Biocarbon compositions with optimized fixed carbon and processes for producing same

Abstract

In some variations, the invention provides a bio-carbon composition comprising a low fixed carbon material having a fixed carbon concentration of 20% to 55% by weight, a high fixed carbon material having a fixed carbon concentration of 50% to 100% by weight (higher than the fixed carbon concentration of the low fixed carbon material), 0 to 30% by weight moisture, 0 to 15% by weight ash, and 0 to 20% by weight of one or more additives (such as binders). Some variations provide a process for producing a bio-carbon composition comprising pyrolyzing a first biomass-containing feedstock to produce a low fixed carbon material, separately pyrolyzing a second biomass-containing feedstock to produce a high fixed carbon material, blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material, optionally blending one or more additives into the intermediate material, optionally drying the intermediate material, and recovering a bio-carbon composition containing the intermediate material or a thermally treated form thereof.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 180,240, filed April 27, 2021, which is incorporated by reference in its entirety.

[0002] The present invention relates generally to biocarbon compositions optimized for various chemical and physical properties, and processes for making and using such 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 to reduce metal oxides to metals during processing, as a fuel to provide heat for processing, and as a component of metal alloys.

[0004] Carbonaceous materials generally include fossil resources such as natural gas, petroleum, coal, and lignite. There is growing interest in the increased use of lignocellulosic biomass and various carbon-rich waste materials.

[0005] Various techniques exist for converting feedstocks into carbon materials for industrial use. Pyrolysis is a process for the 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 the 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. Higher temperatures and longer residence times increase the feedstock conversion to syngas, while moderate temperatures and short steam residence times are generally optimal for producing liquids. Historically, the slow pyrolysis of wood has been carried out in large piles, in simple batch processes, and without emissions controls. Traditional charcoal production techniques are not only energy inefficient, but also highly polluting.

[0006] Improved or optimized biocarbon compositions and processes for making biocarbon compositions that can improve or optimize stability, reactivity (e.g., thermal reactivity and self-heating), hydrophobicity, energy content, overall yield, and final composition including fixed carbon, ash, and moisture are desired. Summary of the Invention

[0007] Disclosed herein is a biocarbon composition. The biocarbon composition of the present disclosure may comprise a low fixed carbon material of at least about 1% to at most about 99% by weight, the low fixed carbon material comprising a first fixed carbon concentration of at least about 20% to at most about 55% by weight of fixed carbon on an absolute basis, a high fixed carbon material of at least about 1% to at most about 99% by weight, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% by weight of fixed carbon on an absolute basis, the second fixed carbon concentration being greater than the first fixed carbon concentration, at least about 0% to at most about 30% by weight moisture, at least about 0% to at most about 15% by weight ash, and at least about 0% to at most about 20% by weight additives, the total weight percentage calculated as the sum of the low fixed carbon material, the high fixed carbon material, the moisture, the ash, and the additives being up to 100% by weight.

[0008] In some embodiments, the bio-carbon composition comprises a homogenous physical blend of the low set carbon material and the high set carbon material. In some embodiments, the low set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the high set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the low set carbon material and the high set carbon material are uniformly dispersed throughout the bio-carbon composition. In some embodiments, the bio-carbon composition comprises a heterogenous physical blend of the low set carbon material and the high set carbon material. In some embodiments, the bio-carbon composition comprises distinct layers of the low set carbon material and the high set carbon material. In some embodiments, the bio-carbon composition comprises a core and a shell, the core is contained within the shell, the core comprises the high set carbon material, and the shell comprises the low set carbon material. In some embodiments, the bio-carbon composition comprises a core and a shell, the core is contained within the shell, the core comprises the low set carbon material, and the shell comprises the high 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 some embodiments, the low set carbon material is in the form of particulates in a continuous phase of the high set carbon material.

[0009] In some embodiments, the biocarbon composition comprises at least about 10% to about 90% by weight of the low set carbon material. In some embodiments, the biocarbon composition comprises at least about 10% to about 90% by weight of the high set carbon material. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.1 to about 10. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.2 to about 5. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.5 to about 2. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.8 to about 1.2. In some embodiments, the first fixed carbon concentration is at least about 20% to about 40% by weight. In some embodiments, the first fixed carbon concentration is at least about 25% to about 50% by weight. In some embodiments, the first fixed carbon concentration is at least about 30% to about 55% by weight. In some embodiments, the second fixed carbon concentration is at least about 80% by weight and up to about 100% by weight. In some embodiments, the second fixed carbon concentration is at least about 70% by weight and up to about 95% by weight. In some embodiments, the second fixed carbon concentration is at least about 60% by weight and up to about 90% by weight.

[0010] In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30% and up to about 90% by weight. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40% and up to about 80% by weight. In some embodiments, the biocarbon composition comprises 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. In some embodiments, the low fixed carbon material comprises at least about 45% and up to about 80% by weight volatile carbon on an absolute basis. In some embodiments, the high fixed carbon material comprises at least about 0% and up to about 50% by weight volatile carbon on an absolute basis. In some embodiments, the biocarbon composition comprises at least about 0.1% and up to about 20% by weight moisture. The biocarbon composition may be completely dry, with less than 0.1% moisture by weight, less than 0.01% moisture by weight, or essentially no moisture. In some embodiments, the biocarbon composition comprises at least about 0.1% and up to about 10% ash by weight.

[0011] In some embodiments, the bio-carbon composition comprises at least about 0.1% to up to about 10% by weight of the additive. In some embodiments, the bio-carbon composition comprises at least about 1% to up to about 15% by weight of the additive. In some embodiments, the bio-carbon composition comprises at least about 3% to up to about 18% by weight of the additive. In some embodiments, the additive comprises an organic additive. In some embodiments, the additive comprises an inorganic additive. In some embodiments, the additive comprises a renewable material. In some embodiments, the additive comprises a material that can be oxidized or combusted. In some embodiments, the additive comprises a binder. In some embodiments, the binder comprises 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, met coke, 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, or derivatives thereof, or combinations thereof.

[0012] In some embodiments, the binder comprises starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof. In some embodiments, the binder comprises thermoplastic starch. In some embodiments, the thermoplastic starch is crosslinked. In some embodiments, the thermoplastic starch is a reaction product of starch and a polyol. In some embodiments, the polyol in the reaction to produce the starch can be ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. In some embodiments, the thermoplastic starch is formed from a reaction catalyzed by an acid. In some embodiments, the acid comprises formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof. In some embodiments, the thermoplastic starch is formed from a reaction catalyzed by a base.

[0013] The stability of the bio-carbon composition can be increased by the addition of an additive. In some embodiments, the additive reduces the reactivity of the bio-carbon composition compared to an otherwise comparable bio-carbon composition without the additive. In some embodiments, the reactivity is thermal reactivity. In some embodiments, the bio-carbon composition comprises less self-heating compared to an otherwise comparable bio-carbon composition without the additive. In some embodiments, the reactivity is chemical reactivity with oxygen. In some embodiments, the reactivity is chemical reactivity with water. In some embodiments, the reactivity is chemical reactivity with hydrogen. In some embodiments, the reactivity is chemical reactivity with carbon monoxide. In some embodiments, the reactivity is chemical reactivity with a metal. In some embodiments, the metal comprises iron.

[0014] In some embodiments, the bio-carbon composition comprises greater than 0 wt.% additive. In other words, there are embodiments in which the additive is present in the composition. The low set carbon material may comprise pores, and the pores may comprise the additive. In some embodiments, the high set carbon material comprises pores that comprise the additive, and the low set carbon material comprises pores that comprise the additive. In some embodiments, the additive is on the surface of the bio-carbon composition.

[0015] In some embodiments, the bio-carbon composition is in the form of a powder. In some embodiments, the bio-carbon composition is in the form of a pellet. In some embodiments, the bio-carbon composition is in the form of a pellet and includes an additive, the additive includes a binder. In some embodiments, the binder is a low fixation carbon material. In some embodiments, the bio-carbon composition includes an additive, the low fixation carbon material includes the additive, or the high fixation carbon material includes the additive.

[0016] 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”.

[0017] In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the energy content associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the bulk density associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the hydrophobicity associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the pore size associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the ratio of pore sizes associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the surface area associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the reactivity associated with the bio-carbon composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives are selected to optimize the ion exchange capacity associated with the biocarbon composition.

[0018] In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, and optionally the type and / or concentration of additives are selected to optimize a hardgrove grindability index associated with the pellets. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives are selected to optimize a pellet durability index associated with the pellets.

[0019] In some embodiments, the bio-carbon composition is in the form of a pellet, and the first fixed carbon concentration, the second fixed carbon concentration, and optionally the type or concentration of additives are selected to optimize a pellet durability index associated with the pellet.

[0020] The biocarbon compositions of the present disclosure may comprise a low set carbon material having at least about 1% to about 99% by weight, the low set carbon material comprising a first fixed carbon concentration of at least about 10% to about 55% by weight of fixed carbon on an absolute basis; a high set carbon material having at least about 1% to about 99% by weight, the high set carbon material comprising 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; at least about 0% to about 30% by weight moisture, at least about 0% to about 15% by weight ash, and at least about 0% to about 20% by weight additives, the low set carbon material or the high set carbon material comprising biocarbon, the total weight percent being calculated as the sum of the low set carbon material, the high set carbon material, the moisture, the ash, and the additives, up to 100% by weight.

[0021] In some embodiments, the low fixed carbon material comprises non-pyrolytic biomass, pyrolytic biomass, non-pyrolytic polymers, pyrolytic polymers, coal, pyrolytic coal, or combinations thereof. In some embodiments, the high fixed carbon material comprises pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0022] In all embodiments of the present disclosure of compositions and processes for making compositions, the biocarbon composition may comprise total carbon. In some embodiments, at least 50% of the total carbon is 14 C / 12 In some embodiments, the biomolecular composition is essentially composed of biogenic carbon, as determined by measuring the C isotope ratio. In some embodiments, at least 50% of the total carbon is 14 C / 12In some embodiments, the biomolecular composition is essentially composed of biogenic carbon, as determined by measuring the C isotope ratio. In some embodiments, at least 90% of the total carbon is 14 C / 12 In some embodiments, the total carbon is essentially comprised of biogenic carbon as determined by measuring the C isotope ratio. 14 C / 12 It consists essentially of biogenic carbon, as determined from measurements of C isotope ratios.

[0023] Disclosed herein is a process for producing a bio-carbon composition. The disclosed process may include pyrolyzing a first feedstock, the first feedstock comprising biomass, thereby producing a low fixed carbon material and a first pyrolysis exhaust gas, the low fixed carbon material comprising a first fixed carbon concentration of at least about 20% by weight to at most about 55% by weight of fixed carbon on an absolute basis, pyrolyzing a second feedstock, the second feedstock comprising biomass, thereby producing a high fixed carbon material and a second pyrolysis exhaust gas, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% by weight to at most about 100% by weight of fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration, blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material, and recovering a bio-carbon composition comprising the intermediate material or a heat-treated derivative of the intermediate material.

[0024] In some embodiments, the process includes drying the intermediate material.

[0025] In some embodiments, the process includes blending the intermediate material with the additive, thereby producing a blended intermediate material. In some embodiments, the process includes drying the blended intermediate material. In some embodiments, pyrolyzing the second feedstock is independent of pyrolyzing the first feedstock. In some embodiments, the first feedstock and the second feedstock are the same type of feedstock. In some embodiments, the first feedstock and the second feedstock are not the same type of feedstock.

[0026] In some embodiments, the first feedstock is selected from the group consisting of softwood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugar cane, sugar cane bagasse, sugar cane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, and the like. pumice), 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 wastewater, or combinations thereof.

[0027] In some embodiments, the second feedstock comprises softwood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugar cane, sugar cane bagasse, sugar cane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit skins, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper shavings, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof.

[0028] In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out in separate pyrolysis reactors. In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out in a common pyrolysis reactor in another case. The pyrolysis reactors are typically all continuous or all batch, although in principle a mixture of reaction modes can be used. Also, when separate pyrolysis reactors are used, they can be in a common location or in different locations.

[0029] In some embodiments, the blending comprises blending essentially all of the low set carbon material with the high set carbon material. In some embodiments, the blending comprises blending essentially all of the high set carbon material with the low set carbon material. In some embodiments, the blending of the low set carbon material with the high set carbon material comprises blending the low set carbon material and the high set carbon material with an additive. In some embodiments, the process comprises simultaneously drying while blending. In some embodiments, the process comprises blending the additive with an intermediate material, thereby producing a blended intermediate material, and then drying the intermediate material.

[0030] In some embodiments, the process includes recovering a biocarbon composition comprising at least about 1% to up to 99% by weight of low set carbon material, at least about 1% to up to 99% by weight of high set carbon material, at least about 0% to up to 30% by weight of moisture, at least about 0% to up to 15% by weight of ash, and at least about 0% to up to 20% by weight of additives.

[0031] In some embodiments, pyrolyzing the first feedstock comprises pyrolyzing at a first pyrolysis temperature, the first pyrolysis temperature being at least about 250° C. and up to about 1250° C. In some embodiments, pyrolyzing the first feedstock comprises pyrolyzing at a first pyrolysis temperature, the first pyrolysis temperature being at least about 300° C. and up to about 700° C. In some embodiments, pyrolyzing the second feedstock comprises pyrolyzing at a second pyrolysis temperature, the second pyrolysis temperature being at least about 250° C. and up to about 1250° C. In some embodiments, pyrolyzing the second feedstock comprises pyrolyzing at a second pyrolysis temperature, the second pyrolysis temperature being at least about 300° C. and up to about 700° C.

[0032] In some embodiments, pyrolyzing the first feedstock comprises pyrolyzing for at least about 10 seconds up to about 24 hours. In some embodiments, pyrolyzing the second feedstock comprises pyrolyzing for at least about 10 seconds up to about 24 hours.

[0033] In some embodiments, the first pyrolysis exhaust gas is oxidized, thereby producing heat. In some embodiments, the second pyrolysis exhaust gas is oxidized, thereby producing heat. In some embodiments, the first pyrolysis exhaust gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide. In some embodiments, the second pyrolysis exhaust gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide.

[0034] In some embodiments, the process includes a first milling of the low carbon material prior to blending, the first milling including using a mechanical processing device 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. In some embodiments, the process includes a second milling of the high carbon material prior to blending, the second milling including using a mechanical processing device 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. In some embodiments, the blending includes using a mechanical processing device 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.

[0035] In some embodiments of the process, the bio-carbon composition comprises a homogenous physical blend of the low set carbon material and the high set carbon material. In some embodiments, the low set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the high set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the low set carbon material and the high set carbon material are uniformly dispersed throughout the bio-carbon composition. In some embodiments, the bio-carbon composition comprises a heterogenous physical blend of the low set carbon material and the high set carbon material. In some embodiments, the bio-carbon composition comprises distinct layers of the low set carbon material and the high set carbon material. In some embodiments, the bio-carbon composition comprises a core and a shell, the core is contained within the shell, the core comprises the high set carbon material, and the shell comprises the low set carbon material. In some embodiments, the bio-carbon composition comprises a core and a shell, the core is contained within the shell, the core comprises the low set carbon material, and the shell comprises the high 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 some embodiments, the low fixation carbon material is in the form of fine particles in a continuous phase of the high fixation carbon material.

[0036] In some embodiments of the process, the bio-carbon composition comprises at least about 10% and up to about 90% by weight of the low set carbon material. In some embodiments, the bio-carbon composition comprises at least about 10% and up to about 90% by weight of the high set carbon material. In some embodiments, the bio-carbon composition comprises a weight ratio of the low set carbon material to the high set carbon material, the ratio being at least about 0.1 and up to about 10.

[0037] In some embodiments of the process, the biocarbon composition comprises a weight ratio of low fixation carbon material to high fixation carbon material, the ratio being at least about 0.2 and at most about 5. In some embodiments, the biocarbon composition comprises a weight ratio of low fixation carbon material to high fixation carbon material, the ratio being at least about 0.5 and at most about 2. In some embodiments, the biocarbon composition comprises a weight ratio of low fixation carbon material to high fixation carbon material, the ratio being at least about 0.8 and at most about 1.2.

[0038] In some embodiments, the first fixed carbon concentration is at least about 20% to about 40% by weight. In some embodiments, the first fixed carbon concentration is at least about 25% to about 50% by weight. In some embodiments, the first fixed carbon concentration is at least about 30% to about 55% by weight. In some embodiments, the second fixed carbon concentration is at least about 80% to about 100% by weight. In some embodiments, the second fixed carbon concentration is at least about 70% to about 95% by weight. In some embodiments, the second fixed carbon concentration is at least about 60% to about 90% by weight. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30% to about 90% by weight. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40% to about 80% by weight.

[0039] In some embodiments of the process, the biocarbon composition comprises 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. In some embodiments, the low fixed carbon material comprises at least about 45% and up to about 80% by weight volatile carbon on an absolute basis. In some embodiments, the high fixed carbon material comprises at least about 0 and up to about 50% by weight volatile carbon on an absolute basis.

[0040] In some embodiments of the process, the biocarbon composition comprises at least about 0.1% to about 20% moisture by weight. In some embodiments, the biocarbon composition comprises at least about 0.1% to about 10% ash by weight. In some embodiments, the biocarbon composition comprises at least about 0.1% to about 10% additive by weight. In some embodiments, the biocarbon composition comprises at least about 1% to about 15% additive by weight. In some embodiments, the biocarbon composition comprises at least about 3% to about 18% additive by weight.

[0041] In some embodiments of the process, the bio-carbon composition includes an additive, and the additive includes an organic additive. In some embodiments, the additive includes an inorganic additive. In some embodiments, the additive includes a renewable material. In some embodiments, the additive includes a material that can be oxidized or combusted. In some embodiments, the additive includes a binder.

[0042] In some embodiments, the process includes pelletizing, which can be accomplished using 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.

[0043] In some embodiments of the process, the biocarbon composition includes a binder, which may include 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, pyrolytic 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.

[0044] In some embodiments of the process, the biocarbon composition comprises a binder, the binder comprising starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof.

[0045] In some embodiments of the process, the biocarbon composition includes a binder, and the binder includes a thermoplastic starch. The thermoplastic starch can be a reaction product of a starch and a polyol. The polyol can be ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination thereof. The thermoplastic starch can be formed from a reaction catalyzed by an acid. The acid can include formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof. The thermoplastic starch can be formed from a reaction catalyzed by a base.

[0046] In some embodiments of the process, the additive reduces the reactivity of the bio-carbon composition compared to an otherwise comparable bio-carbon composition without the additive. In some embodiments, the reactivity is thermal reactivity. In some embodiments, the bio-carbon composition comprises less self-heating compared to an otherwise comparable bio-carbon composition without the additive. In some embodiments, the reactivity is chemical reactivity with oxygen. In some embodiments, the reactivity is chemical reactivity with water. In some embodiments, the reactivity is chemical reactivity with hydrogen. In some embodiments, the reactivity is chemical reactivity with carbon monoxide. In some embodiments, the reactivity is chemical reactivity with a metal. In some embodiments, the metal comprises iron.

[0047] In some embodiments, the process includes blending the additive with an intermediate material, thereby introducing the additive into the pores of the low set carbon material. In some embodiments, the process includes blending the additive with an intermediate material, thereby introducing the additive into the pores of the high set carbon material. In some embodiments, the process includes blending the additive with an intermediate material, thereby introducing the additive into the pores of the low set carbon material and introducing the additive into the pores of the high set carbon material. In some embodiments, the process includes blending the additive with an intermediate material, thereby disposing the additive on an exterior surface of the bio-carbon composition.

[0048] In some embodiments, the process includes forming the bio-carbon composition into a powder. In some embodiments, the process includes pelletizing the bio-carbon composition.

[0049] In some embodiments, the process includes blending an additive with an intermediate material, where the additive includes a binder. In some embodiments, the binder includes a low set carbon material. In some embodiments, the process includes blending an additive with an intermediate material, where the low set carbon material includes the additive or the high set carbon material includes the additive.

[0050] In some embodiments of the process, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances." In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives are selected to optimize the energy content associated with the biocarbon composition.

[0051] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or a type or concentration of additive, thereby optimizing the bulk density of the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or a type or concentration of additive, thereby optimizing the hydrophobicity of the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or a type or concentration of additive, thereby optimizing the pore size of the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or a type or concentration of additive, thereby optimizing the pore size ratio of the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or a type or concentration of additive, thereby optimizing the surface area of ​​the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or a type or concentration of additive, thereby optimizing the reactivity of the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the ion exchange capacity (IEC) of the biocarbon.

[0052] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing a hardgrove grindability index of the biocarbon. In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing a pellet durability index of the biocarbon.

[0053] In some embodiments of the process, the biocarbon composition is at least 50% of the total carbon. 14 C / 12 In some embodiments of the process, the biocarbon composition comprises total carbon that consists essentially of biogenic carbon, as determined from C isotope ratio measurements. In some embodiments of the process, the biocarbon composition comprises at least 90% of the total carbon. 14 C / 12 In some embodiments of the process, the biocarbon composition comprises total carbon consisting essentially of biogenic carbon, as determined from a measurement of the C isotope ratio. 14 C / 12 Includes total carbon, consisting essentially of biogenic carbon, as determined from C isotope ratio measurements.

[0054] The process of the present disclosure may include pyrolyzing a first feedstock, the first feedstock comprising biomass, thereby producing a low fixed carbon material and a first pyrolysis exhaust gas, the low fixed carbon material comprising a first fixed carbon concentration of at least about 20% to at most about 55% fixed carbon on an absolute basis, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration, blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material, optionally blending one or more additives into the intermediate material, optionally drying the intermediate material, and recovering a bio-carbon composition comprising the intermediate material or a thermally treated derivative thereof.

[0055] In some embodiments of the process, the high fixed carbon material comprises pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0056] The process of the present disclosure may include providing a low fixed carbon material, the low fixed carbon material comprising a first fixed carbon concentration of at least about 10% to at most about 55% fixed carbon on an absolute basis; pyrolyzing a feedstock, the feedstock comprising biomass, thereby producing a high fixed carbon material and a pyrolysis off-gas, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration; blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material; optionally blending an additive with the intermediate material; optionally drying the intermediate material; and recovering a bio-carbon composition comprising the intermediate material or a thermally treated derivative thereof.

[0057] In some embodiments of the process, the low fixed carbon material comprises non-pyrolyzed biomass, pyrolyzed biomass, non-pyrolyzed polymers, pyrolyzed polymers, or combinations thereof.

[0058] The process of the present disclosure may include providing a low fixed carbon material, the low fixed carbon material comprising a first fixed carbon concentration of at least about 10% to at most about 55% fixed carbon on an absolute basis; providing a high fixed carbon material, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration; blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material; optionally blending an additive with the intermediate material; optionally drying the intermediate material; and recovering a bio-carbon composition comprising the intermediate material or a thermally treated derivative thereof.

[0059] In some embodiments of the process, the low fixed carbon material comprises non-pyrolytic biomass, pyrolytic biomass, non-pyrolytic polymers, pyrolytic polymers, or combinations thereof. In some embodiments of the process, the high fixed carbon material comprises pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof. [Brief description of the drawings]

[0060] [Figure 1] FIG. 1 is a simplified block flow diagram of a process for producing a bio-carbon composition having a high-fixation carbon material and a low-fixation carbon material optionally blended with additives (such as binders to make pellets) according to some embodiments. The dotted boxes and lines indicate optional units and flows, respectively.

[0061] [Diagram 2] FIG. 1 is a simplified block flow diagram of a process for producing a bio-carbon composition having a low set carbon material blended with a high set carbon material, where the low set carbon material acts as a pellet binder according to some embodiments. The dotted boxes and lines indicate optional units and flows, respectively.

[0062] [Diagram 3] 1 is a photograph of a biocarbon composition in the form of a pellet containing a mixture of high and low set carbon materials, with the low set carbon material acting as the pellet binder. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0063] While the present disclosure can be embodied in various forms, the following description of several embodiments is made with the understanding that the present disclosure should be considered as an example of the present invention and is not intended to limit the present invention to the specific embodiments shown. Headings are provided for convenience only and should not be construed as limiting the present invention in any way. Embodiments shown under any heading can be combined with embodiments shown under other headings.

[0064] The use of numerical values ​​in the various quantitative values ​​specified in this application is referred to as approximations, unless expressly indicated otherwise, as if both the minimum and maximum values ​​in the ranges mentioned were preceded by the word "about". Although not always explicitly stated, all numerical designations should be understood to be preceded by the term "about". Such range formats are used for convenience and brevity, and include numerical values ​​explicitly specified as the limits of the ranges, but should be understood to be flexible to include all individual numerical values ​​or subranges subsumed within the ranges, as if each numerical value and subrange were explicitly specified. For example, a ratio in the range of about 1 to about 200 should be understood to include the explicitly recited limits of about 1 to about 200, but also include individual ratios such as about 2, about 3, and about 4, as well as subranges such as about 10 to about 50, about 20 to about 100, etc. Also, although not always explicitly stated, it should be understood that the reagents described herein are merely exemplary, and that equivalents of such are known in the art.

[0065] The term "about" as used herein when referring to a measurable value, such as an amount or concentration, is meant to encompass a variation of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount.

[0066] Also, the disclosure of ranges is intended as a continuous range, including every value between the minimum and maximum values ​​recited, as well as any ranges that may be formed by such values. Also disclosed herein are any and all ratios (and ranges of any such ratios) that may be formed by dividing a disclosed numerical value into another disclosed numerical value. Thus, one skilled in the art will understand that many such ratios, ranges, and ratio ranges can be clearly derived from the numerical values ​​presented herein, and in all cases, such ratios, ranges, and ratio ranges represent various embodiments of the present disclosure. If no lower limit is provided, the lower limit is 0 or a trace amount. For example, if "up to about 90%" is stated, the lower limit is "about 0%" or a trace amount. If no upper percentage limit is provided, the upper limit is 100%. For example, if "at least about 5%" is stated, the upper limit is "about 100%".

[0067] "Comprising" or "comprises" is intended to mean that the compositions and methods include the recited elements but do not exclude other elements. When used to define compositions and methods, "consisting essentially of" is intended to mean excluding other elements that have essential importance to the combination for the stated purpose. Thus, a composition consisting essentially of elements as defined herein will not exclude other materials or steps that do not materially affect the basic and novel characteristics of the claimed invention. "Consisting of" is intended to mean excluding more minor elements of other ingredients and substantial method steps. Embodiments defined by each of these transition terms are within the scope of the present invention.

[0068] 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, such 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, either as a range, a preferred range, or a list of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed from any pair of any upper or preferred value and any lower or preferred value, regardless of whether the ranges are individually disclosed.

[0069] For the present purposes, "biogenic" is intended to mean a material (feedstock, product, or intermediate) that contains elements such as carbon that are renewable on time scales of months, years, or decades. Non-biogenic materials may be non-renewable or may be renewable on time scales of centuries, millennia, millions of years, or even longer geological time scales. Note that biomaterials may include a mixture of biological and non-biogenic sources.

[0070] 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 molecule, an additive, a blend component, a solvent, etc. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. A reagent may or may not be a chemical reactant, and may or may not be consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in the adjustment of mechanical, physical, or hydrodynamic properties of a material to which it may be added. For example, a reagent may be introduced into a metal to give it certain strength properties. 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.

[0071] The terms "low fixed carbon" and "high fixed carbon" are used herein for practical purposes to describe materials that may be produced by the processes and systems as disclosed, in various embodiments. Any limitations on carbon content or any other concentration are to be implied only by reference to specific embodiments and their equivalents, and not from the terms themselves.

[0072] "Ash" refers to non-carbon components that are not vaporized during pyrolysis. Ash content can be measured by ASTM D3175 or other techniques. Ash composition can be analyzed by ASTM D4326 or other techniques. Ash can contain, for example, Fe2O3, CaO, MgO, K2O, Na2O, SiO2, Al2O3, and TiO2. Silica (SiO2) is typically the most important component of ash derived from biomass.

[0073] Biocarbon Composition The carbon-based reagents herein are derived at least in part from renewable resources. Such reagents are particularly useful due, at least in part, to the rising economic, environmental, and social costs associated with fossil resources.

[0074] As used herein, "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 carbon source.

[0075] Disclosed herein is a biocarbon composition. The biocarbon composition of the present disclosure may comprise a low fixed carbon material of at least about 1% to at most about 99% by weight, the low fixed carbon material comprising a first fixed carbon concentration of at least about 20% to at most about 55% by weight of fixed carbon on an absolute basis, a high fixed carbon material of at least about 1% to at most about 99% by weight, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% by weight of fixed carbon on an absolute basis, the second fixed carbon concentration being greater than the first fixed carbon concentration, at least about 0% to at most about 30% by weight moisture, at least about 0% to at most about 15% by weight ash, and at least about 0% to at most about 20% by weight additives, the total weight percentage calculated as the sum of the low fixed carbon material, the high fixed carbon material, the moisture, the ash, and the additives being up to 100% by weight. As used herein, "absolute basis" includes ash and moisture.

[0076] In some embodiments, the bio-carbon composition comprises a homogenous physical blend of the low set carbon material and the high set carbon material. In other words, the low set carbon material and the high set carbon material may be present in the bio-carbon composition as a homogenous physical blend. In some embodiments, the low set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the high set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the low set carbon material and the high set carbon material are uniformly dispersed throughout the bio-carbon composition.

[0077] In some embodiments, the biocarbon composition comprises a heterogeneous physical blend of the low set carbon material and the high set carbon material. In other words, the low set carbon material and the high set carbon material may be present in the biocarbon composition as a heterogeneous physical blend. In some embodiments, the biocarbon composition comprises separate layers of the low set carbon material and the high set carbon material. In some embodiments, the biocarbon composition comprises a core and a shell, or a core and a coating, where the core is contained within the shell, where the core comprises the high set carbon material, and where the shell comprises the low set carbon material. In some embodiments, the biocarbon composition comprises a core and a shell, or a core and a coating, where the core is contained within the shell, where the core comprises the low set carbon material, and where the shell comprises the high 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 some embodiments, the low set carbon material is in the form of particulates in a continuous phase of the high set carbon material.

[0078] The low and high set carbon materials may form separate phases that are insoluble in one another at equilibrium and relatively low temperatures. In some embodiments, the low and high set carbon materials may have high equilibrium (thermodynamic) solubility in one another, but nevertheless remain kinetically frozen in the composition such that separate materials are observable. The separate materials may be observable by measuring composition, density, particle size, reactivity, or other physical or chemical properties. During the end use of the biocarbon composition, the distinction of the materials may be lost (e.g., at high temperatures or during carbon oxidation).

[0079] 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 has two peaks characteristic of distinct mass loss events that correlate with the low and high fixed carbon materials. This can be compared to a control sample of a biocarbon composition containing 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 has three or more peaks, while the TGA heat curve of the control sample has at least one less peak than the test sample.

[0080] 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 low and high set carbon materials are different, or when the particle size distributions associated with low and high set carbon materials are different. For example, high set carbon materials tend to have larger particles compared to low set carbon materials. In some embodiments, a bimodal particle size distribution results from the presence of both low and high set carbon materials, as opposed to a control sample having a unimodal particle size distribution characteristic of a homogenous material. In similar embodiments, a test sample may have a particle size distribution with at least one more mode than the particle size distribution of the control sample. For example, it is possible that each of the low and high set carbon materials has a bimodal particle size distribution (peaks centered at different sizes), and that the control sample has a bimodal particle size distribution depending on how the control sample was generated.

[0081] 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 sized 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 micrographs, or other images. Finally, sieving is a conventional technique for separating particles by size.

[0082] 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.

[0083] Alternatively or additionally, spectroscopic techniques may 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.

[0084] The species and concentration ranges of the various biocarbon compositions will now be further described.

[0085] In some embodiments, 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. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.1 to at most about 10. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.2 to at most about 5. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.5 to at most about 2. In some embodiments, the weight ratio of the low set carbon material to the high set carbon material is at least about 0.8 to at most about 1.2.

[0086] In some embodiments, the first fixed carbon concentration is at least about 20% to about 40% by weight. In some embodiments, the first fixed carbon concentration is at least about 25% to about 50% by weight. In some embodiments, the first fixed carbon concentration is at least about 30% to about 55% by weight. In some embodiments, the second fixed carbon concentration is at least about 80% to about 100% by weight. In some embodiments, the second fixed carbon concentration is at least about 70% to about 95% by weight. In some embodiments, the second fixed carbon concentration is at least about 60% to about 90% by weight.

[0087] In some embodiments, the unweighted average of the first and second fixed carbon concentrations is at least about 30% and up to about 90% by weight. In some embodiments, the unweighted average of the first and second fixed carbon concentrations is at least about 40% and up to about 80% by weight. In some embodiments, the biocarbon composition comprises 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. In some embodiments, the low fixed carbon material comprises at least about 45% and up to about 80% volatile carbon on an absolute basis (i.e., including ash and moisture). In various embodiments, the low carbon material may contain about, at least about, or up to about 45, 50, 55, 60, 65, 70, 75, or 80% volatile carbon on an absolute basis. A low fixed carbon material may contain, for example, from about 1% to about 20% by weight oxygen on an absolute basis. A low fixed carbon material may contain, for example, from about 0.1% to about 10% by weight hydrogen on an absolute basis.

[0088] The high-fixed carbon material may contain from about 0 to about 50% volatile carbon by weight on an absolute basis. In various embodiments, the high-fixed carbon material may contain about, at least about, or up to about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% volatile carbon by weight on an absolute basis. The high-fixed carbon material may contain, for example, from about 1% to about 20% oxygen by weight on an absolute basis. The high-fixed carbon material may contain, for example, from about 0.1% to about 10% hydrogen by weight on an absolute basis.

[0089] In some embodiments, the biocarbon composition comprises about 0.1% 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 fixed carbon material can contain 0 to about 50% moisture by weight, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, including all intervening ranges. Independently, the high fixed carbon material can contain from 0 to about 50% moisture by weight, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% moisture by weight, including all intervening ranges.

[0090] In some embodiments, the biocarbon composition comprises about 0.1% to about 10% by weight ash. 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% by weight ash, inclusive of all intervening ranges. The low fixed carbon material may contain 0 to about 25% by weight ash, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25% by weight ash, inclusive of all intervening ranges. Independently, the high fixed carbon material can contain from 0 to about 50 weight percent ash, for example, about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 weight percent ash, inclusive of all intervening ranges.

[0091] In some embodiments, the bio-carbon composition comprises about 0.1% to about 10% by weight of one or more additives. In some embodiments, the bio-carbon composition comprises about 1% to about 15% by weight of one or more additives. In some embodiments, the bio-carbon composition comprises about 3% to about 18% by weight of one or more additives. In various embodiments, the bio-carbon composition comprises about, at least about, or up to about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight of the additive, including all intervening ranges.

[0092] The low set carbon material may contain 0 to about 20 weight percent additive, such as 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 may contain 0 to about 50 weight percent additive, such as 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.

[0093] 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.

[0094] In some embodiments, the one or more additives include a binder. In some embodiments, the binder includes starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or derivatives thereof, or combinations thereof.

[0095] In certain embodiments, the binder comprises starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof. In some embodiments, the binder comprises crosslinked thermoplastic starch. In some embodiments, the thermoplastic starch comprises a reaction product of starch and a polyol. In some embodiments, the polyol comprises ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. The reaction product can be formed from a reaction catalyzed by an acid. In some embodiments, the acid comprises formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof. Alternatively, the reaction product can be formed from a reaction catalyzed by a base.

[0096] The one or more additives may reduce the reactivity of the biocarbon composition compared to an otherwise equivalent biocarbon composition without the one or more additives. The reactivity may be thermal reactivity. For example, a biocarbon composition with one or more additives may have lower self-heating 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).

[0097] When additives are used, they do not need to be distributed uniformly throughout the biomass composition. The additives may be present preferentially in either the low or high carbon fixation materials, or only in one of these materials. For example, a 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 carbon fixation material and 1 percentage point is located in the high carbon fixation material (i.e., 80% of the binder is located in the low carbon fixation 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%.

[0098] When one or more additives are present, some or all of the additives may be pore-filling in the low fixation carbon material. When one or more additives are present, some or all of the additives may be pore-filling in the high fixation carbon material. In some embodiments, one or more additives are present and pore-filling in both the low fixation carbon material and the high fixation carbon material.

[0099] Alternatively, or additionally, the 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).

[0100] In some embodiments, the bio-carbon composition is in the form of a powder.

[0101] In some embodiments of the present invention, 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.

[0102] In some embodiments, the high fixed carbon material comprises at least about 0% and up to about 50% volatile carbon by weight on an absolute basis. In some embodiments, the biocarbon composition comprises at least about 0.1% and up to about 20% moisture by weight. In some embodiments, the biocarbon composition comprises at least about 0.1% and up to about 10% ash by weight.

[0103] In some embodiments, the bio-carbon composition comprises at least about 0.1% to up to about 10% by weight of the additive. In some embodiments, the bio-carbon composition comprises at least about 1% to up to about 15% by weight of the additive. In some embodiments, the bio-carbon composition comprises at least about 3% to up to about 18% by weight of the additive. In some embodiments, the additive comprises an organic additive. In some embodiments, the additive comprises an inorganic additive. In some embodiments, the additive comprises a renewable material. In some embodiments, the additive comprises a material that can be oxidized or combusted. In some embodiments, the additive comprises a binder. In some embodiments, the binder comprises starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or derivatives thereof, or combinations thereof.

[0104] In some embodiments, the binder comprises starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof. In some embodiments, the binder comprises thermoplastic starch. In some embodiments, the thermoplastic starch is crosslinked. In some embodiments, the thermoplastic starch is a reaction product of starch and a polyol. In some embodiments, the polyol in the reaction to produce the starch can be ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. In some embodiments, the thermoplastic starch is formed from a reaction catalyzed by an acid. In some embodiments, the acid comprises formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof. In some embodiments, the thermoplastic starch is formed from a reaction catalyzed by a base.

[0105] The stability of the biocarbon composition can be increased by the addition of an additive. In some embodiments, the additive reduces the reactivity of the biocarbon composition compared to an otherwise equivalent biocarbon composition without the additive. In some embodiments, the reactivity is thermal reactivity. In some embodiments, the biocarbon composition includes less self-heating compared to an otherwise equivalent biocarbon composition without the additive. The reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, or a metal. In some embodiments, the metal includes iron.

[0106] When the biocarbon composition contains additives, the biocarbon composition is less susceptible to oxidation, which can occur in the presence of oxygen, water, hydrogen, or carbon monoxide, resulting in undesirable degradation of the beneficial capabilities of the biocarbon composition.

[0107] In some embodiments, the bio-carbon composition comprises greater than 0 wt.% additive. In other words, there are embodiments in which additives are present in the composition. The low set carbon material may comprise pores and the pores may comprise the additive. In some embodiments, the additive is a pore fill of the pores of the low set carbon material. In some embodiments, the additive is a pore fill of the pores of the high set carbon material. In some embodiments, the high set carbon material comprises pores that comprise the additive and the low set carbon material comprises pores that comprise the additive. In some embodiments, the additive is a pore fill of the high set carbon material pores and the low set carbon pores.

[0108] Alternatively or additionally, the additive can be disposed on an outer surface of the biocarbon composition (e.g., an outer surface of a pellet or powder particle). The process can include, for example, spray coating the additive onto the biocarbon composition.

[0109] In some embodiments, the biocarbon composition is in the form of a powder. A variety of particle sizes can be present in the powder. For example, the average particle diameter can be at least about 100 nanometers up to about 500 microns, at least about 0.5 microns up to about 500 microns, at least about 1 micron up to about 500 microns, at least about 2 microns up to about 500 microns, at least about 3 microns up to about 500 microns, at least about 4 microns up to about 500 microns, at least about 5 microns up to about 500 microns, at least about 10 microns up to about 500 microns, at least about 25 microns up to about 500 microns, at least about 50 ...60 microns up to about 500 microns, at least about 70 microns up to about 500 microns, at least about 80 microns up to about 500 microns, at least about 90 microns up to about 500 microns, at least about 100 microns up to about 500 microns, at least about 150 microns up to about 500 microns, at least about 200 microns up to about 500 microns, at least about 300 microns up to about 500 microns, at least about 400 microns up to about 500 microns, at least about 500 microns up to about 500 microns, at least about 500 microns up to about 500 microns, at 0 microns, at least about 75 microns up to about 500 microns, at least about 100 microns up to about 500 microns, at least about 150 microns up to about 500 microns, at least about 200 microns up to about 500 microns, at least about 250 microns up to about 500 microns, at least about 300 microns up to about 500 microns, at least about 350 microns up to about 500 microns, at least about 400 microns up to about 500 microns, at least about 450 microns up to about 500 microns, or about 500 microns.

[0110] In some embodiments, the biocarbon composition is in the form of pellets. The average pellet diameter or effective diameter can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters. In some embodiments, the average pellet diameter is about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns. When the composition is in the form of pellets, the one or more additives can include a binder for the pellets. In some embodiments, the pellets can utilize the low fixed carbon material itself as a binder within the pellets.

[0111] If an additive is present, the additive may be located in one of the low fixation carbon material or the high fixation carbon material, hi some embodiments, the additive is uniformly distributed such that the additive has the same average concentration in the low fixation carbon material and the high fixation carbon material.

[0112] In some embodiments, 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". The energy content of the biocarbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additive are selected to optimize the energy content associated with the biocarbon composition.

[0113] The bulk density of the biocarbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive are selected to optimize the bulk density associated with the biocarbon composition.

[0114] The hydrophobicity of the bio-carbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive are selected to optimize the hydrophobicity associated with the bio-carbon composition.

[0115] The hydrophobicity of a biocarbon composition can be characterized by water uptake in an immersion test. For example, dried biocarbon pellets can be tested for hydrophobicity using immersion in excess water for 24 hours at room temperature (about 25°C). After immersion, a sieve is used to filter out free water droplets, and the sample is then tested for total moisture by ASTM D3173. To calculate net moisture uptake (also referred to herein as "water uptake"), the initial moisture content of the dried pellets is subtracted from the total moisture by ASTM D3173. For example, if a dried biocarbon pellet has an initial moisture of 5%, and then the immersed pellet after 24 hours has a moisture of 25%, the water uptake is 25%-5%=20%. The same procedure can be used for biocarbon compositions that are not pellets, such as powders or granules.

[0116] The biocarbon composition can be characterized by a water uptake of less than 20% by weight at 25° C. after 24 hours of immersion in water (i.e., in excess liquid water relative to the mass of the pellets). In some embodiments, the biocarbon composition is characterized by a water uptake of less than about 15% by weight at 25° C. after 24 hours of immersion in water. In certain embodiments, the biocarbon composition is characterized by a water uptake of less than about 10% by weight at 25° C. after 24 hours of immersion in water. In certain embodiments, the biocarbon composition is characterized by a water uptake of less than about 5% by weight at 25° C. after 24 hours of immersion in water, e.g., a water uptake of about 2% to about 4% by weight at 25° C. after 24 hours of immersion in water. In various embodiments, the biocarbon composition is characterized by a water uptake at 25°C of about or up to about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1% by weight after 24 hours of immersion in water.

[0117] The pore size of the bio-carbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives are selected to optimize the pore size associated with the bio-carbon composition.

[0118] The pore size ratio of the bio-carbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additive is selected to optimize the pore size ratio associated with the bio-carbon composition.

[0119] The surface area of ​​the bio-carbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of an additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of an additive is selected to optimize the surface area associated with the bio-carbon composition.

[0120] The reactivity of the bio-carbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive are selected to optimize the reactivity associated with the bio-carbon composition.

[0121] The ion exchange capacity of the biocarbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive are selected to optimize the ion exchange capacity associated with the biocarbon composition.

[0122] The Hardgrove Crushability Index of the biocarbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, and optionally the type and / or concentration of additives are selected to optimize the Hardgrove Crushability Index associated with the pellets.

[0123] The pellet durability index of the biocarbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additives is selected to optimize the pellet durability index associated with the pellets.

[0124] FIG. 1 is a simplified block flow diagram of a process for producing a biocarbon composition having a high set carbon material and a low set carbon material optionally blended with additives (such as binders to make pellets) in some embodiments. The dotted boxes and lines indicate optional units and flows, respectively. In FIG. 1, biomass is fed to a first pyrolysis reactor operated at effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low set carbon material that is optionally milled to reduce particle size. The biomass is also fed to a second pyrolysis reactor operated at effective pyrolysis conditions described herein. The biomass fed to the second pyrolysis reactor may be the same or different than the biomass fed to the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high set carbon material that is optionally milled to reduce particle size. Milling of the low set carbon material or high set carbon material, if used, may be prior to combining the streams together, simultaneously with combining the streams together, or after combining the streams. The low and high fixed carbon materials are combined (e.g., blended or co-milled) to produce the LCF-HFC combined reagent shown in Figure 1. The LCF-HFC combined reagent is optionally conveyed to a pelletizing unit or another unit where additives are provided. Alternatively or additionally, the LCF-HFC combined reagent is provided to a drying unit operated to remove water from the LCF-HFC combined reagent. The final product is a biocarbon pellet or powder.

[0125] FIG. 2 is a simplified block flow diagram of a process for producing a biocarbon composition having a low set carbon material blended with a high set carbon material, where the low set carbon material acts as a pellet binder, in some embodiments. The dashed boxes and lines indicate optional units and flows, respectively. In FIG. 2, biomass is fed to a first pyrolysis reactor operated at effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low set carbon material that is optionally milled to reduce particle size. The biomass is also fed to a second pyrolysis reactor operated at effective pyrolysis conditions described herein. The biomass fed to the second pyrolysis reactor may be the same or different than the biomass fed to the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high set carbon material that is optionally milled to reduce particle size. Milling of the low set carbon material or high set carbon material, if used, may be prior to combining the streams together, simultaneously with combining the streams together, or after combining the streams. Both the low set carbon material and the high set carbon material are fed to a pelletizing unit, where pellets are formed using the low set carbon material as a binder. A separate binder material may also be fed to the pelletizing unit in other embodiments. Optionally, the pellets are fed to a drying unit that operates to remove water from the pellets. The end product is biocarbon pellets with the low set carbon material acting as a pellet binder.

[0126] Fixed carbon is a measure of the amount of non-volatile carbon remaining in a sample. It is a calculated value determined from other parameters measured by proximate analysis rather than direct measurement (see ASTM method D3172-07a; American Society for Testing and Materials, 2013, p. 492-493). Fixed carbon is the calculated percentage of material lost during the moisture, volatile matter, and ash tests: wt% fixed carbon = 100 - wt% moisture + wt% volatile matter + wt% ash

[0127] Total carbon is the sum of fixed and non-fixed carbon present in the volatile matter. 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 dry and ash-free basis. The compositions of low and high fixed carbon materials have been addressed above.

[0128] The biocarbon compositions of the present disclosure may comprise a low set carbon material having at least about 1% to about 99% by weight, the low set carbon material comprising a first fixed carbon concentration of at least about 10% to about 55% by weight of fixed carbon on an absolute basis; a high set carbon material having at least about 1% to about 99% by weight, the high set carbon material comprising 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; at least about 0% to about 30% by weight moisture, at least about 0% to about 15% by weight ash, and at least about 0% to about 20% by weight additives, the low set carbon material or the high set carbon material comprising biocarbon, the total weight percent being calculated as the sum of the low set carbon material, the high set carbon material, the moisture, the ash, and the additives, up to 100% by weight.

[0129] In some embodiments, the low fixed carbon material comprises non-pyrolytic biomass, pyrolytic biomass, non-pyrolytic polymers, pyrolytic polymers, coal, pyrolytic coal, or combinations thereof. In some embodiments, the high fixed carbon material comprises pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0130] The three naturally occurring isotopes of carbon, 12 C. 13 C, and 14 C exists. 12 C and13 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, 14 The amount of C is one of the methods used for radiometric dating of biological materials.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] In all embodiments of the present disclosure of compositions and processes for making compositions, the biocarbon composition may comprise total carbon. In some embodiments, at least 50% of the total carbon is 14 C / 12 In some embodiments, the biomolecular composition is essentially composed of biogenic carbon, as determined by measuring the C isotope ratio. In some embodiments, at least 50% of the total carbon is 14 C / 12 In some embodiments, the biomolecular composition is essentially composed of biogenic carbon, as determined by measuring the C isotope ratio. In some embodiments, at least 90% of the total carbon is 14 C / 12 In some embodiments, the total carbon is essentially comprised of biogenic carbon as determined by measuring the C isotope ratio. 14 C / 12 It consists essentially of biogenic carbon, as determined by measurements of C isotope ratios. 14 C / 12 C isotope ratio measurements can be performed using ASTM D6866.

[0135] Process for producing biocarbon compositions Disclosed herein is a process for producing a bio-carbon composition. The disclosed process may include pyrolyzing a first feedstock, the first feedstock comprising biomass, thereby producing a low fixed carbon material and a first pyrolysis exhaust gas, the low fixed carbon material comprising a first fixed carbon concentration of at least about 20% by weight to at most about 55% by weight of fixed carbon on an absolute basis, pyrolyzing a second feedstock, the second feedstock comprising biomass, thereby producing a high fixed carbon material and a second pyrolysis exhaust gas, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% by weight to at most about 100% by weight of fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration, blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material, and recovering a bio-carbon composition comprising the intermediate material or a heat-treated derivative of the intermediate material.

[0136] In some embodiments, the process includes drying the intermediate material. Drying can be used at one or more points in the process.

[0137] In some embodiments, the process includes blending the intermediate material with the additive, thereby producing a blended intermediate material. In some embodiments, the process includes drying the blended intermediate material. In some embodiments, pyrolyzing the second feedstock is independent of pyrolyzing the first feedstock. In some embodiments, the first feedstock and the second feedstock are the same type of feedstock. In some embodiments, the first feedstock and the second feedstock are not the same type of feedstock.

[0138] In some embodiments, the first feedstock comprises softwood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugar cane, sugar cane bagasse, sugar cane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit skins, 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 bales, paper cuttings, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof.

[0139] In some embodiments, the second feedstock comprises softwood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugar cane, sugar cane bagasse, sugar cane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit skins, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper shavings, food packaging, construction and / or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof.

[0140] In some embodiments, the biomass-containing feedstock includes biomass (such as the biomass sources listed above), as well as non-renewable feedstocks such as coal. Thus, a biomass-coal mixture can be utilized for the first biomass-containing feedstock and / or the second biomass-containing feedstock.

[0141] In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out in separate pyrolysis reactors. The pyrolysis reactors are typically all continuous or all batch, although in principle a mixture of reaction modes can be used. Also, when separate pyrolysis reactors are used, they can be at a common location or at different locations.

[0142] In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out in a common pyrolysis reactor in another instance. If a single pyrolysis reactor is used, it can be operated in a batch mode with separate batches of low and high fixed carbon materials. Alternatively, the single pyrolysis reactor can be operated continuously or semi-continuously to produce low fixed carbon materials for a first period of time and then high fixed carbon materials for a second period of time (after which the reactor can be returned to producing low fixed carbon materials or something else).

[0143] In one particular embodiment, a low set carbon material is produced and stored. Later, potentially at a different location, a first portion of the low set carbon material can then be converted to a high set carbon material via additional pyrolysis, while a second portion of the initial low set carbon material is blended with the produced high set carbon material.

[0144] In some embodiments, the blending comprises blending essentially all of the low set carbon material with the high set carbon material. In some embodiments, the blending comprises blending essentially all of the high set carbon material with the low set carbon material. In some embodiments, the blending of the low set carbon material with the high set carbon material comprises blending the low set carbon material and the high set carbon material with an additive. In some embodiments, the process comprises simultaneously drying while blending. In some embodiments, the process comprises blending the additive with an intermediate material, thereby producing a blended intermediate material, and then drying the intermediate material.

[0145] The blending of the low and high set carbon materials can be done immediately after each is produced in a batch or continuous process. The low set carbon material can be stored before blending or can be treated (e.g., thermally treated, mechanically treated, or combined with additives) before blending. Similarly, the high set carbon material can be stored before blending or can be treated (e.g., thermally treated, mechanically treated, or combined with additives) before blending.

[0146] In some embodiments, the process includes recovering a biocarbon composition comprising at least about 1% to up to 99% by weight of low set carbon material, at least about 1% to up to 99% by weight of high set carbon material, at least about 0% to up to 30% by weight of moisture, at least about 0% to up to 15% by weight of ash, and at least about 0% to up to 20% by weight of additives.

[0147] In some embodiments, pyrolyzing the first feedstock comprises pyrolyzing at a first pyrolysis temperature, the first pyrolysis temperature being at least about 250° C. and up to about 1250° C. In some embodiments, pyrolyzing the first feedstock comprises pyrolyzing at a first pyrolysis temperature, the first pyrolysis temperature being at least about 300° C. and up to about 700° C. In some embodiments, pyrolyzing the second feedstock comprises pyrolyzing at a second pyrolysis temperature, the second pyrolysis temperature being at least about 250° C. and up to about 1250° C. In some embodiments, pyrolyzing the second feedstock comprises pyrolyzing at a second pyrolysis temperature, the second pyrolysis temperature being at least about 300° C. and up to about 700° C. The second pyrolysis temperature is typically higher than the first pyrolysis temperature, but is not necessarily so, at least because the feedstocks of steps (a) and (b) may be different, and because other pyrolysis conditions (e.g., time, catalyst, or moisture concentration) may vary.

[0148] In some embodiments, pyrolyzing the first feedstock comprises pyrolyzing for at least about 10 seconds up to about 24 hours. In some embodiments, pyrolyzing the second feedstock comprises pyrolyzing for at least about 10 seconds up to about 24 hours. The first pyrolysis time can be longer than the second pyrolysis time, but this is not necessarily the case, at least because the feedstocks of steps (a) and (b) may be different, and because other pyrolysis conditions (e.g., temperature, catalyst, or water concentration) may vary.

[0149] In some embodiments, the first pyrolysis exhaust gas is oxidized, thereby producing heat. In some embodiments, the heat is used in a process, thereby recycling heat. In some embodiments, the second pyrolysis exhaust gas is oxidized, thereby producing heat. In some embodiments, the heat is used in a process, thereby recycling heat. In some embodiments, the use of heat in a process can be to provide heat to a pyrolysis reactor.

[0150] In some embodiments, the first pyrolysis exhaust gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide. In some embodiments, the second pyrolysis exhaust gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide.

[0151] In some embodiments, the process includes a first milling of the low carbon material prior to blending, the first milling including using a mechanical processing device 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. In some embodiments, the process includes a second milling of the high carbon material prior to blending, the second milling including using a mechanical processing device 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. In some embodiments, the blending includes using a mechanical processing device 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.

[0152] If both low and high fixed carbon materials are milled, they can be milled together in the same unit (during blending) or they can be milled separately in the same type of equipment or different types of equipment.

[0153] In some embodiments of the process, the bio-carbon composition comprises a homogenous physical blend of the low set carbon material and the high set carbon material. In some embodiments, the low set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the high set carbon material is uniformly dispersed throughout the bio-carbon composition. In some embodiments, the low set carbon material and the high set carbon material are uniformly dispersed throughout the bio-carbon composition.

[0154] In some embodiments, the bio-carbon composition comprises a heterogeneous physical blend of low set carbon material and high set carbon material. In some embodiments, the bio-carbon composition comprises distinct layers of low set carbon material and high set carbon material. In some embodiments, the bio-carbon composition comprises a core and a shell, the core is contained within the shell, the core comprises the high set carbon material, and the shell comprises the low set carbon material. In some embodiments, the bio-carbon composition comprises a core and a shell, the core is contained within the shell, the core comprises the low set carbon material, and the shell comprises the high 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 some embodiments, the low set carbon material is in the form of particulates in a continuous phase of the high set carbon material.

[0155] In some embodiments of the process, the bio-carbon composition comprises at least about 10% and up to about 90% by weight of the low set carbon material. In some embodiments, the bio-carbon composition comprises at least about 10% and up to about 90% by weight of the high set carbon material. In some embodiments, the bio-carbon composition comprises a weight ratio of the low set carbon material to the high set carbon material, the ratio being at least about 0.1 and up to about 10.

[0156] In some embodiments of the process, the biocarbon composition comprises a weight ratio of low fixation carbon material to high fixation carbon material, the ratio being at least about 0.2 and at most about 5. In some embodiments, the biocarbon composition comprises a weight ratio of low fixation carbon material to high fixation carbon material, the ratio being at least about 0.5 and at most about 2. In some embodiments, the biocarbon composition comprises a weight ratio of low fixation carbon material to high fixation carbon material, the ratio being at least about 0.8 and at most about 1.2.

[0157] In some embodiments, the first fixed carbon concentration is at least about 20% to about 40% by weight. In some embodiments, the first fixed carbon concentration is at least about 25% to about 50% by weight. In some embodiments, the first fixed carbon concentration is at least about 30% to about 55% by weight. In some embodiments, the second fixed carbon concentration is at least about 80% to about 100% by weight. In some embodiments, the second fixed carbon concentration is at least about 70% to about 95% by weight. In some embodiments, the second fixed carbon concentration is at least about 60% to about 90% by weight. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30% to about 90% by weight. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40% to about 80% by weight.

[0158] In some embodiments of the process, the biocarbon composition comprises 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. In some embodiments, the low fixed carbon material comprises at least about 45% and up to about 80% by weight volatile carbon on an absolute basis. In some embodiments, the high fixed carbon material comprises at least about 0 and up to about 50% by weight volatile carbon on an absolute basis.

[0159] In some embodiments of the process, the biocarbon composition comprises at least about 0.1% to about 20% moisture by weight. In some embodiments, the biocarbon composition comprises at least about 0.1% to about 10% ash by weight. In some embodiments, the biocarbon composition comprises at least about 0.1% to about 10% additive by weight. In some embodiments, the biocarbon composition comprises at least about 1% to about 15% additive by weight. In some embodiments, the biocarbon composition comprises at least about 3% to about 18% additive by weight.

[0160] In some embodiments of the process, the bio-carbon composition includes an additive, and the additive includes an organic additive. In some embodiments, the additive includes an inorganic additive. In some embodiments, the additive includes a renewable material. In some embodiments, the additive includes a material that can be oxidized or combusted. In some embodiments, the additive includes a binder.

[0161] In some embodiments, the process includes pelletizing, which can be accomplished using 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.

[0162] In some embodiments of the process, the biocarbon composition includes a binder, which may include 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, pyrolytic 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.

[0163] In some embodiments of the process, the biocarbon composition comprises a binder, the binder comprising starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof.

[0164] In some embodiments of the process, the biocarbon composition includes a binder, and the binder includes a thermoplastic starch. In some embodiments, the thermoplastic starch is crosslinked. The thermoplastic starch can be a reaction product of a starch and a polyol. The polyol can be ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. The thermoplastic starch can be formed from an acid catalyzed reaction. The acid can include formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof. Alternatively or additionally, the thermoplastic starch can be formed from a base catalyzed reaction.

[0165] In some embodiments of the process, the additive reduces the reactivity of the biocarbon composition as compared to an otherwise comparable biocarbon composition without the additive. In some embodiments, the reactivity is thermal reactivity. For example, the biocarbon composition may include less self-heating as compared to an otherwise comparable biocarbon composition without the additive. In some embodiments, the reactivity is chemical reactivity with oxygen. In some embodiments, the reactivity is chemical reactivity with water. In some embodiments, the reactivity is chemical reactivity with hydrogen. In some embodiments, the reactivity is chemical reactivity with carbon monoxide. In some embodiments, the reactivity is chemical reactivity with a metal. In some embodiments, the metal includes iron.

[0166] In some embodiments, the process includes blending the additive with an intermediate material, thereby introducing the additive into the pores of the low fixation carbon material. In some embodiments, the process includes blending the additive with an intermediate material, thereby introducing the additive into the pores of the high fixation carbon material. In some embodiments, the process includes blending the additive with an intermediate material, thereby introducing the additive into the pores of the low fixation carbon material and introducing the additive into the pores of the high fixation carbon material.

[0167] In some embodiments, the process includes blending the additive with an intermediate material, thereby disposing the additive on an outer surface of the biocarbon composition. The composition (e.g., the outer surface of a pellet or powder particle). The process may include, for example, spray coating the additive onto the biocarbon composition.

[0168] In some embodiments, the process includes forming the bio-carbon composition into a powder.

[0169] In some embodiments, the process includes pelletizing the bio-carbon composition.

[0170] In some embodiments, the process includes blending an additive with an intermediate material, where the additive includes a binder. In some embodiments, the binder includes a low set carbon material. In some embodiments, the process includes blending an additive with an intermediate material, where the low set carbon material includes the additive or the high set carbon material includes the additive.

[0171] In some embodiments of the process, the biocarbon composition is characterized as non-self-heating when subjected to a self-heating test in accordance with Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances". The energy content of the biocarbon composition can be varied by adjusting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additive. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of additive are selected to optimize the energy content associated with the biocarbon composition.

[0172] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the bulk density of the biocarbon.

[0173] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the hydrophobicity of the biocarbon.

[0174] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the pore size of the biocarbon.

[0175] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the pore size ratio of the biocarbon.

[0176] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the surface area of ​​the biocarbon.

[0177] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the reactivity of the biocarbon.

[0178] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the ion exchange capacity (IEC) of the biocarbon.

[0179] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing the hardgrove grindability index of the biocarbon.

[0180] In some embodiments of the process, the process includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or an additive type or concentration, thereby optimizing a pellet durability index of the biocarbon.

[0181] In some embodiments of the process, the biocarbon composition is at least 50% of the total carbon. 14 C / 12 In some embodiments of the process, the biocarbon composition comprises total carbon that consists essentially of biogenic carbon, as determined from C isotope ratio measurements. In some embodiments of the process, the biocarbon composition comprises at least 90% of the total carbon. 14 C / 12 In some embodiments of the process, the biocarbon composition comprises total carbon consisting essentially of biogenic carbon, as determined from a measurement of the C isotope ratio. 14 C / 12 Includes total carbon, consisting essentially of biogenic carbon, as determined from C isotope ratio measurements.

[0182] It is important to note that while renewable bio-carbon compositions are preferred, the principles of the present invention can be applied to non-renewable materials.

[0183] The process of the present disclosure may include pyrolyzing a first feedstock, the first feedstock comprising biomass, thereby producing a low fixed carbon material and a first pyrolysis exhaust gas, the low fixed carbon material comprising a first fixed carbon concentration of at least about 20% to at most about 55% fixed carbon on an absolute basis, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration, blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material, optionally blending one or more additives into the intermediate material, optionally drying the intermediate material, and recovering a bio-carbon composition comprising the intermediate material or a thermally treated derivative thereof.

[0184] In some embodiments of the process, the high fixed carbon material comprises pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0185] The process of the present disclosure may include providing a low fixed carbon material, the low fixed carbon material comprising a first fixed carbon concentration of at least about 10% to at most about 55% fixed carbon on an absolute basis; pyrolyzing a feedstock, the feedstock comprising biomass, thereby producing a high fixed carbon material and a pyrolysis off-gas, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration; blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material; optionally blending an additive with the intermediate material; optionally drying the intermediate material; and recovering a bio-carbon composition comprising the intermediate material or a thermally treated derivative thereof.

[0186] In some embodiments of the process, the low fixed carbon material comprises non-pyrolyzed biomass, pyrolyzed biomass, non-pyrolyzed polymers, pyrolyzed polymers, or combinations thereof.

[0187] The process of the present disclosure may include providing a low fixed carbon material, the low fixed carbon material comprising a first fixed carbon concentration of at least about 10% to at most about 55% fixed carbon on an absolute basis; providing a high fixed carbon material, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% to at most about 100% fixed carbon on an absolute basis, the second fixed carbon concentration being higher than the first fixed carbon concentration; blending the low fixed carbon material and the high fixed carbon material, thereby producing an intermediate material; optionally blending an additive with the intermediate material; optionally drying the intermediate material; and recovering a bio-carbon composition comprising the intermediate material or a thermally treated derivative thereof.

[0188] In some embodiments of the process, the low fixed carbon material comprises non-pyrolytic biomass, pyrolytic biomass, non-pyrolytic polymers, pyrolytic polymers, or combinations thereof. In some embodiments of the process, the high fixed carbon material comprises pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0189] FIG. 1 is a simplified block flow diagram of a process for producing a biocarbon composition having a high set carbon material and a low set carbon material optionally blended with additives (such as binders to make pellets) in some embodiments. The dotted boxes and lines indicate optional units and flows, respectively. In FIG. 1, biomass is fed to a first pyrolysis reactor operated at effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low set carbon material that is optionally milled to reduce particle size. The biomass is also fed to a second pyrolysis reactor operated at effective pyrolysis conditions described herein. The biomass fed to the second pyrolysis reactor may be the same or different than the biomass fed to the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high set carbon material that is optionally milled to reduce particle size. Milling of the low set carbon material or high set carbon material, if used, may be prior to combining the streams together, simultaneously with combining the streams together, or after combining the streams. The low and high fixed carbon materials are combined (e.g., blended or co-milled) to produce the LCF-HFC combined reagent shown in Figure 1. The LCF-HFC combined reagent is optionally conveyed to a pelletizing unit or another unit where additives are provided. Alternatively or additionally, the LCF-HFC combined reagent is provided to a drying unit operated to remove water from the LCF-HFC combined reagent. The final product is a biocarbon pellet or powder.

[0190] FIG. 2 is a simplified block flow diagram of a process for producing a biocarbon composition having a low set carbon material blended with a high set carbon material, where the low set carbon material acts as a pellet binder, in some embodiments. The dashed boxes and lines indicate optional units and flows, respectively. In FIG. 2, biomass is fed to a first pyrolysis reactor operated at effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low set carbon material that is optionally milled to reduce particle size. The biomass is also fed to a second pyrolysis reactor operated at effective pyrolysis conditions described herein. The biomass fed to the second pyrolysis reactor may be the same or different than the biomass fed to the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high set carbon material that is optionally milled to reduce particle size. Milling of the low set carbon material or high set carbon material, if used, may be prior to combining the streams together, simultaneously with combining the streams together, or after combining the streams. Both the low set carbon material and the high set carbon material are fed to a pelletizing unit, where pellets are formed using the low set carbon material as a binder. A separate binder material may also be fed to the pelletizing unit in other embodiments. Optionally, the pellets are fed to a drying unit that operates to remove water from the pellets. The end product is biocarbon pellets with the low set carbon material acting as a pellet binder.

[0191] According to one or more processes as disclosed herein, for example, various potential techniques can be utilized to demonstrate, either for quality control or as evidence of practice of the invention, that a given biocarbon composition contains both low fixed carbon materials and distinct high fixed carbon materials, rather than a biocarbon composition containing a single material having a uniform fixed carbon concentration.

[0192] 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 has two peaks characteristic of distinct mass loss events that correlate with the low and high fixed carbon materials. This can be compared to a control sample of a biocarbon composition containing 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 has three or more peaks, while the TGA heat curve of the control sample has at least one less peak than the test sample.

[0193] 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 low and high set carbon materials are different, or when the particle size distributions associated with low and high set carbon materials are different. For example, high set carbon materials tend to have larger particles compared to low set carbon materials. In some embodiments, a bimodal particle size distribution results from the presence of both low and high set carbon materials, as opposed to a control sample having a unimodal particle size distribution characteristic of a homogenous material. In similar embodiments, a test sample may have a particle size distribution with at least one more mode than the particle size distribution of the control sample. For example, it is possible that each of the low and high set carbon materials has a bimodal particle size distribution (peaks centered at different sizes), and that the control sample has a bimodal particle size distribution depending on how the control sample was generated.

[0194] 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 sized 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 micrographs, or other images. Finally, sieving is a conventional technique for separating particles by size.

[0195] 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.

[0196] Alternatively or additionally, spectroscopic techniques may 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.

[0197] Some embodiments are based on optimized pyrolysis of biomass to produce a carbon substrate, mechanical size reduction of the carbon substrate, and the use of a binder to aggregate the carbon substrate to form bio-carbon pellets. The carbon substrate may be or contain a blend of low and high fixation carbon materials.

[0198] 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.

[0199] In some embodiments, varying the proportions and compositions of low and high fixed carbon materials allows for optimization of HGI. The incorporation of binders or other additives may also allow for HGI tunability.

[0200] The ability to adjust the HGI of biocarbon pellets is beneficial because downstream applications utilizing biocarbon pellets (e.g., replacing coal in a boiler) have different HGI requirements. HGI adjustability addresses the well-known problems industrially of the difficulty in grinding crude biomass and the difficulty in grinding pellets. Furthermore, there are numerous downstream uses of biocarbon pellets, each with its own requirements, so being able to adjust the grindability of the pellets is highly advantageous. It is desirable to be able to adjust the HGI to suit a particular application, such as combustion in a boiler to make syngas, metals production, or gasification.

[0201] 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.

[0202] In some cases, the pellets need to be crushed or pulverized into a powder, such as when a boiler or gasifier utilizes a fluidized bed or a suspension of carbon particles. Another example is pulverized carbon injection into a blast furnace to reduce metal ores to metals. In these cases, high pellet grindability is desirable, but not too high that the pellets fall apart during delivery and handling. In other cases, it is desirable to feed the pellets themselves to a process, such as a metal making process. In these cases, lower grindability may be desirable, since some pellet strength may be needed to support the bed of material in the reactor. Different technologies have different pellet grindability requirements.

[0203] The Hardgrove Grindability Index of the biocarbon pellets can be at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. In some embodiments, the Hardgrove Grindability Index is from about 30 to about 50 or from about 50 to about 70. ASTM-Standard D409 / D409M for "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method" is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to Hardgrove Grindability Index or HGI in this disclosure refer to ASTM-Standard D409 / D409M.

[0204] 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.

[0205] In some embodiments, the bio-carbon pellets comprise a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. In some embodiments, the bio-carbon pellets comprise 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.

[0206] In some embodiments of the present invention, biocarbon pellets are utilized as starting materials for making smaller objects, which may also be referred to as biocarbon pellets, since "pellets" does not limit the geometric shape. For example, initial biocarbon pellets with an average pellet diameter of 10 mm can be made. These initial biocarbon pellets can then be crushed using various mechanical means (e.g., using a hammer mill). The crushed pellets can be separated according to size, such as by screening. In this manner, smaller biocarbon pellets can be produced, for example, having an average pellet diameter of about, at least about, or up to about 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, or 5000 microns. The average pellet diameter of the smaller biocarbon pellets may be greater than the average particle diameter of the initial carbon-containing particles used to make the pellets with the binder.

[0207] When the bio-carbon pellets are crushed to produce smaller bio-carbon pellets, the crushing (and optionally screening) step can be integrated with another process step, including potentially at the point of industrial use. In some embodiments, producing the smaller bio-carbon pellets includes utilizing a crushing device. In some embodiments, the crushing device includes 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.

[0208] In various process embodiments, the Hardgrove Crushability Index is at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. For example, the Hardgrove Crushability Index can be from about 30 to about 50, or from about 50 to about 70.

[0209] 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.

[0210] In some embodiments, the bio-carbon pellets comprise a pellet durability index of at least about 80%, at least about 90%, or at least about 95%.

[0211] 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 may achieve within ±10% or within ±5% of the preselected hardgrove grindability index for the biocarbon pellets.

[0212] The size and geometric shape of the biocarbon pellets may vary. As used herein, "pellets" refers to aggregated bodies, not loose powders. The geometric shape of the pellets is not limited to spherical or nearly spherical. Also, in this disclosure, "pellets" is synonymous with "briquettes." The geometric shape of the pellets may be spherical (round or ball shaped), cubic (square), octagonal, hexagonal, honeycomb / honeycomb shaped, elliptical, ovoid, cylindrical, rod shaped, pillow shaped, random, or combinations thereof. For convenience of disclosure, the term "pellets" is used generally for any body containing powders aggregated using a binder. Also, it is reiterated that the present invention is in no way limited to biocarbon compositions in the form of pellets.

[0213] Biocarbon pellets can be characterized by an average pellet diameter, which is the true diameter in the case of a sphere, 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 can be 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 can be about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns, including all intervening ranges.

[0214] In some embodiments, there are a plurality of bio-carbon pellets that are relatively uniform in size, such as a standard deviation of less than ±100%, less than ±50%, less than ±25%, less than ±10%, or less than ±5% of the average pellet diameter. In other embodiments, there are a wide range of sizes of bio-carbon pellets, as this may be advantageous in some applications.

[0215] 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.

[0216] Various moisture levels can be present. For example, the biocarbon pellets can contain about 1% to about 30% (e.g., 32%) by weight, such as about 5% to about 15% moisture, about 2% to about 10% moisture, or about 0.1% to about 1% moisture. In some embodiments, the biocarbon pellets contain about 4-8% moisture. In various embodiments, the biocarbon pellets contain about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% moisture, including all intervening ranges. The moisture level of the biocarbon pellets can be optimized to vary the density within the pellets.

[0217] In some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. In other market applications, such as metallurgy, lower moisture levels may be desirable (e.g., 1% moisture by weight or even lower). Note that water is present in the process of making biocarbon pellets, but these pellets are then optionally dried, which means that the final biocarbon pellets do not necessarily contain moisture.

[0218] In some biocarbon pellets, the biocarbon pellets include about 2% to about 25% binder by weight, about 5% to about 20% binder by weight, or about 1% to about 5% binder by weight. In various embodiments, the biocarbon pellets include about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, or 30% binder by weight, including all intervening ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0219] The binder may be pore-filling within the bio-reagent of the bio-carbon pellet. Alternatively or additionally, the binder may be disposed on a surface of the bio-carbon pellet.

[0220] 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.

[0221] In some embodiments, the binder comprises starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, 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, or derivatives thereof, or combinations thereof. In some embodiments, the binder comprises a grindable plasticizer.

[0222] In some embodiments, the binder comprises starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), or derivatives thereof, or combinations thereof. In some embodiments, the starch comprises nonionic starch, anionic starch, cationic starch, or zwitterionic starch.

[0223] 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 relatively low levels of molecules that can hydrogen bond with starch hydroxyl groups, such as water, glycerol, or sorbitol.

[0224] 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.

[0225] In some embodiments, the starch-containing binder is or comprises a cross-linked starch. Various methods for cross-linking starch are known in the art. Starch materials can be cross-linked, for example, under acidic or alkaline conditions after dissolving or dispersing in an aqueous medium. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to cross-link starch.

[0226] 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 alternatively be formed from a crosslinking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0227] 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.

[0228] 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.

[0229] In some embodiments, the binder reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the binder, which may refer to thermal or chemical reactivity (or both).

[0230] In the case of thermal reactivity, the biocarbon pellets may have lower self-heating compared to otherwise comparable biocarbon pellets without the binder. "Self-heating" refers to the biocarbon pellets undergoing a spontaneous exothermic reaction in the absence of any external ignition, at a relatively low temperature and in an oxidizing atmosphere, to increase the internal temperature of the biocarbon pellets.

[0231] 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.

[0232] Optionally, the biocarbon pellets include one or more additives (not necessarily binders), such as inorganic bentonite clay, limestone, starch, cellulose, lignin, or acrylamide. If 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. As previously explained, the optional additives can be included in the low fixed carbon material, the high fixed carbon material, or both.

[0233] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additives include acids, bases, or salts thereof. In some embodiments, the additives include metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In some embodiments, the additives include sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron 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 it is harvested.

[0234] The biocarbon pellets disclosed herein have a wide variety of downstream uses. They can be stored, sold, distributed, and converted into other products. They can be pulverized for use in boilers to burn carbon and generate electrical energy and / or heat. They can be pulverized, crushed, or milled for feeding into furnaces, such as blast furnaces in metal production. They can be fed directly into furnaces, such as Tecnored furnaces in metal production. They can be pulverized, crushed, or milled for feeding into gasifiers for the purpose of making syngas from the biocarbon pellets.

[0235] 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.

[0236] It should be noted that despite the Hardgrove Crushability Index of biocarbon pellets, they do not necessarily undergo a subsequent grinding process. For example, biocarbon pellets can be used directly in agricultural applications. As another example, biocarbon pellets can be directly incorporated into engineered structures, such as landscape walls. Then, at the end of the life of the structure containing the biocarbon pellets, the pellets can be crushed, burned, gasified, or otherwise reused or recycled.

[0237] Pyrolysis Processes and Systems Suitable processes and systems for pyrolyzing biomass feedstocks to produce low and / or high fixed carbon materials will now be described in more detail. References herein to a "biocarbon reagent" will in various instances be understood as a reference to a biocarbon composition containing (a) a low fixed carbon material in some instances, or (b) a high fixed carbon material, or (c) a blend of low and high fixed carbon materials, depending on process conditions and product characteristics. Similarly, a description of a pyrolysis reactor (or reaction) will in some instances be understood as a reference to a reactor (or reaction) specifically for producing a low fixed carbon material, and in some instances, a reactor (or reaction) specifically for producing a high fixed carbon material. A description of the use (commercial application) of the biocarbon reagent will typically relate to a biocarbon composition containing a blend of low and high fixed carbon materials, unless otherwise noted.

[0238] "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.

[0239] 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.

[0240] 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.

[0241] In some embodiments, the starting biomass feedstock comprises softwood chips, hardwood chips, wood harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugar cane, sugar cane bagasse, sugar cane straw, energy cane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit skins, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper shavings, food packaging, construction and / or demolition waste, lignin, animal manure, municipal solid waste, municipal wastewater, or combinations thereof. Biomass feedstocks contain at least carbon, hydrogen, and oxygen.

[0242] In some embodiments, the bioreagent comprises at least about 50%, at least about 75%, or at least about 90% total carbon by weight. In some embodiments, the bioreagent comprises about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% carbon by weight, including intervening values. Total carbon is the sum of fixed carbon and non-fixed carbon present in the volatile matter. 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 fixed carbon materials and high fixed carbon materials are discussed in detail above.

[0243] 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.

[0244] 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.

[0245] In some non-limiting embodiments, the temperature and residence time can be selected to achieve a relatively slow pyrolysis chemical reaction. An advantage can be substantial preservation of the cell walls contained in the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, it is preferable to utilize equipment that does not mechanically disrupt the cell walls or otherwise convert the biomass particles into small fines. Preferred reactor configurations are discussed in accordance with the process description below.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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 any 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, the final carbonaceous material will not simply be the solid devolatilized residue of the processing step, but may include additional carbon deposited from the gas phase, such as by decomposition of organic vapors (e.g., tars) that can form carbon.

[0250] Certain embodiments extend the concept of additional carbon formation by including a separate unit in which the cooled carbon is subjected to an environment containing carbon-containing species to enhance the carbon content of the final 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.

[0251] 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.

[0252] 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.

[0253] In some embodiments, the pyrolysis process for producing a bio-reagent comprises the following steps: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in the presence of a substantially inert gas phase at at least one temperature selected from about 250° C. to about 700° C. for at least 10 minutes to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the high temperature pyrolysis solid to produce a cooled pyrolysis solid; (g) recovering the biological reagent comprising at least a portion of the cooled pyrolysis solids.

[0254] "Biomass" for the purposes of this disclosure shall be construed as any living material or mixture of living and non-living materials. Essentially, biomass contains at least carbon, hydrogen, and oxygen. The method and apparatus of the present invention can accommodate a wide range of materials of different types, sizes, and moisture contents.

[0255] 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 of the present invention 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.

[0256] The present invention can also be used with carbon-containing feedstocks other than biomass, such as fossil fuels (e.g., coal or petroleum coke), or any mixture of biomass and fossil fuels (e.g., biomass / coal blends). In some embodiments, the biofeedstock is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Feedstocks can include 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.

[0257] The selection of the particular raw material(s) is not considered technically critical, but is done in a manner that tends to favor an economical process. Typically, regardless of the raw material selected, there may (in some embodiments) be screening to remove undesirable materials. The raw material may be optionally dried prior to processing.

[0258] 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.

[0259] It should be noted that size reduction is a costly and energy intensive process. Pyrolyzed materials can be sized with significantly less energy input, i.e., it may be preferable to reduce the particle size of the product rather than the feedstock. This is an option in the present invention 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 of the present invention. 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, produced, and sold.

[0260] If it is desired to produce a final carbonaceous bio-reagent with structural integrity, such as a cylindrical shape, there are at least two options in the context of the present invention. First, the material produced from the process can be collected and then further mechanically processed into the desired form. For example, the product can be pressed or pelletized with a binder. A second option is to utilize a feed material that generally has the desired size 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 have similar geometric shapes, such as spheres, cylinders, or cubes.

[0261] 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.

[0262] The starting feedstock may be provided at a range of moisture levels, as will be appreciated. In some embodiments, the feedstock may already be sufficiently dry that it does not need to be further dried prior to pyrolysis. Typically, it is desirable to utilize commercial sources of biomass that normally contain moisture, and feed the biomass through a drying step prior to introduction into the pyrolysis reactor. However, in some embodiments, dry feedstock may be utilized.

[0263] Typically, it is desirable to provide a relatively low oxygen environment in the pyrolysis reactor, such as about or up to about 10 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.02 mol%, or 0.01 mol% 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.

[0264] 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 feedstock.

[0265] 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 with 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 degassed gas, but adding significant moisture back to the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or to an exhaust treatment unit) or recycled.

[0266] In principle, the effluent from the degassing unit (or a portion thereof) could be introduced into the pyrolysis reactor itself, since the oxygen removed from the solids would be highly diluted. In this embodiment, it may be advantageous to introduce the degassed effluent gas into the last zone of the reactor if the reactor is operated in a countercurrent configuration.

[0267] 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.

[0268] The optionally dried and optionally degassed feedstock is introduced into the pyrolysis reactor or multiple reactors in series or parallel. The feedstock can be introduced using any known means including, for example, a screw feeder or a lock hopper. In some embodiments, the feed system incorporates an air knife.

[0269] When a single reactor is used, there can be multiple zones, such as two, three, four or more zones, which can allow separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, and / or pressure to adjust the overall process performance.

[0270] References to "zones" shall be interpreted broadly to include regions of space within a single physical unit, physically separated units, or any combination thereof. For continuous reactors, the zone boundaries 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 zone boundaries in continuous reactors may relate to functions such as, for example, separate temperatures, fluid flow patterns, solids flow patterns, extent of reaction, etc. In single batch reactors, a "zone" is an operating regime in time rather than space. Multiple batch reactors may also be used.

[0271] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary, some amount of pyrolysis may occur in a portion of the preheat zone, and some amount of "preheat" may continue to occur in the pyrolysis zone. The temperature profile in the reactor is typically continuous, including the zone boundaries within the reactor.

[0272] Some embodiments employ a first zone operated under preheat and / or mild pyrolysis conditions. The temperature of the first zone can be selected from about 150° C. to about 500° C., e.g., about 300° C. to about 400° C. The temperature of the first zone is not so high as to bombard the biomass material and rupture the cell walls and initiate rapid decomposition of the solid phase into steam and gas.

[0273] All references to zone temperatures herein should be interpreted without limitation to include temperatures that may be applied to the bulk solids present, or the gas phase, or the reactor walls (process side). It will be understood that temperature gradients exist in each zone, both axially and radially, and over time (i.e., after start-up or due to transients). Thus, references to zone temperatures may be references to average temperatures or other effective temperatures that may affect actual kinetics. Temperatures may be measured directly by thermocouples or other temperature probes, or may be measured or estimated indirectly by other means.

[0274] The second zone, or generally the primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone can be selected from about 250°C to about 700°C, for example, about, or as low as about, or as high as about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemical reactions releasing gases and condensable vapors, leaving behind a significant amount of solid material as a high carbon reaction intermediate. Biomass components (mainly cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or by creating new pores. The preferred temperature depends at least on the residence time of the second zone, as well as the nature of the feedstock and the desired product properties.

[0275] The third zone, or cooling zone, is operated to cool the high carbon reaction intermediates to various degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone can be selected from about 100°C to about 550°C, for example, from about 150°C to about 350°C.

[0276] Chemical reactions can continue to occur in the cooling zone. Without being limited to a particular theory, it is believed that a secondary pyrolysis reaction can be initiated in the third zone. Carbon-containing components that are in the gas phase can condense (due to the reduction in temperature in the third zone). However, the temperature remains high enough to promote reactions that can form additional fixed carbon from the condensed liquid (secondary pyrolysis) or at least reactions that can form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that can occur is the Boudoir reaction to convert carbon monoxide to carbon dioxide and fixed carbon.

[0277] The residence time of the reactor zones can vary. There is an interaction of time and temperature, so a higher temperature can allow for a shorter reaction time for a desired amount of pyrolysis, 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.

[0278] It should be recognized that in a multiphase reactor, there are multiple residence times. In the present context, there are residence times (and residence time distributions) for both solid and vapor phases in each zone. For a given apparatus using multiple zones, at a given throughput, the residence times across the zones are generally combined on the solid side, but if multiple inlet and outlet ports are utilized in the individual zones, the residence times may not be combined on the vapor side. The residence times of the solids and vapor are not combined.

[0279] The solids residence time in the preheat zone can be selected from about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a time sufficient to allow the biomass to reach the desired preheat temperature is desirable. Heat transfer rates, which depend on particle type and size, physical equipment, and heating parameters, dictate the minimum residence time required to allow the solids to reach the desired preheat temperature. 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.

[0280] The solids residence time in the pyrolysis zone can be selected from about 10 minutes to about 120 minutes, for example, about 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be enough time for the necessary heat transfer to occur followed by the chemical reaction of carbonization. For times less than about 10 minutes, the temperature needs to be very high, such as above 700° C., to remove a large amount of non-carbon elements. This temperature promotes fast pyrolysis and its production of steam and gases derived from the carbon itself, but should be avoided if the intended product is solid carbon.

[0281] In a static system, there will be an equilibrium conversion that can be substantially reached at a certain time. When steam is continuously flowing over the solids with continuous devolatilization, as in certain embodiments, the equilibrium constraint can be removed to allow pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times do not tend to substantially change the remaining refractory solids.

[0282] The solids residence time in the cooling zone can be selected from about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be enough time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature dictate the minimum residence time required to allow the carbon to cool. Additional time may not be desirable unless some amount of secondary pyrolysis is desired.

[0283] As discussed above, the residence times of the vapor phases can be selected and controlled separately. The vapor residence time of the preheat zone can be selected from about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time of the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time of the cooling zone can be selected from about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. A short vapor residence time promotes rapid clearing of volatiles from the system, while a longer vapor residence time promotes reaction of components in the vapor phase with the solid phase.

[0284] 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 also in simulated countercurrent vapor, for example, by periodically introducing and removing the vapor phase from the batch vessel.

[0285] 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.

[0286] The pressure in each zone can be separately selected and controlled. The pressure in each zone can be independently selected from about 1 kPa to about 3000 kPa, for example, about 101.3 kPa (standard atmospheric pressure). Independent zone control of pressure is possible when multiple gas inlets and outlets are used, including vacuum ports for withdrawing gas when subatmospheric zone pressures are desired.

[0287] 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).

[0288] Vacuum operation (e.g., 10-100 kPa) facilitates rapid sweeping of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) may be useful if the exhaust gas is fed to high pressure operation. Higher pressures may also be useful to facilitate heat transfer, chemical reactions, or separations.

[0289] The step of separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids can be accomplished in the reactor itself or using a separate separation unit. A substantially inert sweep gas can be introduced into one or more zones. The condensable vapors and non-condensable gases are then carried away from the zones in the sweep gas and exit the reactor.

[0290] In some embodiments, the sweep gas comprises N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. In some embodiments, the sweep gas is preheated prior to introduction, or cooled if derived from a heating source.

[0291] 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.

[0292] 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.

[0293] In certain embodiments, the sweep gas, in conjunction with a relatively low process pressure, such as atmospheric pressure, provides rapid vapor removal without requiring large amounts of inert gas.

[0294] 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.

[0295] 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.

[0296] 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.

[0297] The sweep gas can be introduced continuously, especially if the solids flow is continuous. If the pyrolysis reaction is run 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 run continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, with suitable valves and controls.

[0298] 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 control of 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.

[0299] 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. The energy content of the thermal oxidizer effluent can be recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (such as a sweep gas). The energy content can be utilized by directly or indirectly heating or assisting in heating units elsewhere in the process, such as a dryer or reactor. In some embodiments, essentially all of the thermal oxidizer effluent is used to indirectly heat (utility side) the dryer. The thermal oxidizer can use fuels other than natural gas.

[0300] The yield of carbonaceous materials may vary depending on the factors mentioned above, including the type of feedstock and process conditions. In some embodiments, the net yield of solids as a percentage of the starting material on a dry basis is at least 25%, 30%, 35%, 40%, 45%, 50% or more. The remainder is split between condensable vapors, such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases, such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on the process conditions, including the water present.

[0301] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80% or more. For example, in some embodiments, the carbonaceous material contains from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon forms methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0302] In alternative embodiments, some portion of these molecules 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.

[0303] 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 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.

[0304] In some embodiments, the process further comprises operating a cooling unit to cool the warm pyrolyzed solids with steam, thereby producing low temperature pyrolyzed solids and superheated steam, and drying is performed at least in part with the superheated steam obtained from the external cooler. Optionally, the cooling unit can be operated to first cool the warm pyrolyzed solids with steam to reach a first cooling unit temperature and then with air to reach a second cooling unit temperature, the second cooling unit temperature being lower than the first cooling unit temperature and associated with a reduced risk of combustion of the warm pyrolyzed solids in the presence of air.

[0305] 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.

[0306] Some other means for screening or separation based on particle size may be included. Grinding, if present, may be upstream or downstream of grinding. A portion of the screened material (e.g., large chunks) may be returned to the grinding unit. Small and large particles may be recovered for separate downstream uses. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as a finely divided carbon or activated carbon product.

[0307] 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 product additives selected to improve one or more properties of the bioreagent or of downstream products incorporating the reagent. Certain additives may provide enhanced process and product (bioreagent or bioreagent-containing product) properties.

[0308] 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.

[0309] 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, and combinations thereof.

[0310] 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.

[0311] In some embodiments, the additive is selected from metal halides. Metal halides are molecules between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many molecules 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.

[0312] 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 the removal of 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.

[0313] Without being limited to any particular hypothesis, the additives may 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 may increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0314] 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 the 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 a portion of the bioreagent that contains the additive, thereby improving the final strength.

[0315] 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.

[0316] 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.

[0317] In some embodiments, the additives applied to the feedstock may 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 may provide functionality desirable for the intended use of the carbonaceous product.

[0318] Throughput or process capacity can vary widely from small laboratory scale units to full scale operations, including any pilot, demonstration, or semi-commercial scale. In various embodiments, the process capacity (of feedstock, product, or both) is at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day, or more.

[0319] In some embodiments, a portion of the solids produced may be recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the reactor. By returning to the front end and passing through the process again, the treated solids may be higher in fixed carbon. The solids, liquids, and gas streams produced or present in the process may be independently recycled, passed to a subsequent step, or removed / purged from the process at any point.

[0320] In some embodiments, the pyrolyzed material is recovered and then fed to a separate unit for further pyrolysis to create a product with higher carbon purity (e.g., conversion of low fixed carbon material to high fixed carbon material). In some embodiments, the secondary process can be carried out in a simple container such as a steel drum through which a heated inert gas (such as heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas containing volatiles can be sent, for example, to a thermal oxidizer or returned to the main process reactor. To cool the 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.

[0321] Some variations of the present invention include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor configured to contain at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone and having an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a 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.

[0322] Some variations include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained within 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 recovery unit disposed in operative communication with the cooler, The system utilizes a bioreagent production system configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0323] 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.

[0324] 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) can be located within a single unit or can be located in separate units.

[0325] Optionally, the dryer can be configured as a drying zone within a multi-zone reactor. Optionally, a solids cooler can be located within the multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0326] The system may include a purging means for removing oxygen from the system. For example, the purging means may comprise one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the system. In some embodiments, the purging means is a degasser disposed in operative communication between the dryer and the multi-zone reactor.

[0327] The multi-zone reactor can be configured with at least a first gas inlet and a first gas outlet, which can be disposed in communication with different zones or the same zone.

[0328] 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.

[0329] 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.

[0330] In a preferred embodiment, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful for extracting gases and analyzing them to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as by adjusting the feed rate, the rate of inert gas sweep, temperature (in one or more zones), pressure (in one or more zones), additives, etc.

[0331] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more samplings via the reactive gas probe, and, optionally, making process or equipment adjustments based on the measurements, if deemed necessary or desirable, using well-known principles of process control (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0332] The reaction gas probe can be configured to extract a gas sample in many ways. For example, the sampling line can have a pressure lower than the pyrolysis reactor pressure so that when the sampling line is opened, a quantity of gas can be easily extracted from the pyrolysis zone. The sampling line can be under vacuum, such as when the pyrolysis zone is at near atmospheric pressure. Typically, the reaction gas probe is associated with one gas output or a portion thereof (e.g., a line branched off from the gas output line).

[0333] In some embodiments, both the gas input and gas output are utilized as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with a process sample ("sample sweep"). Such configurations can be used in zones that do not have a gas inlet / outlet for a substantially inert gas for processing, or the reactive gas probe can be associated with a separate gas inlet / outlet in addition to the process inlet and outlet. The sampling inert gas that is periodically introduced and withdrawn for sampling (in embodiments utilizing a sample sweep) may be different from the process inert gas, if desired, either for reasons of analytical accuracy or to introduce an analytical tracer.

[0334] 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.

[0335] 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).

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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, fixed bed reactors, fluidized bed reactors, entrained bed reactors, augers, ablation reactors, rotating cones, rotating drum kilns, calciners, roasters, moving bed reactors, transport bed reactors, ablation reactors, rotating cones, or microwave-assisted pyrolysis reactors.

[0340] In some embodiments where an auger is used, sand or another heat carrier can optionally be used. For example, the feedstock and sand can be fed at one end of a screw. The screw mixes the sand and feedstock and conveys them through the reactor. The screw can provide good control of feedstock residence time and does not dilute the pyrolysis products with carrier or fluidizing gas. The sand can be reheated in a separate vessel.

[0341] 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.

[0342] In some embodiments where a fluidized bed reactor is used, the feedstock may be introduced into a bed of hot sand fluidized by a gas, typically a recycled product gas. References herein to "sand" also include similar substantially inert materials such as glass particles, recovered ash particles, etc. 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.

[0343] 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.

[0344] In some embodiments, a multi-zone reactor is a continuous reactor comprising a feed inlet, a plurality of spatially separated reaction zones configured to separately control temperature and mixing within each of the reaction zones, and a carbonaceous solids outlet, one of the reaction zones configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the reaction zones configured with a first gas outlet.

[0345] In some embodiments, the reactor comprises at least two, three, or four reaction zones. Each of the reaction zones is disposed in operative communication with an independently adjustable heating means. In some embodiments, the heating means independently comprise 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.

[0346] The reactor can be configured to separately adjust the gas phase composition and gas phase residence time of at least two reaction zones up to all reaction zones present in the reactor.

[0347] 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.

[0348] 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.

[0349] Certain embodiments utilize a rotary calciner with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotational speed affects the solids flow patterns, as well as heat and mass transport. Each of the reaction zones can be configured with flights disposed on the interior walls to provide agitation of the solids. The flights can be separately adjustable in each of the reaction zones.

[0350] 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.

[0351] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., to process biomass feedstock without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not contain augers, screws, or rakes, which tend to significantly reduce the size of the feedstock being pyrolyzed.

[0352] In some embodiments of the invention, the system further includes a thermal oxidizer disposed in operative communication with the outlet through which the condensable vapors and non-condensable gases are removed. The thermal oxidizer may be 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 some of the condensable vapors. Certain non-condensable gases, such as CO or CH4, may also be oxidized to CO2.

[0353] When a thermal oxidizer is used, the system may include a heat exchanger disposed between the thermal oxidizer and the dryer configured to utilize at least a portion of the heat of combustion for the dryer. This embodiment can contribute significantly to the overall energy efficiency of the process.

[0354] 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.

[0355] The system may further include a separate pyrolysis unit adapted to further pyrolyze the bio-reagent to further increase its carbon content. The separate pyrolysis unit may be a relatively simple container, unit, or device, such as a tank, barrel, bin, drum, tote, sack, or roll-off.

[0356] The entire system may be at a fixed location or 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.

[0357] Several variations on solid carbon enrichment will now be further described. In some embodiments, the process for producing a bio-reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes and at a pyrolysis temperature selected from about 250° C. to about 700° C. to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) optionally cooling the warm pyrolysis solids to produce cooler pyrolysis solids; (h) thereafter, passing at least a portion of the condensable vapors and / or at least a portion of the non-condensable gases from step (e) through the warm pyrolysis solids and / or the cold pyrolysis solids to form enhanced pyrolysis solids having increased carbon content; (i) recovering the biological reagent comprising at least a portion of the enhanced pyrolysis solid.

[0358] In some embodiments, step (h) comprises passing at least a portion of the condensable vapors 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 a portion of the non-condensable gases from step (e) through the warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content.

[0359] Alternatively or additionally, the vapor or gas may be contacted with the low temperature pyrolytic solids. In some embodiments, step (h) comprises passing at least a portion of the condensable vapors from step (e) in vapor 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 a portion of the non-condensable gases from step (e) through the low temperature pyrolytic solids to produce enhanced pyrolytic solids having increased carbon content.

[0360] 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.

[0361] In some embodiments, the process includes a method for treating or separating the steam or gas prior to using the steam or gas for carbon enrichment. In some embodiments, the intermediate feed stream comprising condensable steam or non-condensable gas resulting from step (e) can be fed to a separation unit configured to produce first and second output streams. In some embodiments, the intermediate feed stream comprises condensable steam and non-condensable gas.

[0362] 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.

[0363] 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.

[0364] 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 molecule selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapors from pyrolysis may include aromatic molecules such as benzene, toluene, ethylbenzene, and xylenes. Heavier aromatic molecules such as refractory tars may be present in the vapors. In some embodiments, the non-condensable gases include carbon-containing molecules. In some embodiments, the carbon-containing molecules include carbon monoxide, carbon dioxide, or methane, or a combination thereof.

[0365] 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.

[0366] In some embodiments, the first output stream comprises polar molecules and the second output stream comprises non-polar molecules. In some embodiments, the polar molecules comprise carbon-containing molecules. In some embodiments, the carbon-containing molecules comprise methanol, furfural, or acetic acid, or combinations thereof. In some embodiments, the non-polar molecules comprise carbon-containing molecules. In some embodiments, the carbon-containing molecules comprise carbon monoxide, carbon dioxide, methane, terpenes, terpene derivatives, or combinations thereof.

[0367] 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.

[0368] 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 molecules (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.

[0369] Depending on the conditions associated with step (h), it is possible for some amount of the volatile carbon to become fixed carbon (e.g., via Boudoir carbon formation from CO). Typically, the volatiles enter the micropores of the fixed carbon and exist as condensed / adsorbed species but remain relatively volatile. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0370] 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.

[0371] 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.

[0372] As another example, separation of acetic acid can be performed followed by reduction of the acetic acid to ethanol, which can be achieved, at least in part, using hydrogen derived from the non-condensable gases produced.

[0373] Condensable vapors can be used for either 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 above is also possible.

[0374] 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.

[0375] 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.

[0376] In some embodiments, a batch or continuous process for producing a bioreagent comprises: (a) providing a solids stream comprising a carbon-containing material; (b) providing a gas stream comprising a condensable carbon-containing vapor, a non-condensable carbon-containing gas, or a mixture of a condensable carbon-containing vapor and a non-condensable carbon-containing gas; (c) passing the gas stream through the solids stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0377] In some embodiments, the starting carbon-containing material is a pyrolyzed or torrefied biomass. The gas stream can be obtained during an integrated process to provide the carbon-containing material. Or, the gas stream can be obtained from a separate processing of the carbon-containing material. The gas stream or a portion thereof can be obtained from an external source (e.g., a sawmill oven). Mixtures of gas streams from various sources are possible, as well as mixtures of carbon-containing materials.

[0378] 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.

[0379] In some embodiments, the process further includes introducing the gas stream into a separation unit configured to produce at least first and second output streams, the gas streams including a mixture of condensable carbon-containing vapors and non-condensable carbon-containing gases. The first and second output streams can be separated based on relative volatility, relative polarity, or any other characteristic. The gas streams can be obtained from separate processing of carbon-containing materials.

[0380] 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.

[0381] The carbon-containing product can have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, relative to the starting carbon-containing material.

[0382] In a related variation, the bioreagent production system comprises: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor configured to contain at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone and having an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a 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.

[0383] The system may further comprise a preheat zone disposed in operative communication with the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within the multi-zone reactor. Each of the zones may be located within a single unit or within separate units. Also, a solids cooler may be disposed within the multi-zone reactor.

[0384] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet, thereby producing a substantially countercurrent flow of the gas phase relative 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 produce a substantially countercurrent flow of the gas phase relative to the solid phase.

[0385] 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; and (iv) a passageway defined between the upper and lower portions of the housing; and (v) a transport system following the pathway, the transport system configured to transport the solid, the housing being shaped such that the solid adsorbs at least a portion of the condensable vapors and / or at least a portion of the non-condensable gases.

[0386] The present invention can produce a variety of compositions useful as bioreagents, and products incorporating such reagents. In some variations, the bioreagents can be prepared using any of the processes disclosed herein, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes and at a pyrolysis temperature selected from about 250° C. to about 700° C. to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; and (h) recovering the bio-reagent comprising at least a portion of the low temperature pyrolysis solids.

[0387] 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.

[0388] 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., 0.1% or less by weight, sulfur on a dry basis.

[0389] 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.

[0390] Certain embodiments provide reagents that contain little or essentially no hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture present. Thus, some embodiments provide bioreagents that have 100% or less carbon on a dry / ash-free (DAF) basis.

[0391] 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.

[0392] Varying amounts of non-combustible materials, such as ash, may be present. The bioreagent may include about 10% or less, e.g., about 5%, about 2%, about 1% or less, by weight of non-combustible materials on a dry basis. In certain embodiments, the reagent contains little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon, including 100% carbon on a dry basis.

[0393] Various amounts of moisture may be present. On a total mass basis, the bioreagent may contain at least 1%, 2%, 5%, 10%, 15%, 25%, 35%, 50% or more moisture by weight. As intended herein, "moisture" should be interpreted as including any form of water present in the bioreagent, including absorbed moisture, adsorbed water molecules, chemical hydrates, and physical hydrates. The equilibrium moisture content may vary at least depending 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.

[0394] The bioreagent may have a variety of energy contents, which for the present purposes means an energy density based on the higher calorific value associated with the total combustion of the bone dry reagent. For example, the bioreagent may have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In certain embodiments, the energy content is about 14,000-15,000 Btu / lb. The energy content may be measured, for example, using ASTM D5865.

[0395] 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.

[0396] In some embodiments, the biological reagents are formed into structural objects comprising compressed, bound, or aggregated particles. The starting material for forming these objects may be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The objects may be formed by mechanical pressing or other forces, optionally with binders or other means of agglomerating the particles together.

[0397] In some embodiments, the bio-reagent is produced 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.

[0398] A bioreagent according to the present invention may be produced or formed into an object having a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or more. In various embodiments, the minimum or maximum dimension may be a length, width, or diameter.

[0399] Other variations of the invention relate to the incorporation of additives into the process, into the product, or both. In some embodiments, the biological reagent includes at least one process additive that is incorporated during the process. In these or other embodiments, the reagent includes at least one product additive that is introduced into the reagent after the process.

[0400] 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.

[0401] The additives may be selected from, but are in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0402] 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.

[0403] 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.

[0404] 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.

[0405] The first additive may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof, and the second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0406] In some 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 consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, ferric chloride, ferric bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0407] In some embodiments, the biological reagent consists essentially of, on a dry basis, carbon, hydrogen, nitrogen, phosphorus, sulfur, a non-combustible material, and an additive selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, and combinations thereof.

[0408] The amount of additive (or total additives) can vary widely, such as from about 0.01% to about 25% by weight, including about 0.1%, about 1%, about 5%, about 10%, or about 20% by weight. It will be appreciated, therefore, that when relatively large amounts of additives, such as greater than about 1% by weight, are incorporated, the energy content calculated based on the total reagent weight (including additives) will be reduced. Further, in various embodiments, the bioreagent with additives can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0409] The above discussion regarding product form also applies to embodiments incorporating additives, and indeed certain embodiments incorporate additives as binders, fluxing agents, or other modifiers to enhance final properties for particular applications.

[0410] In preferred embodiments, the majority of the carbon contained in the bioreagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. There may be certain market mechanisms (e.g., renewable identification numbers, tax credits, etc.) whereby value is attributed to the renewable carbon content in the bioreagent.

[0411] In certain embodiments, the fixed carbon can be classified as non-renewable carbon (e.g., from coal), while the volatile carbon, which can be added separately, can be renewable carbon to increase not only the energy content but also the renewable carbon value.

[0412] The bioreagents produced as described herein are useful for a wide variety of carbonaceous products. The bioreagents may themselves be desirable market products. Bioreagents as provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including higher renewable carbon content) compared to the state of the art.

[0413] In variations, the product comprises any of the biological reagents obtainable by the disclosed processes or described in the compositions set forth herein, or any portion, combination, or derivative thereof.

[0414] Generally speaking, bioreagents can be combusted to produce energy (including electricity and heat); partially oxidized, gasified, or steam reformed to produce syngas; utilized for their adsorption or absorption properties; utilized for their reactive properties in metal refining (such as reduction of metal oxides) or other industrial processes; or utilized for their material properties in carbon steels and various other metal alloys. Essentially, bioreagents can be utilized in any market application of carbon-based commodities or advanced materials, including specialized uses to be developed.

[0415] Prior to suitability or actual use in any product application, the disclosed bioreagents can be analyzed, measured, and optionally modified (such as by additives) in a variety of ways. Some potentially important properties beyond chemical composition and energy content include density, particle size, surface area, microporosity, absorbency, adsorption, binding capacity, reactivity, desulfurization activity, and basicity, to name a few.

[0416] Products or materials into which these biological reagents may be incorporated include, but are in no way limited to, carbon-based blast furnace addition products, carbon-based taconite pellet addition products, ladle addition carbon-based products, metcoke carbon-based products, coal replacement products, carbon-based coking products, carbon breeze products, fluidized bed carbon-based feedstocks, carbon-based furnace addition products, injectable carbon-based products, pulverized carbon-based products, stoker carbon-based products, carbon electrodes, or activated carbon products.

[0417] Use of the disclosed bio-reagents in metal production can reduce slag, increase overall efficiency, and reduce life cycle environmental impacts. Thus, embodiments of the present invention are particularly well suited for metals processing and production.

[0418] Some variations of the present invention utilize bio-reagents as carbon-based blast furnace addition products. A blast furnace is a type of metallurgical furnace used in smelting to produce industrial metals such as (but not limited to) iron. Smelting is a form of extractive metallurgy and its primary use is to produce metals from their ores. Smelting uses heat and chemical reducing agents to break down the ore. Carbon and / or carbon monoxide derived from the carbon removes the oxygen from the ore, leaving behind the elemental metal.

[0419] In some embodiments, the reducing agent comprises a bio-reagent. In some embodiments, the reducing agent consists essentially of a bio-reagent. In a blast furnace, the bio-reagent, ore, and limestone can be continuously fed through the top of the furnace, while air (optionally with oxygen enrichment) is blown into the bottom of the chamber, so that chemical reactions occur throughout the furnace as the material moves downward. The end products include molten metal and slag phases removed from the bottom, and flue gases exiting the top of the furnace. The downward flow of ore in contact with the upward flow of hot carbon monoxide enriched gas is a countercurrent process.

[0420] Carbon quality in a blast furnace is measured by its resistance to degradation. The role of carbon as a permeable medium is important in economical blast furnace operation. Carbon decomposition varies with location in the blast furnace and involves a combination of reactions with CO2, H2O, or O2 and attrition of carbon particles to each other and to other components of the charge. Decomposed carbon particles can cause clogging and reduced performance.

[0421] Coke reactivity test is a highly regarded measure of the performance of carbon in a blast furnace. This test has two components: Coke Reactivity Index (CRI) and Reacted Coke Strength (CSR). Carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​are preferred for better blast furnace performance. CRI can be determined as received according to any suitable method known in the art, for example, by ASTM method DS341.

[0422] In some embodiments, the bio-reagent provides a carbon product with properties suitable for direct introduction into a blast furnace.

[0423] The strength of the bio-reagent can be determined by any suitable method known in the art, for example, by drop splash test or CSR test. In some embodiments, the bio-reagent, when optionally blended with another carbon source, provides a final carbon product having a CSR of at least about 50%, 60%, or 70%. The combined product may also provide a final coke product having a suitable reactivity for combustion in a blast furnace. In some embodiments, the product has a CRI such that the bio-reagent is suitable for use as an additive or replacement for met-coal, met-coke, coke breeze, foundry coke, or injectable coal.

[0424] Some embodiments employ one or more additives in an amount sufficient to provide a bio-reagent that, when added to another carbon source (e.g., coke) having insufficient CRI or CSR for use as a blast furnace product, provides a composite product having sufficient CRI and / or CSR for use in a blast furnace. In some embodiments, the one or more additives are present in an amount sufficient to provide a bio-reagent with a CRI of about 40%, 30%, or 20% or less.

[0425] In some embodiments, one or more additives selected from alkaline earth metals, or their oxides or carbonates, are introduced during or after the process of producing the bio-reagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate can be introduced as additives. By adding these molecules before, during, or after pyrolysis, the reactivity of the bio-reagent in the blast furnace can be increased. These molecules can result in stronger materials, i.e., higher CSR, thereby improving the blast furnace efficiency. In addition, additives such as those selected from alkaline earth metals, or their oxides or carbonates, can result in lower emissions (e.g., SO2).

[0426] In some embodiments, the blast furnace replacement product is a bioreagent according to the present invention comprising at least about 55% carbon by weight, about 0.5% or less sulfur, about 8% or less non-combustible materials, and a calorific value of at least about 11,000 Btu / lb. In some embodiments, the blast furnace replacement product further comprises about 0.035% or less phosphorus, about 0.5% to about 50% volatile materials by weight, and optionally one or more additives. In some embodiments, the blast furnace replacement product comprises about 2% to about 15% dolomite by weight, about 2% to about 15% dolomitic lime by weight, about 2% to about 15% bentonite by weight, and / or about 2% to about 15% calcium oxide by weight. In some embodiments, the blast furnace replacement product has a size substantially in the range of about 1 cm to about 10 cm.

[0427] In some embodiments, the bio-reagents according to the present invention are useful as foundry coke replacement products. Foundry coke generally comprises at least about 85% by weight carbon content, about 0.6% by weight sulfur content, about 1.5% by weight or less volatile matter, about 13% by weight or less ash, about 8% by weight or less moisture, about 0.035% by weight phosphorus, a CRI value of about 30, and dimensions ranging from about 5 cm to about 25 cm.

[0428] Some variations of the invention utilize bio-reagents as carbon-based taconite pellet addition products. The ores used in making iron and steel are iron oxides. The main iron oxide ores include hematite, limonite (also called brown ore), taconite, and magnetite, a black ore. Taconite is a low-grade but important ore that contains both magnetite and hematite. The iron content of taconite is generally between 25% and 30% by weight. Blast furnaces typically require at least 50% iron-containing ore by weight for efficient operation. Iron ore can undergo beneficiation, including crushing, screening, tumbling, flotation, and magnetic separation. Refined ore is often concentrated to over 60% iron and formed into pellets before delivery.

[0429] For example, taconite can be ground into a fine powder and combined with a binder such as bentonite clay and limestone. For example, pellets about one centimeter in diameter containing about 65% iron by weight can be formed. The pellets are calcined to oxidize the magnetite to hematite. The pellets are durable and ensure that the blast furnace charge remains porous enough to allow heated gases to pass through and react with the pelletized ore.

[0430] The taconite pellets can be fed into a blast furnace to produce iron, as described above with respect to blast furnace addition products. In some embodiments, bio-reagents are introduced into the blast furnace. In these or other embodiments, the bio-reagents are incorporated into the taconite pellets themselves. For example, beneficiated taconite ore powder can be mixed with bio-reagents and binders, rolled into small bodies, and then baked until hard. In such embodiments, taconite-carbon pellets having the appropriate composition can be conveniently introduced into a blast furnace without the need for a separate carbon source.

[0431] Some variations of the present invention utilize bio-reagents as ladle-added carbon-based products. A ladle is a vessel used to transport and pour out molten metal. A casting ladle is used to pour molten metal into a mold to produce a casting. A transfer ladle is used to transfer large quantities of molten metal from one process to another. A processing ladle is used for processes that occur in the ladle to change some aspect of the molten metal, such as the conversion of cast iron to ductile iron by the addition of various elements to the ladle.

[0432] The bio-reagent can be introduced into any type of ladle, but typically, carbon is added to a treatment ladle in a suitable amount based on the target carbon content. The carbon injected into the ladle can be in the form of a fine powder for good mass transfer of the carbon to the final composition. In some embodiments, the bio-reagent according to the present invention, when used as a ladle-added product, has a minimum dimension of about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or more.

[0433] In some embodiments, the high carbon bio-reagents according to the present invention are useful as ladle added carbon additives, for example, in basic oxygen furnace or electric arc furnace facilities where ladle addition of carbon is used (e.g., added to ladle carbon during steel production).

[0434] In some embodiments, the ladle added carbon additive further comprises up to about 5% by weight manganese, up to about 5% by weight calcium oxide, and / or up to about 5% by weight dolomitic lime.

[0435] Direct reduced iron (DRI), also called sponge iron, is produced from the direct reduction of iron ore (in lump, pellet, or fine form) with reducing gases traditionally produced from natural gas or coal. The reducing gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide, which act as reducing agents. The bio-reagents provided herein can be converted into a gas stream containing CO to act as a reducing agent to produce direct reduced iron.

[0436] Iron nuggets are a high quality steelmaking and iron casting feed material. Iron nuggets are essentially all iron and carbon with little gangue (slag) and low levels of metallic residuals. They are a premium grade pig iron product with excellent shipping and handling characteristics. The carbon contained in the iron nuggets or any portion thereof can be a bio-reagent as provided herein. Iron nuggets can be produced by reducing iron ore in a rotary hearth furnace using a bio-reagent as a reducing agent and energy source.

[0437] Some variations of the present invention utilize the bioreagent as a metallurgical coke carbon-based product. Metallurgical coke, also known as "meth" coke, is a carbonaceous material typically produced by destructive distillation of various blends of bituminous coal. The final solid is unmelted carbon, called metallurgical coke. As a result of the loss of volatile gases and partial melting, met-coke has an open-porous morphology. Met-coke has a very low volatile content. However, ash components that were part of the original bituminous coal feedstock remain encapsulated in the resulting coke. Met-coke feedstock is available in a wide range of sizes, from fine powder to basketball-sized chunks. Typical purity ranges from 86-92% fixed carbon by weight.

[0438] Metallurgical coke is used wherever high quality, tough, resilient wear carbon is required. Applications include, but are not limited to, conductive flooring, friction materials (e.g., carbon linings), foundry coatings, foundry carbon risers, corrosion materials, drilling applications, reducing agents, heat treating agents, ceramic packing media, electrolytic processes, and oxygen scavenging.

[0439] Metcoke generally comprises a heating value of about 10,000-14,000 Btu / lb and an ash content of about 10% or more by weight. Thus, in some embodiments, the metcoke replacement product comprises a bioreagent according to the present invention comprising at least about 80%, 85%, or 90% by weight carbon, about 0.8% or less by weight sulfur, about 3% or less by weight volatiles, about 15% or less by weight ash, about 13% or less by weight moisture, and about 0.035% or less by weight phosphorus. The bioreagent according to the present invention, when used as a metcoke replacement product, can have a size range of, for example, about 2 cm to about 15 cm.

[0440] In some embodiments, the metcoke replacement product further comprises additives such as chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorospar, calcium oxide, lime, dolomitic lime, bentonite, and combinations thereof.

[0441] Some variations of the present invention utilize bio-reagents as coal replacement products. Any process or system that uses coal can in principle be adapted to use bio-reagents.

[0442] In some embodiments, the bio-reagents are combined with one or more coal-based products to form a composite product that has a higher grade than the coal-based product and / or has lower emissions when combusted than the pure coal-based product.

[0443] For example, low rank coal, such as sub-bituminous coal, can be used in applications that would normally require a higher rank coal product, such as bituminous coal, by combining a selected amount of a bio-reagent according to the present invention with the low rank coal product. In other embodiments, the grade of a blended coal product (e.g., a combination of multiple coals of different ranks) can be improved by combining the blended coal with an amount of bio-reagent. The amount of bio-reagent to be mixed with the coal product can vary depending on the grade of the coal product, the properties of the bio-reagent (e.g., carbon content, heating value, etc.), and the desired grade of the final combined product.

[0444] For example, anthracite coal may have at least about 80% by weight carbon, about 0.6% by weight sulfur, about 5% by weight volatile matter, up to about 15% by weight ash, up to about 10% by weight moisture, and a heating value of about 12,494 Btu / lb. In some embodiments, the anthracite coal substitute product is a bioreagent that includes at least about 80% by weight carbon, up to about 0.6% by weight sulfur, up to about 15% by weight ash, and a heating value of at least about 12,000 Btu / lb.

[0445] In some embodiments, the bio-reagent is useful as a thermal coal replacement product. Thermal coal products can generally have high sulfur levels, high phosphorus levels, high ash content, and a heating value of up to about 15,000 Btu / lb. In some embodiments, the thermal coal replacement product is a bio-reagent that includes about 0.5% or less by weight sulfur, about 4% or less by weight ash, and a heating value of at least about 12,000 Btu / lb.

[0446] Some variations of the present invention utilize the bio-reagent as a carbon-based coking product. Any coking process or system can be adapted to use the bio-reagent to produce coke or to use the bio-reagent as a coke feedstock.

[0447] In some embodiments, the bio-reagent is useful as a thermal coal or coke substitute product. In some embodiments, the thermal coal or coke substitute product comprises a bio-reagent comprising at least about 50% by weight carbon, up to about 8% by weight ash, up to about 0.5% by weight sulfur, and a heating value of at least about 11,000 Btu / lb. In some embodiments, the thermal coke substitute product further comprises between about 0.5% by weight and about 50% by weight volatile matter. In some embodiments, the thermal coal or coke substitute product comprises at least about 0.4% by weight and up to about 15% by weight moisture.

[0448] In some embodiments, the bio-reagent is useful as a petroleum (pet) coke or calcined pet coke replacement product. Calcined pet coke can generally have at least about 66% carbon by weight, up to about 4.6% sulfur by weight, up to about 5.5% volatiles by weight, up to about 19.5% ash by weight, and up to about 2% moisture by weight, typically about 3 mesh or less in size. In some embodiments, the calcined pet coke replacement product is a bio-reagent that includes at least about 66% carbon by weight, up to about 4.6% sulfur by weight, up to about 19.5% ash by weight, and up to about 2% moisture by weight, and is about 3 mesh or less in size.

[0449] In some embodiments, the bio-reagent is useful as a coking carbon replacement carbon (e.g., co-calcined with metallurgical coal in a coking furnace). In one embodiment, the coking carbon replacement product is a bio-reagent that includes at least about 55% by weight carbon, no more than about 0.5% by weight sulfur, no more than about 8% by weight non-combustible materials, and a heating value of at least about 11,000 Btu / lb. In some embodiments, the coking carbon replacement product includes about 0.5% to about 50% by weight volatile materials, and / or one or more additives.

[0450] Some variations of the invention utilize the bio-reagent as a carbon breeze product, which typically has a very fine particle size, such as 6 mm, 3 mm, 2 mm, 1 mm, or less. In some embodiments, the bio-reagent according to the invention is useful as a coke breeze replacement product. Coke breeze may generally have a maximum dimension of about 6 mm or less, a carbon content of at least about 80% by weight, 0.6-0.8% by weight sulfur, 1%-20% by weight volatile matter, up to about 13% by weight ash, and up to about 13% by weight moisture. In some embodiments, the coke breeze replacement product is a bio-reagent according to the invention that includes at least about 80% by weight carbon, about 0.8% by weight or less sulfur, about 20% by weight or less volatile matter, about 13% by weight or less ash, about 13% by weight or less moisture, and a maximum dimension of about 6 mm.

[0451] In some embodiments, the bio-reagents are useful as carbon breeze replacement products, for example, during taconite pellet production or in the steelmaking process.

[0452] Some variations utilize the bioreagent as a feedstock for various fluidized beds or as a fluidized bed carbon-based feedstock alternative product. The carbon can be used in the fluidized bed for total combustion, partial oxidation, gasification, steam reforming, etc. The carbon can be primarily converted to synthesis gas for various downstream uses including the production of energy (e.g., combined heat and power) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel fuel).

[0453] In some embodiments, bio-reagents according to the present invention are useful as fluidized bed coal replacement products, for example in fluidized bed furnaces, wherever coal is used (e.g., for process heat or energy generation).

[0454] Some variations utilize bioreagent as a carbon-based furnace addition product. Coal-based carbon furnace addition products can generally have high sulfur levels, high phosphorus levels, and high ash content, which contribute to the degradation of metal products and create air pollution. In some embodiments, the carbon furnace addition replacement product with bioreagent contains about 0.5% or less by weight sulfur, about 4% or less by weight ash, about 0.03% or less by weight phosphorus, and a maximum dimension of about 7.5 cm. In some embodiments, the carbon furnace addition replacement product contains about 0.5% to about 50% by weight volatiles and about 0.4% to about 15% by weight moisture.

[0455] In some embodiments, the bio-reagents are useful as furnace-added carbon additives wherever furnace-added carbon is used, for example, in basic oxygen furnaces or electric arc furnace facilities. For example, furnace-added carbon can be added to scrap steel during steel production in electric arc furnace facilities. In electric arc furnace applications, high purity carbon is desirable so that impurities are not added back into the process after early removal.

[0456] In some embodiments, the furnace-added carbon additive is a bioreagent comprising at least about 80% by weight carbon, up to about 0.5% by weight sulfur, up to about 8% by weight non-combustible material, and a heating value of at least about 11,000 Btu / lb. In some embodiments, the furnace-added carbon additive further comprises up to about 5% by weight manganese, up to about 5% by weight fluorospar, from about 5% to about 10% by weight dolomite, from about 5% to about 10% by weight dolomitic lime, and / or from about 5% to about 10% by weight calcium oxide.

[0457] Some variations utilize the bio-reagent as a stoker furnace carbon-based product. In some embodiments, the bio-reagent according to the present invention is useful as a stoker coal replacement product, for example, in stoker furnace facilities, wherever coal is used (e.g., for process heat or energy generation).

[0458] Some variations utilize the bio-reagent as an injectable (e.g., pulverized) carbon-based material. In some embodiments, the bio-reagent is useful as an injection grade calcined pet coke replacement product. Injection grade calcined pet coke can generally have at least about 66% carbon by weight, about 0.55 to about 3% sulfur by weight, up to about 5.5% volatiles by weight, up to about 10% ash by weight, up to about 2% moisture by weight, and is about 6 mesh or less in size. In some embodiments, the calcined pet coke replacement product is a bio-reagent that includes at least about 66% carbon by weight, up to about 3% sulfur by weight, up to about 10% ash by weight, up to about 2% moisture by weight, and is about 6 mesh or less in size.

[0459] In some embodiments, the bio-reagents are useful as injectable carbon replacement products in any application where injectable carbon is used (e.g., injected into slag or ladles during steel production), such as in basic oxygen furnace or electric arc furnace facilities.

[0460] In some embodiments, the bio-reagent is useful, for example, as a pulverized charcoal replacement product wherever pulverized charcoal is used (e.g., for process heat or energy generation). In some embodiments, the pulverized charcoal replacement product comprises up to about 10 percent calcium oxide.

[0461] Some variations utilize the bio-reagent as a carbon addition product for metal production. In some embodiments, the bio-reagent according to the present invention is useful as a carbon addition product for the production of carbon steel or another metal alloy containing carbon. Coal-based late stage carbon addition products generally may have high sulfur levels, high phosphorus levels, and high ash content, as well as high mercury levels that reduce metal quality and contribute to air pollution. In some embodiments of the present invention, the carbon addition product comprises about 0.5% by weight or less of sulfur, about 4% by weight or less of ash, about 0.03% by weight or less of phosphorus, a minimum dimension of about 1-5 mm, and a maximum dimension of about 8-12 mm.

[0462] Some variations utilize a bio-reagent within a carbon electrode, which in some embodiments is useful as an electrode (e.g., anode) material suitable for use in aluminum production and the like.

[0463] Other uses of bioagents in carbon electrodes include applications in batteries, fuel cells, capacitors, and other energy storage or energy delivery devices. For example, in lithium ion batteries, bioagents can be used on the anode side to intercalate lithium. In these applications, carbon purity and low ash content can be very important.

[0464] Some variations of the present invention utilize the bioreagent as a catalyst support. Carbon is a known catalyst support in a wide range of catalytic chemical reactions, such as the synthesis of mixed alcohols from syngas using sulfided cobalt-molybdenum metal catalysts supported on a carbon phase, or iron-based catalysts supported on carbon for the Fischer-Tropsch synthesis of higher hydrocarbons from syngas.

[0465] Some variations utilize bioreagents as activated carbon products. Activated carbon is used in a wide variety of liquid and gas phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, and pharmaceuticals. For activated carbon, the porosity and surface area of ​​the material are generally important. The bioreagents provided herein, in various embodiments, can provide superior activated carbon products due to (i) greater surface area than fossil fuel-based activated carbons; (ii) carbon renewables; (iii) the vascular nature of the biomass feedstock in combination with additives allows better penetration / distribution of additives to enhance pollutant control; and (iv) less inert material (ash) resulting in greater reactivity.

[0466] In the above description of market applications for bioreagents, it should be recognized that the applications described are not exclusive or exhaustive. Thus, a bioreagent described as suitable for one type of carbon product may, in various embodiments, be suitable for any other application described. These applications are exemplary only, and there are other applications for bioreagents.

[0467] Additionally, in some embodiments, the same physical material may be used in multiple market processes, either in an integrated manner or sequence. Thus, for example, a bio-reagent used as a carbon electrode or activated charcoal may, at the end of its useful life as a performance material, be introduced into a combustion process for energy value or into a metal production (e.g., reduction of metal ores) process, etc.

[0468] Some embodiments may use the bio-reagent both for its reactivity / adsorption properties and as a fuel, for example, a bio-reagent injected into the exhaust stream may be suitable for removing contaminants and subsequently combusting the bio-reagent particles and possibly the contaminants to generate energy and thermally destroy or chemically oxidize the contaminants.

[0469] Compared to traditional fossil fuel-based products, bioreagents can entail significant environmental and product use advantages: Not only can bioreagents be environmentally superior, they can also be functionally superior from a processing standpoint, for example, due to their higher purity.

[0470] For some embodiments of metal production, production of bio-reagents by the disclosed process produces significantly less CO, CO2, NO, and CO2 than the coking of coal-based products required to prepare them for use in metal production. x , SO2, and harmful air pollutants.

[0471] The use of bioreagents instead of coal or coke also significantly reduces environmental emissions of SO2, hazardous air pollutants, and mercury.

[0472] Additionally, due to the purity of these bio-reagents (including low ash content), the disclosed bio-reagents have the potential to reduce slag and increase production capacity in batch metal fabrication processes.

[0473] In some embodiments, the bio-reagent functions as activated carbon, for example, a low fixed carbon material can be activated, a high fixed carbon material can be activated, or both materials can be activated such that the bio-carbon composition (blend) functions as activated carbon.

[0474] In certain embodiments, a portion of the bio-reagent is recovered as an activated carbon product, and another portion (e.g., the remaining portion) of the bio-reagent is pelletized using a binder to produce bio-carbon pellets. In other embodiments, the bio-reagent is pelletized using a binder to produce bio-carbon pellets, and these bio-carbon pellets are delivered for later conversion to the activated carbon product. Later conversion may include pulverization back to a powder, or may include chemical treatment, for example, with steam, acid, or base. In these embodiments, the bio-carbon pellets may be considered activated carbon precursor pellets.

[0475] In certain embodiments, the fixed carbon in the bio-reagent can be used primarily to make activated carbon and the volatile carbon in the bio-reagent can be used primarily to make reducing gas. For example, at least 50% by weight, at least 90% by weight, or essentially all of the fixed carbon in the bio-reagent produced in step (b) can be recovered as activated carbon in step (f), while, for example, at least 50% by weight, at least 90% by weight, or essentially all of the volatile carbon in the bio-reagent produced in step (b) can be directed to reducing gas (e.g., via a steam reforming reaction of the volatile carbon to CO).

[0476] In some embodiments, the activated carbon comprises an iodine value of at least about 500, 750, 800, 1000, 1500, or 2000. In some embodiments, the activated carbon comprises 14 C / 12 In some embodiments, the activated carbon comprises at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95% renewable carbon content as determined from C isotope ratio measurements. 14 C / 12 It consists essentially of renewable activated carbon, as determined from C isotope ratio measurements.

[0477] In some embodiments, the pyrolysis reactor is configured to optimize the production of different types of activated carbon. For example, reaction conditions (e.g., time, temperature, and water vapor concentration) can be selected for an activated carbon product with a particular attribute, such as iodine value. Different reaction conditions can be selected for a different activated carbon product, such as one with a higher iodine value. The pyrolysis reactor can operate in a campaign mode to produce one product and then switch to another mode for another product. The first product may be continuously or periodically removed during the first campaign, or may be removed before switching the reaction conditions of the pyrolysis reactor.

[0478] In some embodiments, the activated carbon comprises an iodine value of at least about 500, at least about 750, at least about 1000, at least about 1500, or at least about 2000. ... 14 C / 12 The activated carbon comprises at least about 90% renewable carbon content as determined from C isotope ratio measurements. In some embodiments, the activated carbon comprises 14 C / 12 It consists essentially of renewable activated carbon, as determined from C isotope ratio measurements.

[0479] The activated carbon produced by the processes disclosed herein can be used in a number of ways.

[0480] In some embodiments, activated carbon is utilized internally at a process site to purify one or more primary products. In some embodiments, activated carbon is utilized on-site to purify water. In these or other embodiments, activated carbon is utilized on-site to treat liquid waste streams to reduce liquid phase emissions and / or to treat steam waste streams to reduce air emissions. In some embodiments, activated carbon is utilized as a soil amendment to aid in the generation of new biomass, which may be the same type of biomass utilized on-site as the local feedstock.

[0481] Activated carbon prepared according to the processes disclosed herein may have the same or better properties than conventional fossil fuel-based activated carbon. In some embodiments, the activated carbon has a surface area comparable to, equal to, or greater than that associated with fossil fuel-based activated carbon. In some embodiments, the activated carbon can control contaminants similar to or better than conventional activated carbon products. In some embodiments, the activated carbon has an inert material (e.g., ash) level comparable to, equal to, or less than that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle size or particle size distribution comparable to, equal to, greater than, and / or less than that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle shape comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle shape substantially different from that associated with conventional activated carbon products. In some embodiments, the activated carbon has a pore volume that is comparable, equal to, or greater than the pore volume associated with a conventional activated carbon product. In some embodiments, the activated carbon has a pore size that is comparable, substantially similar, or the same as the pore size associated with a conventional activated carbon product. In some embodiments, the activated carbon has a particle abrasion resistance value that is comparable, substantially similar, or the same as the particle abrasion resistance value associated with a conventional activated carbon product. In some embodiments, the activated carbon has a hardness value that is comparable, substantially similar, or the same as the hardness value associated with a conventional activated carbon product. In some embodiments, the activated carbon has a bulk density value that is comparable, substantially similar, or the same as the bulk density value associated with a conventional activated carbon product. In some embodiments, the activated carbon product has an adsorption capacity that is comparable, substantially similar, or the same as the adsorption capacity associated with a conventional activated carbon product.

[0482] Prior to suitability or actual use in any product application, the disclosed activated carbons can be analyzed, measured, and optionally modified (such as by additives) in a variety of ways. Some properties of potential importance include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, basicity, hardness, and iodine number.

[0483] Activated carbon is used commercially in a wide variety of liquid and gas phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, sugar and sweetener refining, automotive applications, and pharmaceuticals. For activated carbon, key product attributes can include particle size, shape, composition, surface area, pore volume, pore dimensions, particle size distribution, carbon surface and internal chemistry, particle attrition resistance, hardness, bulk density, and adsorption capacity.

[0484] The bulk density for bioactivated carbon can be, for example, from about 50 g / liter to about 650 g / liter.

[0485] The surface area of ​​the bioactivated carbon can vary widely. An exemplary surface area (e.g., BET surface area) is about 400 m 2 / g~about 2000m 2 / g or more, e.g., about 500m 2 / g, 600m 2 / g, 800m 2 / g, 1000m 2 / g, 1200m 2 / g, 1400m 2 / g, 1600m 2 / g, or 1800m 2 / g. Surface area generally correlates with adsorption capacity.

[0486] The pore size distribution can be important in determining the ultimate performance of the activated carbon. Pore size measurements can include micropore content, mesopore content, and macropore content.

[0487] Iodine number is a parameter used to characterize activated carbon performance. Iodine number measures the degree of activation of the carbon and is a measure of the micropore (e.g., 0-20 Å) content. It is an important measurement for liquid phase applications. Exemplary iodine numbers for activated carbon products produced by embodiments of the present disclosure include about 500, 600, 750, 900, 1000, 1100, 1200, 1300, 1500, 1600, 1750, 1900, 2000, 2100, and 2200, including all intervening ranges. The units of iodine number are milligrams of iodine per gram of carbon.

[0488] Another pore-related measurement is the Methylene Blue Number, which measures mesopore content (e.g., from 20 to 500 Å). Exemplary Methylene Blue Numbers for activated carbon products produced by embodiments of the present disclosure include about 100, 150, 200, 250, 300, 350, 400, 450, and 500, including all intervening ranges. The units of Methylene Blue Number are milligrams of methylene blue (methylthioninium chloride) per gram of carbon.

[0489] Another pore-related measurement is the Molasses Number, which measures macropore content (e.g., >500 Å). Exemplary Molasses Numbers for activated carbon products produced by embodiments of the present disclosure include 100, 150, 200, 250, 300, 350, and 400, including all intervening ranges. The units of Molasses Number are milligrams of molasses per gram of carbon.

[0490] In some embodiments, the activated carbon has a density of at least about 0.5 cm3 / g, e.g., at least about 1 cm3 / g. 3 / g mesopore volume.

[0491] Activated carbon can be characterized by its water retention capacity. In various embodiments, activated carbon products produced according to embodiments of the present disclosure have a water retention capacity at 25° C. of about 10% to about 300% (weight of water divided by weight of dry activated carbon), e.g., about 50% to about 100%, e.g., about 60% to about 80%.

[0492] Hardness or wear number is a measure of the wear resistance of activated carbon. It is an indication of the physical integrity of activated carbon to withstand frictional forces and mechanical stresses during handling or use. While some hardness is desirable, too much hardness can cause excessive equipment wear. Exemplary wear numbers measured according to ASTM D3802 range from about 1% to greater than about 99%, for example, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or at least greater than about 99%.

[0493] In some embodiments, the activated carbon can achieve an optimum range of hardness that is moderately abrasive but does not cause wear and tear on the capital equipment that processes the activated carbon. This optimum is possible in some embodiments of the present disclosure through the selection of feedstocks and processing conditions. In some embodiments where downstream uses can handle high hardness, the process of the present disclosure can be operated to increase or maximize hardness to produce a bioactivated carbon product having an abrasion number of about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or at least about 99%.

[0494] The biogenic activated carbon provided by the present disclosure has a wide range of commercial uses. For example, but not limited to, the biogenic activated carbon can be utilized in emission control, water purification, ground water treatment, wastewater treatment, air stripper applications, PCB removal applications, odor removal applications, soil vapor extraction, manufactured gas plants, industrial water filtration, industrial fumigation, tanks and process vents, pumps, blowers, filters, pre-filters, mist filters, piping, piping modules, adsorber, absorbers, and columns.

[0495] In one embodiment, a method of using activated carbon to reduce emissions includes: (a) providing activated carbon particles comprising a bioactivated carbon composition recovered from a second reactor as disclosed herein; (b) providing a gas phase exhaust stream containing at least one selected contaminant; (c) providing an additive selected to assist in the removal of selected contaminants from the gas phase effluent stream; (d) introducing the activated carbon particles and the additive into the gas-phase exhaust stream, thereby adsorbing at least a portion of the selected contaminants onto the activated carbon particles, thereby producing contaminant-adsorbed carbon particles in the gas-phase exhaust stream; (e) separating a portion of the contaminant-adsorbed carbon particles from the gas-phase exhaust stream to produce a contaminant-reduced gas-phase exhaust stream.

[0496] The additive for the bioactivated carbon composition may be provided as part of the activated carbon particles. Alternatively or additionally, the additive may be introduced directly into the gas phase exhaust stream, fuel bed, or combustion zone. As will be appreciated by those skilled in the art, other methods of introducing the additive directly or indirectly into the gas phase exhaust stream for removal of selected pollutants are also possible.

[0497] In some embodiments, the selected contaminant (in the gas-phase exhaust stream) comprises a metal. In some embodiments, the metal comprises mercury, boron, selenium, arsenic, salts thereof, or combinations thereof. In some embodiments, the selected contaminant comprises a hazardous air pollutant, an organic molecule (such as a volatile organic compound, or "VOC"), or a non-condensable gas. In some embodiments, the biogenic activated carbon product adsorbs, absorbs, or chemisorbs the contaminant in a greater amount than a comparable amount of a non-biogenic activated carbon product. In some embodiments, the contaminant is a metal, a hazardous air pollutant, an organic molecule (such as a VOC), a non-condensable gas, or a combination thereof. In some embodiments, the contaminant comprises mercury. In some embodiments, the contaminant comprises a VOC. In some embodiments, the biogenic activated carbon comprises at least about 1% hydrogen by weight or at least about 10% oxygen by weight.

[0498] A hazardous air pollutant is a pollutant that causes or may cause cancer or other serious health effects, such as reproductive effects or birth defects, or adverse environmental and ecological effects. Section 112 of the Clean Air Act, as amended, is incorporated herein by reference in its entirety. Pursuant to Section 112 of the Clean Air Act, the United States Environmental Protection Agency (EPA) is mandated to control 189 hazardous air pollutants. Any current or future molecule classified by the EPA as a hazardous air pollutant is included in the possible selected pollutants in this context.

[0499] Volatile organic molecules, some of which are hazardous air pollutants, are organic chemicals that have high vapor pressures at normal room temperature conditions. Examples include short-chain alkanes, olefins, alcohols, ketones, and aldehydes. Many volatile organic molecules are hazardous to human health or harmful to the environment. The EPA regulates volatile organic molecules in air, water, and land. The EPA definition of a volatile organic molecule is set forth in 40 CFR Section 51.100, which is incorporated herein by reference in its entirety.

[0500] A non-condensable gas is a gas that does not condense under normal room temperature conditions and may include, but is not limited to, oxides of nitrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, sulfur dioxide, sulfur trioxide, methane, ethane, ethylene, ozone, ammonia, or combinations thereof.

[0501] Multiple contaminants can be removed by the disclosed activated carbon particles. In some embodiments, the contaminant-adsorbed carbon particles include at least two contaminants, at least three contaminants, or more. The activated carbons disclosed herein can allow for the control of multiple contaminants as well as the control of specific target contaminants (e.g., selenium).

[0502] In some embodiments, the pollutant-adsorbed carbon particles are treated to regenerate the activated carbon particles. In some embodiments, the method includes thermally oxidizing the pollutant-adsorbed carbon particles. The pollutant-adsorbed carbon particles, or a regenerated form thereof, can be combusted to provide energy.

[0503] In some embodiments, the additive for the activated carbon is selected from an acid, a base, a salt, a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. In some embodiments, the additive comprises magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, an organic acid (e.g., citric acid), or a combination thereof.

[0504] In some embodiments, the gas phase exhaust stream is derived from metal processing, such as the processing of high sulfur content metal ores.

[0505] As an exemplary embodiment for mercury control, activated carbon can be injected (such as into piping) upstream of a particulate control device such as an electrostatic precipitator or fabric filter. In some cases, a flue gas desulfurization (dry or wet) system can be located downstream of the activated carbon injection point. The activated carbon can be pneumatically injected as a powder. The injection location can be determined by the existing plant configuration (unless it is a new site) and whether additional downstream particulate control equipment is being modified.

[0506] For boilers currently equipped with particulate control devices, implementing bioactivated carbon injection for mercury control may involve (i) injecting powdered activated carbon upstream of the existing particulate control device (electrostatic precipitator or woven filter), (ii) injecting powdered activated carbon downstream of the existing electrostatic precipitator and upstream of a retrofit woven filter, or (iii) injecting powdered activated carbon between the fields of the electrostatic precipitator. The inclusion of iron or iron-containing molecules can dramatically improve the performance of electrostatic precipitators for mercury control. Additionally, the inclusion of iron or iron-containing molecules can dramatically change end-of-life options by separating spent activated carbon solids from other ash.

[0507] In some embodiments, the powdered activated carbon injection approach can be used in combination with an existing SO2 control device. The activated carbon can be injected before the SO2 control device or after the SO2 control device, depending on the availability of a means to collect the activated carbon sorbent downstream of the injection point.

[0508] In some embodiments, the same physical material can be used in multiple processes, either in an integrated manner or sequence, so for example, activated carbon can be introduced at the end of its useful life as a performance material, into a combustion process for its energy value, or into a metal fabrication process that requires carbon but does not require the properties of activated carbon, etc.

[0509] The bioactivated carbon and principles of the present disclosure can be applied to liquid phase applications including, for example, the treatment of water, aqueous streams of various purities, solvents, liquid fuels, polymers, molten salts, and molten metals. As intended herein, "liquid phase" includes slurries, suspensions, emulsions, multi-phase systems, or any other material that has (or can be adjusted to have) at least some amount of a liquid state present.

[0510] In one embodiment, the present disclosure, in some variations, provides a method of using activated carbon to purify a liquid, comprising: (a) providing activated carbon particles recovered from a second reactor; (b) providing a liquid containing at least one selected contaminant; (c) providing an additive selected to assist in the removal of the selected contaminant from the liquid; (d) contacting the liquid with the activated carbon particles and the additive to adsorb at least one selected contaminant onto the activated carbon particles, thereby producing contaminant-adsorbing carbon particles and a contaminant-reducing liquid.

[0511] The additive may be provided as part of the activated carbon particles. Alternatively, the additive may be introduced directly into the liquid. In some embodiments, the additive (which may be the same or different) is introduced both as part of the activated carbon particles and directly into the liquid.

[0512] In some embodiments related to liquid phase applications, the additive comprises an acid, a base, a salt, a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. In some embodiments, the additive comprises magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, an organic acid (e.g., citric acid), or a combination thereof.

[0513] In some embodiments, the contaminant (as in the liquid to be treated) comprises a metal. In some embodiments, the metal comprises arsenic, boron, selenium, mercury, salts thereof, or combinations thereof. In some embodiments, the selected contaminant comprises an organic molecule (such as a VOC), a halogen, a biological molecule, a pesticide, or a herbicide. In some embodiments, the contaminant-adsorbed carbon particles comprise two, three, or more contaminants, or derivatives thereof. In some embodiments, the activated carbon product adsorbs, absorbs, or chemisorbs contaminants in greater amounts than a comparable amount of a non-biogenic activated carbon product. In some embodiments, the contaminant comprises a metal, a hazardous air pollutant, an organic molecule (such as a VOC), a non-condensable gas, or combinations thereof. In some embodiments, the selected contaminant comprises mercury. In some embodiments, the selected contaminant comprises a VOC. In some embodiments, the biogenic activated carbon comprises at least about 1% hydrogen by weight or at least about 10% oxygen by weight.

[0514] The liquid to be treated may typically be aqueous, but this is not required by the principles of the present disclosure. In some embodiments, the liquid is treated with activated carbon particles in a fixed bed. In other embodiments, the liquid is treated with activated carbon particles in solution or in a moving bed.

[0515] In one embodiment, the present disclosure provides a method for removing at least a portion of a sulfur-containing contaminant from a liquid using a biogenic activated carbon composition, comprising: (a) providing activated carbon particles recovered from a second reactor as disclosed herein; (b) providing a liquid containing sulfur-containing contaminants; (c) providing an additive selected to assist in the removal of sulfur-containing contaminants from the liquid; and (d) contacting the liquid with the activated carbon particles and the additive to adsorb or absorb at least a portion of the sulfur-containing contaminants onto or within the activated carbon particles.

[0516] In some embodiments, the sulfur-containing contaminant comprises elemental sulfur, sulfuric acid, sulfurous acid, sulfur dioxide, sulfur trioxide, sulfate anion, bisulfate anion, sulfite anion, bisulfite anion, thiol, sulfide, disulfide, polysulfide, thioether, thioacetal, sulfoxide, sulfone, thiosulfinate, sulfimide, sulfoximide, sulfondiimine, sulfur halide, thioketone, thioaldehyde, sulfur oxide, thiocarboxylic acid, thioamide, sulfonic acid, sulfinic acid, sulfenic acid, sulfonium, oxosulfonium, sulfurfuran, persulfuran, or salts thereof, or combinations thereof. For example, the sulfur-containing contaminant can be sulfate in anionic and / or salt form.

[0517] The liquid may be an aqueous liquid, such as water. In some embodiments, the water is wastewater associated with a process. In some embodiments, the process includes metal mining, acid mine drainage, mineral processing, municipal sewage treatment, pulp and paper, ethanol, or another industrial process that may discharge sulfur-containing contaminants into wastewater. In some embodiments, the water includes a natural body of water, such as a lake, river, or stream.

[0518] In one embodiment, the present disclosure provides a process for reducing the concentration of sulfate in water, comprising: (a) providing activated carbon particles recovered from a second reactor as disclosed herein; (b) providing a volume or flow of water containing sulfate; (c) providing an additive selected to assist in the removal of sulfates from the water; and (d) contacting the water with the activated carbon particles and the additive to adsorb or absorb at least a portion of the sulfate onto or into the activated carbon particles.

[0519] In some embodiments, sulfate is reduced to a concentration of about 50 mg / L or less in water, such as a concentration of about 10 mg / L or less in water. In some embodiments, sulfate is present primarily in the form of sulfate and / or bisulfate anions. Depending on the pH, sulfate may also be present in the form of sulfate salts.

[0520] The water may be derived from some or all of a wastewater stream. Exemplary wastewater streams may be associated with metal mining, acid mine drainage, mineral processing, municipal sewage treatment, pulp and paper, ethanol, or any other industrial process that may discharge sulfur-containing contaminants into the wastewater. The water may be a natural body of water, such as a lake, river, or stream. In some embodiments, the process is performed continuously. In other embodiments, the process is performed in batches.

[0521] When water is treated with activated carbon, there may be filtration of the water, permeation of the water, and / or direct addition of activated carbon particles to the water (with sedimentation, clarification, etc.). When permeation is used, activated carbon can be used in several ways within or to assist the permeation device. In some embodiments, activated carbon particles and additives are introduced directly into the water prior to permeation. Activated carbon particles and additives are optionally used in pre-filtration prior to permeation. In certain embodiments, activated carbon particles and additives are incorporated into the membrane for permeation.

[0522] In some embodiments, activated carbon is effective in removing sulfur-containing contaminants, including elemental sulfur, sulfuric acid, sulfurous acid, sulfur dioxide, sulfur trioxide, sulfate anion, bisulfate anion, sulfite anion, bisulfite anion, thiol, sulfide, disulfide, polysulfide, thioether, thioacetal, sulfoxide, sulfone, thiosulfinate, sulfimide, sulfoximide, sulfondiimine, sulfur halide, thioketone, thioaldehyde, sulfur oxide, thiocarboxylic acid, thioamide, sulfonic acid, sulfinic acid, sulfenic acid, sulfonium, oxosulfonium, sulfurfuran, persulfuran, or salts thereof, or combinations thereof.

[0523] Generally speaking, the disclosed activated carbon can be used in any application where conventional activated carbon may be used. In some embodiments, the activated carbon is used as a total (i.e., 100%) replacement for conventional activated carbon. In some embodiments, the activated carbon comprises essentially all or substantially all of the activated carbon used in a particular application. In some embodiments, the activated carbon comprises about 1% to about 100% bioactivated carbon.

[0524] For example, but not by way of limitation, activated carbon can be used in filters, either alone or in combination with conventional activated carbon products. In some embodiments, a packed bed or packed column comprises the disclosed activated carbon. In such embodiments, the biogenic activated carbon comprises a size suitable for the particular packed bed or packed column. Injection of biogenic activated carbon into gas streams can be useful for controlling pollutant emissions in gas or liquid streams from coal-fired power plants, biomass-fired power plants, metal processing plants, crude oil refineries, chemical plants, polymer plants, pulp and paper plants, cement plants, waste incinerators, food processing plants, gasification plants, and syngas plants.

[0525] Use of biocarbon compositions in metal oxide reduction There are various embodiments in which bio-carbon pellets or a pulverized form thereof or other bio-carbon compositions disclosed herein are fed to a metal ore furnace and / or a chemical reduction furnace.

[0526] The metal ore furnace or chemical reduction furnace may 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.

[0527] Metal ore furnaces or chemical reduction furnaces can be arranged horizontally, vertically, or inclined. The flow of solids and fluids (liquids and / or gases) can be co-current or counter-current. The solids in the furnace can be in a fixed bed and / or a fluidized bed. Metal ore furnaces or chemical reduction furnaces can be operated at a variety of process conditions of temperature, pressure, and residence time.

[0528] Some variations of the invention relate specifically to blast furnaces. A blast furnace is a type of metallurgical furnace used in smelting to produce industrial metals such as iron or copper. Blast furnaces are utilized in smelting iron ore to produce pig iron, an intermediate material used in the production of commercial iron and steel. Blast furnaces are also used in conjunction with sintering plants, for example in base metal smelting.

[0529] The term "blast" refers to the forced or fed combustion air above atmospheric pressure. In a blast furnace, metal ore, carbon (e.g., in this disclosure, bioagents or their derivatives), and usually flux (e.g., limestone) are continuously fed through the top of the furnace, while a hot blast of air (optionally with oxygen enrichment) is blown into the lower part of the furnace through a series of pipes called tuyere. Chemical reduction reactions occur throughout the furnace as the material falls downward. The end products are usually molten metal and slag phases removed from the bottom, and waste gases (reduced off-gas) exiting the top of the furnace. The downward flow of metal ore along the flux in countercurrent contact with the rising flow of hot CO2-enriched gas allows for efficient chemical reactions that reduce the metal ore to metal.

[0530] Air furnaces (such as reverberatory furnaces) are usually naturally aspirated by convection of hot gases in the chimney flue. According to this broad definition, bloomery furnaces for iron, blowing houses for tin, and smelting plants for lead are classified as blast furnaces.

[0531] Blast furnaces remain an important part of modern iron production. Modern furnaces are highly efficient and include cowper stoves that preheat the incoming blast air with waste heat from the flue gases, and recovery systems that extract heat from the hot gases leaving the furnace. Blast furnaces are typically built in the form of tall structures lined with refractory bricks and contoured to expand as the feed material heats on its descent, then reduce in size as melting begins to occur.

[0532] In some embodiments for iron production, biocarbon pellets, iron ore (iron oxide), and limestone flux are charged to the top of a blast furnace. The iron ore and / or limestone flux can be incorporated into the biocarbon pellets. Optionally, the biocarbon pellets are reduced in size before feeding into the blast furnace. For example, the biocarbon pellets can be pulverized into a powder that is fed into the blast furnace.

[0533] The blast furnace may be constructed so that hot, dirty gases with high carbon monoxide content exit the furnace throat, while a bleeder valve may protect the top of the furnace from sudden gas pressure surges. Coarse particles in the exhaust gas may settle and be disposed of, while the gas may flow through a venturi scrubber and / or electrostatic precipitator and / or gas cooler to reduce the temperature of the cleaned gas. A casting chamber at the bottom of the furnace houses equipment for casting liquid iron and slag. A tap hole may be drilled into the refractory plug so that the liquid iron and slag flow down the launder through the opening, separating the iron and slag. Once the pig iron and slag have been tapped, the tap hole may be plugged with fireclay. Nozzles called tuyere are used to deliver hot air to increase the efficiency of the blast furnace. The hot air is directed into the furnace through a cool...

Claims

1. (a) a low fixed carbon material comprising a first fixed carbon concentration of at least about 1% to at most about 99% by weight of fixed carbon on an absolute basis, the first fixed carbon concentration being at least about 10% to at most about 55% by weight of fixed carbon; (b) a high fixed carbon material comprising at least about 1% by weight and up to about 99% by weight of a high fixed carbon material, the high fixed carbon material comprising a second fixed carbon concentration of at least about 50% by weight and up 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) at least 0 and up to about 30% by weight moisture; (d) an ash content of at least 0 and up to about 15% by weight; and (e) at least 0 and up to about 20 weight percent of an additive.

2. 10. The bio-carbon composition of claim 1, wherein the low fixation carbon material and the high fixation carbon material are present in the bio-carbon composition as a homogenous physical blend.

3. 2. The bio-carbon composition of claim 1, wherein the first fixed carbon concentration is uniform throughout the bio-carbon composition.

4. 2. The bio-carbon composition of claim 1, wherein the second fixed carbon concentration is uniform throughout the bio-carbon composition.

5. 2. The bio-carbon composition of claim 1, wherein both the first fixed carbon concentration and the second fixed carbon concentration are uniform throughout the bio-carbon composition.

6. 10. The bio-carbon composition of claim 1, wherein the low fixation carbon material and the high fixation carbon material are present in the bio-carbon composition as a heterogeneous physical blend.

7. 10. The bio-carbon composition of claim 1, wherein the low fixation carbon material and the high fixation carbon material are present in the bio-carbon composition as distinct layers.

8. 10. The biocarbon composition of claim 1, wherein the low fixation carbon material is contained within a shell or coating around a core comprising the high fixation carbon material.

9. 10. The biocarbon composition of claim 1, wherein the high fixation carbon material is contained within a shell or coating around a core comprising the low fixation carbon material.

10. 2. The biocarbon composition of claim 1, wherein the high fixation carbon material is in the form of fine particles in a continuous phase of the low fixation carbon material.

11. 2. The biocarbon composition of claim 1, wherein the low fixation carbon material is in the form of fine particles in a continuous phase of the high fixation carbon material.

12. 2. The bio-carbon composition of claim 1, wherein the bio-carbon composition comprises at least about 10% by weight and up to about 90% by weight of the low fixed carbon material.

13. 2. The bio-carbon composition of claim 1, wherein the bio-carbon composition comprises at least about 10% by weight and up to about 90% by weight of the high fixed carbon material.

14. 2. The biocarbon composition of claim 1, wherein a weight ratio of the low fixation carbon material to the high fixation carbon material is selected from at least about 0.1 to at most about 10, 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.

15. 2. The biocarbon composition of claim 1, wherein the first fixed carbon concentration is at least about 15% by weight and up to about 40% by weight, at least about 20% by weight and up to about 50% by weight, or at least about 30% by weight and up to about 55% by weight.

16. 2. The biocarbon composition of claim 1, wherein the second fixed carbon concentration is at least about 80% by weight and up to about 100% by weight, 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.

17. 2. The biocarbon composition of claim 1, wherein an unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30% by weight and at most about 90% by weight, or at least about 40% by weight and at most about 80% by weight.

18. 2. The bio-carbon composition of claim 1, wherein the bio-carbon composition contains a fixed carbon concentration of at least about 25% by weight and up to about 95% by weight, or at least about 35% by weight and up to about 85% by weight, on an absolute basis.

19. 19. The biocarbon composition of any one of claims 1 to 18, wherein the low fixed carbon material contains at least about 45% and up to about 80% volatile carbon by weight on an absolute basis.

20. 19. The biocarbon composition of any one of claims 1 to 18, wherein the high fixed carbon material contains at least about 0% and up to about 50% volatile carbon by weight on an absolute basis.

21. The biocarbon composition according to any one of claims 1 to 18, at least about 0.1% by weight and up to about 20% by weight moisture; an ash content of at least about 0.1% by weight and up to about 10% by weight; or at least about 0.1% to about 10% by weight, at least about 1% to about 15% by weight, or at least about 3% to about 18% by weight of said additive; The biocarbon composition comprising:

22. 19. The biocarbon composition according to any one of claims 1 to 18, wherein the additive comprises an organic additive, an inorganic additive, a renewable material, a material that can be partially oxidized or combusted, or a binder.

23. The binder may be selected from the group consisting of 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, pyrolytic 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 Preferably, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or any combination of the foregoing; more preferably, the binder is an optionally crosslinked thermoplastic starch; even more preferably, the thermoplastic starch is a reaction product of starch and a polyol, optionally comprising: the polyol is selected from ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof; the reaction product is formed from a reaction catalyzed by an acid, preferably the acid is selected from formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof; or 23. The biocarbon composition of claim 22, wherein the reaction product is formed from a reaction catalyzed by a base.

24. the additive reduces the reactivity of the bio-carbon composition compared to an otherwise equivalent bio-carbon composition without the additive; and optionally, The reactivity is a thermal reactivity, and preferably the biocarbon composition has a lower self-heating tendency compared to an otherwise equivalent biocarbon composition without the additive; or The biocarbon composition according to any one of claims 1 to 18, wherein said reactivity is chemical reactivity with oxygen, water, hydrogen, carbon monoxide or metals, preferably said metals comprising iron.

25. The biocarbon composition according to any one of claims 1 to 18, wherein the additive is present and the additive is filling pores within said low fixation carbon material; filling the pores within said high fixation carbon material; filling pores within both the low fixation carbon material and the high fixation carbon material; or The biocarbon composition disposed on an exterior surface of the biocarbon composition.

26. 19. The biocarbon composition according to any one of claims 1 to 18, wherein the biocarbon composition is in the form of a powder or in the form of a pellet, optionally wherein the biocarbon composition is in the form of a pellet and the additive comprises a binder for the pellet.

27. 19. The biocarbon composition of any one of claims 1 to 18, wherein the pellets utilise the low fixed carbon material as a binder within the pellets.

28. 19. The biocarbon composition of any one of claims 1-18, wherein the pellets are characterized by a Hardgrove Crushability Index of at least about 30, at least about 50, at least about 30 up to about 100, or at least about 50 up to about 100; or a Pellet Durability Index of at least about 80%, at least about 90%, or at least about 95%.

29. 19. The biocarbon composition of any one of claims 1 to 18, wherein the additive is present, optionally contained within one of the low fixation carbon material or the high fixation carbon material.

30. 19. The biocarbon composition of any one of claims 1 to 18, 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".

31. The biocarbon composition according to any one of claims 1 to 18, wherein at least one of the low fixed carbon material and the high fixed carbon material contains biogenic carbon.

32. 31. The biocarbon composition of claim 30, wherein the low fixed carbon material is selected from non-pyrolytic biomass, pyrolytic biomass, non-pyrolytic polymers, pyrolytic polymers, coal, pyrolytic coal, or combinations thereof.

33. 32. The biocarbon composition of claim 31 , wherein the high fixed carbon material is selected from pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

34. The total carbon is １４ C / １２ 19. The biocarbon composition of any one of claims 1 to 18, which is at least 50%, at least 90%, or essentially completely renewable, as determined from C isotope ratio measurements.

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