to a process, such as a metal making process. In these cases, lower grindability may be desirable, since some pellet strength may be required to support the bed of material in the reactor. Different technologies include different pellet grindability requirements.

[0463] The Hardgrove Grindability Index of the biocarbon pellets can be at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. In some embodiments, the Hardgrove Grindability Index is at least about 30 to a maximum of about 50, or at least about 50 to a maximum of about 70. ASTM-Standard D409 / D409M for "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method" is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to Hardgrove Grindability Index or HGI in this disclosure refer to ASTM-Standard D409 / D409M.

[0464] In various embodiments, the Hard Glove Crushability Index is about, at least about, or up to about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 13 , 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0465] The bio-carbon pellets may be characterized by a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. The bio-carbon pellets may be characterized by a pellet durability index of less than 99%, less than 95%, less than 90%, less than 85%, or less than 80%. Unless otherwise indicated, all references to pellet durability index in this disclosure refer to ISO 17831-1:2015 "Solid biofuels - Determination of mechanical durability of pellets and briquettes - Part 1: Pellets", which is incorporated herein by reference in its entirety.

[0466] In some embodiments, biocarbon pellets are utilized as starting materials for making smaller objects, and "pellets" may also be referred to as biocarbon pellets, since "pellets" does not limit the geometric shape. For example, initial biocarbon pellets can be made with an average pellet diameter of 10 mm. These initial biocarbon pellets can then be crushed using various mechanical means (e.g., using a hammer mill). The crushed pellets can be separated according to size, such as by screening. In this manner, smaller biocarbon pellets can be produced with an average pellet diameter of, for example, about, at least about, or up to about 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, or 5000 microns. In some embodiments, the average pellet diameter of the smaller biocarbon pellets is greater than the average particle diameter of the initial carbon-containing particles used to make the pellets with the binder.

[0467] When the bio-carbon pellets are crushed to produce smaller bio-carbon pellets, the crushing and in some embodiments screening steps can be integrated with other process steps, including potential points of industrial use. The optional step to produce smaller bio-carbon pellets can utilize a crushing device selected from the group including a hammer mill, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, a rock crusher, or a combination thereof.

[0468] In various process embodiments, the Hardgrove Crushability Index is at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. For example, the Hardgrove Crushability Index can be at least about 30 and up to about 50, or at least about 50 and up to about 70.

[0469] In various processes, the process conditions may range from about, at least about, or up to about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1081, 1092, 1094, 1096, 1098, 1098, 1099, 1000, 1001, 1002, 10 8, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0470] In some processes, the biocarbon pellets are characterized by a pellet durability index of at least 80%, at least 90%, or at least 95%.

[0471] In some embodiments, the process includes preselecting a hardgrove grindability index, adjusting process conditions based on the preselected hardgrove grindability index, and achieving within ±20% of the preselected hardgrove grindability index for the biocarbon pellets, where the adjusted process conditions include adjusting one or more of pyrolysis temperature, pyrolysis time, mechanical treatment conditions, pelletizing conditions, binder type, binder concentration, binding conditions, and drying. The process of certain embodiments can achieve within ±10%, or within ±5%, of the preselected hardgrove grindability index for the biocarbon pellets.

[0472] The size and geometry of the biocarbon pellets may vary. As used herein, "pellets" refers to aggregated bodies, not loose powders. The geometry of the pellets is not limited to spherical or nearly spherical. Also, in this disclosure, "pellets" is synonymous with "briquettes." The geometry of the pellets may be spherical (round or ball shaped), cylindrical, cubic (square), octagonal, hexagonal, honeycomb / honeycomb shaped, elliptical, ovoid, cylindrical, rod shaped, pillow shaped, random shaped, or combinations thereof. For convenience of disclosure, the term "pellets" is used generally for any body containing powders aggregated using a binder. Also, it is reiterated that this technology is in no way limited to biocarbon compositions in the form of pellets.

[0473] Biocarbon pellets can be characterized by an average pellet diameter, which is the true diameter in the case of a sphere or cylinder, or an equivalent diameter in the case of any other 3D geometric shape. The equivalent diameter of a non-spherical pellet is the diameter of a sphere of equivalent volume to the actual pellet. In some embodiments, the average pellet diameter is about or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters, including all intervening ranges. In some embodiments, the average pellet diameter is about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns, including all intervening ranges.

[0474] In some embodiments, there are a plurality of bio-carbon pellets that are uniform in size, such as a standard deviation of less than ±100%, less than ±50%, less than ±25%, less than ±10%, or less than ±5% of the average pellet diameter. In other embodiments, there are a wide range of sizes of bio-carbon pellets, as this may be advantageous in some applications.

[0475] The biocarbon pellets may contain moisture. The moisture present in the biocarbon pellets may be water that is chemically bound to the carbon or binder, water that is physically bound (absorbed or adsorbed) to the carbon or binder, free water present in the water phase that is not chemically or physically bound to the carbon or binder, or a combination thereof. When moisture is desired during the binding process, it is preferred that such moisture is chemically or physically bound to the carbon and / or binder, rather than being free water.

[0476] Various moisture levels may be present. For example, the biocarbon pellets may contain at least about 1% to up to about 30% (e.g., 32%) moisture by weight, such as at least about 5% to up to about 15% moisture, at least about 2% to up to about 10% moisture, or at least about 0.1% to up to about 1% moisture by weight. In some embodiments, the biocarbon pellets contain about 4-8% moisture by weight. In various embodiments, the biocarbon pellets contain about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% moisture by weight, including all intervening ranges. The moisture level of the biocarbon pellets can be optimized to vary the density within the pellets.

[0477] In some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. In other market applications, such as metallurgy, lower moisture levels may be desirable (e.g., 1% moisture by weight or even lower). Note that water is present in the process of making biocarbon pellets, but these pellets can then be dried, meaning that the final biocarbon pellets do not necessarily contain moisture.

[0478] In some biocarbon pellets, the biocarbon pellets include at least about 2% to about 25% by weight binder, at least about 5% to about 20% by weight binder, or at least about 1% to about 5% by weight binder. In various embodiments, the biocarbon pellets include about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, or 30% by weight binder, including all intervening ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0479] The binder may be pore-filled within the bio-reagent of the bio-carbon pellet. Alternatively or additionally, the binder may be disposed on the surface of the bio-carbon pellet.

[0480] The binder may be an organic binder or an inorganic binder. In some embodiments, the binder is or comprises a renewable material. In some embodiments, the binder is or comprises a biodegradable material. In some embodiments, the binder is capable of being partially oxidized and / or combusted.

[0481] In various embodiments, the binder is selected from the group including starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations thereof. The binder may be or may include a grindable plasticizer.

[0482] In certain embodiments, the binder is selected from the group including starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), derivatives thereof, or combinations thereof. The starch can be a nonionic starch, anionic starch, cationic starch, or zwitterionic starch.

[0483] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and can be easily chemically modified. The ring structure of starch molecules, together with the strong hydrogen bonds, give starch a rigid structure, resulting in highly ordered crystalline and granular regions. Starch in its granular state is generally not suitable for thermoplastic processing. To obtain thermoplastic starch, semicrystalline starch granules can be decomposed by thermal and mechanical forces. Since the melting point of pure starch is significantly higher than its decomposition temperature, plasticizers such as water and / or glycols can be added. The native crystallinity can then be destroyed by vigorous mixing (shear) at high temperatures resulting in thermoplastic starch. Starch can be plasticized (destroyed) by low levels of molecules that can hydrogen bond with starch hydroxyl groups, such as water, glycerol, or sorbitol.

[0484] Thermoplastic starch can be chemically modified and / or blended with other biopolymers to produce stronger, more ductile and resilient bioplastics. For example, starch can be blended with natural and synthetic (biodegradable) polyesters such as polylactic acid, polycaprolactone, or polyhydroxybutyrate. To improve the compatibility of starch / polyester blends, suitable compatibilizers such as poly(ethylene-co-vinyl alcohol) and / or polyvinyl alcohol can be added. The hydrophilic hydroxyl groups (-OH) of starch can be replaced with hydrophobic reactive groups, such as by esterification or etherification.

[0485] In some embodiments, the starch-containing binder is or comprises crosslinked starch. Various methods for crosslinking starch are known in the art. Starch materials can be crosslinked, for example, under acidic or alkaline conditions after dissolving or dispersing in an aqueous medium. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to crosslink starch.

[0486] An example of a crosslinked starch is the reaction product of starch with glycerol or another polyol, such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. The reaction product can be formed from a crosslinking reaction catalyzed by an acid, such as (but not limited to) formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof. Inorganic acids, such as sulfuric acid, can also be utilized to catalyze the crosslinking reaction. In some embodiments, the thermoplasticized and / or crosslinked reaction product can instead be formed from a crosslinking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0487] In some embodiments, the binder is designed to be a water-resistant binder, for example, in the case of starch, the hydrophilic groups can be replaced by hydrophobic groups that better resist water.

[0488] In some embodiments, the binder serves other purposes such as (but not limited to) moisture retention within the biocarbon pellets and as a food source for microorganisms.

[0489] In some embodiments, the binder reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the binder, which can refer to thermal or chemical reactivity (or both).

[0490] In the case of thermal reactivity, the bio-carbon pellets may include reduced self-heating as compared to otherwise comparable bio-carbon pellets without the binder. "Self-heating" refers to the bio-carbon pellets undergoing a spontaneous exothermic reaction in the absence of any external ignition, at low temperature and in an oxidizing atmosphere, to increase the internal temperature of the bio-carbon pellets.

[0491] The chemical reactivity may be with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. The chemical reactivity may be associated with, for example, a reaction to CO, CO2, HO, pyrolysis oil, and heat.

[0492] In some embodiments, the biocarbon pellets include one or more additives (not necessarily binders), such as inorganic bentonite clay, limestone, starch, cellulose, lignin, or acrylamide. When lignin is used as a binder or other additive, the lignin can be obtained from the same biomass feedstock used in the pyrolysis process. For example, the starting biomass feedstock can be subjected to a lignin extraction step to remove some amount of lignin for use as a binder or additive.

[0493] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additives are selected from acids, bases, or salts thereof. In some embodiments, at least one additive is selected from the group including metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. For example, the additives can be selected from the group including (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, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof. The additives can be added before, during, or after any one or more steps of the process, including adding to the feedstock itself at any time before or after the feedstock is harvested.

[0494] The bio-carbon pellets disclosed herein include a wide variety of downstream uses. The bio-carbon pellets can be stored, sold, distributed, and converted into other products. The bio-carbon pellets can be pulverized for use in boilers to burn carbon and generate electrical energy and / or heat. The bio-carbon pellets can be pulverized, crushed, or milled for feeding into furnaces, such as blast furnaces in metal production. The bio-carbon pellets can be fed directly into furnaces, such as Tecnored furnaces in metal production. The bio-carbon pellets can be pulverized, crushed, or milled for feeding into gasifiers for the purpose of making syngas from the bio-carbon pellets.

[0495] In many embodiments, the biocarbon pellets are fed into a furnace, either directly or after a step of pulverizing, crushing, milling, or otherwise reducing the particle size. The furnace can be a blast furnace, a top gas recirculating blast furnace, a shaft furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a silencer furnace, a retort furnace, a flash furnace, a Tecnored furnace, an Ausmelt furnace, an ISASMELT furnace, a puddle furnace, a bogie hearth furnace, a continuous chain furnace, a pusher furnace, a rotary hearth furnace, a walking beam furnace, an electric arc furnace, an induction furnace, a basic oxygen furnace, a puddle furnace, a Bessemer furnace, a direct reduction metal furnace, or a combination or derivative thereof.

[0496] It should be noted that despite the Hardgrove Crushability Index of biocarbon pellets, they do not necessarily undergo a subsequent grinding process. For example, biocarbon pellets can be used directly in agricultural applications. As another example, biocarbon pellets can be directly incorporated into engineered structures, such as landscape walls. At the end of the life of the structure containing the biocarbon pellets, the pellets can then be crushed, combusted, gasified, or otherwise reused or recycled.

[0497] Pyrolysis Processes and Systems Suitable processes and systems for pyrolyzing biomass feedstock or bioreagents together with condenser liquid will now be described in more detail. Descriptions of pyrolysis reactors (or reactions) will in some cases be understood as references to reactors (or reactions) for producing high fixed carbon materials.

[0498] "Pyrolysis" and "pyrolyzing" generally refer to the thermal decomposition of a carbonaceous material. In pyrolysis, less oxygen is present than is required for complete combustion of the material, such as less than 10%, 5%, 1%, 0.5%, 0.1%, or 0.01% of the oxygen required for complete combustion (O2 molar basis). In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0499] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the temperature within the feedstock; (ii) the initiation of primary pyrolysis reactions at this higher temperature liberates volatiles and forms char; (iii) the flow of hot volatiles toward the cooler solids results in heat transfer between the hot volatiles and the cooler non-pyrolyzed feedstock; (iv) some of the volatiles in the cooler portions of the feedstock may condense and subsequently undergo secondary reactions to produce tars; (v) autocatalytic secondary pyrolysis reactions proceed while competing primary pyrolysis reactions occur simultaneously; and (vi) further pyrolysis, reforming, water-gas shift reactions, free radical recombination, and / or dehydration may also occur, which are a function of residence time, temperature, and pressure profiles.

[0500] Pyrolysis can at least partially dewater the starting material (e.g., lignocellulosic biomass). In various embodiments, pyrolysis removes about 50%, 75%, 90%, 95%, 99% or more of the water from the starting material.

[0501] In some embodiments, the starting biomass feedstock is softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit husk ... The biomass feedstock may be selected from the group comprising stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper shavings, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. It is noted that typically, biomass feedstock comprises at least carbon, hydrogen, and oxygen.

[0502] The bioreagent may comprise at least about 50%, at least about 75%, or at least about 90% total carbon by weight. In various embodiments, the bioreagent comprises about, at least about, or up to about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% carbon by weight. Total carbon is the sum of fixed and non-fixed carbon present in the volatile materials. In some embodiments, the weight percentages of the components are on an absolute basis, which is assumed unless otherwise stated. In other embodiments, the component weight percentages are on a water-free and ash-free basis. The compositions of low and high fixed carbon materials are discussed in detail above.

[0503] Pyrolysis conditions can vary widely depending on the desired composition of the bioreagents and pyrolysis exhaust gas, the starting materials, the reactor configuration, and other factors.

[0504] In some embodiments, multiple reactor zones are designed and operated to optimize carbon yield and product quality from pyrolysis while maintaining flexibility and adjustability to feedstock variations and product requirements.

[0505] In some non-limiting embodiments, the temperature and residence time are selected to achieve slow pyrolysis chemical reactions. An advantage can be substantial preservation of the cell walls contained in the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, it is preferable to utilize equipment that does not mechanically disrupt the cell walls or otherwise convert the biomass particles into small fines. Certain reactor configurations are considered in accordance with the process description below.

[0506] Additionally, if the feedstock is a milled or sized feedstock, such as wood chips or pellets, it may be desirable to carefully mill or size the feedstock. Careful initial processing tends to preserve the strength and cell wall integrity present in the natural feedstock source (e.g., wood). This may also be important if the final product is to retain some, most, or all of the shape and strength of the starting biomass.

[0507] In some embodiments, the first zone of the pyrolysis reactor is configured to feed biomass (or another carbon-containing feedstock) in a manner that does not "shock" the biomass, which ruptures cell walls and initiates rapid decomposition of the solid phase into steam and gas. This first zone can be considered mild pyrolysis.

[0508] In some embodiments, the second zone of the pyrolysis reactor is configured as a primary reaction zone, where the preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, leaving behind a significant amount of solid material that is a high-carbon reaction intermediate. Biomass components (mainly cellulose, hemicellulose, and lignin) decompose to create vapors that escape by penetrating pores or creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0509] In some embodiments, the third zone of the pyrolysis reactor is configured to receive the high carbon reaction intermediates and to cool the solids to some extent. Typically, the third zone is at a lower temperature than the second zone. In the third zone, the chemical reactions and mass transfer can be surprisingly complex. Without being limited by a particular theory or proposed mechanism, it is believed that secondary reactions can occur in the third zone. Essentially, carbon-containing components in the gas phase can decompose to form additional fixed carbon and / or become adsorbed onto the carbon. Thus, in some embodiments, the final carbonaceous material is not simply a solid degassed residue of the processing step, but can include additional carbon deposited from the gas phase, such as by decomposition of organic vapors (e.g., tars) that can form carbon.

[0510] Certain embodiments extend the concept of additional carbon formation by including a separate unit in which the cooled carbon is subjected to an environment containing carbonaceous species to enhance the carbon content of the product. If the temperature of this unit is below the pyrolysis temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0511] There are numerous options with regard to intermediate input and output (purge or probe) streams of one or more phases present in any particular zone, various mass and energy recycle schemes, various additives that can be introduced anywhere in the process, adjustability of process conditions, including both reaction and separation conditions to tailor product distribution, etc. Zone-specific input and output streams allow for better process monitoring and control, such as by FTIR sampling and dynamic process adjustments.

[0512] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis.Surprisingly, high quality carbon materials, including compositions having a very high percentage of fixed carbon, can be obtained from the disclosed processes and systems.

[0513] In some embodiments, the pyrolysis process for producing a bio-reagent comprises the following steps: (a) providing a carbon-containing feedstock comprising biomass; (b) pyrolyzing the feedstock in the presence of a substantially inert gas phase at at least one temperature selected from at least about 250° C. to at most about 700° C. for at least 10 minutes to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (c) separating at least the condensable vapors and at least the non-condensable gases from the high temperature pyrolysis solids; (d) cooling the high temperature pyrolysis solid to produce a cooled pyrolysis solid; (e) recovering the biological reagent comprising at least the cooled pyrolysis solid. The pyrolysis process is (f) drying the raw material to remove at least the water contained therein; and / or (g) degassing the feedstock to remove at least interstitial oxygen, if present, contained in the feedstock.

[0514] "Biomass" for the purposes of this disclosure should be construed as any living material or mixture of living and non-living materials. Essentially, biomass contains at least carbon, hydrogen, and oxygen. The methods and apparatus can accommodate a wide range of materials of different types, sizes, and moisture contents.

[0515] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal waste, poultry waste, and municipal solid waste. In various embodiments utilizing biomass, the biomass feedstock may include one or more materials selected from wood harvest residues, softwood chips, hardwood chips, tree branches, tree stumps, knots, leaves, bark, sawdust, off-spec paper pulp, cellulose, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal waste, municipal sewage, commercial waste, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, carbohydrates, plastics, and fabrics. Those skilled in the art will readily appreciate that the options for feedstock are virtually limitless.

[0516] The present technology can also be used with carbon-containing feedstocks other than biomass, such as fossil fuels (e.g., coal or petroleum coke), or any mixture of biomass and fossil fuels (e.g., biomass / coal blends). In some embodiments, the biofeedstock is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Feedstocks can include waste tires, recycled plastics, recycled paper, construction waste, demolition waste, and other waste or recycled materials. For clarity, any method, apparatus, or system described herein can be used with any carbonaceous feedstock. The carbon-containing feedstock can be transportable by any known means, such as trucks, trains, ships, barges, tractor trailers, or any other vehicle or conveyance.

[0517] The selection of the particular raw material(s) is not considered technically critical, but is done in a manner that tends to favor an economical process. Typically, regardless of the raw material selected, there may (in some embodiments) be screening to remove undesirable materials. In some embodiments, the raw material may be dried prior to processing.

[0518] The raw materials used can be provided or processed into a wide variety of particle sizes or shapes. For example, the feed material can be a fine powder, or a mixture of fine and coarse particles. The feed material can be in the form of larger pieces of material, such as wood chips or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the feed material comprises pellets or other agglomerated forms of particles that are pressed together or otherwise bound, such as with a binder.

[0519] It should be noted that size reduction is a costly and energy intensive process. Pyrolyzed material can be sized with significantly less energy input, i.e., it may be preferable to reduce the particle size of the product rather than the feedstock. This is an option since the process does not require fine starting material and there is not necessarily any significant particle size reduction during processing. The ability to process very large feedstock pieces is an important economic advantage. In particular, some market applications of high carbon products actually require large sizes (e.g., on the order of centimeters), so in some embodiments, large pieces are supplied, manufactured and sold.

[0520] If it is desired to produce a final carbonaceous bio-reagent that includes 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 utilize a feed material that generally has the desired size and / or shape for the final product, and use processing steps that do not destroy the basic structure of the feed material. In some embodiments, the feed and product include similar geometric shapes, such as spheres, cylinders, or cubes.

[0521] The ability to maintain the approximate size of the feed material throughout the process is beneficial when product strength is important, and it avoids the difficulty and cost of pelletizing high fixed carbon materials.

[0522] The starting feedstock may be provided with a range of moisture levels, as will be appreciated. In some embodiments, the feedstock may already be sufficiently dry that further drying prior to pyrolysis is not required. Typically, it is desirable to utilize commercial sources of biomass that are normally moist, and to feed the biomass through a drying step prior to introduction into the pyrolysis reactor. However, in some embodiments, dry feedstock may be utilized.

[0523] Typically, it is desirable to provide a low oxygen environment in the pyrolysis reactor, such as about or up to about 10 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.02 mol%, or 0.01 mol% O2 in the gas phase. First, uncontrolled combustion should be avoided in the pyrolysis reactor for safety reasons. Some amount of total carbon oxidation to CO2 may occur, and the heat released from the exothermic oxidation may support the endothermic decomposition chemical reaction. Large amounts of carbon oxidation, including partial oxidation to synthesis gas, will reduce the carbon yield to solids.

[0524] In practice, it can be difficult to achieve a strictly oxygen-free environment in the reactor. This limit can be approached, and in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that there is little or no oxygen in the pyrolysis reactor, it may be desirable to remove air from the feed before it is introduced into the reactor. There are various methods to remove or reduce air in the feed.

[0525] In some embodiments, a degassing unit is utilized where the feedstock is conveyed in the presence of another gas that can remove adsorbed oxygen before or after drying and permeate the feedstock pores to remove oxygen from the pores. Essentially any gas containing less than 21% O2 by volume can be used with varying effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO and / or CO2 are used. Mixtures can be used, such as a mixture of nitrogen and small amounts of oxygen. Water vapor may be present in the degassing gas, but adding significant moisture back to the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or to an exhaust treatment unit) or recycled.

[0526] In principle, the effluent from the degassing unit can be introduced into the pyrolysis reactor itself, since the oxygen removed from the solids is highly diluted. In this embodiment, it may be advantageous to introduce the degassed effluent gas into the last zone of the reactor if the reactor is operated in a countercurrent configuration.

[0527] Various types of degassing units can be used. If drying is performed, it may be inefficient to clean soluble oxygen from the moisture present, so drying and then degassing may be preferred. In certain embodiments, the drying and degassing steps are combined in a single unit, or some amount of degassing is achieved during drying, etc.

[0528] In some embodiments, the dried and / or degassed feedstock is introduced into the pyrolysis reactor or multiple reactors in series or parallel. The feedstock can be introduced using any known means including, for example, a screw feeder or a lock hopper. In some embodiments, the feed system incorporates an air knife.

[0529] In some embodiments, when a single reactor is used, there are multiple zones, such as two, three, four or more zones, which can allow separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, and / or pressure to adjust the overall process performance.

[0530] References to "zones" should be interpreted broadly to include regions of space within a single physical unit, physically separated units, or combinations thereof. With respect to continuous reactors, the boundaries of zones may relate to structures such as the presence of flights within the reactor or separate heating elements to provide heat to separate zones. Alternatively or additionally, the boundaries of zones in continuous reactors may relate to functions such as, for example, separate temperatures, fluid flow patterns, solids flow patterns, extent of reaction, etc. In single batch reactors, a "zone" is an operating regime in time rather than space. Multiple batch reactors may also be used.

[0531] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary, some amount of pyrolysis may occur in the preheat zone, and some amount of "preheat" may continue to occur in the pyrolysis zone. The temperature profile within the reactor is typically continuous, including at the zone boundaries within the reactor.

[0532] Some embodiments employ a first zone operated under preheating and / or mild pyrolysis conditions. The temperature of the first zone can be selected to be at least about 150° C. and up to about 500° C., for example, from about 300° C. and up to about 400° C. In some embodiments, the temperature of the first zone is not so high as to bombard the biomass material and rupture cell walls and initiate rapid decomposition of the solid phase into steam and gas.

[0533] All references to zone temperatures herein should be interpreted without limitation to include temperatures that may be applied to the bulk solids present, or the gas phase, or the reactor walls (process side). It will be understood that there are temperature gradients in each zone, both axially and radially, and over time (i.e., after start-up or due to transients). Thus, references to zone temperatures may be references to average temperatures or other effective temperatures that may affect the actual kinetics. Temperatures may be measured directly by thermocouples or other temperature probes, or may be measured or estimated indirectly by other means.

[0534] The second zone, or generally the primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone can be selected at least about 250°C to up to about 700°C, for example, about, or at least about, or up to about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, leaving behind a significant amount of solid material as a high carbon reaction intermediate. The biomass components (mainly cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or by creating new pores. The preferred temperature depends on at least the residence time of the second zone, as well as the nature of the feedstock and the desired product properties.

[0535] The third zone, or cooling zone, is operated to cool the high carbon reaction intermediates to various degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone can be selected from at least about 100° C. to a maximum of about 550° C., for example, from about 150° C. to a maximum of about 350° C.

[0536] Chemical reactions can continue to occur in the cooling zone. Without being limited to a particular theory, it is believed that a secondary pyrolysis reaction can be initiated in the third zone. Carbonaceous components that are in the gas phase can condense (due to the reduction in temperature in the third zone). However, the temperature remains high enough to promote reactions that can form additional fixed carbon from the condensed liquids (secondary pyrolysis), or at least reactions that can form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that can occur is the Boudouard reaction to convert carbon monoxide to carbon dioxide and fixed carbon.

[0537] The residence time of the reactor zones can vary. There is an interaction of time and temperature, such that for a desired amount of pyrolysis, higher temperatures can allow for shorter reaction times and vice versa. The residence time in a continuous reactor (zone) is the volume divided by the volumetric flow rate. The residence time in a batch reactor is the batch reaction time after heating to the reaction temperature.

[0538] It should be recognized that in a multiphase reactor, there are multiple residence times. In the present context, there is a residence time (and residence time distribution) for both the solid and vapor phases in each zone. For a given apparatus using multiple zones, at a given throughput, the residence times across the zones are generally combined on the solid side, but if multiple inlet and outlet ports are utilized in the individual zones, the residence times may not be combined on the vapor side. The residence times of the solids and vapor are not combined.

[0539] The solids residence time in the preheat zone can be selected from at least about 5 minutes up to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a sufficient time is desirable to allow the biomass to reach the desired preheat temperature. The heat transfer rate, which depends on the particle type and size, physical equipment, and heating parameters, dictates the minimum residence time required to allow the solids to reach the desired preheat temperature. Additional time may not be desirable unless some amount of mild pyrolysis is intended in the preheat zone, as it contributes to higher capital costs.

[0540] The solids residence time in the pyrolysis zone can be selected from at least about 10 minutes up to about 120 minutes, for example, about 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be enough time for the necessary heat transfer to occur followed by the chemical reaction of carbonization. For times less than about 10 minutes, the temperature would need to be very high, such as over 700° C., to remove a significant amount of non-carbon elements. This temperature promotes fast pyrolysis and its production of steam and gases derived from the carbon itself, but should be avoided if the intended product is solid carbon.

[0541] In a static system, there will be an equilibrium conversion that can be substantially reached at a certain time. When steam is continuously flowing over the solids with continuous devolatilization, as in certain embodiments, the equilibrium constraint can be removed to allow pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times will not tend to substantially change the remaining refractory solids.

[0542] The solids residence time in the cooling zone can be selected from at least about 5 minutes up to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be enough time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature dictate the minimum residence time necessary to allow the carbon to cool. Additional time may not be desirable unless some amount of secondary pyrolysis is desired.

[0543] As discussed above, the residence times of the vapor phases can be selected and controlled separately. The vapor residence time of the preheat zone can be selected from at least about 0.1 minutes up to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time of the pyrolysis zone can be selected from at least about 0.1 minutes up to about 20 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time of the cooling zone can be selected from at least about 0.1 minutes up to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. A short vapor residence time promotes rapid sweeping of volatiles from the system, while a longer vapor residence time promotes reaction of components in the vapor phase with the solid phase.

[0544] The mode of operation of the reactor, and the overall system, can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the reactor is a continuous countercurrent reactor, with solids and vapor flowing in substantially opposite directions. The reactor can also be operated in batch, but with simulated countercurrent flow of vapor, for example, by periodically introducing and removing the gas phase from the batch vessel.

[0545] A variety of flow patterns may be desired or observed. In chemical reactions and simultaneous separations involving multiple phases in multiple reactor zones, the fluid dynamics can become very complex. Typically, the flow of solids can approach plug flow (well mixed in the radial dimension), while the flow of vapor can approach perfectly mixed flow (high velocity transport in both radial and axial dimensions). Multiple inlet and outlet ports for the vapor can contribute to the overall mixing.

[0546] The pressure in each zone can be separately selected and controlled. The pressure in each zone can be independently selected from at least about 1 kPa to a maximum of about 3000 kPa, for example, about 101.3 kPa (standard atmospheric pressure). Independent zone control of pressure is possible when multiple gas inlets and outlets are used, including vacuum ports for withdrawing gas when subatmospheric zone pressures are desired.

[0547] The process may be conveniently operated at atmospheric pressure in some embodiments. Operation at atmospheric pressure has many advantages ranging from mechanical simplicity to improved safety. In certain embodiments, the pyrolysis zone is operated at a pressure of about 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute).

[0548] Vacuum operation (e.g., 10-100 kPa) promotes rapid clearing of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) may be useful when feeding exhaust gas to high pressure operation. Higher pressures may also be useful to promote heat transfer, chemical reactions, or separations.

[0549] The step of separating at least the condensable vapors and at least the non-condensable gases from the high temperature pyrolysis solids can be accomplished in the reactor itself or using a separate separation unit. A substantially inert sweep gas can be introduced into one or more zones. The condensable vapors and non-condensable gases are then carried away from the zones in the sweep gas and exit the reactor.

[0550] The sweep gas can be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweep gas can be first preheated before introduction, or it can be cooled if obtained from a heating source.

[0551] The sweep gas removes volatile components more completely by removing them from the system before they can condense or further react. The sweep gas allows volatiles to be removed at a higher rate than would be possible from simply volatilization at a given process temperature. Alternatively, the use of a sweep gas allows a more gentle temperature to be used to remove a particular amount of volatiles. The reason the sweep gas improves volatile removal is because the mechanism of separation is not simply relative volatility, but rather liquid / vapor phase separation assisted by the sweep gas. The sweep gas can reduce the mass transfer limitations of volatilization as well as the thermodynamic limitations by continuously depleting a given volatile species to allow more volatile species to evaporate and achieve thermodynamic equilibrium.

[0552] Some embodiments remove gases full of volatile organic carbon from subsequent processing steps to produce products with high fixed carbon. Otherwise, the volatile carbon may be adsorbed or absorbed onto the pyrolyzed solids, thereby requiring additional energy (cost) to achieve a purer form of carbon that may be desired. It is also speculated that the rapid removal of steam can increase porosity in the pyrolyzed solids. Higher porosity is desirable for some products.

[0553] In certain embodiments, the sweep gas, in conjunction with a low process pressure, such as atmospheric pressure, provides rapid vapor removal without requiring large amounts of inert gas.

[0554] In some embodiments, the sweep gas flows countercurrent to the feed flow direction. In other embodiments, the sweep gas flows cocurrent to the feed flow direction. In some embodiments, the flow patterns of the solids approach plug flow, while the flow patterns of the sweep gas and vapor phase generally approach perfectly mixed flow in one or more zones.

[0555] The sweep may be performed in any one or more of the reactor zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted (along with generated volatiles) from the cooling and / or pyrolysis zone. In some embodiments, the sweep gas is introduced into the pyrolysis zone and extracted from the pyrolysis and / or preheating zone. In some embodiments, the sweep gas is introduced into the preheating zone and extracted from the pyrolysis zone. In these or other embodiments, the sweep gas may be introduced into each of the preheating zone, pyrolysis zone, and cooling zone, and may also be extracted from each of the zones.

[0556] In some embodiments, the zone or zones in which the separation is carried out are units physically separated from the reactor. Separation units or zones can be located between reactor zones, if desired. For example, a separation unit can be installed between a pyrolysis unit and a cooling unit.

[0557] The sweep gas can be introduced continuously, especially if the solids flow is continuous. If the pyrolysis reaction is operated as a batch process, the sweep gas can be introduced after a certain amount of time or periodically to remove volatiles. Even if the pyrolysis reaction is operated continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, with suitable valves and controls.

[0558] The volatiles-containing sweep gas can exit one or more reactor zones or can be combined if obtained from multiple zones. The resulting gas stream containing various vapors can then be fed to a thermal oxidizer for controlled air emissions. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are fed to the thermal oxidizer to reach a temperature sufficient to substantially destroy the volatiles contained therein.

[0559] The effluent of the thermal oxidizer is a hot gas stream containing water, carbon dioxide, and nitrogen. This effluent stream can be purged directly to an air exhaust if desired. In some embodiments, the energy content of the thermal oxidizer effluent is recovered, such as in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (such as a sweep gas). The energy content can be utilized by directly or indirectly heating or assisting in heating units elsewhere in the process, such as a dryer or reactor. In some embodiments, essentially all of the thermal oxidizer effluent is used to indirectly heat (utility side) the dryer. The thermal oxidizer can use fuels other than natural gas.

[0560] The yield of carbonaceous materials may vary depending on the factors mentioned above, including the type of feedstock and process conditions. In some embodiments, the net yield of solids as a percentage of the starting material on a dry basis is at least 25%, 30%, 35%, 40%, 45%, 50%, or higher. The remainder is split between condensable vapors, such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases, such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on the process conditions, including the water present.

[0561] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or higher. For example, in some embodiments, the carbonaceous material comprises from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon forms methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0562] In alternative embodiments, these compounds are combined with carbon-rich solids to enrich the carbon and energy content of the product. In these embodiments, some or all of the gas stream resulting from the reactor, containing various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids originating from a cooling zone and / or a separate cooling unit. These embodiments are described in more detail below.

[0563] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids may be introduced into a separate cooling unit. In some embodiments, the solids are collected and simply cooled at a slow rate. If the carbonaceous solids are reactive or unstable in air, it may be desirable to maintain an inert atmosphere and / or to rapidly cool the solids, e.g., to a temperature below 40° C., such as ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. "Cooling unit" should be interpreted broadly to include vessels, tanks, pipes, or portions thereof.

[0564] In some embodiments, the process further includes operating a cooling unit to cool the warm pyrolyzed solids with steam, thereby producing low temperature pyrolyzed solids and superheated steam, and drying is performed at least in part with the superheated steam obtained from the external cooler. In some embodiments, the cooling unit can be operated to first cool the warm pyrolyzed solids with steam to reach a first cooling unit temperature, and then with air to reach a second cooling unit temperature, the second cooling unit temperature being lower than the first cooling unit temperature and associated with a reduced risk of combustion of the warm pyrolyzed solids in the presence of air.

[0565] Following cooling to ambient conditions, the carbonaceous solids may be collected and stored, conveyed to another on-site operation, transported to another site, or otherwise disposed of, traded, or sold. The solids may be fed to a unit to reduce particle size. A variety of size reduction units are known in the art, including crushers, shredders, grinders, pulverizers, jet mills, pin mills, and ball mills.

[0566] Some other means for screening or separation based on particle size may be included. Grinding, if present, may be upstream or downstream of grinding. Screened material (e.g., large chunks) may be returned to the grinding unit. Small and large particles may be recovered for separate downstream uses. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as a finely divided carbon or activated carbon product.

[0567] Various additives can be introduced throughout the process before, during, or after any of the steps disclosed herein. Additives can be broadly categorized as process additives selected to improve process performance, such as carbon yield or pyrolysis time / temperature to achieve a desired carbon purity, and as process additives selected to improve one or more properties of the bioreagent or of downstream products incorporating the reagent. Certain additives can provide enhanced process and product (bioreagent or products containing bioreagent) properties.

[0568] The additives can be added before, during, or after any one or more steps of the process, including adding to the feedstock itself at any time before or after the feedstock is harvested. The additive treatment can be incorporated before, during, or after sizing, drying, or other preparation of the feedstock. The additives can be incorporated into or on the feedstock supply facility, transport truck, landing equipment, storage bin, conveyor (including open or closed conveyor), dryer, process heater, or any other unit. The additives can be added anywhere in the pyrolysis process itself, using a suitable means for introducing the additives. If desired, the additives can be added after carbonization, or even after pulverization.

[0569] In some embodiments, the additive is selected from a metal, a metal oxide, a metal hydroxide, or a combination thereof. For example, the additive can be selected from, but is in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or a combination thereof.

[0570] In some embodiments, the additive is selected from an acid, a base, or a salt thereof. For example, the additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof.

[0571] In some embodiments, the additive is selected from metal halides. Metal halides are compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are generally obtained by direct combination of basic metal salts with hydrohalic acids, or more commonly by neutralization. In some embodiments, the additive is selected from iron chloride (FeCl2 and / or FeCl3), iron bromide (FeBr2 and / or FeBr3), or hydrates thereof, and any combination thereof.

[0572] The additives can result in a final product with a higher energy content (energy density). The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content can result from the removal of non-combustible materials or materials with a lower energy density than carbon. In some embodiments, the additives reduce the extent of liquid formation in favor of the formation of solids and gases, or in favor of the formation of solids.

[0573] Without being limited to any particular hypothesis, the additives can chemically modify the starting biomass, or the treated biomass prior to pyrolysis, to reduce cell wall fracture for greater strength / integrity. In some embodiments, the additives can increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0574] The additives may result in the bioreagent having improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. The additives may improve mechanical properties by simply being present (e.g., the additive itself imparts strength to the mixture) or by some transformation that occurs within the additive phase or the resulting mixture. For example, a reaction such as vitrification may occur within the bioreagent containing the additive, thereby improving the final strength.

[0575] Chemical additives can be applied to wet or dry biomass feedstock. The additives can be applied as a solid powder, spray, mist, liquid, or vapor. In some embodiments, the additives can be introduced by spraying of a liquid solution (such as in an aqueous solution or solvent) or by immersion in a tank, bin, bag, or other container.

[0576] In certain embodiments, an immersion pretreatment is used in which the solid feedstock is immersed, either batchwise or continuously, in a bath containing the additive for a time sufficient to impregnate the additive into the solid feed material.

[0577] In some embodiments, the additives applied to the feedstock can reduce the energy requirements for pyrolysis and / or increase the yield of the carbonaceous product. In these or other embodiments, the additives applied to the feedstock can provide desirable functionality for the intended use of the carbonaceous product.

[0578] Throughput or process capacity can vary widely from small laboratory scale units to full operations including any pilot, demonstration, or semi-commercial scale. In various embodiments, the process capacity (of feedstock, product, or both) is at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day, or more.

[0579] In some embodiments, the solids produced can be recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the reactor. By returning to the front end and passing through the process again, the treated solids can be higher in fixed carbon. The solids, liquids, and gas streams produced or present in the process can be independently recycled, passed to a subsequent step, or removed / purged from the process at any point.

[0580] In some embodiments, the pyrolyzed material is recovered and then fed to a separate unit for further pyrolysis to create a product with higher carbon purity (e.g., conversion of low fixed carbon material to high fixed carbon material). In some embodiments, the secondary process can be carried out in a simple container, such as a steel drum, through which a heated inert gas (such as heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas containing the volatiles can be sent, for example, to a thermal oxidizer or returned to the main process reactor. To cool the final product, another flow of inert gas, initially at, for example, ambient temperature, can be passed through the solids to cool them and then returned to the inert gas preheat system.

[0581] Some variations include: (a) a feed apparatus configured to introduce a carbonaceous feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solid-state cooler disposed in operative communication with the multi-zone reactor; and (e) a biological reagent production system comprising a biological reagent recovery unit disposed in operative communication with the solid-state cooler.

[0582] Some variations include: (a) a feed apparatus configured to introduce a carbonaceous feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; (c) an optional preheater disposed in operative communication with the dryer and configured to heat and / or gently pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operative communication with the preheater and configured to pyrolyze the feedstock; (e) a cooler disposed in operative communication with the pyrolysis reactor and configured to cool the pyrolysis solids; (f) a biological reagent retrieval unit disposed in operative communication with the cooler, A bioreagent production system is utilized, the system being configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0583] The feed system can be physically integrated with the multi-zone reactor, such as through the use of a screw feeder or auger mechanism to introduce the feed solids into the first reaction zone.

[0584] In some embodiments, the system further comprises a preheat zone disposed in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheat zone (if present) may be located in a single unit or may be located in separate units.

[0585] In some embodiments, the dryer may be configured as a drying zone within a multi-zone reactor. In some embodiments, a solids cooler may be located within the multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0586] The system may include a purging means for removing oxygen from the system. For example, the purging means may include one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the system. In some embodiments, the purging means is a degasser disposed in operative communication between the dryer and the multi-zone reactor.

[0587] In some embodiments, the multi-zone reactor is configured with at least a first gas inlet and a first gas outlet, which can be disposed in communication with different zones or the same zone.

[0588] In some embodiments, the multi-zone reactor is configured with a second gas inlet and / or a second gas outlet. In some embodiments, the multi-zone reactor is configured with a third gas inlet and / or a third gas outlet. In some embodiments, the multi-zone reactor is configured with a fourth gas inlet and / or a fourth gas outlet. In some embodiments, each zone present in the multi-zone reactor is configured with a gas inlet and a gas outlet.

[0589] The gas inlets and outlets not only allow for the introduction and removal of vapors, but the gas outlets (probes) in particular allow for accurate process monitoring and control over various stages of the process, up to and potentially including all stages of the process. Accurate process monitoring is expected to result in improved yields and efficiency, both dynamically and over time, when operating history can be utilized to adjust process conditions.

[0590] In certain embodiments, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful for extracting and analyzing gases to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as by adjusting the feed rate, the rate of inert gas sweep, the temperature (in one or more zones), the pressure (in one or more zones), additives, etc.

[0591] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more samplings via the reactive gas probe, and in some embodiments, making process or equipment adjustments based on the measurements, if deemed necessary or desirable, using well-known principles of process control (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0592] The reaction gas probe can be configured to extract a gas sample in many ways. For example, the sampling line may contain a pressure lower than the pyrolysis reactor pressure, so that when the sampling line is opened, a quantity of gas can be easily extracted from the pyrolysis zone. The sampling line may be under vacuum, such as when the pyrolysis zone is at near atmospheric pressure. Typically, the reaction gas probe is associated with one gas output or a portion thereof (e.g., a line branched off from the gas output line).

[0593] In some embodiments, both the gas input and gas output are utilized as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with a process sample ("sample sweep"). Such configurations can be used in zones that do not include a gas inlet / outlet for a substantially inert gas for processing, or the reactive gas probe can be associated with a separate gas inlet / outlet in addition to the process inlet and outlet. The sampling inert gas that is periodically introduced and withdrawn for sampling (in embodiments utilizing a sample sweep) may be different from the process inert gas, if desired, either for reasons of analytical accuracy or to introduce an analytical tracer.

[0594] For example, the acetic acid concentration in the gas phase of the pyrolysis zone can be measured using a gas probe to extract a sample, which is then analyzed using a suitable technique (gas chromatography, GC; mass spectrometry, MS; GC-MS, or Fourier transform infrared spectroscopy, FTIR, etc.). The CO and / or CO2 concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity to gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity to liquid.

[0595] In some embodiments, the system further comprises at least one additional gas probe disposed in operative communication with the cooling zone, or the drying zone (if present) or the pre-heating zone (if present).

[0596] A gas probe for the cooling zone may be useful, for example, to determine the extent of any additional chemical reactions occurring in the cooling zone. A gas probe in the cooling zone may also be useful as an independent measurement of temperature (e.g., in addition to a thermocouple located in the cooling zone). This independent measurement may be a correlation between cooling temperature and a measured amount of a particular species. The correlation may be developed separately or may be established after a period of process operation.

[0597] A gas probe for the drying zone can be useful to determine the degree of drying, for example by measuring the moisture content. A gas probe in the preheat zone can be useful, for example, to determine the extent of any mild pyrolysis that occurs.

[0598] In certain embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase to the solid phase. Alternatively or additionally, the preheating zone (if present) can be configured with a gas outlet to generate a substantially countercurrent flow of the gas phase to the solid phase. Alternatively or additionally, the drying zone can be configured with a gas outlet to generate a substantially countercurrent flow.

[0599] The pyrolysis reactor or reactors can be selected from any suitable reactor configuration capable of carrying out a pyrolysis process. Exemplary reactor configurations include, but are not limited to, a fixed bed reactor, a fluidized bed reactor, an entrained bed reactor, an ablation reactor, a rotating cone, a rotating drum kiln, a calciner, a roaster, a moving bed reactor, a transport bed reactor, an ablation reactor, a rotating cone, or a microwave-assisted pyrolysis reactor.

[0600] In some embodiments where an auger is used, sand or another heat carrier can be used. For example, the feedstock and sand can be fed at one end of the screw. The screw mixes the sand and feedstock and conveys them through the reactor. The screw can provide good control of feedstock residence time and does not dilute the pyrolysis products with carrier or fluidizing gas. The sand can be reheated in a separate vessel.

[0601] In some embodiments where an ablation process is used, the feedstock is moved at high velocity relative to the hot metal surface. Ablation of any char formed on the surface can maintain a high heat transfer rate. Such an arrangement can prevent dilution of the product. Alternatively, the feedstock particles can be suspended in a carrier gas and introduced at high velocity through a cyclone with heated walls.

[0602] In some embodiments where a fluidized bed reactor is used, the feedstock may be introduced into a bed of hot sand fluidized by a gas, typically a recycled product gas. References herein to "sand" are intended to include similar substantially inert materials such as glass particles, recovered ash particles, and the like. The high rate of heat transfer from the fluidized sand may result in rapid heating of the feedstock. There may be some ablation due to friction with the sand particles. Heat is typically provided by heat exchanger tubes through which the hot combustion gases flow.

[0603] A circulating fluidized bed reactor can be used where gas, sand, and feedstock move together. Exemplary transport gases include recycled product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the feedstock, and ablation is expected to be stronger than in a conventional fluidized bed. A separator can be used to separate the product gas from the sand and char particles. The sand particles can be reheated in a fluidized burner vessel and recycled to the reactor.

[0604] In some embodiments, the multi-zone reactor is a continuous reactor comprising a feed inlet, a plurality of spatially separated reaction zones configured to separately control temperature and mixing within each of the reaction zones, and a carbonaceous solids outlet, one of the reaction zones configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the reaction zones configured with a first gas outlet.

[0605] In various embodiments, the reactor comprises at least two, three, four, or more reaction zones, each of which is disposed in communication with a separately adjustable heating means independently selected from the group including electrical heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat transfer, or combinations thereof. In some embodiments, at least one reactor zone is heated with an effluent stream from a thermal oxidizer, if present.

[0606] The reactor can be configured to separately adjust the gas phase composition and gas phase residence time of at least two reaction zones up to and including all reaction zones present in the reactor.

[0607] The reactor can be equipped with a second gas inlet and / or a second gas outlet. In some embodiments, the reactor is configured with a gas inlet for each reaction zone. In these or other embodiments, the reactor is configured with a gas outlet for each reaction zone. The reactor can be a co-current or counter-current reactor.

[0608] In some embodiments, the feedstock inlet comprises a screw or auger feed mechanism. In some embodiments, the carbonaceous solids outlet comprises a screw or auger output mechanism.

[0609] Certain embodiments utilize a rotary calciner with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotational speed affects the solids flow patterns, as well as heat and mass transfer. Each of the reaction zones can be configured with flights disposed on the interior walls to provide agitation of the solids. The flights can be separately adjustable in each of the reaction zones.

[0610] Other means of agitating the solids can be used, such as an auger, screw, or paddle conveyor. In some embodiments, the reactor includes a single continuous auger positioned throughout each of the reaction zones. In other embodiments, the reactor includes twin screws positioned throughout each of the reaction zones.

[0611] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., to process the biomass feedstock without destroying or significantly damaging its structure, hi some embodiments, the pyrolysis zone does not include augers, screws, or rakes, which would tend to significantly reduce the size of the feedstock being pyrolyzed.

[0612] In some embodiments, the system further includes a thermal oxidizer disposed in operative communication with the outlet through which the condensable vapors and non-condensable gases are removed. In some embodiments, the thermal oxidizer is configured to receive a separate fuel (such as natural gas) and oxidant (such as air) into a combustion chamber adapted to combust the fuel and at least the condensable vapors. Certain non-condensable gases, such as CO or CH4, can also be oxidized to CO2.

[0613] When a thermal oxidizer is used, the system may include a heat exchanger disposed between the thermal oxidizer and the dryer configured to utilize heat of combustion for the dryer. This embodiment may contribute significantly to the overall energy efficiency of the process.

[0614] In some embodiments, the system further comprises a carbon enrichment unit disposed in operative communication with the solids cooler and configured to combine the condensable vapors in at least partially condensed form with the solids. The carbon enrichment unit may increase the carbon content of the biological reagent obtained from the recovery unit.

[0615] The system may further comprise a separate pyrolysis unit adapted to further pyrolyze the bio-reagent to further increase its carbon content. The separate pyrolysis unit may be a simple container, unit or device such as a tank, barrel, bin, drum, tote, sack, or roll-off.

[0616] The entire system may be at a fixed location or may be distributed over several locations. The system may be built using modules that can be easily replicated for practical scale-up. The system may also be built using economy of scale principles, as is well known in the process industries.

[0617] Several variations on solid carbon enrichment will now be further described. In some embodiments, the process for producing a bio-reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes and at a pyrolysis temperature selected from at least about 250° C. to at most about 700° C. to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (c) separating at least the condensable vapors and at least the non-condensable gases from the high temperature pyrolysis solids; and (d) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (e) thereafter, passing at least the condensable vapors and / or at least the non-condensable gases from step (e) through the warm pyrolysis solids and / or the cold pyrolysis solids to form an enhanced pyrolysis solid having an increased carbon content; (f) recovering the biological reagent comprising at least the enhanced pyrolysis solid. The process is (g) drying the raw material to remove at least the water contained therein; (h) degassing the feedstock to remove at least interstitial oxygen, if present, contained therein; and / or (i) cooling the warm pyrolysis solids to produce cooler pyrolysis solids.

[0618] In some embodiments, step (h) comprises passing at least the condensable vapor from step (e) in vapor and / or condensed form through the warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content. In some embodiments, step (h) comprises passing at least the non-condensable gas from step (e) through the warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content.

[0619] Alternatively or additionally, the steam or gas may be contacted with the low temperature pyrolytic solids. In some embodiments, step (h) comprises passing at least the condensable steam from step (e) in steam and / or condensed form through the low temperature pyrolytic solids to produce enhanced pyrolytic solids having increased carbon content. In some embodiments, step (h) comprises passing at least the non-condensable gas from step (e) through the low temperature pyrolytic solids to produce enhanced pyrolytic solids having increased carbon content.

[0620] In certain embodiments, step (h) comprises passing substantially all of the condensable vapors from step (e) in vapor and / or condensed form through a low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content. In certain embodiments, step (h) comprises passing substantially all of the non-condensable gases from step (e) through a low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0621] The process may include various methods of treating or separating the steam or gas prior to using the steam or gas for carbon enrichment. For example, the intermediate feed stream comprising at least condensable steam and at least non-condensable gas obtained from step (e) may be fed to a separation unit configured to produce at least a first and a second output stream. In certain embodiments, the intermediate feed stream comprises all of the condensable steam, all of the non-condensable gas, or both.

[0622] Separation techniques may include or use distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separation may be primarily based on, for example, distillation, absorption, adsorption, or diffusion and may exploit differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to a stationary phase, and any combination thereof.

[0623] In some embodiments, the first and second output streams are separated from the intermediate feed stream based on relative volatility. For example, the separation unit can be a distillation column, a flash tank, or a condenser.

[0624] Thus, in some embodiments, the first output stream includes condensable vapors and the second output stream includes non-condensable gases. The condensable vapors may include at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapors from pyrolysis may include aromatic compounds such as benzene, toluene, ethylbenzene, and xylenes. Heavier aromatic compounds such as refractory tars may be present in the vapors. The non-condensable gases may include at least one carbon-containing molecule selected from the group including carbon monoxide, carbon dioxide, and methane.

[0625] In some embodiments, the first and second output streams are intermediate feed streams that have been separated based on their relative polarity. For example, the separation unit can be a stripping column, a packed bed, a chromatography column, or a membrane.

[0626] Thus, in some embodiments, the first output stream comprises polar compounds and the second output stream comprises non-polar compounds. The polar compounds may comprise at least one carbon-containing molecule selected from the group comprising methanol, furfural, and acetic acid. The non-polar compounds may comprise at least one carbon-containing molecule selected from the group comprising carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives.

[0627] Step (h) may increase the total carbon content of the bioreagent relative to an otherwise identical process without step (h). The degree of increase in carbon content may be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more in various embodiments.

[0628] In some embodiments, step (h) increases the fixed carbon content of the bioreagent. In these or other embodiments, step (h) increases the volatile carbon content of the bioreagent. Volatile carbon content is carbon that is attributable to volatile materials in the reagent. Volatile materials can be, but are not limited to, aliphatic or aromatic compounds (e.g., terpenes); oxygenates, including alcohols, aldehydes, or ketones; and hydrocarbons, including various tars. Volatile carbon typically remains bound or adsorbed to solids at ambient conditions, but is released upon heating before the fixed carbon is oxidized, gasified, or otherwise released as vapor.

[0629] Depending on the conditions associated with step (h), it is possible for some amount of volatile carbon to become fixed carbon (e.g., via Boudouard carbon formation from CO). Typically, volatiles enter the micropores of the fixed carbon and remain volatile, although they exist as condensed / adsorbed species. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0630] Step (h) can increase the energy content (i.e., energy density) of the biological reagent. The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. The degree of increase in energy content can be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher in various embodiments.

[0631] Further separation can be used to recover one or more non-condensable gases or condensable vapors for use within the process or further processing, for example, further processing can be included to produce purified carbon monoxide and / or hydrogen.

[0632] As another example, separation of acetic acid can be performed followed by reduction of the acetic acid to ethanol, which can be accomplished, at least in part, using hydrogen derived from the produced non-condensable gases.

[0633] Condensable vapors can be used either for energy in the process (such as by thermal oxidation) or carbon enrichment to increase the carbon content of the bioreagent. Certain non-condensable gases, such as CO or CH4, can be utilized for energy in the process or as part of the substantially inert gas for the pyrolysis step. Any combination of the foregoing is also possible.

[0634] A potential advantage of including step (h) is that the gas stream is scrubbed and the resulting gas stream is enriched for CO and CO2. The resulting gas stream can be utilized for energy recovery, recycled for carbon enrichment of solids, and / or used as an inert gas in the reactor. Similarly, by separating non-condensable gases from condensable vapors, the CO / CO2 stream is prepared for use as an inert gas in, for example, a reactor system or a cooling system.

[0635] Other variations are premised on the recognition that the principles of the carbon enrichment step can be applied to any feedstock to which it is desired to add carbon.

[0636] In some embodiments, a batch or continuous process for producing a bioreagent comprises: (a) providing a solids stream comprising a carbon-containing material; (b) providing a gas stream comprising a condensable carbonaceous vapor, a non-condensable carbonaceous gas, or a mixture of a condensable carbonaceous vapor and a non-condensable carbonaceous gas; (c) passing the gas stream through the solids stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0637] In some embodiments, the starting carbonaceous material is a pyrolyzed or torrefied biomass. The gas stream can be obtained during an integrated process to provide the carbonaceous material. Or the gas stream can be obtained from a separate processing of the carbonaceous material. The gas stream can be obtained from an external source (e.g., a sawmill oven). Mixtures of gas streams from various sources are possible, as well as mixtures of carbonaceous materials.

[0638] In some embodiments, the process further comprises repeating the process to recycle or reuse the gas stream to further increase the carbon and / or energy content of the carbon-containing product. In some embodiments, the process further comprises performing the process to recycle or reuse the gas stream to increase the carbon and / or energy content of another feedstock different from the carbon-containing material.

[0639] In some embodiments, the process further includes introducing the gas stream into a separation unit configured to produce at least first and second output streams, the gas stream comprising a mixture of condensable carbonaceous vapors and non-condensable carbonaceous gases. The first and second output streams can be separated based on relative volatility, relative polarity, or any other characteristic. The gas streams can be obtained from separate processing of carbonaceous materials.

[0640] In some embodiments, the process further comprises repeating the process to recycle or reuse the gas stream to further increase the carbon content of the carbon-containing product. In some embodiments, the process further comprises performing the process to recycle or reuse the gas stream to increase the carbon content of another feedstock.

[0641] The carbon-containing product may include increased total carbon content, higher fixed carbon content, higher volatile carbon content, higher energy content, or a combination thereof, relative to the starting carbon-containing material.

[0642] In a related variation, the bioreagent production system comprises: (a) a feed apparatus configured to introduce a carbonaceous feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solid-state cooler disposed in operative communication with the multi-zone reactor; and (e) a material enrichment unit disposed in operative communication with the solids cooler and configured to pass condensable vapors and / or non-condensable gases through the solids to form an enhanced solid having an increased carbon content; (f) a biological reagent recovery unit disposed in operative communication with the material concentrating unit.

[0643] The system may further include a preheat zone disposed in operative communication with the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within the multi-zone reactor. Each of the zones may be located within a single unit or in separate units. A solids cooler may also be disposed within the multi-zone reactor.

[0644] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase to the solid phase. In these or other embodiments, the preheating zone and / or drying zone (or dryer) are configured with a gas outlet to generate a substantially countercurrent flow of the gas phase to the solid phase.

[0645] In certain embodiments, the system incorporates an ingredient enrichment unit, the ingredient enrichment unit comprising: (i) a housing having an upper portion and a lower portion; (ii) an inlet at a bottom of the lower portion of the housing configured to carry condensable vapors and non-condensable gases; (iii) an outlet at the top of the upper portion of the housing configured to carry a concentrated gas stream derived from the condensable vapors and non-condensable gases; (iv) a passageway defined between the upper and lower portions of the housing; and (v) a transport system following the pathway, the transport system configured to transport the solid, the housing being shaped such that the solid adsorbs condensable vapors and / or non-condensable gases.

[0646] The present technology can produce a variety of compositions useful as bioreagents, and products incorporating such reagents. In some variations, the bioreagents can be prepared using any of the processes disclosed herein, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes and at a pyrolysis temperature selected from at least about 250° C. up to about 700° C. to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (c) separating at least the condensable vapors and at least the non-condensable gases from the high temperature pyrolysis solids; (d) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (e) cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; and (f) recovering the biological reagent comprising at least the low temperature pyrolysis solid. In some embodiments, the process comprises: (g) drying the raw material to remove at least the moisture contained in the raw material; and / or (h) degassing the feedstock to remove at least interstitial oxygen, if present, contained in the feedstock.

[0647] In some embodiments, the reagent comprises about at least 70%, at least 80%, at least 90%, or at least 95% total carbon by weight on a dry basis. Total carbon includes at least fixed carbon and may further include carbon from volatile matter. In some embodiments, carbon from volatile matter is about at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the bioreagent. For example, fixed carbon can be measured using ASTM D3172 and volatile carbon can be measured using ASTM D3175.

[0648] The biological reagent may include about 10% or less by weight, e.g., about 5% or less by weight, hydrogen on a dry basis. The biological reagent may include about 1% or less by weight, e.g., about 0.5% or less by weight, nitrogen on a dry basis. The biological reagent may include about 0.5% or less by weight, e.g., about 0.2% or less by weight, phosphorus on a dry basis. The biological reagent may include about 0.2% or less by weight, e.g., about 0.1% or less by weight, sulfur on a dry basis.

[0649] 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.

[0650] Certain embodiments provide reagents that contain little or essentially no hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture present. Thus, some embodiments provide bioreagents having up to and including 100% carbon on a dry / ash-free (DAF) basis.

[0651] Generally speaking, feedstocks such as biomass contain non-volatile species, including silica and various metals, that are not readily released during pyrolysis. Of course, ashless feedstocks can also be utilized, in which case there should not be a substantial amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0652] Varying amounts of non-combustible materials, such as ash, may be present. The bioreagent may include about 10% or less by weight of non-combustible materials on a dry basis, e.g., about 5%, about 2%, about 1% or less by weight. In certain embodiments, the reagent includes little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon that includes 100% carbon on a dry basis.

[0653] Various amounts of moisture may be present. On a total mass basis, the bioreagent may contain at least 1%, 2%, 5%, 10%, 15%, 25%, 35%, 50% or more moisture by weight. As intended herein, "moisture" should be interpreted to include any form of water present in the bioreagent, including absorbed moisture, adsorbed water molecules, chemical hydrates, and physical hydrates. The equilibrium moisture content may vary depending at least on the local environment, such as relative humidity. Moisture may also vary during transportation, preparation for use, and other logistics. Moisture may be measured, for example, using ASTM D3173.

[0654] The bioreagent may include a variety of energy contents, which for the present purposes means an energy density based on the higher calorific value associated with the total combustion of the bone dry reagent. For example, the bioreagent may have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In certain embodiments, the energy content is about 14,000-15,000 Btu / lb. The energy content may be measured, for example, using ASTM D5865.

[0655] The biological reagents can be formed into a powder, such as a coarse or fine powder. For example, the reagents can, in embodiments, be formed into a powder having an average mesh size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0656] In some embodiments, the bio-reagents are formed into structural objects comprising compressed, bound, or aggregated particles. The starting material for forming these objects can be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The objects can be formed by mechanical pressing or other forces. In some embodiments, the objects can be formed by mechanical pressing or other forces, using binders or other means to aggregate the particles together.

[0657] In some embodiments, the bio-reagent is manufactured in the form of a structural object whose structure is substantially derived from the source material. For example, a source tip may produce a product tip of the bio-reagent. Or, a source cylinder may produce a bio-reagent cylinder, which may be somewhat smaller but otherwise maintain the basic structure and geometry of the starting material.

[0658] The bioreagent may be produced or formed into an object that includes a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or more. In various embodiments, the minimum or maximum dimension may be a length, width, or diameter.

[0659] Other variations relate to the incorporation of additives into the process, into the product, or both. In some embodiments, the biological reagent includes at least one process additive that is incorporated during the process. In these or other embodiments, the reagent includes at least one product additive that is introduced into the reagent after the process.

[0660] In some embodiments, the biological reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

[0661] The additives may be selected from, but are in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0662] In some embodiments, the biological reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from an acid, a base, or a salt thereof.

[0663] The additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0664] In certain embodiments, the biological reagents are, on a dry basis, 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight or less of phosphorus; 0.2% by weight or less of sulfur; a first additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; a second additive selected from an acid, a base, or a salt thereof; The first additive is different from the second additive.

[0665] The first additive may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or a combination thereof, and the second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof.

[0666] In certain embodiments, the bio-reagent, on a dry basis, consists essentially of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible materials, and additives selected from the group including magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0667] In certain ...

Claims

1. 1. A process for producing a biocarbon composition, said process comprising: pyrolyzing a feedstock in a first pyrolysis reactor, the feedstock comprising biomass, thereby producing first pyrolysis solids and first pyrolysis vapors; introducing the first pyrolysis vapor into a condensation system, thereby producing a condenser liquid and a condenser vapor; thermally treating the condenser liquid in a second reactor, thereby producing a solid or semi-solid material; blending the first pyrolysis solid with the solid or semi-solid material, thereby producing a bio-reagent; recovering the bio-reagent as a bio-carbon composition.

2. The feedstock may be selected from the group consisting of softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, 10. The process of claim 1, wherein the waste material is selected from 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 and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

3. 10. The process of claim 1, further comprising drying or heat treating the bioreagent.

4. The process of claim 1 further comprising pelleting the bioreagent.

5. 10. The process of claim 1, further comprising drying or heat treating the bioreagent and further comprising pelleting the bioreagent, wherein the pelleting and the drying or heat treating are integrated.

6. The blending and the pelletizing are integrated; or further comprising introducing a binder into the bioreagent, wherein the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, 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 combinations of the foregoing; or 5. The process of claim 4, wherein no external binders are introduced into the bioreagent during pelleting.

7. the condensation system includes multiple condenser stages; and the condenser liquid is the condensation product of a first stage of the plurality of condenser stages; or 2. The process of claim 1, wherein the condenser liquid is a condensation product of multiple stages of the multiple condenser stages, the multiple stages not including the final stage of the multiple condenser stages.

8. 10. The process of claim 1, wherein the second reactor is a second pyrolysis reactor, the second pyrolysis reactor producing the solid or semi-solid material and a pyrolysis exhaust gas.

9. 10. The process of claim 1, wherein the second reactor is a non-pyrolytic thermal reactor or a non-pyrolytic catalytic reactor.

10. further comprising conveying the pyrolysis exhaust gas to the condensation system; or the first pyrolysis reactor is separate from the second pyrolysis reactor; or 9. The process of claim 8, wherein the first pyrolysis reactor and the second pyrolysis reactor are the same unit, and the pyrolysis of the feedstock and the thermal treatment of the condenser liquid occur at different times.

11. 10. The process of claim 1, wherein at least 25% by weight of the total carbon contained in the condenser liquid is converted to fixed carbon in the solid or semi-solid material.

12. 2. The process of claim 1, wherein the solid or semi-solid material forms at least 5% by weight of the bioreagent on an absolute basis.

13. 10. The process of claim 1, wherein at least about 10% and up to about 80% by weight of the fixed carbon in the bioreagent is derived from the condenser liquid.

14. heat treating all of the condenser liquid in the second reactor; or 10. The process of claim 1, wherein less than all of the condenser liquid is heat treated in the second reactor.

15. 10. The process of claim 1, wherein the condenser liquid is thermally treated in the second reactor without any intermediate chemical treatment between the condensation system and the second reactor.

16. 10. The process of claim 1, wherein the condenser liquid is subjected to a purification step and / or a reaction step before thermal treatment in the second reactor.

17. 10. The process of claim 1, wherein said pyrolyzing said feedstock is conducted at a first pyrolysis temperature of at least about 250°C and up to about 1250°C.

18. 10. The process of claim 1, wherein the second reactor is a second pyrolysis reactor operated at a second pyrolysis temperature, the second pyrolysis temperature being at least about 250°C and up to about 1250°C.

19. and / or further comprising oxidizing the condenser vapor, thereby producing heat; and / or 10. The process of claim 1 further comprising oxidizing the reactor exhaust gas, thereby producing heat.

20. 10. The process of claim 1, further comprising grinding the bioreagent using a mechanical processing device, wherein the mechanical processing device is selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

21. 5. The process of claim 4, wherein said pelletizing said bioreagent utilizes a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquette, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

22. the biocarbon composition comprises at least 50% by weight of fixed carbon; and / or 10. The process of claim 1, wherein the biocarbon composition comprises less than 10% by weight of ash.

23. 10. The process of claim 1, wherein the condenser liquid contains less than 1% by weight of ash.

24. The total carbon in the biocarbon composition is １４ C / １２ 10. The process of claim 1, wherein the process is at least 50% renewable as determined from C isotope ratio measurements.

25. The biocarbon composition has a dry weight of at least about 5 lb / ft. ３ and / or the biocarbon composition is characterized by a water uptake of up to 20% by weight at 25°C after immersion in water for 24 hours; and / or 10. The process of claim 1, wherein the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test according to Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N. 4: "Test method for self-heating substances."

26. the biocarbon composition is in the form of pellets; and The pellets have a mass of at least about 10 lb / ft on a dry basis. ３ characterized by a bulk density of the pellets are characterized by a Hardgrove Friability Index of at least 30; or The pellets are at least about 100 lbs. ｆ / in ２ 2. The process of claim 1, characterized by a pellet compressive strength at 25°C of

27. 1. A system for producing a biocarbon composition, the system comprising: a first pyrolysis reactor configured to pyrolyze a feedstock comprising biomass to produce first pyrolysis solids and first pyrolysis vapors; a condensation system in fluid communication with the first pyrolysis reactor, the condensation system configured to condense the first pyrolysis vapor to produce a condenser liquid and a condenser vapor; a second reactor in fluid communication with the condensation system, the second reactor configured to thermally process the condenser liquid to produce a solid or semi-solid material; a mixing unit in fluid communication with the first pyrolysis reactor and the second reactor, the mixing unit configured to blend the first pyrolysis solid with the solid or semi-solid material to produce a bio-reagent; a system output in fluid communication with the mixing unit, the system output configured to recover the bio-reagent as a bio-carbon composition.

28. 28. The system of claim 27, wherein the mixing unit is a pelletizing unit.

29. 28. The system of claim 27, wherein the system includes a pelletizing unit separate from the mixing unit, the pelletizing unit being disposed between the mixing unit and the system output.

30. 30. The system of claim 27, wherein the condensation system comprises multiple condenser stages.

31. 28. The system of claim 27, wherein the second reactor is a second pyrolysis reactor.

32. 32. The system of claim 31, further comprising a recycle line configured to recycle pyrolysis exhaust gas to the condensation system.

33. 28. The system of claim 27, wherein the second reactor is a non-pyrolytic thermal reactor or a non-pyrolytic catalytic reactor.

34. further comprising a mechanical processing device configured to pulverize the bioreagent, the mechanical processing device being selected from a hammer mill, an extruder, an attrition mill, a disk mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof; and / or 28. The system of claim 27, further comprising a pelletizing device configured to pelletize the bioreagent, wherein the pelletizing device is selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquette, a wet agglomeration mill, a dry agglomeration mill, or a combination thereof.

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