Biochar composition with optimized fixed carbon and methods for its production

Abstract

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

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 180,240, filed April 27, 2021, which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention generally relates to biochar compositions optimized for various chemical and physical properties, as well as methods for preparing and using such biochar compositions. Background Technology

[0004] Carbon is a platform element in many industries and has numerous chemical, materials, and fuel applications. It is an excellent fuel for generating energy, including electricity. Carbon also has immense chemical value for a wide range of commodities and advanced materials, including metals, metal alloys, composites, carbon fibers, electrodes, and catalyst supports. In metal preparation, carbon can be used as a reactant to reduce metal oxides to metals during processing; it can be used as a fuel to provide heat during processing; and it can be used as a component in metal alloys.

[0005] Carbon-containing materials typically include fossil resources such as natural gas, oil, coal, and lignite. Increasing the use of lignocellulosic biomass and various carbon-rich wastes is of interest.

[0006] Various technologies exist to convert raw materials into industrial carbon materials. Pyrolysis is a thermal conversion process of solid materials in the complete absence of an oxidant (air or oxygen), or with a limited supply of oxidant, such that oxidation does not occur to any perceptible degree. Depending on process conditions and additives, biomass pyrolysis can be tailored to produce a wide variety of gases, liquids, and solids. Lower process temperatures and longer steam residence times favor solid production. Higher temperatures and longer residence times increase the conversion of raw materials into syngas, while moderate temperatures and shorter steam residence times are generally optimal for producing liquids. Historically, the slow pyrolysis of wood was carried out in large quantities in simple batch processes without emission controls. Traditional charcoal production technologies are not only energy inefficient but also highly polluting.

[0007] A biochar composition for improvement or optimization is desired, and a method for preparing the biochar composition, said method being able to improve or optimize stability, reactivity (e.g., thermal reactivity and self-heating), hydrophobicity, energy content, total yield, and final composition comprising fixed carbon, ash, and moisture. Summary of the Invention

[0008] This document discloses a biochar composition. The biochar composition disclosed herein may include: at least about 1 wt% to at most about 99 wt% of a low-fixed carbon material, wherein, on an absolute basis, the low-fixed carbon material comprises a first fixed carbon concentration of at least about 20 wt% to at most about 55 wt%; at least about 1 wt% to at most about 99 wt% of a high-fixed carbon material, wherein, on an absolute basis, the high-fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; at least about 0 wt% to at most about 30 wt% of moisture; at least about 0 wt% to at most about 15 wt% of ash; and at least about 0 wt% to at most about 20 wt% of additives; wherein the total wt% calculated as the sum of the low-fixed carbon material, the high-fixed carbon material, the moisture, the ash, and the additives is at most 100 wt%.

[0009] In some embodiments, the biochar composition comprises a homogeneous physical blend of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the low-fixed carbon material is uniformly dispersed throughout the biochar composition. In some embodiments, the high-fixed carbon material is uniformly dispersed throughout the biochar composition. In some embodiments, the low-fixed carbon material and the high-fixed carbon material are uniformly dispersed in the biochar composition. In some embodiments, the biochar composition comprises a heterogeneous physical blend of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises different layers of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, wherein the core is included within the shell, wherein the core comprises the high-fixed carbon material, and wherein the shell comprises the low-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, wherein the core is included within the shell, wherein the core comprises the low-fixed carbon material, and wherein the shell comprises the high-fixed carbon material. In some embodiments, the high-fixed carbon material is in the form of particles in the continuous phase of the low-fixed carbon material. In some embodiments, the low-fixed carbon material is in the form of particles in the continuous phase of the high-fixed carbon material.

[0010] In some embodiments, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the low-fixed carbon material. In some embodiments, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the high-fixed carbon material. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.1 to at most about 10. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.2 to at most about 5. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.5 to at most about 2. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.8 to at most about 1.2. In some embodiments, the first fixed carbon concentration is at least about 20 wt% to at most about 40 wt%. In some embodiments, the first fixed carbon concentration is at least about 25 wt% to at most about 50 wt%. In some embodiments, the first fixed carbon concentration is at least about 30 wt% to at most about 55 wt%. In some embodiments, the second fixed carbon concentration is at least about 80 wt% to at most about 100 wt%. In some embodiments, the second fixed carbon concentration is at least about 70 wt% to at most about 95 wt%. In some embodiments, the second fixed carbon concentration is at least about 60 wt% to at most about 90 wt%.

[0011] In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30 wt% to at most about 90 wt%. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40 wt% to at most about 80 wt%. In some embodiments, on an absolute basis, the biochar composition comprises at least about 25 wt% to at most about 95 wt% of total fixed carbon concentration. In some embodiments, on an absolute basis, the biochar composition comprises at least about 35 wt% to at most about 85 wt% of total fixed carbon concentration. In some embodiments, on an absolute basis, the low fixed carbon material comprises at least about 45 wt% to at most about 80 wt% of volatile carbon. In some embodiments, on an absolute basis, the high fixed carbon material comprises at least about 0 wt% to at most about 50 wt% of volatile carbon. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 20 wt% of moisture. The biochar composition may be completely dry, having less than 0.1 wt% moisture, less than 0.01 wt% moisture, or substantially no moisture. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% ash.

[0012] In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% of the additive. In some embodiments, the biochar composition comprises at least about 1 wt% to at most about 15 wt% of the additive. In some embodiments, the biochar composition comprises at least about 3 wt% to at most about 18 wt% 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 burned. In some embodiments, the additive comprises a binder. In some embodiments, the adhesive comprises starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, coal tar pitch, petroleum asphalt, asphalt, pyrolytic tar, hard asphalt, bentonite, 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, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, or derivatives thereof or combinations thereof.

[0013] In some embodiments, the binder comprises starch, thermoplastic starch, cross-linked starch, starch polymers, derivatives thereof, or combinations thereof. In some embodiments, the binder comprises thermoplastic starch. In some embodiments, the thermoplastic starch is cross-linked. In some embodiments, the thermoplastic starch is a reaction product of starch and a polyol. In some embodiments, the polyol that produces the starch in the reaction may be ethylene glycol, propylene glycol, glycerol, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or combinations thereof. In some embodiments, the thermoplastic starch is formed by an acid-catalyzed reaction. In some embodiments, the acid includes 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 by a base-catalyzed reaction.

[0014] The stability of the biochar composition can be increased by adding additives. In some embodiments, the additives reduce the reactivity of the biochar composition compared to an otherwise equivalent biochar composition without the additives. In some embodiments, the reactivity is thermal reactivity. In some embodiments, the biochar composition has lower self-heating compared to an otherwise equivalent biochar composition without the additives. 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 metals. In some embodiments, the metal includes iron.

[0015] In some embodiments, the biochar composition includes more than 0 wt% of the additive. In other words, there are embodiments in which the additive is present in the composition. The low-fixed carbon material may include pores, and the pores may include the additive. In some embodiments, the high-fixed carbon material includes pores containing the additive, and the low-fixed carbon material includes pores containing the additive. In some embodiments, the additive is on the surface of the biochar composition.

[0016] In some embodiments, the biochar composition is in powder form. In some embodiments, the biochar composition is in granular form. In some embodiments, the biochar composition is in granular form and includes the additive, wherein the additive includes a binder. In some embodiments, the binder is the low-carbon-fixed material. In some embodiments, the biochar composition includes the additive, wherein the low-carbon-fixed material includes the additive or the high-carbon-fixed material includes the additive.

[0017] In some embodiments, when a self-heating test is performed according to the Manual of Tests and Criteria, 7th Revision 2019, United Nations, page 375, 33.4.6 Test N.4: “Test method for self-heating substances”, the biochar composition is characterized as non-self-heating.

[0018] In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the energy content associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the bulk density associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the hydrophobicity associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the pore size associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the pore size ratio associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the surface area associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the reactivity associated with the biochar composition. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the ion exchange capacity associated with the biochar composition.

[0019] In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, and optionally the additive type and / or concentration are selected to optimize the Hardgrove Grindability Index associated with the agglomerates. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the additive type or concentration are selected to optimize the Pellet Durability Index associated with the agglomerates.

[0020] In some embodiments, the biochar composition is in the form of granules, and the first fixed carbon concentration, the second fixed carbon concentration, and optionally the type or concentration of the additives are selected to optimize the granule durability index associated with the granules.

[0021] The biochar composition disclosed herein may include: at least about 1 wt% to at most about 99 wt% of a low fixed carbon material, wherein, on an absolute basis, the low fixed carbon material comprises a first fixed carbon concentration of at least about 10 wt% to at most about 55 wt%; at least about 1 wt% to at most about 99 wt% of a high fixed carbon material, wherein, on an absolute basis, the high fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt%, wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; at least about 0 wt% to at most about 30 wt% of moisture; at least about 0 wt% to at most about 15 wt% of ash; and at least about 0 wt% to at most about 20 wt% of additives; wherein the low fixed carbon material or the high fixed carbon material comprises biochar; and wherein the total wt% calculated as the sum of the low fixed carbon material, the high fixed carbon material, the moisture, the ash, and the additives is at most 100 wt%.

[0022] In some embodiments, the low-carbon-fixed material includes unpyrolyzed biomass, pyrolyzed biomass, unpyrolyzed polymer, pyrolyzed polymer, coal, pyrolyzed coal, or a combination thereof. In some embodiments, the high-carbon-fixed material includes pyrolyzed biomass, coal, pyrolyzed coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolyzed polymer, or a combination thereof.

[0023] In all embodiments of the compositions and methods for preparing the compositions disclosed herein, the biochar composition may comprise total carbon. In some embodiments, at least 50% of the total carbon is substantially composed of biochar, as indicated by the total carbon content. 14 C / 12 The carbon isotope ratio is determined by measurement. In some embodiments, at least 50% of the total carbon is substantially composed of biogenic carbon, as determined by the total carbon... 14 C / 12 The carbon isotope ratio is determined by measurement. In some embodiments, at least 90% of the total carbon is substantially composed of biogenic carbon, as determined by the total carbon... 14 C / 12 The total carbon is determined by measurements of the C isotope ratio. In some embodiments, the total carbon consists essentially of biogenic carbon, as determined by the total carbon... 14 C / 12 Determined by measurements of C isotope ratios.

[0024] This document discloses a method for producing a biochar composition. The method may include: pyrolyzing a first feedstock comprising biomass, thereby producing a low-fixed-carbon material and a first pyrolysis exhaust gas, wherein, on an absolute basis, the low-fixed-carbon material comprises a first fixed-carbon concentration of at least about 20 wt% to at most about 55 wt%; pyrolyzing a second feedstock comprising biomass, thereby producing a high-fixed-carbon material and a second pyrolysis exhaust gas, wherein, on an absolute basis, the high-fixed-carbon material comprises a second fixed-carbon concentration of at least about 50 wt% to at most about 100 wt% and wherein the second fixed-carbon concentration is higher than the first fixed-carbon concentration; blending the low-fixed-carbon material with the high-fixed-carbon material, thereby producing an intermediate material; and recovering a biochar composition comprising the intermediate material or a heat-treated derivative of the intermediate material.

[0025] In some embodiments, the method includes drying the intermediate material.

[0026] In some embodiments, the method includes blending the intermediate material with an additive, thereby producing a blended intermediate material. In some embodiments, the method includes drying the blended intermediate material. In some embodiments, the second raw material is pyrolyzed independently of the first raw material. In some embodiments, the first raw material and the second raw material are of the same type. In some embodiments, the first raw material and the second raw material are not of the same type.

[0027] In some embodiments, the first raw material includes softwood chips, hardwood chips, logging residues, branches, stumps, leaves, bark, sawdust, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, bagasse, sugarcane stalks, energy sugarcane, sugar beets, beet pulp, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stalks, fruit peels, fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable pits, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, food scraps, commercial waste, grass pellets, hay pellets, sawdust pellets, cardboard, paper, pulp, paper packaging, paper decorations, food packaging, construction and / or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0028] In some embodiments, the second raw material includes softwood chips, hardwood chips, logging residues, branches, stumps, leaves, bark, sawdust, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, bagasse, sugarcane stalks, energy sugarcane, sugar beets, beet pulp, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stalks, fruit peels, fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable pits, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, food scraps, commercial waste, grass pellets, hay pellets, sawdust pellets, cardboard, paper, pulp, paper packaging, paper decorations, food packaging, construction and / or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0029] In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out in different 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 under different conditions. The pyrolysis reactors are typically either entirely continuous or entirely batch-based, but in principle, a mixture of reaction modes can be used. Furthermore, when different pyrolysis reactors are used, they can be located in a common location or in different locations.

[0030] In some embodiments, the blending includes blending substantially all of the low-fixed carbon material with the high-fixed carbon material. In some embodiments, the blending includes blending substantially all of the high-fixed carbon material with the low-fixed carbon material. In some embodiments, the blending of the low-fixed carbon material and the high-fixed carbon material includes blending the low-fixed carbon material and the high-fixed carbon material with an additive. In some embodiments, the method includes drying simultaneously with the blending. In some embodiments, the method includes blending the additive with the intermediate material, thereby producing a blended intermediate material, and then drying the intermediate material.

[0031] In some embodiments, the method includes recovering the biochar composition, the biochar composition comprising at least about 1 wt% to at most about 99 wt% of the low-fixed carbon material; at least about 1 wt% to at most about 99 wt% of the high-fixed carbon material; at least about 0 wt% to at most about 30 wt% of moisture; at least about 0 wt% to at most about 15 wt% of ash; and at least about 0 wt% to at most about 20 wt% of additives.

[0032] In some embodiments, pyrolyzing the first raw material includes pyrolysis at a first pyrolysis temperature, wherein the first pyrolysis temperature is at least about 250°C to at most about 1250°C. In some embodiments, pyrolyzing the first raw material includes pyrolysis at a first pyrolysis temperature, wherein the first pyrolysis temperature is at least about 300°C to at most about 700°C. In some embodiments, pyrolyzing the second raw material includes pyrolysis at a second pyrolysis temperature, wherein the second pyrolysis temperature is at least about 250°C to at most about 1250°C. In some embodiments, pyrolyzing the second raw material includes pyrolysis at a second pyrolysis temperature, wherein the second pyrolysis temperature is at least about 300°C to at most about 700°C.

[0033] In some embodiments, pyrolyzing the first raw material includes pyrolyzing for at least about 10 seconds to at most about 24 hours. In some embodiments, pyrolyzing the second raw material includes pyrolyzing for at least about 10 seconds to at most about 24 hours.

[0034] In some embodiments, the first pyrolysis waste gas is oxidized, thereby generating heat. In some embodiments, the second pyrolysis waste gas is oxidized, thereby generating heat. In some embodiments, the first pyrolysis waste gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide. In some embodiments, the second pyrolysis waste gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide.

[0035] In some embodiments, the method includes performing a first grinding of the low fixed carbon material prior to the blending, wherein the first grinding includes using mechanical processing equipment, the mechanical processing equipment including hammer mills, extruders, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof. In some embodiments, the method includes performing a second grinding of the high fixed carbon material prior to the blending, wherein the second grinding includes using mechanical processing equipment, the mechanical processing equipment including hammer mills, extruders, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof. In some embodiments, the blending includes using mechanical processing equipment, the mechanical processing equipment including hammer mills, extruders, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof.

[0036] In some embodiments of the method, the biochar composition comprises a homogeneous physical blend of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the low-fixed carbon material is uniformly dispersed throughout the biochar composition. In some embodiments, the high-fixed carbon material is uniformly dispersed throughout the biochar composition. In some embodiments, the low-fixed carbon material and the high-fixed carbon material are uniformly dispersed in the biochar composition. In some embodiments, the biochar composition comprises a heterogeneous physical blend of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises distinct layers of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, wherein the core is contained within the shell, wherein the core comprises the high-fixed carbon material, and wherein the shell comprises the low-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, wherein the core is contained within the shell, wherein the core comprises the low-fixed carbon material, and wherein the shell comprises the high-fixed carbon material. In some embodiments, the high-fixed carbon material is in the form of particulate matter in the continuous phase of the low-fixed carbon material. In some embodiments, the low-fixed carbon material is in the form of particulate matter in the continuous phase of the high-fixed carbon material.

[0037] In some embodiments of the method, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the low-fixed carbon material. In some embodiments, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the high-fixed carbon material. In some embodiments, the biochar composition comprises the weight ratio of the low-fixed carbon material to the high-fixed carbon material, and wherein the ratio is at least about 0.1 to at most about 10.

[0038] In some embodiments of the method, the biochar composition comprises a weight ratio of the low-fixed carbon material to the high-fixed carbon material, wherein the ratio is at least about 0.2 to at most about 5. In some embodiments, the biochar composition comprises a weight ratio of the low-fixed carbon material to the high-fixed carbon material, wherein the ratio is at least about 0.5 to at most about 2. In some embodiments, the biochar composition comprises a weight ratio of the low-fixed carbon material to the high-fixed carbon material, wherein the ratio is at least about 0.8 to at most about 1.2.

[0039] In some embodiments, the first fixed carbon concentration is at least about 20 wt% to at most about 40 wt%. In some embodiments, the first fixed carbon concentration is at least about 25 wt% to at most about 50 wt%. In some embodiments, the first fixed carbon concentration is at least about 30 wt% to at most about 55 wt%. In some embodiments, the second fixed carbon concentration is at least about 80 wt% to at most about 100 wt%. In some embodiments, the second fixed carbon concentration is at least about 70 wt% to at most about 95 wt%. In some embodiments, the second fixed carbon concentration is at least about 60 wt% to at most about 90 wt%. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30 wt% to at most about 90 wt%. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40 wt% to at most about 80 wt%.

[0040] In some embodiments of the method, the biochar composition comprises, on an absolute basis, at least about 25 wt% to at most about 95 wt% of total fixed carbon. In some embodiments, the biochar composition comprises, on an absolute basis, at least about 35 wt% to at most 85 wt% of total fixed carbon. In some embodiments, the low fixed carbon material comprises, on an absolute basis, at least about 45 wt% to at most about 80 wt% of volatile carbon. In some embodiments, the high fixed carbon material comprises, on an absolute basis, at least about 0 to at most about 50 wt% of volatile carbon.

[0041] In some embodiments of the method, the biochar composition comprises at least about 0.1 wt% to at most about 20 wt% water. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% ash. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% additives. In some embodiments, the biochar composition comprises at least about 1 wt% to at most about 15 wt% additives. In some embodiments, the biochar composition comprises at least about 3 wt% to at most about 18 wt% additives.

[0042] In some embodiments of the method, the biochar composition includes additives, and the additives include organic additives. In some embodiments, the additives include inorganic additives. In some embodiments, the additives include renewable materials. In some embodiments, the additives include materials that can be oxidized or burned. In some embodiments, the additives include binders.

[0043] In some embodiments, the method includes granulation. The granulation can be achieved using an extruder, a ring die granulator, a flat die granulator, a roller compactor, a roller briquetting machine, a wet agglomerating mill, a dry agglomerating mill, or a combination thereof.

[0044] In some embodiments of the method, the biochar composition includes a binder. The binder may include starch, thermoplastic starch, cross-linked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, coal tar pitch, petroleum asphalt, pitch, pyrolytic tar, hard asphalt, bentonite, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, derivatives thereof, or combinations thereof.

[0045] In some embodiments of the method, the biochar composition includes a binder, and the binder includes starch, thermoplastic starch, cross-linked starch, starch polymers, derivatives thereof, or combinations thereof.

[0046] In some embodiments of the method, the biochar composition includes a binder, and the binder includes thermoplastic starch. The thermoplastic starch can be a reaction product of starch and a polyol. The polyol can be ethylene glycol, propylene glycol, glycerol, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or a combination thereof. The thermoplastic starch can be formed via an acid-catalyzed reaction. 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 also be formed via a base-catalyzed reaction.

[0047] In some embodiments of the method, the additive reduces the reactivity of the biochar composition compared to an otherwise equivalent biochar composition without the additive. In some embodiments, the reactivity is thermal reactivity. In some embodiments, the biochar composition has lower self-heating compared to an otherwise equivalent biochar 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 metals. In some embodiments, the metal includes iron.

[0048] In some embodiments, the method includes blending an additive with the intermediate material, thereby introducing the additive into the pores of the low-fixed-carbon material. In some embodiments, the method includes blending an additive with the intermediate material, thereby introducing the additive into the pores of the high-fixed-carbon material. In some embodiments, the method includes blending an additive with the intermediate material, thereby introducing the additive into the pores of both the low-fixed-carbon material and the high-fixed-carbon material. In some embodiments, the method includes blending an additive with the intermediate material, thereby disposing the additive on the outer surface of the biochar composition.

[0049] In some embodiments, the method includes forming the biochar composition into a powder. In some embodiments, the method includes granulating the biochar composition.

[0050] In some embodiments, the method includes blending an additive with the intermediate material, wherein the additive includes a binder. In some embodiments, the binder includes the low-fixed carbon material. In some embodiments, the method includes blending an additive with the intermediate material, wherein the low-fixed carbon material includes the additive or the high-fixed carbon material includes the additive.

[0051] In some embodiments of the method, when a self-heating test is performed according to the Test and Standards Manual, 7th Revision 2019, United Nations, page 375, 33.4.6 Test N.4: “Test Methods for Self-Heating Substances”, the biochar composition is characterized as non-self-heating. In some embodiments, the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive is selected to optimize the energy content associated with the biochar composition.

[0052] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the bulk density of the biochar. In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the hydrophobicity of the biochar. In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the pore size of the biochar. In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the pore size ratio of the biochar. In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the surface area of ​​the biochar. In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the reactivity of the biochar. In some embodiments of the method, the method includes selecting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the ion exchange capacity (IEC) of the biocarbon.

[0053] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the Hardgrove grindability index of the biochar. In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the pellet durability index of the biochar.

[0054] In some embodiments of the method, the biochar composition comprises total carbon, wherein at least 50% of the total carbon is substantially composed of biochar, as determined by the total carbon composition. 14 C / 12 The determination is made by measuring the C isotope ratio. In some embodiments of the method, the biochar composition comprises total carbon, wherein at least 90% of the total carbon is substantially composed of biochar, as determined by the total carbon... 14 C / 12 The determination is made by measuring the C isotope ratio. In some embodiments of the method, the biochar composition comprises total carbon, wherein the total carbon is substantially composed of biochar, as determined according to the total carbon... 14 C / 12 Determined by measurements of C isotope ratios.

[0055] The method disclosed herein may include: pyrolyzing a first feedstock, wherein the first feedstock comprises biomass, thereby producing a low-fixed carbon material and a first pyrolysis exhaust gas, wherein, on an absolute basis, the low-fixed carbon material comprises a first fixed carbon concentration of at least about 20 wt% to at most about 55 wt%; providing a high-fixed carbon material, wherein, on an absolute basis, the high-fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; blending the low-fixed carbon material with 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 biochar composition comprising the intermediate material or a heat-treated derivative thereof.

[0056] In some embodiments of the method, the high carbon-fixed material includes pyrolytic biomass, coal, pyrolytic coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolytic polymers, or combinations thereof.

[0057] The method disclosed herein may include: providing a low fixed carbon material, wherein, on an absolute basis, the low fixed carbon material comprises a first fixed carbon concentration of at least about 10 wt% to at most about 55 wt% fixed carbon; pyrolyzing a feedstock, wherein the feedstock comprises biomass, thereby producing a high fixed carbon material and pyrolysis exhaust gas, wherein, on an absolute basis, the high fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% fixed carbon, and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; blending the low fixed carbon material with 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 biochar composition comprising the intermediate material or a heat-treated derivative thereof.

[0058] In some embodiments of the method, the low fixed carbon material includes unpyrolyzed biomass, pyrolyzed biomass, unpyrolyzed polymers, pyrolyzed polymers, or combinations thereof.

[0059] The method disclosed herein may include: providing a low-fixed carbon material, wherein, on an absolute basis, the low-fixed carbon material comprises a first fixed carbon concentration of at least about 10 wt% to at most about 55 wt% of fixed carbon; providing a high-fixed carbon material, wherein, on an absolute basis, the high-fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% of fixed carbon, and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; blending the low-fixed carbon material with the high-fixed carbon material to produce an intermediate material; optionally blending an additive with the intermediate material; optionally drying the intermediate material; and recovering a biochar composition comprising the intermediate material or a heat-treated derivative thereof.

[0060] In some embodiments of the method, the low-carbon-fixed material includes unpyrolyzed biomass, pyrolyzed biomass, unpyrolyzed polymers, pyrolyzed polymers, or combinations thereof. In some embodiments of the method, the high-carbon-fixed material includes pyrolyzed biomass, coal, pyrolyzed coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolyzed polymers, or combinations thereof. Attached Figure Description

[0061] Figure 1 This is a simplified block flowchart of a method for producing a biochar composition in some embodiments, the biochar composition having a low-carbon-fixed material blended with a high-carbon-fixed material, optionally with additives (such as binders for preparing granules). Dashed boxes and lines represent optional units and flows, respectively.

[0062] Figure 2 This is a simplified block flowchart of a method for producing a biochar composition in some embodiments, the biochar composition having a low-fixed carbon material blended with a high-fixed carbon material, wherein the low-fixed carbon material serves as a pellet binder. Dashed boxes and lines represent optional units and flows, respectively.

[0063] Figure 3 The image shows a biochar composition in granular form containing a mixture of high-fixed carbon material and low-fixed carbon material, wherein the low-fixed carbon material is used as a granular binder. Detailed Implementation

[0064] While this disclosure can be embodied in various forms, the following description of several embodiments is made with the understanding that this disclosure is to be regarded as illustrative of the invention and is not intended to limit the invention to the specific embodiments shown. Headings are provided merely for convenience and should not be construed as limiting the invention in any way. Embodiments shown under any heading can be combined with embodiments shown under any other heading.

[0065] It is further explicitly stated that, otherwise, the numerical values ​​used in the various quantitative values ​​specified in this application are expressed as approximations, as if the minimum and maximum values ​​within the stated ranges were both preceded by the word "about". It should be understood that, although not always explicitly stated, all numerical identifiers are preceded by the term "about". It should be understood that such range formats are used for convenience and brevity and should be flexibly interpreted to include not only numerical values ​​explicitly designated as limits of a range, but also all individual numerical values ​​or subranges covered within the stated range, as if each numerical value and subrange were explicitly specified. For example, ratios in the range of about 1 to about 200 should be understood to include the explicitly enumerated limits of about 1 and about 200, but also individual ratios such as about 2, about 3, and about 4, and subranges such as about 10 to about 50, about 20 to about 100, etc. It should also be understood that, although not always explicitly stated, the reagents described herein are merely exemplary, and their equivalents are known in the art.

[0066] As used herein, the term “about” when referring to measurable values ​​such as amount or concentration is intended to cover variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount.

[0067] Similarly, the disclosure of ranges is intended as a continuous range encompassing every value between the stated minimum and maximum values, and any range that can be formed from these values. This document also discloses any and all ratios (and ranges of any such ratios) that can be formed by dividing the disclosed numerical values ​​by any other disclosed numerical values. Therefore, those skilled in the art will recognize that many such ratios, ranges, and ranges of ratios can be explicitly derived from the numerical values ​​presented herein, and in all cases, such ratios, ranges, and ranges of ratios represent various embodiments of this disclosure. If no lower limit is provided, the lower limit is 0 or trace. For example, if "at most about 90%" exists, the lower limit is "about 0%" or trace. If no upper limit of the percentage is provided, the upper limit is 100%. For example, if "at least about 5%" exists, the lower limit is "about 100%".

[0068] The terms "comprising" or "comprise" are intended to mean that a composition and method includes the described elements but does not exclude other elements. When used to define compositions and methods, "consisting essentially of" should mean excluding other elements that have any substantial significance for the combination for the stated purpose. Therefore, 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" should mean excluding other components in greater than trace amounts and numerous method steps. Examples defined by each of these transitional terms are within the scope of the invention.

[0069] As used herein, when the indefinite article “a / an” is used in a statement or description of the existence of a step in a method disclosed herein, the use of such an indefinite article does not limit the existence of a step in the process to one, unless the statement or description expressly provides otherwise. As used herein, when a quantity, concentration, or other value or parameter is given as a range, preferred range, or a list of preferred upper and lower limits, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually.

[0070] For the purposes of this invention, "bio-derived" is intended to mean materials containing elements such as carbon (whether raw materials, products, or intermediates) that are renewable on timescales of months, years, or decades. Non-bio-derived materials may be non-renewable or renewable on geological timescales of hundreds, thousands, millions, or even longer. Note that bio-derived materials may comprise mixtures of bio- and non-bio-derived sources.

[0071] For the purposes of this invention, "reagent" is intended to mean a material in its broadest sense; a reagent can be a fuel, chemical, material, molecule, additive, blend component, solvent, etc. A reagent is not necessarily a chemical agent that causes or participates in a chemical reaction. A reagent may or may not be a chemical reactant; the reagent may or may not be consumed in the reaction. A reagent can be a chemical catalyst for a specific reaction. A reagent can cause or participate in modifying the mechanical, physical, or hydrodynamic properties of a material to which the reagent can be added. For example, a reagent can be introduced into a metal to impart certain strength properties to the metal. A reagent can be a substance having sufficient purity for chemical analysis or physical testing (which is typically carbon purity in the current context).

[0072] For practical purposes, the terms "low fixed carbon" and "high fixed carbon" are used herein to describe materials that can be produced by the disclosed methods and systems in the various embodiments. Limitations regarding carbon content or any other concentration should not be attributed to the terms themselves, but only by reference to specific embodiments and their equivalents.

[0073] "Ash" refers to the non-carbon components that do not evaporate during pyrolysis. Ash content can be measured using ASTM D3175 or other techniques. Ash composition can be analyzed using ASTM D4326 or other techniques. For example, ash can contain Fe2O3, CaO, MgO, K2O, Na2O, SiO2, Al2O3, and TiO2. Silica (SiO2) is typically the most prominent component of ash derived from biomass.

[0074] Biochar composition

[0075] The carbon-based reagents described in this article are derived at least in part from renewable resources. Such reagents are particularly useful, at least in part, due to the rising economic, environmental, and social costs associated with fossil resources.

[0076] As used herein, “biomass” is a term used to describe substances produced by living organisms or substances derived from biological sources. The chemical energy contained in biomass is obtained from solar energy through the natural process of photosynthesis. Photosynthesis is the process by which plants absorb carbon dioxide and water from their surrounding environment and use energy from sunlight to convert them into sugars, starches, cellulose, hemicellulose, and lignin. Of all renewable energy sources, biomass is unique because it is essentially stored solar energy. Furthermore, biomass is the only renewable carbon source.

[0077] This document discloses biochar compositions. The biochar compositions disclosed herein may include: at least about 1 wt% to at most about 99 wt% of a low-fixed carbon material, wherein, on an absolute basis, the low-fixed carbon material comprises a first fixed carbon concentration of at least about 20 wt% to at most about 55 wt%; at least about 1 wt% to at most about 99 wt% of a high-fixed carbon material, wherein, on an absolute basis, the high-fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; at least about 0 wt% to at most about 30 wt% of moisture; at least about 0 wt% to at most about 15 wt% of ash; and at least about 0 wt% to at most about 20 wt% of additives; wherein the total wt% calculated as the sum of the low-fixed carbon material, the high-fixed carbon material, the moisture, the ash, and the additives is at most 100 wt%. As used herein, "absolute basis" includes ash and moisture.

[0078] In some embodiments, the biochar composition comprises a homogeneous physical blend of the low-carbon-fixed material and the high-carbon-fixed material. In other words, the low-carbon-fixed material and the high-carbon-fixed material may exist as a homogeneous physical blend in the biochar composition. In some embodiments, the low-carbon-fixed material is uniformly dispersed throughout the biochar composition. In some embodiments, the high-carbon-fixed material is uniformly dispersed throughout the biochar composition. In some embodiments, the low-carbon-fixed material and the high-carbon-fixed material are uniformly dispersed in the biochar composition.

[0079] In some embodiments, the biochar composition comprises a heterogeneous physical blend of the low-fixed carbon material and the high-fixed carbon material. In other words, the low-fixed carbon material and the high-fixed carbon material may exist as a heterogeneous physical blend in the biochar composition. In some embodiments, the biochar composition comprises different layers of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, or a core and a coating, wherein the core is contained within the shell, wherein the core comprises the high-fixed carbon material, and wherein the shell comprises the low-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, or a core and a coating, wherein the core is contained within the shell, wherein the core comprises the low-fixed carbon material, and wherein the shell comprises the high-fixed carbon material. In some embodiments, the high-fixed carbon material is in the form of particulate matter in the continuous phase of the low-fixed carbon material. In some embodiments, the low-fixed carbon material is in the form of particulate matter in the continuous phase of the high-fixed carbon material.

[0080] Low-fixed-carbon and high-fixed-carbon materials can form distinct phases that do not dissolve in each other at equilibrium and at relatively low temperatures. In some embodiments, the low-fixed-carbon and high-fixed-carbon materials can have high equilibrium (thermodynamic) solubility in each other, but remain kinetically frozen in the composition, allowing distinct materials to be observed. These distinct materials can be observed by measuring the composition, density, particle size, reactivity, or other physical or chemical properties. Material differences may disappear during the final use of the biochar composition (e.g., at elevated temperatures or during carbon oxidation).

[0081] In a technique for demonstrating that a given biochar composition contains low-fixed carbon material and different high-fixed carbon materials, thermogravimetric analysis (TGA) is performed on the combustion of a test sample of the biochar composition. In some embodiments, the resulting TGA thermal profile has two peaks, characterized by different mass loss events associated with the low-fixed carbon material and the high-fixed carbon material. This can be compared with a control sample containing a biochar composition of a single material with a uniform fixed carbon concentration to show a TGA thermal profile exhibiting a single-peak characteristic of a mass loss event of said material. In similar embodiments, the TGA thermal profile of the test sample has three or more peaks, while the TGA thermal profile of the control sample has at least one fewer peak than the TGA thermal profile of the test sample.

[0082] Another technique for demonstrating that a given biochar composition contains both low-fixed carbon material and different high-fixed carbon materials is particle size analysis. This is feasible when the particle sizes associated with the low-fixed and high-fixed carbon materials differ, or when the particle size distributions associated with the low-fixed and high-fixed carbon materials differ. For example, high-fixed carbon materials tend to have larger particles compared to low-fixed carbon materials. In some embodiments, a bimodal particle size distribution arises from the presence of both low-fixed and high-fixed carbon materials, which contrasts with the unimodal particle size distribution characteristics of a control sample, which is a homogeneous material. In similar embodiments, the particle size distribution of the test sample may have at least one more pattern than that of the control sample. For example, each of the low-fixed and high-fixed carbon materials may have a bimodal particle size distribution (peaks concentrated at different sizes), and the control sample may also have a bimodal particle size distribution, depending on how the control sample is prepared.

[0083] Particle size can be measured using a variety of techniques, including dynamic light scattering, laser diffraction, image analysis, or sieving. Dynamic light scattering is a non-invasive, well-established technique for measuring the size and size distribution of particles, typically in the submicron region, and the latest techniques can scale down to 1 nanometer. Laser diffraction is a widely used particle-setting technique suitable for materials ranging in size from hundreds of nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction instruments for measuring particle size are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis for estimating 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.

[0084] Imaging techniques can be used alternatively or additionally to demonstrate that a given biochar composition contains both low-carbon-fixed materials and distinct high-carbon-fixed 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 computed tomography (XRT). For example, imaging techniques can be used to show distinct materials in a blend, rather than homogeneous materials. Alternatively, imaging techniques can be used to select subsamples for further analysis. Further analysis could be compositional analysis to show three-dimensional variations in fixed carbon content. Further analysis could be property analysis to show three-dimensional variations in chemical or physical properties, such as density, particle size, or reactivity.

[0085] Spectroscopic techniques can be used alternatively or additionally to demonstrate that a given biochar composition contains both low-carbon-fixed materials and different high-carbon-fixed materials. For example, spectroscopic techniques include, but are not limited to, energy-dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.

[0086] The species and concentration ranges of various biochar compositions will now be described further.

[0087] In some embodiments, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the low-fixed carbon material. In some embodiments, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the high-fixed carbon material. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.1 to at most about 10. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.2 to at most about 5. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.5 to at most about 2. In some embodiments, the weight ratio of the low-fixed carbon material to the high-fixed carbon material is at least about 0.8 to at most about 1.2.

[0088] In some embodiments, the first fixed carbon concentration is at least about 20 wt% to at most about 40 wt%. In some embodiments, the first fixed carbon concentration is at least about 25 wt% to at most about 50 wt%. In some embodiments, the first fixed carbon concentration is at least about 30 wt% to at most about 55 wt%. In some embodiments, the second fixed carbon concentration is at least about 80 wt% to at most about 100 wt%. In some embodiments, the second fixed carbon concentration is at least about 70 wt% to at most about 95 wt%. In some embodiments, the second fixed carbon concentration is at least about 60 wt% to at most about 90 wt%.

[0089] In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30 wt% to at most about 90 wt%. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40 wt% to at most about 80 wt%. In some embodiments, on an absolute basis, the biochar composition comprises at least about 25 wt% to at most about 95 wt% of total fixed carbon concentration. In some embodiments, on an absolute basis, the biochar composition comprises at least about 35 wt% to at most about 85 wt% of total fixed carbon concentration. In some embodiments, on an absolute basis, the low fixed carbon material comprises at least about 45 wt% to at most about 80 wt% of volatile carbon (i.e., containing ash and moisture). In various embodiments, on an absolute basis, the low fixed carbon material may contain about, at least about, or at most about 45, 50, 55, 60, 65, 70, 75, or 80 wt% of volatile carbon. For example, on an absolute basis, the low fixed carbon material may contain about 1 wt% to about 20 wt% of oxygen. For example, on an absolute basis, the low fixed carbon material may contain about 0.1 wt% to about 10 wt% hydrogen.

[0090] On an absolute basis, the high-fixed-carbon material may contain about 0 to about 50 wt% volatile carbon. In various embodiments, on an absolute basis, the high-fixed-carbon material may contain about, at least about, or at most about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 wt% volatile carbon. For example, on an absolute basis, the high-fixed-carbon material may contain about 1 wt% to about 20 wt% oxygen. For example, on an absolute basis, the high-fixed-carbon material may contain about 0.1 wt% to about 10 wt% hydrogen.

[0091] In some embodiments, the biochar composition comprises about 0.1 wt% to about 20 wt% water. In various embodiments, the biochar composition comprises about, at least about, or at most 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 wt% water, encompassing all intermediate ranges. The low-carbon-fixed material may contain 0 to about 50 wt% water, such as about, at least about, or at most 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 wt% water, encompassing all intermediate ranges. Independently, the high fixed carbon material may contain 0 to about 50 wt% moisture, such as about, at least about or at most 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 wt% moisture, encompassing all intermediate ranges.

[0092] In some embodiments, the biochar composition comprises about 0.1 wt% to about 10 wt% ash. In various embodiments, the biochar composition comprises about, at least about, or at most about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% ash, encompassing all intermediate ranges. The low carbon-fixed material may contain 0 to about 25 wt% ash, such as about, at least about, or at most about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 wt% ash, encompassing all intermediate ranges. Independently, the high fixed carbon material may contain 0 to about 50 wt% ash, such as about, at least about or at most about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 wt% ash, encompassing all intermediate ranges.

[0093] In some embodiments, the biochar composition comprises about 0.1 wt% to about 10 wt% of one or more additives. In some embodiments, the biochar composition comprises about 1 wt% to about 15 wt% of one or more additives. In some embodiments, the biochar composition comprises about 3 wt% to about 18 wt% of one or more additives. In various embodiments, the biochar composition comprises about, at least about, or at most about 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% of additives, encompassing all intermediate ranges.

[0094] The low-carbon-fixed material may contain 0 to about 20 wt% of additives, such as about, at least about or at most 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 wt% of additives, encompassing all intermediate ranges. Alternatively, the high-carbon-fixed material may contain 0 to about 50 wt% of additives, such as about, at least about or at most 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 wt% of additives, encompassing all intermediate ranges.

[0095] The additives may comprise organic and / or inorganic additives. In some embodiments, one or more additives comprise renewable materials. In some embodiments, one or more additives comprise materials that can be partially oxidized and / or burned.

[0096] In some embodiments, one or more additives include adhesives. In some embodiments, the adhesives include starch, thermoplastic starch, cross-linked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, coal tar pitch, petroleum asphalt, asphalt, pyrolytic tar, hard asphalt, bentonite, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, or derivatives thereof, or combinations thereof.

[0097] In some embodiments, the binder comprises starch, thermoplastic starch, cross-linked starch, starch polymers, derivatives thereof, or combinations thereof. In some embodiments, the binder comprises cross-linked 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, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or combinations thereof. The reaction product can be formed by an acid-catalyzed reaction. 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 by a base-catalyzed reaction.

[0098] Compared to otherwise equivalent biochar compositions without one or more additives, the one or more additives can reduce the reactivity of the biochar composition. The reactivity can be thermal reactivity. For example, a biochar composition containing the one or more additives may have lower self-heating compared to otherwise equivalent biochar compositions without one or more additives. Alternatively or additionally, reactivity is chemical reactivity with oxygen, water, hydrogen, carbon monoxide, and / or metals (e.g., iron).

[0099] When additives are used, they do not need to be uniformly distributed throughout the biomass composition. The additives may preferably be present in one of the low-carbon-fixed materials or the high-carbon-fixed materials, or even solely in one of these materials. For example, a binder may be present in the entire biomass composition at 5 wt%, but of that amount, 4 percent is located in the low-carbon-fixed material and 1 percent in the high-carbon-fixed material (i.e., 80% of the binder is located in the low-carbon-fixed material). In various embodiments, the percentage of total additives disposed within the low-carbon-fixed material may be about, at least about, or at most about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; the percentage of total additives disposed within the high-carbon-fixed material may be about, at least about, or at most about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%; and the percentage of total additives disposed elsewhere in the biochar composition (e.g., as a separate additive phase) that is neither disposed within the low-carbon-fixed nor the high-carbon-fixed material may be about, at least about, or at most about 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

[0100] When one or more of the additives are present, some or all of the additives may be pore fillers within the low-fixed carbon material. When one or more of the additives are present, some or all of the additives may be pore fillers within the high-fixed carbon material. In some embodiments, one or more additives are present and serve as pore fillers within both the low-fixed carbon material and the high-fixed carbon material.

[0101] Alternatively or additionally, one or more additives may be disposed on the outer surface of the biochar composition (e.g., the outer surface of granules or powder particles).

[0102] In some embodiments, the biochar composition is in powder form.

[0103] In some embodiments of the invention, the biochar composition is in granular form. When in granular form, one or more additives may constitute a binder for the granules. Alternatively or additionally, the granules may utilize a low-fixed carbon material itself as a binder within the granules.

[0104] In some embodiments, on an absolute basis, the high carbon-fixed material comprises at least about 0 wt% to at most about 50 wt% volatile carbon. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 20 wt% moisture. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% ash.

[0105] In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% of the additive. In some embodiments, the biochar composition comprises at least about 1 wt% to at most about 15 wt% of the additive. In some embodiments, the biochar composition comprises at least about 3 wt% to at most about 18 wt% 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 burned. In some embodiments, the additive comprises a binder. In some embodiments, the adhesive comprises starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, coal tar pitch, petroleum pitch, asphalt, pyrolytic tar, hard asphalt, bentonite, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, or derivatives thereof, or combinations thereof.

[0106] In some embodiments, the binder comprises starch, thermoplastic starch, cross-linked starch, starch polymers, derivatives thereof, or combinations thereof. In some embodiments, the binder comprises thermoplastic starch. In some embodiments, the thermoplastic starch is cross-linked. In some embodiments, the thermoplastic starch is a reaction product of starch and a polyol. In some embodiments, the polyol that produces the starch in the reaction may be ethylene glycol, propylene glycol, glycerol, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or combinations thereof. In some embodiments, the thermoplastic starch is formed by an acid-catalyzed reaction. In some embodiments, the acid includes 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 by a base-catalyzed reaction.

[0107] The stability of the biochar composition can be increased by adding additives. In some embodiments, the additives reduce the reactivity of the biochar composition compared to an otherwise equivalent biochar composition without the additives. In some embodiments, the reactivity is thermal reactivity. In some embodiments, the biochar composition has lower self-heating compared to an otherwise equivalent biochar composition without the additives. Reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, or metals. In some embodiments, the metal includes iron.

[0108] When the chemical reactivity of the biochar composition is reduced, the biochar composition is less likely to be oxidized, wherein the biochar composition includes additives. Oxidation occurs in the presence of oxygen, water, hydrogen, or carbon monoxide. Oxidation leads to an undesirable degradation of the beneficial properties of the biochar composition.

[0109] In some embodiments, the biochar composition includes more than 0 wt% of the additive. In other words, there are embodiments in which the additive is present in the composition. The low-fixed carbon material may include pores, and the pores may include the additive. In some embodiments, the additive is a pore filler for the pores of the low-fixed carbon material. In some embodiments, the additive is a pore filler for the pores of the high-fixed carbon material. In some embodiments, the high-fixed carbon material includes pores containing the additive, and the low-fixed carbon material includes pores containing the additive. In some embodiments, the additive is a pore filler for both the pores of the high-fixed carbon material and the pores of the low-fixed carbon material.

[0110] Alternatively or additionally, the additive may be disposed on the outer surface of the biochar composition (e.g., the outer surface of granules or powder particles). The method may include, for example, spraying the additive onto the biochar composition.

[0111] In some embodiments, the biochar composition is in powder form. Various particle sizes may be present in the powder. For example, the average particle diameter may be at least about 100 nanometers to at most about 500 micrometers, at least about 0.5 micrometers to at most about 500 micrometers, at least about 1 micrometer to at most about 500 micrometers, at least about 2 micrometers to at most about 500 micrometers, at least about 3 micrometers to at most about 500 micrometers, at least about 4 micrometers to at most about 500 micrometers, at least about 5 micrometers to at most about 500 micrometers, at least about 10 micrometers to at most about 500 micrometers, at least about 25 micrometers to at most about 500 micrometers, at least about 50 micrometers to at most about 500 micrometers. 500 micrometers, at least about 75 micrometers to at most about 500 micrometers, at least about 100 micrometers to at most about 500 micrometers, at least about 150 micrometers to at most about 500 micrometers, at least about 200 micrometers to at most about 500 micrometers, at least about 250 micrometers to at most about 500 micrometers, at least about 300 micrometers to at most about 500 micrometers, at least about 350 micrometers to at most about 500 micrometers, at least about 400 micrometers to at most about 500 micrometers, at least about 450 micrometers to at most about 500 micrometers or about 500 micrometers.

[0112] In some embodiments, the biochar composition is in the form of granules. The average granule 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 mm. In some embodiments, the average granule diameter is about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 micrometers. When the composition is in the form of granules, one or more additives may contain a binder for the granules. In some embodiments, the granules may utilize the low-fixed carbon material itself as a binder within the granules.

[0113] When additives are present, they can be located within either low-carbon or high-carbon materials. In some embodiments, the additives are uniformly distributed such that they have the same average concentration in both low-carbon and high-carbon materials.

[0114] In some embodiments, when a self-heating test is performed according to the Test and Standards Manual, 7th Revision 2019, United Nations, page 375, 33.4.6 Test N.4: “Test Methods for Self-Heating Substances”, the biochar composition is characterized as non-self-heating. The energy content of the biochar 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 is selected to optimize the energy content associated with the biochar composition.

[0115] The bulk density of the biochar 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 is selected to optimize the bulk density associated with the biochar composition.

[0116] The hydrophobicity of the biochar composition can be altered 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 biochar composition.

[0117] The hydrophobicity of the biochar composition is characterized by its water absorption rate in an immersion test. For example, the hydrophobicity of dried biochar pellets can be tested by immersing them in excess water for 24 hours at room temperature (approximately 25°C). After immersion, free water droplets are filtered off using a sieve, and the total moisture content of the sample is then tested according to ASTM D3173. To calculate the net moisture absorption rate (also referred to herein as "water absorption rate"), the initial moisture content of the dried pellets is subtracted from the total moisture content according to ASTM D3173. For example, if the dried biochar pellets have an initial moisture content of 5%, and the pellets soaked after 24 hours have a moisture content of 25%, then the water absorption rate is 25% - 5% = 20%. The same procedure can be used for biochar compositions that are not pellets, such as powders or granules.

[0118] The biochar composition is characterized in that, after soaking in water for 24 hours (i.e., relative to the mass of the aggregate in excess liquid water), its water absorption rate at 25°C is less than 20 wt%. In some embodiments, the biochar composition is characterized in that, after soaking in water for 24 hours, its water absorption rate at 25°C is less than about 15 wt%. In some embodiments, the biochar composition is characterized in that, after soaking in water for 24 hours, its water absorption rate at 25°C is less than about 10 wt%. In some embodiments, the biochar composition is characterized in that, after soaking in water for 24 hours, its water absorption rate at 25°C is less than about 5 wt%, such as after soaking in water for 24 hours, its water absorption rate at 25°C is from about 2 wt% to about 4 wt%. In various embodiments, the biochar composition is characterized in that, after soaking in water for 24 hours, the water absorption rate at 25°C is about or at most about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 wt%.

[0119] The pore size of the biochar 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 pore size associated with the biochar composition.

[0120] The pore size ratio of the biochar 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 is selected to optimize the pore size ratio associated with the biochar composition.

[0121] The surface area of ​​the biochar 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 surface area associated with the biochar composition.

[0122] The reactivity of the biochar composition can be altered 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 biochar composition.

[0123] The ion exchange capacity of the biochar 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 is selected to optimize the ion exchange capacity associated with the biochar composition.

[0124] The Hadgrove grindability index of the biochar 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, and optionally the type and / or concentration of the additive are selected to optimize the Hadgrove grindability index associated with the agglomerates.

[0125] The agglomeration durability index of the biochar 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 is selected to optimize the agglomeration durability index associated with the agglomerates.

[0126] Figure 1 This is a simplified block flowchart of a method for producing a biochar composition in some embodiments, the biochar composition having a low-carbon-fixed material blended with a high-carbon-fixed material, optionally with additives (such as a binder for preparing granules). Dashed boxes and lines represent optional units and flows, respectively. Figure 1In this process, biomass is fed into a first pyrolysis reactor operating under the effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low fixed carbon material, which is optionally ground to reduce particle size. Biomass is also fed into a second pyrolysis reactor operating under the effective pyrolysis conditions described herein. The biomass fed into the second pyrolysis reactor may be the same as or different from the biomass fed into the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high fixed carbon material, which is optionally ground to reduce particle size. When employed, the grinding of the low fixed carbon material or the high fixed carbon material can be performed before, during, or after the streams are combined. The low fixed carbon material and the high fixed carbon material are combined (e.g., blended or co-ground) to produce a material such as… Figure 1 The reagents of the LCF-HFC combination are shown. The reagents of the LCF-HFC combination are optionally fed to a granulation unit or an additive feed unit therein. Alternatively or additionally, the reagents of the LCF-HFC combination are fed to a drying unit, which is operated to remove water from the reagents of the LCF-HFC combination. The final product is biochar flocs or powder.

[0127] Figure 2 This is a simplified block flowchart of a method for producing a biochar composition in some embodiments, the biochar composition having a low-fixed carbon material blended with a high-fixed carbon material, wherein the low-fixed carbon material serves as a pellet binder. Dashed boxes and lines represent optional units and flows, respectively. Figure 2 In this embodiment, biomass is fed into a first pyrolysis reactor operating under the effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low fixed carbon material, which is optionally ground to reduce particle size. Biomass is also fed into a second pyrolysis reactor operating under the effective pyrolysis conditions described herein. The biomass fed into the second pyrolysis reactor may be the same as or different from the biomass fed into the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high fixed carbon material, which is optionally ground to reduce particle size. When used, the grinding of the low fixed carbon material or the high fixed carbon material may be performed before, during, or after the streams are combined. Both the low fixed carbon material and the high fixed carbon material are fed into a pelletizing unit. In the pelletizing unit, the low fixed carbon material is used as a binder to form pellets. In other embodiments, a separate binder material may also be fed into the pelletizing unit. Optionally, the pellets are fed into a drying unit, which is operated to remove water from the pellets. The final product is bio-carbon flocs, with low-fixed carbon materials used as floc binders.

[0128] Fixed carbon is a measure of the amount of non-volatile carbon remaining in a sample. This measure is a calculated value determined by other parameters measured in an approximate analysis, rather than by direct measurement (see ASTM Method D3172-07a; American Society for Testing and Materials, 2013, pp. 492-493). Fixed carbon is a calculated percentage of material lost during moisture, volatile matter, and ash testing.

[0129] % Fixed Carbon = 100 - % Moisture + % Volatile Matter + % Ash

[0130] Total carbon is fixed carbon plus non-fixed carbon present in volatile substances. In some embodiments, component weight percentages are on an absolute basis, unless otherwise stated, which is assumed. In other embodiments, component weight percentages are on a moisture-free and ash-free basis. Compositions of low-fixed-carbon and high-fixed-carbon materials have been mentioned above.

[0131] The biochar composition disclosed herein may include: at least about 1 wt% to at most about 99 wt% of a low fixed carbon material, wherein, on an absolute basis, the low fixed carbon material comprises a first fixed carbon concentration of at least about 10 wt% to at most about 55 wt%; at least about 1 wt% to at most about 99 wt% of a high fixed carbon material, wherein, on an absolute basis, the high fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt%, wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; at least about 0 wt% to at most about 30 wt% of moisture; at least about 0 wt% to at most about 15 wt% of ash; and at least about 0 wt% to at most about 20 wt% of additives; wherein the low fixed carbon material or the high fixed carbon material comprises biochar; and wherein the total wt% calculated as the sum of the low fixed carbon material, the high fixed carbon material, the moisture, the ash, and the additives is at most 100 wt%.

[0132] In some embodiments, the low-carbon-fixed material includes unpyrolyzed biomass, pyrolyzed biomass, unpyrolyzed polymer, pyrolyzed polymer, coal, pyrolyzed coal, or a combination thereof. In some embodiments, the high-carbon-fixed material includes pyrolyzed biomass, coal, pyrolyzed coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolyzed polymer, or a combination thereof.

[0133] There are three naturally occurring carbon isotopes. 12 C 13 C and 14 C. 12 C and 13C is stable and exists in a natural ratio of approximately 93:1. 14 Carbon (C) is produced by thermal neutrons from cosmic radiation in the upper atmosphere and is transported to Earth to be absorbed by living biological materials. In terms of isotopes, 14 C constitutes a negligible portion; however, because it is radioactive with a half-life of 5,700 years, it can be detected using radiation measurements. Dead tissue does not absorb it. 14 C, therefore 14 The amount of C is one of the methods used for radiometric dating of biological materials.

[0134] Plants absorb carbon by fixing carbon from the atmosphere through photosynthesis. 14 C. Then, when animals eat plants or other animals that eat plants, they will... 14 Carbon is absorbed into their bodies. Therefore, living plants and animals have the same levels of carbon as atmospheric CO2. 14 C and 12 The ratio of carbon (C). Once an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer absorbs new carbon. 14 C. Radioactive decay then gradually depletes the organism's... 14 C. This effect forms the basis of radiocarbon dating.

[0135] Fossil fuels such as coal are primarily made from plant material deposited millions of years ago. This time period corresponds to... 14 C has thousands of half-lives, so it's present in virtually all fossil fuels. 14 C has already decayed. Fossil fuels relative to the atmosphere... 13 C is also depleted because the fossil fuels were originally formed from living organisms. Therefore, carbon from fossil fuels is less abundant than biogenic carbon. 13 C and 14 Both aspects of C are exhausted.

[0136] This difference between the carbon isotopes of recently deceased organic matter, such as organic matter from renewable resources, and the carbon isotopes of fossil fuels, such as coal, allows for the determination of the source of carbon in the composition. Specifically, the carbon in the composition originates from either renewable resources or fossil fuels; in other words, renewable resources or fossil fuels were used in the production of the composition.

[0137] In all embodiments of the compositions and methods for preparing the compositions disclosed herein, the biochar composition may comprise total carbon. In some embodiments, at least 50% of the total carbon is substantially composed of biochar, as indicated by the total carbon content. 14 C / 12 The carbon isotope ratio is determined by measurement. In some embodiments, at least 50% of the total carbon is substantially composed of biogenic carbon, as determined by the total carbon... 14C / 12 The carbon isotope ratio is determined by measurement. In some embodiments, at least 90% of the total carbon is substantially composed of biogenic carbon, as determined by the total carbon... 14 C / 12 The total carbon is determined by measurements of the C isotope ratio. In some embodiments, the total carbon consists essentially of biogenic carbon, as determined by the total carbon... 14 C / 12 The carbon isotope ratio was determined by measurements. 14 C / 12 The measurement of carbon isotope ratios can be performed using ASTM D6866.

[0138] Methods for producing biochar compositions

[0139] This document discloses a method for producing a biochar composition. The method may include: pyrolyzing a first feedstock comprising biomass, thereby producing a low-fixed-carbon material and a first pyrolysis exhaust gas, wherein, on an absolute basis, the low-fixed-carbon material comprises a first fixed-carbon concentration of at least about 20 wt% to at most about 55 wt%; pyrolyzing a second feedstock comprising biomass, thereby producing a high-fixed-carbon material and a second pyrolysis exhaust gas, wherein, on an absolute basis, the high-fixed-carbon material comprises a second fixed-carbon concentration of at least about 50 wt% to at most about 100 wt% and wherein the second fixed-carbon concentration is higher than the first fixed-carbon concentration; blending the low-fixed-carbon material with the high-fixed-carbon material, thereby producing an intermediate material; and recovering a biochar composition comprising the intermediate material or a heat-treated derivative of the intermediate material.

[0140] In some embodiments, the method includes drying the intermediate material. Drying may be performed at one or more points in the method.

[0141] In some embodiments, the method includes blending the intermediate material with an additive, thereby producing a blended intermediate material. In some embodiments, the method includes drying the blended intermediate material. In some embodiments, the second raw material is pyrolyzed independently of the first raw material. In some embodiments, the first raw material and the second raw material are of the same type. In some embodiments, the first raw material and the second raw material are not of the same type.

[0142] In some embodiments, the first raw material includes softwood chips, hardwood chips, logging residues, branches, stumps, leaves, bark, sawdust, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, bagasse, sugarcane stalks, energy sugarcane, sugar beets, beet pulp, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stalks, fruit peels, fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable pits, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, food scraps, commercial waste, grass pellets, hay pellets, sawdust pellets, cardboard, paper, pulp, paper packaging, paper decorations, food packaging, construction and / or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0143] In some embodiments, the second raw material includes softwood chips, hardwood chips, logging residues, branches, stumps, leaves, bark, sawdust, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, bagasse, sugarcane stalks, energy sugarcane, sugar beets, beet pulp, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stalks, fruit peels, fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable pits, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, food scraps, commercial waste, grass pellets, hay pellets, sawdust pellets, cardboard, paper, pulp, paper packaging, paper decorations, food packaging, construction and / or demolition waste, railway sleepers, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0144] In some embodiments, the biomass-containing feedstock comprises biomass (such as the biomass sources listed above) and non-renewable feedstocks such as coal. Therefore, a biomass-coal mixture can be used for a first biomass-containing feedstock and / or a second biomass-containing feedstock.

[0145] In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out in different pyrolysis reactors. The pyrolysis reactors are typically either entirely continuous or entirely batch-based, but in principle, a mixture of reaction modes can be used. Furthermore, when different pyrolysis reactors are used, they can be located in a common location or in different locations.

[0146] In some embodiments, the pyrolysis of the first feedstock and the pyrolysis of the second feedstock are carried out under different conditions in a common pyrolysis reactor. When a single pyrolysis reactor is used, it can be operated in batch mode with different batches of low-fixed carbon material and high-fixed carbon material. Alternatively, the single pyrolysis reactor can be operated continuously or semi-continuously, such that a first time period of low-fixed carbon material is produced, and then a second time period of high-fixed carbon material is produced (after which the reactor can be switched back to producing low-fixed carbon material or other materials).

[0147] In some embodiments, a low-carbon-fixed material is produced and stored. At a later time and possibly at a different location, a first portion of the low-carbon-fixed material can then be converted into a high-carbon-fixed material by further pyrolysis, while a second portion of the initial low-carbon-fixed material is blended with the produced high-carbon-fixed material.

[0148] In some embodiments, the blending includes blending substantially all of the low-fixed carbon material with the high-fixed carbon material. In some embodiments, the blending includes blending substantially all of the high-fixed carbon material with the low-fixed carbon material. In some embodiments, the blending of the low-fixed carbon material and the high-fixed carbon material includes blending the low-fixed carbon material and the high-fixed carbon material with an additive. In some embodiments, the method includes drying simultaneously with the blending. In some embodiments, the method includes blending the additive with the intermediate material, thereby producing a blended intermediate material, and then drying the intermediate material.

[0149] The blending of low-carbon and high-carbon-fixed materials can be carried out immediately after each material is produced using a batch or continuous method. Low-carbon-fixed materials can be stored or treated prior to blending (e.g., heat treatment, mechanical treatment, or in combination with additives). Similarly, high-carbon-fixed materials can be stored or treated prior to blending (e.g., heat treatment, mechanical treatment, or in combination with additives).

[0150] In some embodiments, the method includes recovering the biochar composition, the biochar composition comprising at least about 1 wt% to at most about 99 wt% of the low-fixed carbon material; at least about 1 wt% to at most about 99 wt% of the high-fixed carbon material; at least about 0 wt% to at most about 30 wt% of moisture; at least about 0 wt% to at most about 15 wt% of ash; and at least about 0 wt% to at most about 20 wt% of additives.

[0151] In some embodiments, pyrolyzing the first raw material includes pyrolysis at a first pyrolysis temperature, wherein the first pyrolysis temperature is at least about 250°C to at most about 1250°C. In some embodiments, pyrolyzing the first raw material includes pyrolysis at a first pyrolysis temperature, wherein the first pyrolysis temperature is at least about 300°C to at most about 700°C. In some embodiments, pyrolyzing the second raw material includes pyrolysis at a second pyrolysis temperature, wherein the second pyrolysis temperature is at least about 250°C to at most about 1250°C. In some embodiments, pyrolyzing the second raw material includes pyrolysis at a second pyrolysis temperature, wherein the second pyrolysis temperature is at least about 300°C to at most about 700°C. The second pyrolysis temperature is typically higher than the first pyrolysis temperature, but this is not necessary, at least because the raw materials in steps (a) and (b) can be different, and because other pyrolysis conditions (e.g., time, catalyst, or water concentration) can vary.

[0152] In some embodiments, pyrolyzing the first feedstock includes pyrolyzing for at least about 10 seconds to at most about 24 hours. In some embodiments, pyrolyzing the second feedstock includes pyrolyzing for at least about 10 seconds to at most about 24 hours. The first pyrolysis time may be longer than the second pyrolysis time, but this is not necessary, at least because the feedstocks in steps (a) and (b) may be different, and because other pyrolysis conditions (e.g., temperature, catalyst, or water concentration) may vary.

[0153] In some embodiments, the first pyrolysis waste gas is oxidized, thereby generating heat. In some embodiments, the heat is used in the method, thereby recycling the heat. In some embodiments, the second pyrolysis waste gas is oxidized, thereby generating heat. In some embodiments, the heat is used within the method, thereby recycling the heat. In some embodiments, using the heat within the method can provide heat to the pyrolysis reactor.

[0154] In some embodiments, the first pyrolysis waste gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide. In some embodiments, the second pyrolysis waste gas is oxidized, thereby producing a reducing gas comprising hydrogen or carbon monoxide.

[0155] In some embodiments, the method includes performing a first grinding of the low fixed carbon material prior to the blending, wherein the first grinding includes using mechanical processing equipment, the mechanical processing equipment including hammer mills, extruders, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof. In some embodiments, the method includes performing a second grinding of the high fixed carbon material prior to the blending, wherein the second grinding includes using mechanical processing equipment, the mechanical processing equipment including hammer mills, extruders, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof. In some embodiments, the blending includes using mechanical processing equipment, the mechanical processing equipment including hammer mills, extruders, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, or combinations thereof.

[0156] When grinding both low-carbon and high-carbon materials, they can be ground together in the same unit (during blending), or they can be ground separately in the same type of equipment or different types of equipment.

[0157] In some embodiments of the method, the biochar composition comprises a homogeneous physical blend of the low-carbon-fixed material and the high-carbon-fixed material. In some embodiments, the low-carbon-fixed material is uniformly dispersed throughout the biochar composition. In some embodiments, the high-carbon-fixed material is uniformly dispersed throughout the biochar composition. In some embodiments, both the low-carbon-fixed material and the high-carbon-fixed material are uniformly dispersed in the biochar composition.

[0158] In some embodiments, the biochar composition comprises a heterogeneous physical blend of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises different layers of the low-fixed carbon material and the high-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, wherein the core is contained within the shell, wherein the core comprises the high-fixed carbon material, and wherein the shell comprises the low-fixed carbon material. In some embodiments, the biochar composition comprises a core and a shell, wherein the core is contained within the shell, wherein the core comprises the low-fixed carbon material, and wherein the shell comprises the high-fixed carbon material. In some embodiments, the high-fixed carbon material is in the form of particulate matter within the continuous phase of the low-fixed carbon material. In some embodiments, the low-fixed carbon material is in the form of particulate matter within the continuous phase of the high-fixed carbon material.

[0159] In some embodiments of the method, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the low-fixed carbon material. In some embodiments, the biochar composition comprises at least about 10 wt% to at most about 90 wt% of the high-fixed carbon material. In some embodiments, the biochar composition comprises the weight ratio of the low-fixed carbon material to the high-fixed carbon material, and wherein the ratio is at least about 0.1 to at most about 10.

[0160] In some embodiments of the method, the biochar composition comprises a weight ratio of the low-fixed carbon material to the high-fixed carbon material, wherein the ratio is at least about 0.2 to at most about 5. In some embodiments, the biochar composition comprises a weight ratio of the low-fixed carbon material to the high-fixed carbon material, wherein the ratio is at least about 0.5 to at most about 2. In some embodiments, the biochar composition comprises a weight ratio of the low-fixed carbon material to the high-fixed carbon material, wherein the ratio is at least about 0.8 to at most about 1.2.

[0161] In some embodiments, the first fixed carbon concentration is at least about 20 wt% to at most about 40 wt%. In some embodiments, the first fixed carbon concentration is at least about 25 wt% to at most about 50 wt%. In some embodiments, the first fixed carbon concentration is at least about 30 wt% to at most about 55 wt%. In some embodiments, the second fixed carbon concentration is at least about 80 wt% to at most about 100 wt%. In some embodiments, the second fixed carbon concentration is at least about 70 wt% to at most about 95 wt%. In some embodiments, the second fixed carbon concentration is at least about 60 wt% to at most about 90 wt%. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 30 wt% to at most about 90 wt%. In some embodiments, the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is at least about 40 wt% to at most about 80 wt%.

[0162] In some embodiments of the method, the biochar composition comprises, on an absolute basis, at least about 25 wt% to at most about 95 wt% of total fixed carbon. In some embodiments, the biochar composition comprises, on an absolute basis, at least about 35 wt% to at most 85 wt% of total fixed carbon. In some embodiments, the low fixed carbon material comprises, on an absolute basis, at least about 45 wt% to at most about 80 wt% of volatile carbon. In some embodiments, the high fixed carbon material comprises, on an absolute basis, at least about 0 to at most about 50 wt% of volatile carbon.

[0163] In some embodiments of the method, the biochar composition comprises at least about 0.1 wt% to at most about 20 wt% water. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% ash. In some embodiments, the biochar composition comprises at least about 0.1 wt% to at most about 10 wt% additives. In some embodiments, the biochar composition comprises at least about 1 wt% to at most about 15 wt% additives. In some embodiments, the biochar composition comprises at least about 3 wt% to at most about 18 wt% additives.

[0164] In some embodiments of the method, the biochar composition includes additives, and the additives include organic additives. In some embodiments, the additives include inorganic additives. In some embodiments, the additives include renewable materials. In some embodiments, the additives include materials that can be oxidized or burned. In some embodiments, the additives include binders.

[0165] In some embodiments, the method includes granulation. The granulation can be achieved using an extruder, a ring die granulator, a flat die granulator, a roller compactor, a roller briquetting machine, a wet agglomerating mill, a dry agglomerating mill, or a combination thereof.

[0166] In some embodiments of the method, the biochar composition includes a binder. The binder may include starch, thermoplastic starch, cross-linked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, coal tar pitch, petroleum asphalt, pitch, pyrolytic tar, hard asphalt, bentonite, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, derivatives thereof, or combinations thereof.

[0167] In some embodiments of the method, the biochar composition includes a binder, and the binder includes starch, thermoplastic starch, cross-linked starch, starch polymers, derivatives thereof, or combinations thereof.

[0168] In some embodiments of the method, the biochar composition includes a binder, and the binder includes thermoplastic starch. In some embodiments, the thermoplastic starch is cross-linked. The thermoplastic starch may be a reaction product of starch and a polyol. The polyol may be ethylene glycol, propylene glycol, glycerol, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or a combination thereof. The thermoplastic starch may be formed by an acid-catalyzed reaction. The acid may include formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof. Alternatively or additionally, the thermoplastic starch may be formed by a base-catalyzed reaction.

[0169] In some embodiments of the method, the additive reduces the reactivity of the biochar composition compared to an otherwise equivalent biochar composition without the additive. In some embodiments, the reactivity is thermal reactivity. For example, the biochar composition may include lower self-heating compared to an otherwise equivalent biochar 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 metals. In some embodiments, the metal includes iron.

[0170] In some embodiments, the method includes blending an additive with the intermediate material, thereby introducing the additive into the pores of the low-fixed-carbon material. In some embodiments, the method includes blending an additive with the intermediate material, thereby introducing the additive into the pores of the high-fixed-carbon material. In some embodiments, the method includes blending an additive with the intermediate material, thereby introducing the additive into the pores of both the low-fixed-carbon material and the high-fixed-carbon material.

[0171] In some embodiments, the method includes blending the additive with the intermediate material, thereby disposing the additive on the outer surface of the biochar composition (e.g., the outer surface of granules or powder particles). The method may include, for example, spraying the additive onto the biochar composition.

[0172] In some embodiments, the method includes forming the biochar composition into a powder.

[0173] In some embodiments, the method includes granulating the biochar composition.

[0174] In some embodiments, the method includes blending an additive with the intermediate material, wherein the additive includes a binder. In some embodiments, the binder includes the low-fixed carbon material. In some embodiments, the method includes blending an additive with the intermediate material, wherein the low-fixed carbon material includes the additive or the high-fixed carbon material includes the additive.

[0175] In some embodiments of the method, when a self-heating test is performed according to the Test and Standards Manual, 7th Revision 2019, United Nations, page 375, 33.4.6 Test N.4: “Test Methods for Self-Heating Substances”, the biochar composition is characterized as non-self-heating. The energy content of the biochar 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 is selected to optimize the energy content associated with the biochar composition.

[0176] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the bulk density of the biochar.

[0177] In some embodiments of the method, the method includes selecting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the hydrophobicity of the biocarbon.

[0178] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the pore size of the biochar.

[0179] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the pore size ratio of the biochar.

[0180] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the surface area of ​​the biochar.

[0181] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the reactivity of the biocarbon.

[0182] In some embodiments of the method, the method includes selecting the first fixed carbon concentration, the second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the ion exchange capacity (IEC) of the biocarbon.

[0183] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the Hardgrove grindability index of the biochar.

[0184] In some embodiments of the method, the method includes selecting a first fixed carbon concentration, a second fixed carbon concentration, or the type or concentration of the additive, thereby optimizing the pellet durability index of the biochar.

[0185] In some embodiments of the method, the biochar composition comprises total carbon, wherein at least 50% of the total carbon is substantially composed of biochar, as determined by the total carbon composition. 14 C / 12 The determination is made by measuring the C isotope ratio. In some embodiments of the method, the biochar composition comprises total carbon, wherein at least 90% of the total carbon is substantially composed of biochar, as determined by the total carbon... 14 C / 12 The determination is made by measuring the C isotope ratio. In some embodiments of the method, the biochar composition comprises total carbon, wherein the total carbon is substantially composed of biochar, as determined according to the total carbon... 14 C / 12 Determined by measurements of C isotope ratios.

[0186] It is important to note that while renewable biochar compositions are preferred, the principles of this invention can be applied to non-renewable materials.

[0187] The method disclosed herein may include: pyrolyzing a first feedstock, wherein the first feedstock comprises biomass, thereby producing a low-fixed carbon material and a first pyrolysis exhaust gas, wherein, on an absolute basis, the low-fixed carbon material comprises a first fixed carbon concentration of at least about 20 wt% to at most about 55 wt%; providing a high-fixed carbon material, wherein, on an absolute basis, the high-fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; blending the low-fixed carbon material with 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 biochar composition comprising the intermediate material or a heat-treated derivative thereof.

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

[0189] The method disclosed herein may include: providing a low fixed carbon material, wherein, on an absolute basis, the low fixed carbon material comprises a first fixed carbon concentration of at least about 10 wt% to at most about 55 wt% fixed carbon; pyrolyzing a feedstock, wherein the feedstock comprises biomass, thereby producing a high fixed carbon material and pyrolysis exhaust gas, wherein, on an absolute basis, the high fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% fixed carbon, and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; blending the low fixed carbon material with 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 biochar composition comprising the intermediate material or a heat-treated derivative thereof.

[0190] In some embodiments of the method, the low fixed carbon material includes unpyrolyzed biomass, pyrolyzed biomass, unpyrolyzed polymers, pyrolyzed polymers, or combinations thereof.

[0191] The method disclosed herein may include: providing a low-fixed carbon material, wherein, on an absolute basis, the low-fixed carbon material comprises a first fixed carbon concentration of at least about 10 wt% to at most about 55 wt% of fixed carbon; providing a high-fixed carbon material, wherein, on an absolute basis, the high-fixed carbon material comprises a second fixed carbon concentration of at least about 50 wt% to at most about 100 wt% of fixed carbon, and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; blending the low-fixed carbon material with the high-fixed carbon material to produce an intermediate material; optionally blending an additive with the intermediate material; optionally drying the intermediate material; and recovering a biochar composition comprising the intermediate material or a heat-treated derivative thereof.

[0192] In some embodiments of the method, the low-carbon-fixed material includes unpyrolyzed biomass, pyrolyzed biomass, unpyrolyzed polymers, pyrolyzed polymers, or combinations thereof. In some embodiments of the method, the high-carbon-fixed material includes pyrolyzed biomass, coal, pyrolyzed coal, coke, petroleum coke, metallurgical coke, activated carbon, carbon black, graphite, graphene, pyrolyzed polymers, or combinations thereof.

[0193] Figure 1 This is a simplified block flowchart of a method for producing a biochar composition in some embodiments, the biochar composition having a low-carbon-fixed material blended with a high-carbon-fixed material, optionally with additives (such as a binder for preparing granules). Dashed boxes and lines represent optional units and flows, respectively. Figure 1 In this process, biomass is fed into a first pyrolysis reactor operating under the effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low fixed carbon material, which is optionally ground to reduce particle size. Biomass is also fed into a second pyrolysis reactor operating under the effective pyrolysis conditions described herein. The biomass fed into the second pyrolysis reactor may be the same as or different from the biomass fed into the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high fixed carbon material, which is optionally ground to reduce particle size. When employed, the grinding of the low fixed carbon material or the high fixed carbon material can be performed before, during, or after the streams are combined. The low fixed carbon material and the high fixed carbon material are combined (e.g., blended or co-ground) to produce a material such as… Figure 1 The reagents of the LCF-HFC combination are shown. The reagents of the LCF-HFC combination are optionally fed to a granulation unit or an additive feed unit therein. Alternatively or additionally, the reagents of the LCF-HFC combination are fed to a drying unit, which is operated to remove water from the reagents of the LCF-HFC combination. The final product is biochar flocs or powder.

[0194] Figure 2 This is a simplified block flowchart of a method for producing a biochar composition in some embodiments, the biochar composition having a low-fixed carbon material blended with a high-fixed carbon material, wherein the low-fixed carbon material serves as a pellet binder. Dashed boxes and lines represent optional units and flows, respectively. Figure 2 In this embodiment, biomass is fed into a first pyrolysis reactor operating under the effective pyrolysis conditions described herein. The first pyrolysis reactor is configured to produce a low fixed carbon material, which is optionally ground to reduce particle size. Biomass is also fed into a second pyrolysis reactor operating under the effective pyrolysis conditions described herein. The biomass fed into the second pyrolysis reactor may be the same as or different from the biomass fed into the first pyrolysis reactor. The second pyrolysis reactor is configured to produce a high fixed carbon material, which is optionally ground to reduce particle size. When used, the grinding of the low fixed carbon material or the high fixed carbon material may be performed before, during, or after the streams are combined. Both the low fixed carbon material and the high fixed carbon material are fed into a pelletizing unit. In the pelletizing unit, the low fixed carbon material is used as a binder to form pellets. In other embodiments, a separate binder material may also be fed into the pelletizing unit. Optionally, the pellets are fed into a drying unit, which is operated to remove water from the pellets. The final product is bio-carbon flocs, with low-fixed carbon materials used as floc binders.

[0195] According to one or more methods disclosed herein, for the purpose of quality control or as evidence of the practice of the invention, various potential techniques may be used to demonstrate that a given biochar composition contains both low-fixed carbon material and different high-fixed carbon materials, rather than a biochar composition containing a single material with a uniform fixed carbon concentration.

[0196] In a technique for demonstrating that a given biochar composition contains low-fixed carbon material and different high-fixed carbon materials, thermogravimetric analysis (TGA) is performed on the combustion of a test sample of the biochar composition. In some embodiments, the resulting TGA thermal profile has two peaks, characterized by different mass loss events associated with the low-fixed carbon material and the high-fixed carbon material. This can be compared with a control sample containing a biochar composition of a single material with a uniform fixed carbon concentration to show a TGA thermal profile exhibiting a single-peak characteristic of a mass loss event of said material. In similar embodiments, the TGA thermal profile of the test sample has three or more peaks, while the TGA thermal profile of the control sample has at least one fewer peak than the TGA thermal profile of the test sample.

[0197] Another technique for demonstrating that a given biochar composition contains both low-fixed carbon material and different high-fixed carbon materials is particle size analysis. This is feasible when the particle sizes associated with the low-fixed and high-fixed carbon materials differ, or when the particle size distributions associated with the low-fixed and high-fixed carbon materials differ. For example, high-fixed carbon materials tend to have larger particles compared to low-fixed carbon materials. In some embodiments, a bimodal particle size distribution arises from the presence of both low-fixed and high-fixed carbon materials, which contrasts with the unimodal particle size distribution characteristics of a control sample, which is a homogeneous material. In similar embodiments, the particle size distribution of the test sample may have at least one more pattern than that of the control sample. For example, each of the low-fixed and high-fixed carbon materials may have a bimodal particle size distribution (peaks concentrated at different sizes), and the control sample may also have a bimodal particle size distribution, depending on how the control sample is prepared.

[0198] Particle size can be measured using a variety of techniques, including dynamic light scattering, laser diffraction, image analysis, or sieving. Dynamic light scattering is a non-invasive, well-established technique for measuring the size and size distribution of particles, typically in the submicron region, and the latest techniques can scale down to 1 nanometer. Laser diffraction is a widely used particle-setting technique suitable for materials ranging in size from hundreds of nanometers to several millimeters. Exemplary dynamic light scattering and laser diffraction instruments for measuring particle size are available from Malvern Instruments Ltd., Worcestershire, UK. Image analysis for estimating 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.

[0199] Imaging techniques can be used alternatively or additionally to demonstrate that a given biochar composition contains both low-carbon-fixed materials and distinct high-carbon-fixed 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 computed tomography (XRT). For example, imaging techniques can be used to show distinct materials in a blend, rather than homogeneous materials. Alternatively, imaging techniques can be used to select subsamples for further analysis. Further analysis could be compositional analysis to show three-dimensional variations in fixed carbon content. Further analysis could be property analysis to show three-dimensional variations in chemical or physical properties, such as density, particle size, or reactivity.

[0200] Spectroscopic techniques can be used alternatively or additionally to demonstrate that a given biochar composition contains both low-carbon-fixed materials and different high-carbon-fixed materials. For example, spectroscopic techniques include, but are not limited to, energy-dispersive X-ray spectroscopy (EDS), X-ray fluorescence (XRF), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.

[0201] Some embodiments are based on optimized pyrolysis of biomass to produce a carbon matrix, which reduces the mechanical size of the carbon matrix, and the use of binders to aggregate the carbon matrix to form biocarbon pellets. The carbon matrix can be or contains blends of low- and high-carbon-fixed materials.

[0202] The Hardgrove Grindability Index (“HGI”) is a measure of the grindability of materials such as biomass or coal. The HGI parameter for coal is important in power applications, such as in pulverized coal boilers, where coal is pulverized and suspended for combustion; and in ironmaking, such as in pulverized coal injection, where pulverized coal is injected through lances into a blast furnace, where it can replace coke to reduce iron ore to metallic iron.

[0203] In some embodiments, changing the ratio and composition of low-fixed carbon materials and high-fixed carbon materials can optimize HGI. Adjustable HGI can also be achieved by combining binders or other additives.

[0204] The ability to adjust the HGI of biochar flocs is beneficial because downstream applications utilizing biochar flocs (e.g., coal replacement in boilers) have varying HGI requirements. HGI adjustability addresses well-known industrial problems: the difficulty of grinding feedstock biomass and the difficulty of grinding flocs. Furthermore, because biochar flocs have so many downstream uses, each with its own requirements, the ability to adjust the grindability of the flocs is highly advantageous. It is desirable to be able to adjust the HGI to suit specific applications such as combustion in boilers, metal preparation, or the gasification of syngas.

[0205] For many applications, pellets are superior to powders (separated biomass pellets) due to advantages in transportation, storage, and safety. Ultimately, pellets may need to be converted back to powders, or at least to smaller objects, at some point. Therefore, the grindability of pellets is often an important parameter affecting operating and capital costs.

[0206] In some cases, it is necessary to grind or pulverize agglomerates into powder, such as when boilers or gasifiers utilize fluidized beds or carbon particle suspensions. Another example is the injection of powdered carbon into a blast furnace to reduce metal ore to metal. In these cases, high grindability of the agglomerates is desired, but not so high that the agglomerates break apart during transport and handling. In other cases, it is desirable to feed the agglomerates themselves into the process, such as in metal preparation processes. In these cases, lower grindability may be desirable because some agglomerate strength may be necessary to support the material bed in the reactor. Different technologies have different agglomerate grindability requirements.

[0207] The Hardgrove Grindability Index (HGI) of biochar flocs 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 HGI is about 30 to about 50 or about 50 to about 70. ASTM Standard D 409 / D 409M, entitled "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method," is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to the HGI or Hardgrove Grindability Index in this disclosure are made to ASTM Standard D 409 / D 409M.

[0208] In various embodiments, the Hardgrove grindability index is about, at least about, or at most 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, or 6. 0, 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, including all intermediate ranges (e.g., 25-40, 30-60, etc.).

[0209] In some embodiments, the biochar pellets comprise a pellet durability index of at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%. In some embodiments, the biochar 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 the pellet durability index in this disclosure are made to ISO 17831-1:2015 “Solid biofuels—Determination of mechanicaldurability of pellets and briquettes—Part 1: Pellets”, which is hereby incorporated herein by reference in its entirety.

[0210] In some embodiments of the invention, biochar agglomerates are used as starting materials for preparing smaller objects. Since the term "agglomerate" is not limited to a specific geometry, the objects can also be referred to as biochar agglomerates. For example, initial biochar agglomerates with an average agglomerate diameter of 10 mm can be produced. These initial biochar agglomerates can then be crushed using various mechanical components (e.g., using a hammer mill). The crushed agglomerates can be separated according to size, such as by sieving. In this way, smaller biochar agglomerates can be produced, with an average agglomerate diameter of, for example, about, at least about, or at most about 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, or 5000 micrometers. The average agglomerate diameter of the smaller biochar agglomerates can be larger than the average particle diameter of the initial carbonaceous particles used to prepare the agglomerates with a binder.

[0211] When biochar flocs are crushed to produce smaller biochar flocs, the crushing (and optionally screening) step can be integrated with another process step, potentially at industrial sites of use. In some embodiments, producing smaller biochar flocs includes utilizing crushing equipment. In some embodiments, crushing equipment includes hammer mills, grinding mills, disc mills, pin mills, ball mills, cone crushers, jaw crushers, rock crushers, or combinations thereof.

[0212] In various method embodiments, the Hardgrove grindability 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 grindability index can be about 30 to about 50 or about 50 to about 70.

[0213] Among the various methods, process conditions were selected and optimized to produce Hardgrove grindability indices of approximately, at least approximately, or at most approximately 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, and 59. The final biogenic carbon pellets are 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100, encompassing all intermediate ranges (e.g., 30-60, 33-47, etc.).

[0214] In some embodiments, the biochar flocs include a floc durability index of at least about 80%, at least about 90%, or at least about 95%.

[0215] In some embodiments, the method includes pre-selecting a Hadgrove grindability index; adjusting process conditions based on the pre-selected Hadgrove grindability index; and achieving a range within ±20% of the pre-selected Hadgrove grindability index of the biochar flocs, wherein adjusting the process conditions includes adjusting one or more of the following: pyrolysis temperature, pyrolysis time, mechanical processing conditions, granulation conditions, binder type, binder concentration, binding conditions, and drying. The method in some embodiments can achieve a range within ±10% or ±5% of the pre-selected Hadgrove grindability index of the biochar flocs.

[0216] The size and geometry of biochar agglomerates can vary. As used herein, “agglomerate” refers to an aggregated object rather than loose powder. Agglomerate geometry is not limited to spherical or near-spherical shapes. Furthermore, in this disclosure, “agglomerate” is synonymous with “clump.” Agglomerate geometry can be spherical (circular or spherical), cubic (square), octagonal, hexagonal, honeycomb / honeycomb, elliptical, oval, columnar, strip-shaped, pillow-shaped, random, or a combination thereof. For ease of disclosure, the term “agglomerate” is generally used for any object containing powder agglomerated with a binder. It should also be reiterated that the invention is by no means limited to biochar compositions in agglomerated form.

[0217] The biogenic carbon aggregates may be characterized by an average aggregate diameter, which, in the case of spheres, is the actual diameter, or, in the case of any other 3D geometry, is an equivalent diameter. The equivalent diameter of non-spherical aggregates is the diameter of a sphere with the same volume as the actual aggregate. In some embodiments, the average aggregate diameter may 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, encompassing all intermediate ranges. In some embodiments, the average aggregate diameter may be about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 micrometers, encompassing all intermediate ranges.

[0218] In some embodiments, there are multiple biochar pellets of relatively uniform size, such as those less than ±100%, ±50%, ±25%, ±10%, or ±5% of the average pellet diameter. In other embodiments, the biochar pellets have a wide range of sizes, as this may be advantageous in some applications.

[0219] Biochar flocs may contain moisture. The moisture present in biochar flocs can be water chemically bound to the carbon or binder, water physically bound to the carbon or binder (absorbed or adsorbed), free water present in the aqueous phase that is not chemically or physically bound to the carbon or binder, or a combination thereof. When moisture is required during the bonding process, it is preferable that such moisture is chemically or physically bound to the carbon and / or binder, rather than free water.

[0220] Various moisture contents may be present. For example, biochar flocs may include about 1 wt% to about 30 wt% (e.g., 32 wt%) of moisture, such as about 5 wt% to about 15 wt%, about 2 wt% to about 10 wt%, or about 0.1 wt% to about 1 wt%. In some embodiments, biochar flocs contain about 4 wt% to 8 wt% of moisture. In various embodiments, biochar flocs include about, at least about, or at most about 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 wt% of moisture, encompassing all intermediate ranges. The moisture content of biochar flocs can be optimized to alter densification within the flocs.

[0221] For some market applications, such as in agriculture, higher moisture content is desirable for dust control or other reasons. For other market applications, such as metallurgy, lower moisture content may be desirable (e.g., 1 wt% moisture or even lower). Note that although water is present during the process of preparing biochar flocs, those flocs are then optionally dried, meaning that the final biochar flocs do not necessarily contain moisture.

[0222] In some biochar flocs, the biochar flocs comprise about 2 wt% to about 25 wt% of binder, about 5 wt% to about 20 wt% of binder, or about 1 wt% to about 5 wt% of binder. In various embodiments, the biochar flocs comprise about, at least about, or at most about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, or 30 wt% of binder, encompassing all intermediate ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0223] The binder can be a pore-filling agent within the bio-based reagent of the biochar flocs. Alternatively or additionally, the binder can be applied to the surface of the biochar flocs.

[0224] The adhesive may be an organic or inorganic adhesive. In some embodiments, the adhesive is or contains renewable materials. In some embodiments, the adhesive is or contains biodegradable materials. In some embodiments, the adhesive can be partially oxidized and / or burned.

[0225] In some embodiments, the adhesive comprises starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, coal tar pitch, petroleum asphalt, asphalt, pyrolytic tar, hard asphalt, bentonite, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, or derivatives thereof, or combinations thereof. In some embodiments, the adhesive comprises a grindable plasticizer.

[0226] In some embodiments, the binder comprises starch, thermoplastic starch, cross-linked 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.

[0227] Starch is one of the most abundant biopolymers. It is fully biodegradable, inexpensive, renewable, and readily chemically modified. The cyclic structure of starch molecules, along with strong hydrogen bonds, gives starch a rigid structure and results in highly ordered crystalline and granular regions. Starch in its granular state is generally unsuitable for thermoplastic processing. To obtain thermoplastic starch, semi-crystalline starch granules can be decomposed by heat and mechanical force. Since the melting point of pure starch is significantly higher than its decomposition temperature, plasticizers such as water and / or ethylene glycol can be added. The natural crystallinity can then be destroyed by vigorous mixing (shearing) at elevated temperatures, producing thermoplastic starch. Starch can also be plasticized (modified) by relatively low levels of molecules capable of forming hydrogen bonds with starch hydroxyl groups such as water, glycerol, or sorbitol.

[0228] Thermoplastic starch can be chemically modified and / or blended with other biopolymers to produce stronger, more ductile, and more elastic 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 through esterification or etherification.

[0229] In some embodiments, the starch-containing binder is or comprises cross-linked starch. Various methods for cross-linking starch are known in the art. For example, the starch material can be cross-linked under acidic or alkaline conditions after being dissolved or dispersed in an aqueous medium. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to cross-link starch.

[0230] An example of cross-linked starch is the product of a reaction between starch and glycerol or another polyol such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or combinations thereof. The reaction product can be formed by an acid-catalyzed cross-linking reaction 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 used to catalyze the cross-linking reaction. In some embodiments, the thermoplasticization and / or cross-linking reaction product can be formed by an alternatively base-catalyzed cross-linking reaction such as (but not limited to) ammonia or sodium borate.

[0231] In some embodiments, the adhesive is designed to be waterproof. For example, in the case of starch, the hydrophilic groups can be replaced by hydrophobic groups that offer better waterproofing.

[0232] In some embodiments, the adhesive is used for other purposes, such as (but not limited to) water retention in biochar flocs, serving as a food source for microorganisms, etc.

[0233] In some embodiments, the binder reduces the reactivity of the biochar flocs compared to otherwise equivalent biochar flocs without binders. Reactivity can refer to thermal reactivity or chemical reactivity (or both).

[0234] In thermally reactive cases, biochar pellets can exhibit lower self-heating compared to otherwise equivalent biochar pellets without binders. "Self-heating" refers to the spontaneous exothermic reaction that occurs in the absence of any external ignition, at relatively low temperatures, and in an oxidizing atmosphere, causing the internal temperature of the biochar pellets to rise.

[0235] Chemical reactivity can be reactivity with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. For example, chemical reactivity can be associated with reactions to CO, CO2, H2O, pyrolysis oil, and heat.

[0236] Optionally, the biomass pellets include one or more additives such as inorganic bentonite, limestone, starch, cellulose, lignin, or acrylamide (these additives are not necessarily binders). When lignin is used as a binder or other additive, the lignin can be obtained from the same biomass feedstock used in the pyrolysis process. For example, the starting biomass feedstock can be subjected to a lignin extraction step to remove a certain amount of lignin used as a binder or additive. As previously explained, any additive can be contained within a low-carbon-fixed material, a high-carbon-fixed material, or both.

[0237] Other possible additives include fluxes 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, ferric halide, ferric chloride, ferric bromide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, calcium oxide, lime, or combinations thereof. The additives may be added before, during, or after any one or more steps of the method, including adding them to the raw material itself at any time before or after harvesting the raw material itself.

[0238] The biochar flocs disclosed herein have various downstream applications. Biochar flocs can be stored, sold, transported, and converted into other products. Biochar flocs can be pulverized for use in boilers to burn carbon and generate electricity and / or heat. Biochar flocs can be pulverized, crushed, or ground to feed into furnaces such as blast furnaces in metal processing. Biochar flocs can be directly fed into furnaces such as Tecnored furnaces in metal processing. For the purpose of producing syngas from biochar flocs, the biochar flocs can be pulverized, crushed, or ground to feed into gasifiers.

[0239] In many embodiments, biochar pellets are fed into the furnace directly or after a step of crushing, breaking, grinding, or otherwise reducing the particle size. The furnace can be a blast furnace, a top gas recirculation blast furnace, a vertical furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a muffle furnace, a canned furnace, a flash furnace, a Tecnored furnace, an Osmät furnace, an ISA furnace, a stirring furnace, a live-bottom 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 stirring furnace, a Bessma furnace, a direct reduction metal furnace, or combinations or derivatives thereof.

[0240] Please note that regardless of the Hardgrove Grindability Index of the biochar flocs, the biochar flocs do not necessarily undergo subsequent grinding processes. For example, the biochar flocs can be used directly in agricultural applications. As another example, the biochar flocs can be directly incorporated into engineering structures such as landscape walls. At the end of the life of the structure containing the biochar flocs, the flocs can then be ground, burned, gasified, or otherwise reused or recycled.

[0241] Pyrolysis process and system

[0242] Processes and systems suitable for pyrolyzing biomass feedstocks to produce low- and / or high-carbon-fixed materials will now be described in further detail. Depending on the process conditions and product characteristics, the term “biochar reagent” as used herein will be understood to refer to: (a) in some cases, low-carbon-fixed materials; or (b) high-carbon-fixed materials; or (c) biochar compositions containing blends of low- and high-carbon-fixed materials. Similarly, descriptions of pyrolysis reactors (or reactions) will be understood to refer to reactors (or reactions) specifically designed for producing low-carbon-fixed materials in some cases, and reactors (or reactions) specifically designed for producing high-carbon-fixed materials in some cases. Unless otherwise stated, descriptions of the use (commercial application) of biochar reagents generally refer to biochar compositions containing blends of low- and high-carbon-fixed materials.

[0243] "Pyrolysis" and "pyrolyze" generally refer to the thermal decomposition of carbonaceous materials. In pyrolysis, the amount of oxygen present is less than that 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.

[0244] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the internal temperature of the feedstock; (ii) the initiation of the primary pyrolysis reaction at this higher temperature releases volatiles and forms char; (iii) the flow of hot volatiles to cooler solids results in heat transfer between the hot volatiles and the cooler, unpyrolyzed feedstock; (iv) some of the volatiles condense in the cooler portion of the feedstock, followed by a secondary reaction that may produce tar; (v) an autocatalytic secondary pyrolysis reaction occurs while the primary pyrolysis reaction occurs in competition; and (vi) further thermal decomposition, reforming, water-gas shift reaction, free radical recombination, and / or dehydration may also occur, which are functions of residence time, temperature, and pressure distribution.

[0245] Pyrolysis can dehydrate starting materials (e.g., lignocellulosic biomass) at least partially. In various embodiments, pyrolysis removes more than about 50%, 75%, 90%, 95%, 99% or more of water from the starting material.

[0246] In some embodiments, the starting biomass feedstock includes softwood chips, hardwood chips, logging residues, branches, stumps, leaves, bark, sawdust, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, bagasse, sugarcane stalks, energy sugarcane, sugar beets, beet pulp, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stalks, fruit peels, fruit pits, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable pits, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, food scraps, commercial waste, grass pellets, hay pellets, sawdust pellets, cardboard, paper, pulp, paper packaging, paper decorations, food packaging, construction and / or demolition waste, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. The biomass feedstock includes at least carbon, hydrogen, and oxygen.

[0247] In some embodiments, the bio-derived reagent comprises at least about 50 wt%, at least about 75 wt%, or at least about 90 wt% of total carbon. In various embodiments, the bio-derived reagent comprises about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt% of carbon, including intermediate values. Total carbon is fixed carbon plus non-fixed carbon present in volatile substances. In some embodiments, component weight percentages are on an absolute basis, unless otherwise stated, this is assumed. In other embodiments, component weight percentages are on a moisture-free and ash-free basis. Compositions of low-fixed-carbon and high-fixed-carbon materials have been discussed in detail above.

[0248] Pyrolysis conditions can vary widely, depending on the desired combination of bio-derived reagents and pyrolysis exhaust gases, starting materials, reactor configuration, and other factors.

[0249] In some embodiments, multiple reactor zones are designed and operated in a manner that optimizes carbon yield and product quality from pyrolysis while maintaining flexibility and adjustability for feedstock variations and product requirements.

[0250] In some non-limiting embodiments, the temperature and residence time can be selected to achieve a relatively slow pyrolysis chemical reaction. The benefit is that the cell walls contained within the biomass structure can be largely preserved, meaning 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 use equipment that does not mechanically damage the cell walls or otherwise convert the biomass particles into fine powder. Preferred reactor configurations are discussed after the process description below.

[0251] Additionally, if the raw material is milled or sized, such as sawdust or pellets, it may be desirable for the raw material to be carefully milled or sized. Careful initial processing will tend to preserve the strength and cell wall integrity present in the natural source of the raw material (e.g., trees). This may also be important when the final product should retain some, most, or all of the shape and strength of the starting biomass.

[0252] 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 “impact” the biomass, which will cause cell walls to break down and trigger rapid solid-phase decomposition into vapor and gas. This first zone can be considered as mild pyrolysis.

[0253] In some embodiments, the second zone of the pyrolysis reactor is configured as a primary reaction zone, in which preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, thereby producing a significant amount of solid material, which is a high-carbon reaction intermediate. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose and generate vapors, which escape through permeation pores or by the formation of new nanopores. The latter effect contributes to increased porosity and surface area.

[0254] In some embodiments, the third zone of the pyrolysis reactor is configured to receive high-carbon reaction intermediates and, to some extent, cool the solids. Typically, the temperature in the third zone will be lower than that in the second zone. In the third zone, chemical reactions and mass transport can be unexpectedly complex. Secondary reactions are believed to occur in the third zone, without being limited by any particular theory or proposed mechanism. Essentially, the carbonaceous components in the gas phase can decompose to form additional fixed carbon and / or be adsorbed onto carbon. Therefore, the final carbonaceous material cannot simply be a solid residue of the volatile matter from the processing steps, but may contain additional carbon deposited from the gas phase, such as organic vapors (e.g., tar) that can form carbon through decomposition.

[0255] Some embodiments extend the concept of additional carbon formation by including a separate unit that subjects cooled carbon to an environment containing carbon-containing species, thereby increasing the carbon content of the final product. When the temperature of this unit is below the pyrolysis temperature, additional carbon is expected to be in the form of adsorbed carbon-containing species, rather than additional fixed carbon.

[0256] A wide range of options exist regarding intermediate input and output (purge or probe) flows of one or more phases present in any particular region, various mass and energy recycling schemes, a variety of additives that can be introduced anywhere in the process, and the adjustability of process conditions, including both reaction and separation conditions, to adjust product distribution. Region-specific input and output flows enable good process monitoring and control, such as through FTIR sampling and dynamic process adjustments.

[0257] Some embodiments do not employ rapid pyrolysis, and some embodiments do not employ slow pyrolysis. Surprisingly, high-quality carbon materials comprising compositions with a very high proportion of fixed carbon can be obtained from the disclosed processes and systems.

[0258] In some embodiments, the pyrolysis process for generating bio-derived reagents includes the following steps:

[0259] (a) Providing carbon-containing feedstocks, including biomass;

[0260] (b) Optionally, the raw material is dried to remove at least a portion of the moisture contained in the raw material;

[0261] (c) Optionally, the feedstock is degassed to remove at least a portion of the interstitial oxygen contained in the feedstock (if any);

[0262] (d) Pyrolyze the raw material 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 hot pyrolytic solids, condensable vapors and non-condensable gases.

[0263] (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solid;

[0264] (f) Cooling the hot pyrolysis solid to produce a cooled pyrolysis solid; and

[0265] (g) Recover bio-derived reagents comprising at least a portion of the cooled pyrolysis solids.

[0266] For the purposes of this disclosure, "biomass" should be interpreted as any biological raw material or a mixture of biological and non-biological raw materials. Essentially, biomass contains at least carbon, hydrogen, and oxygen. The methods and apparatus of this invention are adaptable to a wide range of raw materials having various types, sizes, and moisture contents.

[0267] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal-derived waste, poultry-derived waste, and municipal solid waste. In various embodiments of the invention utilizing biomass, the biomass feedstock may comprise one or more materials selected from: logging residues, softwood chips, hardwood chips, branches, stumps, knots, leaves, bark, sawdust, substandard pulp, cellulose, corn, corn stalks, wheat straw, rice straw, bagasse, switchgrass, miscanthus, animal manure, municipal waste, municipal sewage, commercial waste, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, carbohydrates, plastics, and cloth. Those skilled in the art will readily understand that the feedstock options are practically unlimited.

[0268] This invention can also be used with carbonaceous 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 bio-based feedstock is or comprises coal, oil shale, crude oil, bitumen, or solids from crude oil processing (e.g., petroleum coke). Feedstocks may comprise waste tires, recycled plastics, recycled paper, construction waste, deconstruction waste, and other waste or recycled materials. For the avoidance of doubt, any methods, apparatus, or systems described herein can be used with any carbonaceous feedstock. Carbonaceous feedstocks can be transported by any known means, such as by truck, train, ship, barge, tractor-trailer, or any other vehicle or transport.

[0269] The selection of one or more specific raw materials is not considered technically critical, but rather carried out in a manner that favors an economical process. Typically, regardless of the raw materials selected, screening can be performed (in some embodiments) to remove undesirable materials. The raw materials may optionally be dried prior to processing.

[0270] The raw materials used can be supplied or processed into various 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 bulk material, such as sawdust or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the feed material includes granules or other agglomerated forms that have been compressed together or otherwise bound (e.g., with adhesives).

[0271] It should be noted that size reduction is an expensive and energy-intensive process. The size of pyrolysis materials can be set with significantly less energy input; that is, it is preferable to reduce the particle size of the product rather than the feedstock. This is an option of the present invention because the process does not require fine starting materials and there need not be any significant particle size reduction during processing. The ability to process very large pieces of feedstock is a significant economic advantage of the present invention. It is worth noting that some market applications of high-carbon products actually require large sizes (e.g., on the order of centimeters), so that in some embodiments, large pieces of feedstock are fed, produced, and sold.

[0272] When it is desired to produce a final carbon-containing bio-derived reagent with structural integrity, such as in the form of a cylinder, at least two options exist within the context of this invention. First, the material produced by the process can be collected and then further mechanically processed into the desired form. For example, the product can be compressed or granulated using an adhesive. The second option is to utilize a feed material that typically has the desired size and / or shape of the final product, employing processing steps that do not disrupt the basic structure of the feed material. In some embodiments, the feed and product have geometries such as spheres, cylinders, or cubes.

[0273] When product strength is important, the ability to maintain the approximate size of the feed material throughout the process is beneficial. Furthermore, this avoids the difficulties and costs associated with granulating materials with high fixed carbon content.

[0274] The starting feed material can have a range of moisture contents, as will be understood. In some embodiments, the feed material may be sufficiently dry so that further drying is not required prior to pyrolysis. Typically, it is desirable to utilize commercially available biomass that typically contains moisture and to feed the biomass through a drying step before introducing it into the pyrolysis reactor. However, in some embodiments, dried feedstock may be used.

[0275] It is generally desirable to provide a relatively low oxygen environment in the pyrolysis reactor, such as approximately or at most 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. Firstly, for safety reasons, uncontrolled combustion in the pyrolysis reactor should be avoided. Some amount of total carbon can be oxidized to CO2, and the heat released from exothermic oxidation can contribute to the endothermic pyrolysis chemical reaction. Extensive oxidation of carbon, including partial oxidation to syngas, will reduce the yield of carbon converted to solids.

[0276] In practice, achieving a strictly oxygen-free environment in a reactor is difficult. This limit can be approached, and in some embodiments, the reactor is essentially free of molecular oxygen in the gas phase. To ensure the presence of little or no oxygen in a pyrolysis reactor, it may be desirable to remove air from the feed material before introducing it into the reactor. Various methods exist for removing or reducing air in the feed.

[0277] In some embodiments, a degassing unit is used, wherein the feedstock is conveyed before or after drying in the presence of another gas that can remove adsorbed oxygen and permeate the pores of the feedstock to remove oxygen from the pores. Essentially, any gas with less than 21 vol% O2 can be used at varying efficiencies. In some embodiments, nitrogen is used. In some embodiments, CO and / or CO2 is used. Mixtures such as a mixture of nitrogen and a small amount of oxygen can be used. Vapor may be present in the degassing gas, but significant moisture addition back into the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or an emissions treatment unit) or recycled.

[0278] In principle, the effluent (or a portion thereof) from the degassing unit can be introduced into the pyrolysis reactor itself, since the oxygen removed from the solids will now be highly diluted. In this embodiment, it may be advantageous to introduce the degassing effluent into the final zone of the reactor when the reactor is operated in a countercurrent configuration.

[0279] Various types of degassing units can be used. If drying is to be performed, it is preferable to perform drying followed by degassing, as washing away soluble oxygen from the present moisture can be inefficient. In some embodiments, the drying and degassing steps are combined into a single unit, or some amount of degassing is achieved during drying, and so on.

[0280] Optionally dried and optional degassed feed material is introduced into a pyrolysis reactor or multiple reactors connected in series or parallel. Feed material can be introduced using any known method, such as a screw feeder or a closed hopper. In some embodiments, the material feeding system incorporates an air knife.

[0281] When using a single reactor, multiple zones can exist. Multiple zones, such as two, three, four or more, allow for individual control of temperature, solid residence time, gas residence time, gas composition, flow pattern and / or pressure in order to adjust the overall process performance.

[0282] The term "zone" should be interpreted broadly as a spatial region encompassing a single physical unit, a physically separated unit, or any combination thereof. For continuous reactors, zone division may involve structural elements, such as the presence of scrapers or different heating elements within the reactor to provide heat to individual zones. Alternatively or additionally, zone division in continuous reactors may involve functional elements, such as different temperatures, fluid flow patterns, solids flow patterns, degrees of reaction, etc. In a single batch reactor, a "zone" is a temporal rather than spatial operational scheme. Multiple batch reactors may also be used.

[0283] It should be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheating zone and the pyrolysis zone can be somewhat arbitrary; some amount of pyrolysis may occur in a portion of the preheating zone, and some amount of "preheating" may continue in the pyrolysis zone. The temperature distribution within the reactor is generally continuous, encompassing the zone boundaries within the reactor.

[0284] Some embodiments employ a first zone operated under preheating and / or mild pyrolysis conditions. The temperature of the first zone can be selected from about 150°C to about 500°C, such as about 300°C to about 400°C. The temperature of the first zone should not be high enough to impact the biomass material, causing cell walls to rupture and triggering rapid solid-phase decomposition into vapor and gas.

[0285] All references to zone temperatures in this specification should be interpreted in a non-limiting manner to include temperatures applicable to bulk solids, gas phases, or reactor walls (on the process side). It should be understood that temperature gradients will exist axially, radially, and over time in each zone (i.e., after startup or due to transients). Therefore, references to zone temperatures can be to average temperatures or other effective temperatures that can affect actual kinetics. Temperatures can be measured directly by thermocouples or other temperature probes, or indirectly by other means, or estimated.

[0286] The second zone, or typically the primary pyrolysis zone, operates under pyrolysis or carbonization conditions. The temperature in the second zone can be selected from about 250°C to about 700°C, such as about, or at least about, or at most about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. In this zone, the preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, thereby producing a large amount of solid material as high-carbon reaction intermediates. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose and generate vapors, which escape through permeable pores or by creating new pores. Preferred temperatures will depend at least on the residence time in the second zone, as well as the properties of the feedstock and the desired properties of the products.

[0287] The third zone, or cooling zone, is operated to cool the high-carbon reaction intermediate to varying degrees. At a minimum, the temperature of the third zone should be lower than that of the second zone. The temperature of the third zone can be selected from about 100°C to about 550°C, such as from about 150°C to about 350°C.

[0288] The chemical reaction can continue in the cooling zone. Without being bound by any particular theory, it is believed that the secondary pyrolysis reaction can be initiated in the third zone. The carbonaceous components in the gaseous phase can condense (due to the decrease in temperature in the third zone). However, the temperature is maintained high enough to promote reactions that can result in the formation of additional fixed carbon from the condensate (secondary pyrolysis) or at least the formation of bonds between the adsorbed species and the fixed carbon. An exemplary reaction that can be carried out is the Boudouard reaction for the conversion of carbon monoxide to carbon dioxide plus fixed carbon.

[0289] Residence time in the reactor zone can vary. Time and temperature interact, allowing for shorter reaction times at higher temperatures and vice versa for desired pyrolysis yields. In a continuous reactor (zone), residence time is volume divided by volumetric flow rate. In a batch reactor, residence time is the intermittent reaction time after heating to the reaction temperature.

[0290] It should be recognized that in a multiphase reactor, there are multiple residence times. In the context of this invention, within each zone, there will be residence times (and residence time distributions) for both the solid and gas phases. For a given apparatus employing multiple zones, and at a given production rate, the residence times across zones will typically be coupled on the solid side; however, when multiple inlet and outlet ports are used in a single zone, the residence times may be decoupled on the vapor side. Solid and vapor residence times are decoupled.

[0291] The solid residence time in the preheating zone can be selected from approximately 5 minutes to approximately 60 minutes, such as approximately 10, 20, 30, 40, or 50 minutes. Sufficient time is desired, depending on the temperature, to allow the biomass to reach the desired preheating temperature. The minimum residence time required to allow the solids to reach the desired preheating temperature will depend on the particle type and size, the physical equipment, and the heat transfer rate of the heating parameters. Additional times may not be desirable because they would result in higher capital costs unless a certain amount of mild pyrolysis is expected in the preheating zone.

[0292] The solid residence time in the pyrolysis zone can be selected from approximately 10 minutes to approximately 120 minutes, such as approximately 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, sufficient time should be allowed for the carbonization chemical reaction after the necessary heat transfer. For times less than approximately 10 minutes, a considerably high temperature, such as above 700°C, will be required to remove a significant amount of non-carbon elements. This temperature will promote rapid pyrolysis and the generation of vapors and gases derived from carbon itself, which should be avoided when the expected product is solid carbon.

[0293] In a static system, there will be an equilibrium transition that can be substantially reached at some point in time. As in some embodiments, the equilibrium constraint can be removed to allow pyrolysis and devolatiles removal to continue as vapor continuously flows through the solid and continuously removes volatiles, until the reaction rate approaches zero. Over longer periods, there is no tendency to substantially alter the remaining stubborn solid.

[0294] The solid residence time in the cooling zone can be selected from approximately 5 minutes to approximately 60 minutes, such as approximately 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be sufficient time to allow the carbon solid to cool to the desired temperature. The cooling rate and temperature will determine the minimum residence time required to allow the carbon to cool. An additional time may be undesirable unless some amount of secondary pyrolysis is desired.

[0295] As discussed above, the residence time of the gas phase can be selected and controlled individually. The vapor residence time in the preheating zone can be selected from about 0.1 minutes to about 15 minutes, such as about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time in the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, such as about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time in the cooling zone can be selected from about 0.1 minutes to about 15 minutes, such as about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. Shorter vapor residence times promote rapid removal of volatiles from the system, while longer vapor residence times promote the reaction of components in the gas phase with the solid phase.

[0296] The reactor and the entire system can operate in continuous, semi-continuous, batch, or any combination or variation of these modes. In some embodiments, the reactor is a continuous countercurrent reactor, in which solids and vapors flow substantially in opposite directions. While the reactor can also be operated in batches, it simulates countercurrent flow of vapors, such as by periodically introducing and removing the gas phase from the batch vessel.

[0297] Various flow patterns can be desired or observed. For multiphase chemical reactions and simultaneous separations involving multiple reactor zones, the fluid dynamics can be quite complex. Typically, solid flows can approach plug flow (well mixed in the radial dimension), while vapor flows can approach fully mixed flow (rapid delivery in both the radial and axial dimensions). Multiple inlet and outlet ports for vapor can contribute to overall mixing.

[0298] The pressure in each zone can be selected and controlled independently. The pressure in each zone can be independently selected from about 1 kPa to about 3000 kPa, such as about 101.3 kPa (normal atmospheric pressure). Independent zone pressure control is possible when using multiple gas inlets and outlets, including vacuum ports for evacuating gas when zone pressures below atmospheric pressure are desired.

[0299] In some embodiments, the process can be conveniently operated at atmospheric pressure. There are many advantages associated with operation at atmospheric pressure, ranging from mechanical simplicity to enhanced safety. In some embodiments, the pyrolysis zone is operated at pressures of approximately 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute pressure).

[0300] Vacuum operation (e.g., 10-100 kPa) will facilitate the rapid removal of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) may be useful when exhaust gases are to be fed into high-pressure operation. Increased pressure can also be used to facilitate heat transfer, chemical reactions, or separation.

[0301] The step of separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids can be performed within the reactor itself or using different separation units. A substantially inert purge gas can be introduced into one or more of the zones. The condensable vapor and non-condensable gas are then carried away from the zones in the purge gas and exit the reactor.

[0302] In some embodiments, the purge gas includes N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. In some embodiments, the purge gas is preheated before introduction, or if the purge gas is obtained from a heating source, the purge gas is cooled.

[0303] Purge gases remove volatile components more thoroughly by removing them from the system before they condense or react further. Purge gases allow volatiles to be removed at a higher rate than that achievable solely by volatilization at a given process temperature. Alternatively, using purge gases allows for the removal of a certain amount of volatiles at a milder temperature. The reason purge gases improve volatile removal is that the separation mechanism is not merely relative to volatility, but rather through liquid / gas phase separation assisted by the purge gas. Purge gases can both reduce the mass transfer limitation of volatilization and reduce the thermodynamic limitation by continuously depleting a given volatile species, causing more volatile species to evaporate and thus reaching thermodynamic equilibrium.

[0304] Some embodiments remove the gas loaded with volatile organic carbon from subsequent processing stages to produce a product with high fixed carbon content. Without removal, the volatile carbon can be adsorbed or absorbed onto the pyrolysis solid, thus requiring additional energy (and cost) to obtain a potentially purer form of carbon. It is also presumed that the porosity of the pyrolysis solid can be enhanced by rapidly removing the vapor. Higher porosity is desirable for some products.

[0305] In some embodiments, the combination of purge gas and relatively low process pressure, such as atmospheric pressure, enables rapid vapor removal without requiring large amounts of inert gas.

[0306] In some embodiments, the purge gas flows countercurrently to the feedstock. In other embodiments, the purge gas flows concurrently to the feedstock. In some embodiments, the solids flow pattern approximates a piston flow, while the purge gas flow pattern and the gas phase are typically close to a fully mixed flow in one or more zones.

[0307] Purging can be performed in any one or more of the reactor zones. In some embodiments, purge gas is introduced into a cooling zone and extracted from the cooling and / or pyrolysis zone (along with the resulting volatiles). In some embodiments, purge gas is introduced into a pyrolysis zone and extracted from the pyrolysis and / or preheating zone. In some embodiments, purge gas is introduced into a preheating zone and extracted from the pyrolysis zone. In these or other embodiments, purge gas can be introduced into each of the preheating, pyrolysis, and cooling zones, and can also be extracted from each of the zones.

[0308] In some embodiments, the one or more zones to be separated are units physically separated from the reactor. If desired, the separation units or zones can be located between reactor zones. For example, a separation unit can be placed between pyrolysis and cooling units.

[0309] Purge gas can be introduced continuously, especially when the solids stream is continuous. When the pyrolysis reaction is operated as a batch process, purge gas can be introduced after a certain period of time or periodically to remove volatiles. Even when the pyrolysis reaction is operated continuously, purge gas can be introduced semi-continuously or periodically (if desired) using suitable valves and controllers.

[0310] The purge gas containing volatiles can be discharged from one or more reactor zones, and if obtained from multiple zones, can be combined. The resulting gas stream containing various vapors can then be fed into a thermal oxidizer to control air emissions. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are fed into the thermal oxidizer to achieve temperatures that sufficiently destroy the volatiles contained therein.

[0311] The effluent from the thermal oxidizer will be a hot gas stream containing water, carbon dioxide, and nitrogen. This effluent can be directly purged into the air for emission 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 through heat exchange with another stream (such as purge gas). The energy content can be utilized by directly or indirectly heating or auxiliary heating other parts of the process, such as dryers or reactors. In some embodiments, substantially all of the thermal oxidizer effluent is used for indirect heating of the dryer (practical side). The thermal oxidizer can use fuels other than natural gas.

[0312] The yield of carbonaceous materials can vary depending on the factors described above, including the type of raw materials and process conditions. In some embodiments, the net yield of solids, based on dry weight, is at least 25%, 30%, 35%, 40%, 45%, 50%, or higher, as a percentage of the starting material. The remainder will be split between condensable vapors such as terpenes, tar, 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 will also depend on process conditions, including the presence of water.

[0313] Regarding carbon balance, in some embodiments, the net carbon yield is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or higher, based on the percentage of initial carbon in the feedstock. For example, in some embodiments, the carbon-containing material contains between about 40% and about 70% of the carbon contained in the starting feedstock. The remaining carbon results in the formation of methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tar, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0314] In alternative embodiments, portions of these molecules are combined with carbon-rich solids to enrich the carbon and energy content of the products. In these embodiments, some or all of the resulting gas stream containing various vapors from the reactor may be at least partially condensed and then passed through cooled pyrolysis solids originating from a cooling zone and / or from a separate cooling unit. These embodiments are described in more detail below.

[0315] After reaction and cooling within a cooling zone (if present), the carbonaceous solid can be introduced into different cooling units. In some embodiments, the solid is collected and simply allowed to cool at a slow rate. If the carbonaceous solid is reactive or unstable in air, it may be desirable to maintain an inert atmosphere and / or rapidly cool the solid to a temperature, for example, below 40°C, such as ambient temperature. In some embodiments, water quenching is used for rapid cooling. In some embodiments, a fluidized bed cooler is employed. The term "cooling unit" should be interpreted broadly to also include containers, tanks, pipes, or portions thereof.

[0316] In some embodiments, the process further includes operating a cooling unit to cool the warm pyrolysis solids with steam, thereby producing cold pyrolysis solids and superheated steam; wherein drying is carried out at least in part with superheated steam originating from the cooling unit. Optionally, the cooling unit may be operated to first cool the warm pyrolysis solids with steam to reach a first cooling unit temperature, and then cool the warm pyrolysis solids with air to reach a second cooling unit temperature, wherein the second cooling unit temperature is lower than the first cooling unit temperature and is associated with a reduced risk of combustion for the warm pyrolysis solids in the presence of air.

[0317] After cooling to ambient conditions, carbonaceous solids can be recovered and stored, transferred to another location for operation, transported to another location, or otherwise disposed of, traded, or sold. Solids can be fed into the unit to reduce particle size. Various size reduction units are known in the art, including crushers, shredders, grinders, pulverizers, jet mills, pin mills, and ball mills.

[0318] This may include particle size-based screening or some other separation method. If present, grinding can be located upstream or downstream of the grinding process. A portion of the screened material (e.g., large chunks) can be returned to the grinding unit. Small and large particles can be recycled for separate downstream use. In some embodiments, cooled pyrolysis solids are ground into fine powders, such as powdered carbon or activated carbon products.

[0319] Various additives may be introduced throughout the process before, during, or after any of the steps disclosed herein. Additives can be broadly classified into process additives, which are selected to improve process performance, such as carbon yield or pyrolysis time / temperature, to achieve desired carbon purity; and product additives, which are selected to improve one or more properties of the bio-derived reagent or downstream products incorporated into the reagent. Certain additives can provide enhanced process and product (bio-derived reagent or product containing bio-derived reagent) characteristics.

[0320] Additives can be added before, during, or after any one or more steps of the process, including adding them to the feedstock itself at any time before or after harvesting. Additive treatment can be incorporated before, during, or after feedstock sizing, drying, or other preparation. Additives can be incorporated at or on feedstock supply facilities, transport trucks, unloading equipment, storage bins, conveyors (including open or closed conveyors), dryers, process heaters, or any other unit. Additives can be added anywhere within the pyrolysis process itself using suitable methods for introducing additives. Additives can be added after carbonization or even after grinding, if desired.

[0321] In some embodiments, the additive is selected from metals, metal oxides, metal hydroxides, or combinations thereof. For example, the additive may be selected from, but is by no means limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, ferric chloride, ferric bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, calcium oxide, lime, and combinations thereof.

[0322] In some embodiments, the additive is selected from acids, bases, or salts thereof. For example, the additive may be selected from, but is by no means limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0323] In some embodiments, the additive is selected from metal halides. Metal halides are molecules that lie between a metal and a halogen (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many molecules with metals. Metal halides are typically obtained by direct combination or, more commonly, by neutralizing a basic metal salt with a hydrohalic acid. In some embodiments, the additive is selected from ferric chloride (FeCl2 and / or FeCl3), ferric bromide (FeBr2 and / or FeBr3), or their hydrates and any combination thereof.

[0324] Additives can give the final product a higher energy content (energy density). The increase in energy content may be caused by an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content may be caused by the removal of non-flammable substances or materials with an energy density lower than carbon. In some embodiments, additives reduce the degree of liquid formation, which favors solid and gas formation, or favors solid formation.

[0325] Without being limited by any specific assumptions, additives can chemically modify starting or treated biomass prior to pyrolysis to reduce cell wall rupture, thereby achieving greater strength / integrity. In some embodiments, additives can increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0326] Additives can impart improved mechanical properties to bio-derived reagents, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. Additives can improve mechanical properties either by their mere presence (e.g., by the additive itself imparting strength to the mixture) or due to some transformation occurring within the additive phase or in the resulting mixture. For example, reactions such as vitrification can occur within a portion of the bio-derived reagent containing the additive, thereby improving the final strength.

[0327] Chemical additives can be applied to wet or dry biomass feedstocks. Additives can be applied in the form of solid powder, spray, mist, liquid, or vapor. In some embodiments, additives can be introduced by spraying a liquid solution (such as an aqueous solution or in a solvent) or by immersion in a tank, bin, bag, or other container.

[0328] In some embodiments, an impregnation pretreatment is employed, wherein the solid raw material is impregnated in batches or continuously into a bath comprising additives for a duration sufficient to allow the additives to penetrate into the solid feed material.

[0329] In some embodiments, additives applied to the feedstock can reduce the energy requirement for pyrolysis and / or increase the yield of carbon-containing products. In these or other embodiments, additives applied to the feedstock can provide the functionality desired for the intended use of the carbon-containing products.

[0330] Production volumes or process capabilities can vary widely from small laboratory-scale units to full-scale operations (including any pilot, demonstration, or semi-commercial scale). In various embodiments, process capabilities (for feedstock, product, or both) are at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day, or higher.

[0331] In some embodiments, a portion of the solids produced can be recycled back to the front end of the process, i.e., recycled to a drying or degassing unit or directly recycled to the reactor. By returning to the front end and passing through the process again, the solids treated in fixed carbon can be increased. Solids, liquids, and gas streams generated or present within the process can be independently recycled, enter subsequent steps, or removed / purged from the process at any point.

[0332] In some embodiments, pyrolysis material is recovered and then fed into a separate unit for further pyrolysis to produce 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 (e.g., heated N2) is passed. Other containers for this purpose include process tanks, barrels, bins, crates, bags, and roll-off boxes. For example, such a secondary purge gas containing volatiles can be sent to a thermal oxidizer or returned to the main process reactor. To cool the final product, another inert gas stream, for example initially at ambient temperature, can be passed through the solid to cool it and then returned to an inert gas preheating system.

[0333] Some variations of the present invention utilize a bio-based reagent generation system, the bio-based reagent generation system comprising:

[0334] (a) A feeder configured to introduce a carbon-containing raw material;

[0335] (b) An optional dryer, the optional dryer being arranged in operative communication with the feeder, the optional dryer being configured to remove moisture contained in the carbonaceous feedstock;

[0336] (c) A multi-zone reactor arranged in operative communication with the dryer, wherein the multi-zone reactor contains at least one pyrolysis zone arranged in operative communication with a spatially separated cooling zone, and wherein the multi-zone reactor is configured with an outlet to remove condensable vapors and non-condensable gases from the solid.

[0337] (d) A solids cooler, said solids cooler being operatively connected to the multi-zone reactor; and

[0338] (e) A biological reagent recovery unit, wherein the biological reagent recovery unit is arranged to be operatively connected to the solid cooler.

[0339] Some variants utilize a bio-based reagent generation system, said bio-based reagent generation system comprising:

[0340] (a) A feeder configured to introduce a carbon-containing raw material;

[0341] (b) An optional dryer, the optional dryer being arranged in operative communication with the feeder, the optional dryer being configured to remove moisture contained in the carbonaceous feedstock;

[0342] (c) An optional preheater, wherein the optional preheater is arranged to be operatively connected to the dryer, and the optional preheater is configured to heat and / or mildly pyrolyze the raw material;

[0343] (d) A pyrolysis reactor, the pyrolysis reactor being arranged in operative communication with the preheater, the pyrolysis reactor being configured to pyrolyze the raw material;

[0344] (e) a cooler, the cooler being arranged in operative communication with the pyrolysis reactor, the cooler being configured to cool the pyrolysis solids; and

[0345] (f) A biological reagent recovery unit, said biological reagent recovery unit being configured to be operatively connected to the cooler.

[0346] The system is configured with at least one outlet to remove condensable vapors and non-condensable gases from solids.

[0347] The feeder can be physically integrated with a multi-zone reactor, such as by using a screw feeder or auger mechanism to introduce feed solids into the first reaction zone.

[0348] In some embodiments, the system further includes a preheating zone arranged in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) may be located within a single unit or may be located in a separate unit.

[0349] Optionally, the dryer can be configured as a drying zone within a multi-zone reactor. Optionally, the solid cooler can be located within the multi-zone reactor (i.e., configured as a separate cooling zone or integrated with the main cooling zone).

[0350] The system may include a purging member for removing oxygen from the system. For example, the purging member may include one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and the displaced oxygen from the system. In some embodiments, the purging member is a degasser arranged operatively in communication between the dryer and the multi-zone reactor.

[0351] A multi-zone reactor may be configured with at least a first inlet and a first outlet. The first inlet and the first outlet may be arranged to communicate with different zones or the same zone.

[0352] In some embodiments, the multi-zone reactor is configured with a second inlet and / or a second outlet. In some embodiments, the multi-zone reactor is configured with a third inlet and / or a third outlet. In some embodiments, the multi-zone reactor is configured with a fourth inlet and / or a fourth outlet. In some embodiments, each zone in the multi-zone reactor is configured with an inlet and an outlet.

[0353] The inlet and outlet ports not only allow for the introduction and extraction of vapor, but the gas outlet (probe) specifically allows for precise process monitoring and control of each stage of the process, and possibly all stages. When operating history can be used to adjust process conditions, precise process monitoring is expected to dynamically, and over time, lead to improvements in yield and efficiency.

[0354] In a preferred embodiment, a reactive gas probe is positioned in operative communication with the pyrolysis zone. Such a reactive gas probe can be used to extract and analyze gases to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as by adjusting the feed rate, inert gas purging rate, temperature (of one or more zones), pressure (of one or more zones), additives, etc.

[0355] As intended in this document, “monitoring and control” via reactive gas probes should be interpreted as including any one or more sample extractions via reactive gas probes and, optionally, process or equipment adjustments based on measurements (if deemed necessary or desired) using well-known process control principles (feedback, feedforward, proportional-integral-differential logic, etc.).

[0356] Reactive gas probes can be configured to extract gas samples in various ways. For example, the sampling line can have a pressure lower than that of the pyrolysis reactor, allowing a certain amount of gas to be easily extracted from the pyrolysis zone when the sampling line is opened. The sampling line can be under vacuum, such as when the pyrolysis zone is close to atmospheric pressure. Typically, the reactive gas probe will be associated with a gas outlet or a portion thereof (e.g., a line separated from the gas outlet line).

[0357] In some embodiments, both the gas input and gas output are used as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas along with the process sample from the gas output (“sample purging”). Such an arrangement can be used in zones that do not otherwise have inlets / outlets for a substantially inert gas used for processing, or the reactive gas probe can be associated with a separate inlet / outlet in addition to the process inlet and outlet. If desired, the sampling inert gas (in embodiments utilizing sample purging) periodically introduced and withdrawn for sampling (for analytical accuracy or to introduce analytical tracers) can even be different from the process inert gas.

[0358] For example, a gas probe can be used to measure the concentration of acetic acid in the gas phase of the pyrolysis zone to extract a sample, which can then be analyzed using a suitable technique (such as gas chromatography, GC; mass spectrometry, MS; GC-MS, or Fourier transform infrared spectroscopy, FTIR). For example, the concentration of CO and / or CO2 in the gas phase can be measured and used as an indicator of the pyrolysis selectivity of gases / vapors. For example, the concentration of terpenes in the gas phase can be measured and used as an indicator of the pyrolysis selectivity of liquids.

[0359] In some embodiments, the system further includes at least one additional gas probe arranged to be operatively connected to a cooling zone or drying zone (if present) or a preheating zone (if present).

[0360] For example, gas probes used in the cooling zone can be used to determine the extent of any additional chemical reactions occurring within the cooling zone. Gas probes in the cooling zone can also be used as independent temperature measurements (in addition to, for example, thermocouples placed within the cooling zone). This independent measurement can be a correlation between the cooling temperature and a measured quantity of a particular species. This correlation can be established independently or after a certain period of process operation.

[0361] Gas probes used in the drying zone can be used, for example, to determine the degree of dryness by measuring moisture content. Similarly, gas probes in the preheating zone can be used to determine the extent of any mild pyrolysis that may occur.

[0362] In some embodiments, the cooling zone is provided with an air inlet, and the pyrolysis zone is provided with an air outlet to create a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the preheating zone (if present) may be provided with an air outlet to create a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the drying zone may be provided with an air outlet to create a substantially countercurrent flow.

[0363] One or more pyrolysis reactors may be selected from any suitable reactor configuration capable of performing the pyrolysis process. Exemplary reactor configurations include, but are not limited to, fixed-bed reactors, fluidized-bed reactors, entrained flow reactors, augers, ablation reactors, rotating cones, rotary kilns, calcining furnaces, roasting furnaces, moving-bed reactors, conveyed-bed reactors, ablation reactors, rotating cones, or microwave-assisted pyrolysis reactors.

[0364] In some embodiments using an auger, sand or another heat carrier may optionally be used. For example, the feedstock and sand can be fed at one end of the screw. The screw mixes the sand and feedstock and conveys the sand and feedstock through the reactor. The screw provides good control over the feedstock residence time and eliminates the need for a carrier or fluidizing gas to dilute the pyrolysis products. The sand can be reheated in a separate container.

[0365] In some embodiments using the ablation process, the feedstock moves at high speed against a hot metal surface. Ableasing any carbon formed at the surface maintains a high heat transfer rate. Such equipment can prevent product dilution. Alternatively, the feedstock particles can be suspended in a carrier gas and introduced at high speed through a cyclone separator whose walls are heated.

[0366] In some embodiments using fluidized bed reactors, the feedstock can be introduced into a hot sand bed fluidized by a gas, typically a recycled product gas. The term "sand" as used herein should also include similar, substantially inert materials such as glass particles, recycled ash particles, etc. The high heat transfer rate from the fluidized sand can result in rapid heating of the feedstock. Some ablation may occur due to friction with the sand particles. Heat is typically provided by heat exchanger tubes through which the hot combustion gases flow.

[0367] A circulating fluidized bed reactor can be used, in which gas, sand, and feedstock move together. An exemplary delivery gas comprises recirculated product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the feedstock, and stronger ablation is expected than in conventional fluidized beds. A separator can be used to separate the product gas from the sand and carbon particles. The sand particles can be reheated in the fluidized burner vessel and recycled back to the reactor.

[0368] In some embodiments, the multi-zone reactor is a continuous reactor, the continuous reactor including a feed inlet, a plurality of spatially separated reaction zones and a carbonaceous solid outlet, the plurality of spatially separated reaction zones being configured to control the temperature and mixing within each of the reaction zones respectively, wherein one of the reaction zones is configured with a first inlet for introducing a substantially inert gas into the reactor, and wherein one of the reaction zones is configured with a first outlet.

[0369] In some embodiments, the reactor includes at least two, three, or four reaction zones. Each reaction zone is arranged in operative communication with an independently adjustable heating device. In some embodiments, the heating element independently includes electrothermal transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat transfer, or a combination thereof. In some embodiments, if present, at least one reactor zone is heated by an effluent stream from a thermal oxidizer.

[0370] The reactor can be configured to adjust the gas phase composition and gas phase residence time of at least two reaction zones separately, and to include at most all reaction zones present in the reactor.

[0371] The reactor may be equipped with a second air inlet and / or a second air outlet. In some embodiments, the reactor is provided with an air inlet in each reaction zone. In these or other embodiments, the reactor is provided with an air outlet in each reaction zone. The reactor may be a co-current or counter-current reactor.

[0372] In some embodiments, the raw material inlet includes a screw or auger feed mechanism. In some embodiments, the carbonaceous solids outlet includes a screw or auger output mechanism.

[0373] Some embodiments utilize a rotary calcining furnace with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotational speed will affect the solid flow pattern and heat and mass transport. Each reaction zone in the reaction zone may be configured with scrapers disposed on the inner wall to provide agitation of the solids. In each reaction zone, the scrapers can be individually adjusted.

[0374] Other components for agitating solids can be used, such as augers, screws, or paddle conveyors. In some embodiments, the reactor comprises a single continuous auger positioned in each reaction zone throughout the entire reaction zone. In other embodiments, the reactor comprises twin screws positioned in each reaction zone throughout the entire reaction zone.

[0375] Some systems are specifically designed to maintain the approximate size of the feed material throughout the process, that is, to process biomass feedstock without disrupting or significantly damaging its structure. In some embodiments, the pyrolysis zone does not contain augers, screws, or rakes that would tend to greatly reduce the size of the feed material being pyrolyzed.

[0376] In some embodiments of the invention, the system further includes a thermal oxidizer arranged in operative communication with an outlet at which condensable vapors and non-condensable gases are removed. The thermal oxidizer may be configured to receive separate fuels (such as natural gas) and oxidants (such as air) into a combustion chamber adapted for combustion of the fuel and at least a portion of the condensable vapors. Certain non-condensable gases may also be oxidized to CO2, such as CO or CH4.

[0377] When a thermal oxidizer is used, the system may include a heat exchanger disposed between the thermal oxidizer and the dryer, the heat exchanger being configured to use at least some of the heat from combustion for the dryer. This embodiment can significantly improve the overall energy efficiency of the process.

[0378] In some embodiments, the system further includes a carbon enhancement unit disposed in operative communication with a solid cooler, the carbon enhancement unit being configured to combine condensable vapor in at least a partially condensable form with a solid. The carbon enhancement unit can increase the carbon content of the bio-derived reagent obtained from the recovery unit.

[0379] The system may further include a separate pyrolysis unit adapted to further pyrolyze the bio-derived 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, silo, large container, crate, bag, or roll-down container.

[0380] The entire system can be located in a fixed location, or it can be distributed across several locations. The system can be constructed using modules that can be easily replicated for practical scaling. The system can also be constructed using the principles of economies of scale, as is well known in the manufacturing industry.

[0381] Some variations related to carbon enhancement of solids will now be described further. In some embodiments, the process for producing bio-derived reagents includes:

[0382] (a) Providing carbon-containing feedstocks, including biomass;

[0383] (b) Optionally, the raw material is dried to remove at least a portion of the moisture contained in the raw material;

[0384] (c) Optionally, the feedstock is degassed to remove at least a portion of the interstitial oxygen contained in the feedstock (if any);

[0385] (d) In a pyrolysis zone, the raw material is pyrolyzed for at least 10 minutes in the presence of a substantially inert gas and at a pyrolysis temperature selected from about 250°C to about 700°C to produce hot pyrolysis solids, condensable vapors and non-condensable gases.

[0386] (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solid;

[0387] (f) In a cooling zone, the hot pyrolysis solid is cooled for at least 5 minutes in the presence of a substantially inert gas and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid.

[0388] (g) Optionally, the warm pyrolysis solid is cooled to produce a cold pyrolysis solid;

[0389] (h) Subsequently, at least a portion of the condensable vapor and / or at least a portion of the non-condensable gas from step (e) is passed through the warm pyrolysis solid and / or the cold pyrolysis solid to form an enhanced pyrolysis solid with an increased carbon content; and

[0390] (i) Recover bio-derived reagents comprising at least a portion of the enhanced pyrolysis solids.

[0391] In some embodiments, step (h) comprises passing at least a portion of the condensable vapor from step (e) through a warm pyrolysis solid in the form of vapor and / or condensate to produce an enhanced pyrolysis solid with an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gas from step (e) through a warm pyrolysis solid to produce an enhanced pyrolysis solid with an increased carbon content.

[0392] Alternatively or additionally, vapor or gas may be contacted with the cold pyrolysis solid. In some embodiments, step (h) comprises passing at least a portion of the condensable vapor from step (e) through the cold pyrolysis solid in the form of vapor and / or condensate to produce an enhanced pyrolysis solid with an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gas from step (e) through the cold pyrolysis solid to produce an enhanced pyrolysis solid with an increased carbon content.

[0393] In some embodiments, step (h) comprises passing substantially all of the condensable vapors from step (e) through a cold pyrolysis solid in vapor and / or condensate form to produce an enhanced pyrolysis solid with an increased carbon content. In some embodiments, step (h) comprises passing substantially all of the non-condensable gases from step (e) through a cold pyrolysis solid to produce an enhanced pyrolysis solid with an increased carbon content.

[0394] In some embodiments, the process includes a method of treating or separating the vapor or gas before using it for carbon enhancement. In some embodiments, an intermediate feed stream, comprising condensable vapor or non-condensable gas, obtained from step (e), may be fed to a separation unit configured to produce a first output stream and a second output stream. In some embodiments, the intermediate feed stream comprises all condensable vapor, all non-condensable gas, or both.

[0395] Separation techniques can include or utilize distillation columns, flash evaporators, centrifuges, cyclone separators, membranes, filters, packed beds, capillary columns, etc. Separation can be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and can take advantage of differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity for the stationary phase, and any combination thereof.

[0396] In some embodiments, the first and second output streams are separated from the intermediate feed stream based on their relative volatility. For example, the separation unit may be a distillation column, a flash tank, or a condenser.

[0397] Therefore, in some embodiments, the first output stream comprises condensable vapor, and the second output stream comprises non-condensable gas. The condensable vapor may contain at least one carbon-containing molecule selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapor produced by pyrolysis may contain aromatic molecules such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic molecules, such as refractory tar, are present in the vapor. In some embodiments, the non-condensable gas comprises carbon-containing molecules. In some embodiments, the carbon-containing molecules include carbon monoxide, carbon dioxide, or methane, or combinations thereof.

[0398] In some embodiments, the first and second output streams are intermediate feed streams based on relative polarity separation. For example, the separation unit may be a stripping column, a packed bed, a chromatographic column, or a membrane.

[0399] In some embodiments, the first output stream comprises polar molecules, and the second output stream comprises nonpolar 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 nonpolar molecules comprise carbon-containing molecules. In some embodiments, the carbon-containing molecules comprise carbon monoxide, carbon dioxide, methane, terpenes, terpene derivatives, or combinations thereof.

[0400] Compared to other identical processes without step (h), step (h) can increase the total carbon content of the bio-derived reagent. In various embodiments, the increase in carbon content can be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher.

[0401] In some embodiments, step (h) increases the fixed carbon content of the bio-derived reagent. In these or other embodiments, step (h) increases the volatile carbon content of the bio-derived reagent. Volatile carbon content is the carbon attributed to volatile substances in the reagent. Volatile substances can be, but are not limited to, hydrocarbons, including aliphatic or aromatic molecules (e.g., terpenes); oxygenated compounds, including alcohols, aldehydes, or ketones; and various tars. Volatile carbon typically remains bound or adsorbed to a solid under ambient conditions, but upon heating, it will be released before the fixed carbon is oxidized, vaporized, or otherwise released as vapor.

[0402] Depending on the conditions associated with step (h), some amount of volatile carbon may become fixed carbon (e.g., through the formation of Budoar carbon from CO). Typically, the volatile substances will enter the micropores of the fixed carbon and will exist as condensed / adsorbed species, but retain relative volatility. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0403] Step (h) can increase the energy content (i.e., energy density) of the bio-based reagent. This increase in energy content may be caused by an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. In various embodiments, the increase in energy content can be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher.

[0404] Further separation can be employed to recover one or more non-condensable gases or condensable vapors for use in the process or further processing. For example, further processing may be included to produce refined carbon monoxide and / or hydrogen.

[0405] As another example, acetic acid can be separated and subsequently reduced to ethanol. The reduction of acetic acid can be accomplished, at least in part, using hydrogen gas derived from the non-condensable gas produced.

[0406] Condensable vapors can be used for energy in processes (e.g., through thermal oxidation) or for carbon enrichment to increase the carbon content of bio-based reagents. Certain non-condensable gases, such as CO or CH4, can be used for energy in processes or as part of the substantially inert gas mixture in pyrolysis steps. Any combination of the above is also possible.

[0407] A potential benefit of including step (h) is the scrubbing gas stream, in which the resulting gas stream is enriched with CO and CO2. The resulting gas stream can be used for energy recovery, recycling for carbon enrichment in solids, and / or used as an inert gas in a reactor. Similarly, by separating non-condensable gases from condensable vapors, a CO / CO2 stream is prepared for use as an inert gas in, for example, reactor or cooling systems.

[0408] Other variations are based on the understanding that the principles of the carbon enhancement step can be applied to any feedstock for which carbon is desired to be added.

[0409] In some embodiments, the batch or continuous process for generating the bio-derived reagent includes:

[0410] (a) Providing a solid stream comprising carbonaceous materials;

[0411] (b) Providing a gas flow comprising condensable carbonaceous vapor, non-condensable carbonaceous gas, or a mixture of condensable carbonaceous vapor and non-condensable carbonaceous gas; and

[0412] (c) The airflow is passed through the solid flow under suitable conditions to form a carbon-containing product with an increased carbon content relative to the carbon-containing material.

[0413] In some embodiments, the starting carbon-containing material is pyrolyzed biomass or dried biomass. The gas stream can be obtained during the integrated process of providing the carbon-containing material. Alternatively, the gas stream can be obtained from the separate processing of the carbon-containing material. The gas stream, or a portion thereof, can be obtained from an external source (e.g., an oven in a wood processing plant). Mixtures of gas streams from various sources, as well as mixtures of carbon-containing materials, are possible.

[0414] In some embodiments, the process further includes recycling or reusing the gas stream to repeat the process, thereby further increasing the carbon and / or energy content of the carbon-containing product. In some embodiments, the process further includes recycling or reusing the gas stream to carry out the process to increase the carbon and / or energy content of another raw material different from the carbon-containing material.

[0415] In some embodiments, the process further includes introducing a gas flow into a separation unit configured to produce at least a first output stream and a second output stream, wherein the gas flow comprises a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas. The first and second output streams can be separated based on relative volatility, relative polarity, or any other property. The gas flow can be obtained from the separate processing of carbon-containing materials.

[0416] In some embodiments, the process further includes recycling or reusing the gas stream to repeat the process, thereby further increasing the carbon content of the carbon-containing product. In some embodiments, the process further includes recycling or reusing the gas stream to carry out the process to increase the carbon content of another feedstock.

[0417] Compared to the starting carbon-containing material, carbon-containing products can have increased total carbon content, higher fixed carbon content, higher volatile carbon content, higher energy content, or any combination thereof.

[0418] In related variants, the bio-based reagent generation system includes:

[0419] (a) A feeder configured to introduce a carbon-containing raw material;

[0420] (b) An optional dryer, the optional dryer being arranged in operative communication with the feeder, the optional dryer being configured to remove moisture contained in the carbonaceous feedstock;

[0421] (c) A multi-zone reactor arranged in operative communication with the dryer, wherein the multi-zone reactor contains at least one pyrolysis zone arranged in operative communication with a spatially separated cooling zone, and wherein the multi-zone reactor is configured with an outlet to remove condensable vapors and non-condensable gases from the solid.

[0422] (d) A solid cooler, the solid cooler being arranged in operative communication with the multi-zone reactor;

[0423] (e) a material enrichment unit, the material enrichment unit being arranged in operative communication with the solid cooler, the material enrichment unit being configured to allow the condensable vapor and / or the non-condensable gas to pass through the solid to form an enhanced solid with an increased carbon content; and

[0424] (f) A bio-based reagent recovery unit, wherein the bio-based reagent recovery unit is configured to be operatively connected to the material enrichment unit.

[0425] The system may further include a preheating zone arranged in operative communication with the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within a multi-zone reactor. Each of the zones may be located within a single unit or a separate unit. Additionally, a solid cooler may be disposed within the multi-zone reactor.

[0426] In some embodiments, the cooling zone is provided with an air inlet and the pyrolysis zone is provided with an air outlet to create 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) is provided with an air outlet to create a substantially countercurrent flow of the gas phase relative to the solid phase.

[0427] In a particular embodiment, the system incorporates a material enrichment unit, which includes:

[0428] (i) a shell having an upper portion and a lower portion;

[0429] (ii) An inlet located at the bottom of the lower portion of the shell, the inlet being configured to deliver condensable vapors and non-condensable gases;

[0430] (iii) An outlet located at the top of the upper portion of the shell, the outlet being configured to deliver a concentrated gas stream originating from the condensable vapor and the non-condensable gas;

[0431] (iv) The path defined between the upper portion and the lower portion of the shell; and

[0432] (v) A conveying system along the path, the conveying system being configured to convey the solid, wherein the shell is shaped such that the solid adsorbs at least some of the condensable vapors and / or at least some of the non-condensable gases.

[0433] This invention enables the production of various compositions that can be used as bio-based reagents, as well as products incorporating such reagents. In some variations, the bio-based reagents are produced by any of the processes disclosed herein, such as those including the following steps:

[0434] (a) Providing carbon-containing feedstocks, including biomass;

[0435] (b) Optionally, the raw material is dried to remove at least a portion of the moisture contained in the raw material;

[0436] (c) Optionally, the feedstock is degassed to remove at least a portion of the interstitial oxygen contained in the feedstock (if any);

[0437] (d) In a pyrolysis zone, the raw material is pyrolyzed for at least 10 minutes in the presence of a substantially inert gas and at a pyrolysis temperature selected from about 250°C to about 700°C to produce hot pyrolysis solids, condensable vapors and non-condensable gases.

[0438] (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solid;

[0439] (f) In a cooling zone, the hot pyrolysis solid is cooled for at least 5 minutes in the presence of a substantially inert gas and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid.

[0440] (g) Cooling the warm pyrolysis solid to produce a cold pyrolysis solid; and

[0441] (h) Recover the bio-derived reagent, including at least a portion of the cold pyrolysis solids.

[0442] In some embodiments, the reagent comprises, based on dry weight, at least 70 wt%, at least 80 wt%, at least 90 wt%, or at least 95 wt% total carbon. The total carbon comprises at least fixed carbon and may further comprise carbon from volatile substances. In some embodiments, the carbon from volatile substances is at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the bio-derived reagent. For example, fixed carbon can be measured using ASTM D3172, while volatile carbon can be measured using ASTM D3175.

[0443] Based on dry weight, the bio-based reagent may include about 10 wt% or less, such as about 5 wt% or less hydrogen. Based on dry weight, the bio-based reagent may include about 1 wt% or less, such as about 0.5 wt% or less nitrogen. Based on dry weight, the bio-based reagent may include about 0.5 wt% or less, such as about 0.2 wt% or less phosphorus. Based on dry weight, the bio-based reagent may include about 0.2 wt% or less, such as about 0.1 wt% or less sulfur.

[0444] For example, carbon, hydrogen, and nitrogen can be measured using ASTM D5373 for final analysis. For example, oxygen can be measured using ASTM D3176. For example, sulfur can be measured using ASTM D3177.

[0445] Some embodiments provide reagents having little or 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, on a dry / ashless (DAF) basis, some embodiments provide bio-based reagents having up to and containing 100% carbon.

[0446] Generally, feedstocks such as biomass contain non-volatile species, including silica and various metals, which are not easily released during pyrolysis. It is possible to use ash-free feedstocks, in which case there should be no significant amount of ash in the pyrolysis solids. For example, ash content can be measured using ASTM D3174.

[0447] Varying amounts of non-combustible materials, such as ash, may be present. Based on dry weight, bio-derived reagents may include about 10 wt% or less, such as about 5 wt%, about 2 wt%, about 1 wt%, or less of non-combustible materials. In some embodiments, the reagent contains very little ash, or even substantially no ash or other non-combustible materials. Thus, based on dry weight, some embodiments provide substantially pure carbon, containing 100% carbon.

[0448] Varying amounts of moisture may be present. Based on total mass, bio-derived reagents may include at least 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 25 wt%, 35 wt%, 50 wt%, or more of moisture. As intended herein, “moisture” should be interpreted as including water in any form present in the bio-derived reagent, including absorbed moisture, adsorbed water molecules, chemical hydrates, and physical hydrates. The equilibrium moisture content may vary at least with local environmental factors such as relative humidity. Furthermore, moisture can change during transport, preparation for use, and other logistics processes. For example, moisture can be measured using ASTM D3173.

[0449] Bio-derived reagents can have different energy contents. For the purposes of this invention, the energy content refers to the energy density based on a higher heating value associated with the complete combustion of a completely dried reagent. For example, the energy content of a bio-derived reagent can be at least about 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In some embodiments, the energy content is between about 14,000 and 15,000 Btu / lb. For example, the energy content can be measured using ASTM D5865.

[0450] Biological reagents can be formed into powders, such as coarse or fine powders. For example, in the embodiments, the reagents can be formed into powders with an average sieve size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0451] In some embodiments, the bio-derived reagent is formed into a structural object comprising pressed, bound, or agglomerated particles. The starting material for forming these objects may be in powder form of the reagent, such as an intermediate obtained by particle size reduction. The objects may be formed by mechanical pressing or other forces, optionally with an adhesive or other components that agglomerate the particles together.

[0452] In some embodiments, the bio-derived reagent is produced in the form of a structured object whose structure is substantially derived from the raw material. For example, raw material debris can produce product debris of the bio-derived reagent. Alternatively, raw material cylinders can produce bio-derived reagent cylinders, although these cylinders may be slightly smaller, but otherwise retain the basic structure and geometry of the starting material.

[0453] The bio-derived reagent according to the invention can be produced or formed into an object with a minimum size of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm or larger. In various embodiments, the minimum or maximum size can be length, width or diameter.

[0454] Other variations of the invention involve incorporating additives into a process, product, or both. In some embodiments, the bio-derived reagent comprises at least one process additive incorporated during the process. In these or other embodiments, the reagent comprises at least one product additive introduced into the reagent after the process.

[0455] In some embodiments, the bio-derived reagent, based on dry weight, includes:

[0456] 70 wt% or more of total carbon;

[0457] 5 wt% or less hydrogen;

[0458] 1 wt% or less of nitrogen;

[0459] 0.5 wt% or less of phosphorus;

[0460] 0.2 wt% or less sulfur; and

[0461] The additive is selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof.

[0462] The additives may be selected from, but are by no means limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, ferric chloride, ferric bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, calcium oxide, lime, and combinations thereof.

[0463] In some embodiments, the bio-derived reagent, based on dry weight, includes:

[0464] 70 wt% or more of total carbon;

[0465] 5 wt% or less hydrogen;

[0466] 1 wt% or less of nitrogen;

[0467] 0.5 wt% or less of phosphorus;

[0468] 0.2 wt% or less sulfur; and

[0469] Additives, wherein the additives are selected from acids, bases or their salts.

[0470] The additive may be selected from, but is by no means limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0471] In some embodiments, based on dry weight, the biological reagent includes:

[0472] 70 wt% or more of total carbon;

[0473] 5 wt% or less hydrogen;

[0474] 1 wt% or less of nitrogen;

[0475] 0.5 wt% or less of phosphorus;

[0476] 0.2 wt% or less sulfur;

[0477] A first additive, wherein the first additive is selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof; and

[0478] The second additive is selected from acids, bases, or their salts.

[0479] The first additive is different from the second additive.

[0480] The first additive may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, ferric chloride, ferric bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, calcium oxide, lime, and combinations thereof, while 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.

[0481] In some embodiments, based on dry weight, the bio-derived reagent is essentially composed of: carbon, hydrogen, nitrogen, phosphorus, sulfur, non-flammable substances, 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, fluorite, fluorite, bentonite, calcium oxide, lime, and combinations thereof.

[0482] In some embodiments, based on dry weight, the bio-derived reagent consists essentially of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-flammable substances, and additives selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, and combinations thereof.

[0483] The amount of additives (or total additives) can vary widely, from about 0.01 wt% to about 25 wt%, including about 0.1 wt%, about 1 wt%, about 5 wt%, about 10 wt%, or about 20 wt%. It should then be understood that when relatively large amounts of additives are incorporated, such as above about 1 wt%, the energy content calculated based on the total reagent weight (including additives) will be reduced. Still in the various embodiments, the energy content of the bio-derived reagent with additives can be at least about 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0484] The above discussion regarding product form also applies to embodiments incorporating additives. In fact, some embodiments incorporate additives as binders, fluxes, or other modifiers to enhance the final properties for a particular application.

[0485] In a preferred embodiment, most of the carbon contained in the bio-based reagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. Certain market mechanisms (e.g., renewable identification numbers, tax credits, etc.) may exist where value is attributed to the renewable carbon content within the bio-based reagent.

[0486] In some embodiments, fixed carbon can be classified as non-renewable carbon (e.g., from coal), while volatile carbon that can be added separately can be renewable carbon in order to increase not only the energy content but also the value of renewable carbon.

[0487] The bio-based reagents described herein can be used in a variety of carbon-containing products. The bio-based reagents themselves can be desirable market products. Compared to existing technologies, the bio-based reagents provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including higher renewable carbon content).

[0488] In a variant, the product comprises any bio-based reagent that can be obtained by the disclosed process or that is in the composition or any part, combination or derivative thereof described herein.

[0489] Generally, bio-based reagents can be combusted to generate energy (including electricity and heat); partially oxidized, gasified, or steam-reformed to produce syngas; used for their adsorption or absorption properties; used for their reactive properties during metal refining (such as reducing metal oxides) or other industrial processing; or used for their material properties in carbon steel and various other metal alloys. Essentially, bio-based reagents can be used in any market application of carbon-based commercial or advanced materials, including special uses yet to be developed.

[0490] Prior to their suitability for any product application or actual use, the disclosed bio-based reagents can be analyzed, measured, and optionally modified (e.g., by additives) in various ways. In addition to chemical composition and energy content, some properties of potential interest include density, particle size, surface area, microporosity, uptake, adsorption, binding capacity, reactivity, desulfurization activity, and basicity, to name just a few.

[0491] Products or materials that can be incorporated into these bio-derived reagents include, but are by no means limited to, carbon-based blast furnace addition products, carbon-based iron flint pellet addition products, ladle addition carbon-based products, metallurgical coke carbon-based products, coal substitute products, carbon-based coking products, carbon breeze products, fluidized bed carbon-based feedstocks, carbon-based blast furnace addition products, injectable carbon-based products, powdered carbon-based products, furnace operator carbon-based products, carbon electrode or activated carbon products.

[0492] The use of the disclosed bio-derived reagents in metal production can reduce slag, improve overall efficiency, and reduce life-cycle environmental impact. Therefore, embodiments of the present invention are particularly suitable for metal processing and manufacturing.

[0493] Some variations of this invention utilize bio-derived reagents as carbon-based blast furnace addition products. A blast furnace is a metallurgical furnace used for smelting to produce industrial metals, such as (but not limited to) iron. Smelting is a form of extractive metallurgy; its primary purpose is to produce metals from its ores. Smelting uses heat and chemical reducing agents to break down the ore. Carbon and / or carbon monoxide, derived from carbon, remove oxygen from the ore, thereby producing the elemental metal.

[0494] In some embodiments, the reducing agent comprises a bio-based reagent. In some embodiments, the reducing agent consists essentially of a bio-based reagent. In a blast furnace, the bio-based reagent, ore, and limestone can be continuously supplied through the top of the furnace while air (optionally oxygen-enriched) is blown into the bottom of the chamber, causing a chemical reaction to occur throughout the furnace as the material moves downward. The final products include molten metal and slag phases flowing from the bottom, and flue gas exiting from the top of the furnace. The contact between the downward-flowing ore and the upward-flowing carbon monoxide-rich hot gas is a countercurrent process.

[0495] The quality of carbon in a blast furnace is measured by its resistance to degradation. Carbon's role as a permeable medium is crucial for economical blast furnace operation. Carbon degradation varies depending on its location within the blast furnace and involves a combination of reactions with CO2, H2O, or O2, as well as abrasion between carbon particles and with other components of the burden. Degraded carbon particles can lead to blockage and poor performance.

[0496] Coke reactivity testing is a highly considered measure of the performance of carbon in a blast furnace. This test has two components: the coke reactivity index (CRI) and the post-reaction coke strength (CSR). For better blast furnace performance, carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​are preferred. The CRI can be determined according to any suitable method known in the art, such as on a stub basis by ASTM method DS341.

[0497] In some embodiments, the bio-derived reagent provides a carbon product with properties suitable for direct introduction into a blast furnace.

[0498] The strength of the bio-based reagent can be determined by any suitable method known in the art, such as by drop testing or CSR testing. In some embodiments, the bio-based reagent, optionally when blended with another carbon source, provides a final carbon product with a CSR of at least about 50%, 60%, or 70%. The combined product can also provide a final coke product with reactivity suitable for combustion in a blast furnace. In some embodiments, the product has a CRI, making the bio-based reagent suitable as an additive or substitute for metallurgical coal, metallurgical coke, coke chips, foundry coke, or injectable coal.

[0499] Some embodiments employ one or more additives in an amount sufficient to provide a bio-based reagent, when added to another carbon source (e.g., coke) having a CRI or CSR sufficient for use in a blast furnace, to provide a composite product with a CRI and / or CSR sufficient for use in a blast furnace. In some embodiments, one or more additives are present in an amount sufficient to provide no more than about 40%, 30%, or 20% of the bio-based reagent for the CRI.

[0500] 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 generating the bio-based reagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate can be introduced as additives. Adding these molecules before, during, or after pyrolysis can increase the reactivity of the bio-based reagent in the blast furnace. These molecules can produce a stronger material, i.e., a higher CSR, thereby improving blast furnace efficiency. In addition, additives such as those selected from alkaline earth metals or their oxides or carbonates can lead to lower emissions (e.g., SO2).

[0501] In some embodiments, the blast furnace substitute is a bio-based reagent according to the invention, the bio-based reagent comprising at least about 55 wt% carbon, no more than about 0.5 wt% sulfur, no more than about 8 wt% non-combustible material, and having a calorific value of at least about 11,000 Btu / lb. In some embodiments, the blast furnace substitute further comprises no more than about 0.035 wt% phosphorus, about 0.5 wt% to about 50 wt% volatile matter, and optionally one or more additives. In some embodiments, the blast furnace substitute comprises about 2 wt% to about 15 wt% dolomite, about 2 wt% to about 15 wt% dolomitic lime, about 2 wt% to about 15 wt% bentonite, and / or about 2 wt% to about 15 wt% calcium oxide. In some embodiments, the size of the blast furnace substitute is substantially in the range of about 1 cm to about 10 cm.

[0502] In some embodiments, the bio-derived reagent according to the invention can be used as a substitute for foundry coke. Foundry coke typically comprises at least about 85 wt% carbon content, about 0.6 wt% sulfur content, no more than about 1.5 wt% volatile matter, no more than about 13 wt% ash content, no more than about 8 wt% moisture content, about 0.035 wt% phosphorus, a CRI value of about 30, and a size in the range of about 5 cm to about 25 cm.

[0503] Some variations of this invention utilize bio-derived reagents as carbon-based addition products to flint agglomerates. The ore used to produce iron and steel is iron oxide. Major iron oxide ores include hematite, limonite (also known as brown ore), flint, and magnetite (a black ore). Flint is a low-grade but important ore containing both magnetite and hematite. The iron content of flint is typically 25 wt% to 30 wt%. Blast furnaces typically require ore with an iron content of at least 50 wt% for efficient operation. Iron ore can undergo beneficiation processes including crushing, screening, tumbling, flotation, and magnetic separation. Refined ore is enriched to over 60% iron and typically forms agglomerates before transport.

[0504] For example, iron flint can be ground into a fine powder and combined with binders such as bentonite and limestone. This forms agglomerates about one centimeter in diameter, containing, for example, about 65 wt% iron. The agglomerates are then sintered, oxidizing the magnetite into hematite. The agglomerates are durable, ensuring that the blast furnace charge remains sufficiently porous to allow heated gases to pass through and react with the agglomerated ore.

[0505] Iron flint agglomerates can be fed into a blast furnace to produce iron, as described above with reference to blast furnace addition products. In some embodiments, a bio-based agent is introduced into the blast furnace. In these or other embodiments, the bio-based agent is incorporated into the iron flint agglomerates themselves. For example, iron flint ore powder can be mixed with a bio-based agent and binder after beneficiation, rolled into small objects, and then baked to a certain hardness. In such embodiments, iron flint-carbon agglomerates with an appropriate composition can be conveniently introduced into the blast furnace without the need for a separate carbon source.

[0506] Some variations of this invention utilize bio-derived reagents as ladle addition-based carbon-based products. A ladle is a container used for conveying and pouring 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 treatment ladle is used to perform processes within the ladle to alter aspects of the molten metal, such as converting cast iron to ductile iron by adding various elements to the ladle.

[0507] The bio-based reagent can be introduced into any type of ladle, but typically, carbon is added to the ladle in an appropriate amount based on the target carbon content. The carbon injected into the ladle can be in the form of a fine powder so that the carbon is well delivered in large quantities to the final composition. In some embodiments, when the bio-based reagent according to the invention is used as a ladle addition product, the minimum size of the bio-based reagent is about 0.5 cm, such as about 0.75 cm, about 1 cm, about 1.5 cm, or higher.

[0508] In some embodiments, the high-carbon bio-derived reagent according to the invention can be used as a ladle carbon additive in alkaline oxygen furnaces or electric arc furnaces, for example, where ladle carbon is used (e.g., added to ladle carbon during steelmaking).

[0509] In some embodiments, the ladle carbon additive further includes up to about 5 wt% manganese, up to about 5 wt% calcium oxide and / or up to about 5 wt% dolomitic lime.

[0510] Direct reduced iron (DRI), also known as sponge iron, is produced by directly reducing iron ore (in the form of lumps, granules, or fine powder) with a reducing gas conventionally generated from natural gas or coal. The reducing gas is typically a mixture of syngas, hydrogen, and carbon monoxide, which act as the reducing agent. Bio-based reagents, such as those described herein, can be converted into a gas stream including CO to act as the reducing agent in the production of DRI.

[0511] Iron granules are high-quality feedstock for steelmaking and cast iron production. They are essentially iron and carbon, with virtually no gangue (slag) and low levels of metallic residue. These granules are a premium-grade pig iron product with excellent transport and handling properties. The carbon contained in the granules or any part thereof can be a bio-based reagent as described herein. Iron granules can be produced by reducing iron ore in a rotary hearth furnace using a bio-based reagent as a reducing agent and energy source.

[0512] Some variations of this invention utilize bio-derived reagents as products based on metallurgical coke carbon. Metallurgical coke, also known as "metallurgical (met)" coke, is a carbonaceous material typically produced through the decomposition distillation of various blends of bituminous coal. The final solid is non-molten carbon known as metallurgical coke. Due to the loss of volatile gases and partial melting, metallurgical coke has an open, porous morphology. Metallurgical coke has a very low volatile content. However, the ash components, which are part of the original bituminous coal feedstock, are still encapsulated in the resulting coke. Metallurgical coke feedstock can be obtained from a wide range of sizes, from fine powder to basketball-sized lumps. Typical purity ranges from 86-92 wt% fixed carbon.

[0513] Metallurgical coke is used where high-quality, tough, flexible, and abrasion-resistant carbon is required. Applications include, but are not limited to, conductive flooring, friction materials (e.g., carbon linings), casting coatings, casting carburizers, corrosive materials, drilling applications, reducing agents, heat treatment agents, ceramic packaging media, electrolytic processes, and oxygen removal.

[0514] Metallurgical coke typically comprises a calorific value of about 10,000 to 14,000 Btu / lb and an ash content of about 10 wt% or higher. Therefore, in some embodiments, metallurgical coke substitutes include a bio-based reagent according to the invention, said bio-based reagent comprising at least about 80 wt%, 85 wt%, or 90 wt% carbon, no more than about 0.8 wt% sulfur, no more than about 3 wt% volatile matter, no more than about 15 wt% ash, no more than about 13 wt% moisture, and no more than about 0.035 wt% phosphorus. When the bio-based reagent according to the invention is used as a metallurgical coke substitute, the size of said bio-based reagent can range, for example, from about 2 cm to about 15 cm.

[0515] In some embodiments, the metallurgical coke substitute further includes additives such as chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorite, calcium oxide, lime, dolomitic lime, bentonite, and combinations thereof.

[0516] Some variations of this invention utilize bio-based reagents as carbon substitutes. In principle, any process or system using coal can be adapted to use bio-based reagents.

[0517] In some embodiments, a bio-derived reagent is combined with one or more coal-based products to form a composite product having a higher grade than the coal-based product and / or having fewer emissions upon combustion than the pure coal-based product.

[0518] For example, by combining a selected amount of the bio-based reagent according to the invention with low-grade coal products, such as sub-bituminous coal, low-grade coal can be used in applications that typically require high-grade coal products such as bituminous coal. In other embodiments, the grade of the mixed coal product (e.g., a combination of multiple coals with different grades) can be improved by combining the mixed coal with a certain amount of bio-based reagent. The amount of bio-based reagent to be mixed with the coal product can vary depending on the grade of the coal product, the characteristics of the bio-based reagent (e.g., carbon content, calorific value, etc.), and the desired grade of the final combined product.

[0519] For example, anthracite may have at least about 80 wt% carbon, about 0.6 wt% sulfur, about 5 wt% volatile matter, up to about 15 wt% ash, up to about 10 wt% moisture, and a calorific value of about 12,494 Btu / lb. In some embodiments, the anthracite substitute is a bio-based reagent comprising at least about 80 wt% carbon, no more than about 0.6 wt% sulfur, no more than about 15 wt% ash, and a calorific value of at least about 12,000 Btu / lb.

[0520] In some embodiments, the bio-based reagent may be used as a thermal coal substitute. Thermal coal products typically have high sulfur levels, high phosphorus levels, high ash content, and a calorific value of up to about 15,000 Btu / lb. In some embodiments, the thermal coal substitute is a bio-based reagent comprising no more than about 0.5 wt% sulfur, no more than about 4 wt% ash, and a calorific value of at least about 12,000 Btu / lb.

[0521] Some variations of this invention utilize bio-derived reagents as carbon-based coking products. Any coking process or system can be adapted to use bio-derived reagents to produce coke, or to use said bio-derived reagents as coke feedstock.

[0522] In some embodiments, the bio-based reagent may be used as a substitute for thermal coal or coke. In some embodiments, the thermal coal or coke substitute includes the bio-based reagent comprising at least about 50 wt% carbon, at most about 8 wt% ash, at most about 0.5 wt% sulfur, and having a calorific value of at least about 11,000 Btu / lb. In some embodiments, the thermal coke substitute further comprises about 0.5 wt% to about 50 wt% volatile matter. In some embodiments, the thermal coal or coke substitute comprises at least about 0.4 wt% to at most about 15 wt% moisture.

[0523] In some embodiments, the bio-based reagent can be used as a substitute for petroleum (PET) coke or calcined petroleum coke. Calcined petroleum coke typically has at least about 66 wt% carbon, up to 4.6 wt% sulfur, up to about 5.5 wt% volatile matter, up to about 19.5 wt% ash, and up to about 2 wt% moisture, and is typically set to a size of about 3 mesh or smaller. In some embodiments, the calcined petroleum coke substitute is a bio-based reagent comprising at least about 66 wt% carbon, no more than about 4.6 wt% sulfur, no more than about 19.5 wt% ash, no more than about 2 wt% moisture, and a size set to about 3 mesh or smaller.

[0524] In some embodiments, the bio-based reagent may be used as a carbon substitute for coking carbon (e.g., co-fired with metallurgical coal in a coking oven). In one embodiment, the coking carbon substitute is a bio-based reagent comprising at least about 55 wt% carbon, no more than about 0.5 wt% sulfur, no more than about 8 wt% non-combustible material, and having a calorific value of at least about 11,000 Btu / lb. In some embodiments, the coking carbon substitute comprises about 0.5 wt% to about 50 wt% volatile matter and / or one or more additives.

[0525] Some variations of the present invention utilize a bio-derived reagent as a carbon scrap product, which typically has a very fine particle size, such as 6 mm, 3 mm, 2 mm, 1 mm, or smaller. In some embodiments, the bio-derived reagent according to the present invention can be used as a coke scrap substitute product. Coke scrap typically has a maximum size not exceeding about 6 mm, a carbon content of at least about 80 wt%, 0.6 wt% to 0.8 wt% sulfur, 1% to 20 wt% volatile matter, up to about 13 wt% ash, and up to about 13 wt% moisture. In some embodiments, the coke scrap substitute product is a bio-derived reagent according to the present invention, which comprises at least about 80 wt% carbon, no more than about 0.8 wt% sulfur, no more than about 20 wt% volatile matter, no more than about 13 wt% ash, no more than about 13 wt% moisture, and a maximum size of about 6 mm.

[0526] In some embodiments, bio-derived reagents can be used as carbon scrap substitutes, for example, during the generation of iron flint agglomerates or in iron preparation processes.

[0527] Some variants utilize bio-derived reagents as feedstocks for various fluidized beds, or as alternatives to carbon-based feedstocks in fluidized beds. Carbon can be used in fluidized beds for complete combustion, partial oxidation, gasification, steam reforming, etc. Carbon can be primarily converted into syngas for various downstream applications, including energy generation (e.g., combined heat and power) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel fuel).

[0528] In some embodiments, the bio-derived reagents according to the invention can be used as fluidized bed coal substitutes, for example, in fluidized bed furnaces that use coal (e.g., for process heat or energy generation).

[0529] Some variants utilize bio-derived reagents as carbon-based furnace addition products. Coal-based furnace addition products can typically have high sulfur, high phosphorus, and high ash content, which contributes to the degradation of metallic products and generates air pollution. In some embodiments, the furnace addition alternatives incorporating bio-derived reagents comprise no more than about 0.5 wt% sulfur, no more than about 4 wt% ash, no more than about 0.03 wt% phosphorus, and a maximum size of about 7.5 cm. In some embodiments, the furnace addition alternatives comprise about 0.5 wt% to about 50 wt% volatile matter and about 0.4 wt% to about 15 wt% moisture.

[0530] In some embodiments, bio-derived reagents can be used as furnace-additive carbon additives, for example, in alkaline oxygen furnaces or electric arc furnaces where furnace-additive carbon is used. For instance, furnace-additive carbon can be added to scrap steel during steelmaking in an electric arc furnace facility. For electric arc furnace applications, high-purity carbon is desirable so that impurities are not introduced back into the process after earlier impurity removal.

[0531] In some embodiments, the furnace-added carbon additive is a bio-based reagent comprising at least about 80 wt% carbon, no more than about 0.5 wt% sulfur, no more than about 8 wt% non-combustible material, and having a calorific value of at least about 11,000 Btu / lb. In some embodiments, the furnace-added carbon additive further comprises up to about 5 wt% manganese, up to about 5 wt% fluorite, about 5 wt% to about 10 wt% dolomite, about 5 wt% to about 10 wt% dolomitic lime, and / or about 5 wt% to about 10 wt% calcium oxide.

[0532] Some variations utilize bio-derived reagents as stoker-based carbon products. In some embodiments, the bio-derived reagents according to the invention can be used as stoker coal substitutes, for example, in stoker facilities that use coal (e.g., for process heat or energy generation).

[0533] Some variations utilize bio-derived reagents as injectable (e.g., powdered) carbon-based materials. In some embodiments, the bio-derived reagent can be used as an injection-grade calcined petroleum coke substitute. Injection-grade calcined petroleum coke typically has at least about 66 wt% carbon, about 0.55 wt% to about 3 wt% sulfur, up to about 5.5 wt% volatile matter, up to about 10 wt% ash, up to about 2 wt% moisture, and a size set to about 6 mesh or smaller. In some embodiments, the calcined petroleum coke substitute is a bio-derived reagent comprising at least about 66 wt% carbon, no more than about 3 wt% sulfur, no more than about 10 wt% ash, no more than about 2 wt% moisture, and a size set to about 6 mesh or smaller.

[0534] In some embodiments, bio-derived reagents can be used as an injectable carbon alternative in alkaline oxygen furnaces or electric arc furnaces, for example, in any application where injectable carbon will be used (e.g., injected into slag or ladle during steelmaking).

[0535] In some embodiments, bio-derived reagents, such as wherever pulverized coal will be used (e.g., for process heat or energy generation), can be used as a substitute for pulverized carbon. In some embodiments, the pulverized coal substitute comprises up to about 10% calcium oxide.

[0536] Some variants utilize bio-derived reagents as carbide products for metal production. In some embodiments, the bio-derived reagents according to the invention can be used as carbide products for producing carbon steel or other metal alloys comprising carbon. Coal-based late-stage carbide products can typically have high sulfur, phosphorus, and ash content, as well as high mercury levels, which degrade metal quality and contribute to air pollution. In some embodiments of the invention, the carbide products comprise no more than about 0.5 wt% sulfur, no more than about 4 wt% ash, no more than about 0.03 wt% phosphorus, with a minimum size of about 1 mm to 5 mm and a maximum size of about 8 mm to 12 mm.

[0537] Some variations utilize bio-derived reagents within the carbon electrode. In some embodiments, the bio-derived reagent can be used as an electrode (e.g., anode) material suitable for, for example, aluminum production.

[0538] Other uses of bio-derived reagents in carbon electrodes include applications in batteries, fuel cell units, capacitors, and other energy storage or delivery devices. For example, in lithium-ion batteries, bio-derived reagents can be used on the anode side to intercalate lithium. In these applications, carbon purity and low ash content can be very important.

[0539] Some variations of this invention utilize bio-derived reagents as catalyst supports. Carbon is a known catalyst support in a wide range of catalytic chemical reactions, such as the synthesis of higher hydrocarbons from syngas via Fischer-Tropsch synthesis using cobalt sulfide-molybdenum metal catalysts supported on carbon phases or iron-based catalysts supported on carbon, and the synthesis of mixed alcohols from syngas via Fischer-Tropsch synthesis.

[0540] Some variants utilize bio-derived reagents as activated carbon products. Activated carbon is used in a 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. In various embodiments, the bio-derived reagents provided herein can provide high-quality activated carbon products due to (i) a larger surface area than fossil fuel-based activated carbon; (ii) the renewable nature of the carbon; (iii) the vascular properties of the biomass feedstock, combined with additives, better allowing for the penetration / distribution of additives that enhance pollutant control; and (iv) the lower the inert matter (ash) content, the greater the reactivity.

[0541] It should be understood that the applications described above in the market applications of bio-derived reagents are not exclusive or exhaustive. Therefore, a bio-derived reagent described as suitable for one type of carbon product in the various embodiments may be suitable for any other application described. These applications are merely exemplary, and other applications of bio-derived reagents exist.

[0542] Additionally, in some embodiments, the same physical materials may be used in multiple market processes in an integrated manner or sequentially. Thus, for example, a bio-derived reagent used as a carbon electrode or activated carbon may then be introduced into a combustion process to obtain energy or introduced into a metal preparation process (e.g., metal ore reduction) at the end of its service life as a performance material.

[0543] Some embodiments may utilize the bio-based reagent for its reactive / adsorption properties and also as a fuel. For example, a bio-based reagent injected into an emission stream may be adapted to remove contaminants, followed by combustion of the bio-based reagent particles and any remaining contaminants to generate energy and thermally destroy or chemically oxidize the contaminants.

[0544] Compared to conventional fossil fuel-based products, significant environmental and product use advantages can be associated with bio-derived reagents. Bio-derived reagents are not only environmentally superior, but also functionally superior from a processing perspective due to factors such as higher purity.

[0545] Regarding some embodiments of metal generation, the disclosed process for producing bio-derived reagents can result in significantly lower CO, CO2, and NO emissions compared to coking of the coal-based products required for metal generation. x Emissions of SO2 and other harmful air pollutants.

[0546] Using bio-based reagents instead of coal or coke also significantly reduces environmental emissions of SO2, harmful air pollutants, and mercury.

[0547] Furthermore, due to the purity of these bio-based reagents (including low ash content), the disclosed bio-based reagents have the potential to reduce slag and increase production capacity in batch metal preparation processes.

[0548] In some embodiments, the bio-derived reagent is used as activated carbon. For example, a material with low carbon fixation can be activated, a material with high carbon fixation can be activated, or both materials can be activated, such that the bio-carbon composition (blend) is used as activated carbon.

[0549] In some embodiments, a portion of the bio-derived reagent is recovered as an activated carbon product, while another portion (e.g., the remainder) is granulated with a binder to produce biochar flocs. In other embodiments, the bio-derived reagent is granulated with a binder to produce biochar flocs, which are then transported for later conversion into an activated carbon product. This later conversion may involve pulverizing back into powder and may also include chemical treatment with, for example, steam, acid, or alkali. In these embodiments, the biochar flocs can be considered as activated carbon precursor flocs.

[0550] In some embodiments, the fixed carbon in the bio-based reagent can be primarily used to prepare activated carbon, while the volatile carbon in the bio-based reagent can be primarily used to prepare reducing gas. For example, at least 50 wt%, at least 90 wt%, or substantially all of the fixed carbon in the bio-based reagent produced in step (b) can be recovered as activated carbon in step (f), while at least 50 wt%, at least 90 wt%, or substantially all of the volatile carbon in the bio-based reagent produced in step (b) can be directed to reducing gas (e.g., via a steam reforming reaction of volatile carbon to CO).

[0551] In some embodiments, the activated carbon includes an iodine value of at least about 500, 750, 800, 1000, 1500, or 2000. In some embodiments, the activated carbon includes 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 indicated by the activated carbon's... 14 C / 12 The activated carbon is determined by measurements of the carbon isotope ratio. In some embodiments, the activated carbon consists essentially of renewable activated carbon, as determined by the activated carbon composition. 14 C / 12 Determined by measurements of C isotope ratios.

[0552] 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 steam concentration) can be selected for activated carbon products having certain properties such as iodine value. Different reaction conditions can be selected for different activated carbon products, such as activated carbon products with higher iodine values. The pyrolysis reactor can operate in an active mode to produce one product and then switch to another mode to produce another product. The first product can be removed continuously or periodically during the first active period, or it can be removed before switching the reaction conditions of the pyrolysis reactor.

[0553] 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. In some embodiments, the activated carbon comprises at least about 90% renewable carbon, such as according to the activated carbon... 14 C / 12 The activated carbon is determined by measurements of the carbon isotope ratio. In some embodiments, the activated carbon consists essentially of renewable activated carbon, as determined by the activated carbon composition. 14 C / 12 Determined by measurements of C isotope ratios.

[0554] The activated carbon produced by the process disclosed in this article can be used in a variety of ways.

[0555] In some embodiments, activated carbon is used on-site to purify one or more of the main products. In some embodiments, activated carbon is used on-site to purify water. In these or other embodiments, activated carbon is used on-site to treat wastewater streams to reduce liquid phase emissions and / or to treat waste vapor streams to reduce air emissions. In some embodiments, activated carbon is used as a soil conditioner to help generate new biomass, which may be the same type of biomass as that used as a local feedstock on-site.

[0556] Activated carbon prepared according to the processes disclosed herein can have properties that are the same as or better than those of conventional fossil fuel-based activated carbon. In some embodiments, the surface area of ​​the activated carbon is equivalent to, equal to, or greater than the surface area associated with fossil fuel-based activated carbon. In some embodiments, the activated carbon can control pollutants as well as, or better than, conventional activated carbon products. In some embodiments, the level of inert material (e.g., ash) in the activated carbon is equivalent to, equal to, or lower than the level of inert material (e.g., ash) associated with conventional activated carbon products. In some embodiments, the particle size and / or particle size distribution of the activated carbon is equivalent to, equal to, greater than, or smaller than the particle size and / or particle size distribution associated with conventional activated carbon products. In some embodiments, the particle shape of the activated carbon is equivalent to, substantially similar to, or the same as the particle shape associated with conventional activated carbon products. In some embodiments, the particle shape of the activated carbon is substantially different from the particle shape associated with conventional activated carbon products. In some embodiments, the pore volume of the activated carbon is equivalent to, equal to, or greater than the pore volume associated with conventional activated carbon products. In some embodiments, the pore size of the activated carbon is equivalent to, substantially similar to, or the same as the pore size associated with conventional activated carbon products. In some embodiments, the particle abrasion resistance value of the activated carbon is equivalent to, substantially similar to, or identical to the particle abrasion resistance value associated with conventional activated carbon products. In some embodiments, the hardness value of the activated carbon is equivalent to, substantially similar to, or identical to the hardness value associated with conventional activated carbon products. In some embodiments, the bulk density value of the activated carbon is equivalent to, substantially similar to, or identical to the bulk density value associated with conventional activated carbon products. In some embodiments, the adsorption capacity of the activated carbon product is equivalent to, substantially similar to, or identical to the adsorption capacity associated with conventional activated carbon products.

[0557] Prior to suitability for any product application or actual use, the disclosed activated carbon can be analyzed, measured, and optionally modified (e.g., by additives) in various ways. Some properties of potential interest include density, particle size, surface area, microporosity, absorbance, adsorption rate, binding capacity, reactivity, desulfurization activity, alkalinity, hardness, and iodine value.

[0558] Activated carbon is commercially used in a 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. Key product properties for activated carbon can include particle size, shape, composition, surface area, pore volume, pore size, particle size distribution, surface and internal chemical properties of the carbon, particle abrasion resistance, hardness, bulk density, and adsorption capacity.

[0559] For example, the bulk density of bio-derived activated carbon can be from about 50 g / L to about 650 g / L.

[0560] The surface area of ​​bio-derived activated carbon can vary widely. Exemplary surface areas (e.g., BET surface area) are approximately 400 m². 2 / g to approximately 2000m 2 / g or higher, such as approximately 500m 2 / g、600m 2 / g、800m 2 / g, 1000m 2 / g、1200m 2 / g, 1400m 2 / g, 1600m 2 / g or 1800m 2 Within the range of / g. Surface area is usually related to adsorption capacity.

[0561] Pore ​​size distribution can be important for determining the final properties of activated carbon. Pore size measurements can include micropore content, mesopore content, and macropore content.

[0562] Iodine value is a parameter used to characterize the performance of activated carbon. The iodine value measures the degree of activation of the carbon and is a measure of the micropores (e.g., micropores). The iodine value is a measure of the iodine content. It is an important measurement for liquid phase applications. Exemplary iodine values ​​of activated carbon products produced by embodiments of this disclosure include approximately 500, 600, 750, 900, 1000, 1100, 1200, 1300, 1500, 1600, 1750, 1900, 2000, 2100, and 2200, encompassing all intermediate ranges. The unit of iodine value is milligrams of iodine per gram of carbon.

[0563] Another porosity-related measurement is the methylene blue number, which measures the porosity (e.g., Exemplary methylene blue numbers of the activated carbon products produced by embodiments of this disclosure include about 100, 150, 200, 250, 300, 350, 400, 450, and 500, encompassing all intermediate ranges. The unit for methylene blue number is milligrams of methylene blue (methylene blue chloride) per gram of carbon.

[0564] Another porosity-related measurement is the molasses number, which measures the macropore content (e.g., Exemplary molasses numbers of the activated carbon products produced by embodiments of this disclosure include about 100, 150, 200, 250, 300, 350, and 400, encompassing all intermediate ranges. The unit of molasses number is milligrams of molasses per gram of carbon.

[0565] In some embodiments, the activated carbon comprises at least about 0.5 cm³. 3 / g, for example, at least about 1cm 3 / g of mesopore volume.

[0566] Activated carbon can be characterized by its water-holding capacity. In various embodiments, the activated carbon product produced by the embodiments of this disclosure has a water-holding capacity of about 10% to about 300% (weight of water divided by weight of dried activated carbon) at 25°C, such as about 50% to about 100%, for example, about 60-80%.

[0567] Hardness, or abrasion count, is a measure of the abrasion resistance of activated carbon. The hardness or abrasion count is an indicator of the physical integrity of activated carbon under frictional and mechanical stresses during handling or use. A certain level of hardness is desirable, but if the hardness is too high, it can lead to excessive wear on equipment. Exemplary abrasion counts measured according to ASTM D3802 range from about 1% to greater than about 99%, such as 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 greater than about 99%.

[0568] In some embodiments, an optimal hardness range can be obtained, wherein the activated carbon has suitable abrasion resistance but does not cause wear and loss in the capital facilities processing the activated carbon. In some embodiments of this disclosure, this optimization is possible due to the selection of raw materials and processing conditions. In some embodiments used downstream, where high hardness can be processed, the processes of this disclosure can be operated to increase or maximize hardness, thereby producing bio-derived activated carbon products with abrasion numbers of about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or greater than about 99%.

[0569] The bio-based activated carbon provided by this disclosure has a wide range of commercial applications. For example, but not limited to, bio-based activated carbon can be used in emission control, water purification, groundwater treatment, wastewater treatment, air stripping applications, PCB removal applications, odor removal applications, soil vapor extraction, manufactured gas plants, industrial water filtration, industrial fumigation, storage tanks and process vents, pumps, blowers, filters, pre-filters, mist filters, piping systems, piping modules, adsors, absorbers, and columns.

[0570] In one embodiment, a method for reducing emissions using activated carbon includes:

[0571] (a) Providing activated carbon particles comprising a bio-derived activated carbon composition recovered from the second reactor disclosed herein;

[0572] (b) Provide a gaseous emission stream including at least one of the selected pollutants;

[0573] (c) Providing an additive, the additive being selected to help remove the selected contaminants from the gas phase emission stream;

[0574] (d) Introducing the activated carbon particles and the additive into the gas phase emission stream to adsorb at least a portion of the selected pollutant onto the activated carbon particles, thereby generating pollutant-adsorbed carbon particles within the gas phase emission stream; and

[0575] (e) Separating at least a portion of the carbon particles adsorbed by the pollutant from the gas phase emission stream to produce a gas phase emission stream with reduced pollutants.

[0576] Additives for use in bio-derived activated carbon compositions can be provided as part of the activated carbon particles. Alternatively or additionally, additives can be introduced directly into the gas phase exhaust stream, fuel bed, or combustion zone. Other methods of introducing additives directly or indirectly into the gas phase exhaust stream to remove selected contaminants are also possible, as will be understood by those skilled in the art.

[0577] In some embodiments, the selected pollutants (in the gaseous emission stream) include metals. In some embodiments, metals include mercury, boron, selenium, arsenic, their salts, or combinations thereof. In some embodiments, the selected pollutants include hazardous air pollutants, organic molecules (such as volatile organic compounds or “VOCs”), or non-condensable gases. In some embodiments, bio-based activated carbon products adsorb, absorb, or chemisorb a quantity of pollutants greater than an equivalent quantity of non-bio-based activated carbon products. In some embodiments, the pollutants are metals, hazardous air pollutants, organic molecules (such as VOCs), non-condensable gases, or combinations thereof. In some embodiments, the pollutants include mercury. In some embodiments, the pollutants include VOCs. In some embodiments, the bio-based activated carbon includes at least about 1 wt% hydrogen or at least about 10 wt% oxygen.

[0578] Hazardous air pollutants are those pollutants that cause 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 authorized to control 189 hazardous air pollutants. Any current or future molecules classified as hazardous air pollutants by the EPA are included in the possible selected pollutants within the context of this invention.

[0579] Volatile organic molecules (some of which are also hazardous air pollutants) are organic chemicals that have high vapor pressures under normal room temperature conditions. Examples include short-chain alkanes, alkenes, alcohols, ketones, and aldehydes. Many volatile organic molecules are harmful to human health or the environment. The EPA regulates volatile organic molecules in the air, water, and on land. The EPA's definition of volatile organic molecules is described in Section 51.100 of 40 CFR, which is incorporated herein by reference in its entirety.

[0580] Non-condensable gases are gases that do not condense under normal room temperature conditions. Non-condensable gases may include, but are not limited to, nitrogen oxides, carbon monoxide, carbon dioxide, hydrogen sulfide, sulfur dioxide, sulfur trioxide, methane, ethane, ethylene, ozone, ammonia, or combinations thereof.

[0581] Multiple contaminants can be removed using the disclosed activated carbon particles. In some embodiments, the carbon particles adsorbed by the contaminants contain at least two, three, or more contaminants. Activated carbon as disclosed herein can allow for the control of multiple contaminants as well as the control of certain target contaminants (e.g., selenium).

[0582] In some embodiments, the carbon particles adsorbed by the pollutant are treated to regenerate activated carbon particles. In some embodiments, the method comprises thermally oxidizing the carbon particles adsorbed by the pollutant. The carbon particles adsorbed by the pollutant, or their regenerated form, can be burned to provide energy.

[0583] In some embodiments, the additives used for activated carbon are selected from acids, bases, salts, metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In some embodiments, the additives include magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, ferric chloride, ferric bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, organic acids (e.g., citric acid), or combinations thereof.

[0584] In some embodiments, the gaseous emission stream originates from metal processing, such as the processing of high-sulfur metal ores.

[0585] As an exemplary embodiment involving mercury control, activated carbon can be injected upstream of particulate matter control devices such as electrostatic precipitators or fabric filters (e.g., into a ducting system). In some cases, flue gas desulfurization (dry or wet) systems may be located downstream of the activated carbon injection point. Activated carbon can be injected pneumatically as powder. The injection location is typically determined by the existing plant configuration (unless it is a new site) and whether additional downstream particulate matter control equipment has been modified.

[0586] For boilers currently equipped with particulate matter control devices, implementing bio-based activated carbon injection for mercury control may require: (i) injecting powdered activated carbon upstream of the existing particulate matter control device (electrostatic precipitator or fabric filter); (ii) injecting powdered activated carbon downstream of the existing electrostatic precipitator and upstream of the modified fabric filter; or (iii) injecting powdered activated carbon between the electric fields of the electrostatic precipitator. The inclusion of iron or iron-containing molecules can significantly improve the performance of the electrostatic precipitator for mercury control. Furthermore, the inclusion of iron or iron-containing molecules can significantly alter the end-of-life options, as the used activated carbon solids can be separated from other ash.

[0587] In some embodiments, the powdered activated carbon injection method can be used in conjunction with existing SO2 control devices. The activated carbon can be injected before or after the SO2 control device, depending on the availability of methods for collecting the activated carbon adsorbent downstream of the injection point.

[0588] In some embodiments, the same physical material may be used in multiple processes in an integrated manner or sequentially. Thus, for example, activated carbon, at the end of its service life as a performance material, may then be introduced into a combustion process to obtain energy value or into a metal preparation process that requires carbon but does not require the properties of activated carbon, etc.

[0589] For example, bio-derived activated carbon and the principles of this disclosure can be applied to liquid-phase applications, including the processing of water, aqueous streams of varying purities, solvents, liquid fuels, polymers, molten salts, and molten metals. As contemplated herein, “liquid phase” includes slurries, suspensions, emulsions, multiphase systems, or any other material that has (or can be adapted to have) a liquid state in at least some amount.

[0590] In one embodiment, this disclosure provides a method for purifying a liquid using activated carbon, and in some variations, the method includes the following steps:

[0591] (a) Provide activated carbon particles recovered from the second reactor;

[0592] (b) Provide a liquid comprising at least one of the selected contaminants;

[0593] (c) Providing an additive, said additive being selected to aid in the removal of said selected contaminants from said liquid; and

[0594] (d) Contact the liquid with the activated carbon particles and the additive to adsorb at least a portion of the at least one selected contaminant onto the activated carbon particles, thereby producing contaminant-adsorbed carbon particles and a liquid with reduced contaminants.

[0595] The additive can be provided as part of the activated carbon particles. Alternatively, the additive can be introduced directly into the liquid. In some embodiments, the same or different additives can be introduced into the liquid either as part of the activated carbon particles or directly into the liquid.

[0596] In some embodiments involving liquid-phase applications, the additives include acids, bases, salts, metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. In some embodiments, the additives include magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, ferric chloride, ferric bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, organic acids (e.g., citric acid), or combinations thereof.

[0597] In some embodiments, the contaminants (e.g., in the liquid to be treated) include metals. In some embodiments, the metals include arsenic, boron, selenium, mercury, their salts, or combinations thereof. In some embodiments, the selected contaminants include organic molecules (e.g., VOCs), halogens, biomolecules, pesticides, or herbicides. In some embodiments, the carbon particles adsorbed by the contaminants include two, three, or more contaminants or derivatives thereof. In some embodiments, the activated carbon product adsorbs, absorbs, or chemisorbs a quantity of contaminants greater than a comparable quantity of non-biological activated carbon product. In some embodiments, the contaminants include metals, hazardous air pollutants, organic molecules (e.g., VOCs), non-condensable gases, or combinations thereof. In some embodiments, the selected contaminants include mercury. In some embodiments, the selected contaminants include VOCs. In some embodiments, the bio-based activated carbon includes at least about 1 wt% hydrogen or at least about 10 wt% oxygen.

[0598] The liquid to be treated is typically aqueous, but this is not necessary for the principles of this 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 a solution or in a moving bed.

[0599] In one embodiment, this disclosure provides a method for removing at least a portion of sulfur-containing pollutants from a liquid using a bio-derived activated carbon composition, the method comprising:

[0600] (a) Provide activated carbon particles recovered from the second reactor disclosed herein;

[0601] (b) Providing liquids containing sulfur-containing contaminants;

[0602] (c) Providing an additive, said additive being selected to aid in the removal of the sulfur-containing contaminant from said liquid; and

[0603] (d) Contact the liquid with the activated carbon particles and the additive to adsorb or absorb at least a portion of the sulfur-containing pollutants onto or into the activated carbon particles.

[0604] In some embodiments, sulfur-containing contaminants include elemental sulfur, sulfuric acid, sulfurous acid, sulfur dioxide, sulfur trioxide, sulfate anion, bisulfate anion, sulfite anion, bisulfite anion, thiols, sulfides, disulfides, polysulfides, thioethers, thioesters, thioacetals, sulfoxides, sulfones, thiosulfinates, sulfimides, sulfoximides, sulfonediimides, sulfur halides, thioketones, thioaldehydes, sulfur oxides, thiocarboxylic acids, thioamides, sulfonic acids, sulfinic acids, hyposulfonic acids, sulfonium, oxosulfonium, thioalkyl, perthioalkyl, or their salts, or their derivatives, or combinations thereof. For example, sulfur-containing contaminants may be sulfates in anionic and / or salt form.

[0605] The liquid may be an aqueous liquid, such as water. In some embodiments, the water is process-related wastewater. In some embodiments, the process includes metal mining, acid mine drainage, mineral processing, municipal sewer treatment, pulp and paper, ethanol, or other industrial processes that can discharge sulfur-containing pollutants into the wastewater. In some embodiments, the water includes natural water bodies, such as lakes, rivers, or streams.

[0606] In one embodiment, this disclosure provides a process for reducing the concentration of sulfate in water, the process comprising:

[0607] (a) Provide activated carbon particles recovered from the second reactor disclosed herein;

[0608] (b) Provide a certain volume of sulfate-containing water flow;

[0609] (c) Providing an additive, the additive being selected to aid in the removal of the sulfate from the water; and

[0610] (d) Contact 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.

[0611] In some embodiments, the sulfate is reduced in water to a concentration of about 50 mg / L or lower, such as to about 10 mg / L or lower. In some embodiments, the sulfate exists primarily in the form of sulfate anions and / or bisulfate anions. Depending on the pH, the sulfate may also exist in the form of sulfate.

[0612] The water may originate from a portion or all of the wastewater stream. Exemplary wastewater streams are those associated with metal mining, acid mine drainage, mineral processing, municipal sewer treatment, pulp and paper, ethanol, or any other industrial process that may discharge sulfur-containing pollutants into the wastewater. The water may be a natural water body, such as a lake, river, or stream. In some embodiments, the process is carried out continuously. In other embodiments, the process is carried out in batches.

[0613] When treating water with activated carbon, the water can be filtered, permeated, and / or activated carbon particles can be added directly to the water (through sedimentation, clarification, etc.). When permeation is used, activated carbon can be used within or assist the permeation apparatus in several ways. In some embodiments, activated carbon particles and additives are introduced directly into the water prior to permeation. Activated carbon particles and additives may optionally be used for pre-filtration prior to permeation. In some embodiments, activated carbon particles and additives are incorporated into a membrane for permeation.

[0614] In some embodiments, activated carbon is effective for removing sulfur-containing contaminants. In some embodiments, sulfur-containing contaminants include elemental sulfur, sulfuric acid, sulfurous acid, sulfur dioxide, sulfur trioxide, sulfate anion, bisulfate anion, sulfite anion, bisulfite anion, thiols, sulfides, disulfides, polysulfides, thioethers, thioesters, thioacetals, sulfoxides, sulfones, thiosulfinates, thioimides, sulfonylimides, sulfonyldiimides, sulfur halides, thiones, thioaldehydes, sulfur oxides, thiocarboxylic acids, thioamides, sulfonic acids, sulfinic acids, hyposulfonic acids, sulfonium, oxosulfonium, thioanes, perthioanes, or their salts, derivatives, or combinations thereof.

[0615] Generally, the disclosed activated carbon can be used in any application where conventional activated carbon can be used. In some embodiments, the activated carbon is used as a total (i.e., 100%) replacement of conventional activated carbon. In some embodiments, the activated carbon comprises essentially all or substantially all of the activated carbon for a particular application. In some embodiments, the activated carbon comprises about 1% to about 100% bio-derived activated carbon.

[0616] For example, but not limited to, activated carbon can be used in filters alone or in combination with conventional activated carbon products. In some embodiments, the packed bed or packed column includes the disclosed activated carbon. In such embodiments, the bio-derived activated carbon includes a size suitable for a particular packed bed or packed column. Injecting bio-derived activated carbon into a gas stream can be used to control emissions of pollutants originating from gas streams 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.

[0617] Use of biochar compositions in the reduction of metal oxides

[0618] Various embodiments exist of feeding biochar pellets or their powdered form, or other biochar compositions disclosed herein, into metal ore furnaces and / or chemical reduction furnaces.

[0619] A metal ore furnace or chemical reduction furnace can be a blast furnace, a top gas recirculation blast furnace, a vertical furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a muffle furnace, a pot furnace, a flash furnace, a Tecnored furnace, an Osmelt furnace, an Isa furnace, a stirring furnace, a live-bottom 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 stirring furnace, a Bessma furnace, a direct metal reduction furnace, or a combination or derivative thereof.

[0620] 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. Solids within the furnace can be located in fixed beds and / or fluidized beds. Metal ore furnaces or chemical reduction furnaces can operate under a wide range of process conditions, including temperatures, pressures, and residence times.

[0621] Some variations of this invention specifically relate to blast furnaces. A blast furnace is a metallurgical furnace used for smelting industrial metals such as iron or copper. Blast furnaces are used to smelt iron ore to produce pig iron, which is an intermediate material used in the production of commercial iron and steel. For example, blast furnaces are also used in conjunction with sintering plants in basic metal smelting.

[0622] "Blast" refers to combustion air forced or supplied at a pressure higher than atmospheric pressure. In a blast furnace, metallic ore, carbon (in this disclosure, a bio-based agent or a derivative thereof), and typically flux (e.g., limestone) are continuously supplied through the top of the furnace, while a stream of hot air (optionally oxygen-enri...

Claims

1. A method for producing a biochar composition, the method comprising: (a) Pyrolyzing a first biomass-containing feedstock to produce a low fixed carbon material and a first pyrolysis exhaust gas, wherein, on an absolute basis, the low fixed carbon material has a first fixed carbon concentration of 10 wt% to 55 wt%; (b) Separate from step (a), pyrolyze the second biomass-containing feedstock to produce a high fixed carbon material and a second pyrolysis exhaust gas, wherein, on an absolute basis, the high fixed carbon material has a second fixed carbon concentration of 50 wt% to 100 wt%, and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration. (c) Blending at least a portion of the low-carbon-fixed material with at least a portion of the high-carbon-fixed material to produce an intermediate material; (d) Blending one or more additives into the intermediate material; (e) Dry the intermediate material; as well as (f) Recover biochar compositions containing the intermediate material or its heat-treated form. Both the low-fixed carbon material and the high-fixed carbon material produced are solids.

2. The method according to claim 1, wherein the first biomass-containing raw material and the second biomass-containing raw material are of the same type.

3. The method according to claim 1, wherein the first biomass-containing raw material and the second biomass-containing raw material are different types of raw materials.

4. The method according to any one of claims 1 to 3, wherein the first biomass-containing raw material is selected from timber logging residues, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, sugarcane stalks, sugar beets, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, grape pumice, grass pellets, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

5. The method according to any one of claims 1 to 3, wherein the second biomass-containing raw material is selected from timber logging residues, corn, corn stalks, wheat, wheat stalks, rice, rice straw, sugarcane, sugarcane stalks, sugar beets, sunflower, sorghum, rapeseed, algae, miscanthus, alfalfa, switchgrass, grape pumice, grass pellets, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

6. The method according to any one of claims 1 to 3, wherein steps (a) and (b) are carried out in different pyrolysis reactors.

7. The method according to any one of claims 1 to 3, wherein steps (a) and (b) are carried out at different times and with different activities in a common pyrolysis reactor.

8. The method according to any one of claims 1 to 3, wherein all of the low fixed carbon materials from step (a) are blended into the intermediate material.

9. The method according to any one of claims 1 to 3, wherein all of the high fixed carbon materials from step (b) are blended into the intermediate material.

10. The method according to any one of claims 1 to 3, wherein step (d) is performed during step (c).

11. The method according to any one of claims 1 to 3, wherein step (d) is performed after step (c).

12. The method according to any one of claims 1 to 3, wherein step (e) is performed during step (c).

13. The method according to any one of claims 1 to 3, wherein step (e) is performed during step (d).

14. The method according to any one of claims 1 to 3, wherein step (e) is performed after step (d).

15. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 1 wt% to 99 wt% of the low fixed carbon material, 1 wt% to 99 wt% of the high fixed carbon material, 0 to 30 wt% of moisture, 0 to 15 wt% of ash, and 0 to 20 wt% of one or more additives.

16. The method according to any one of claims 1 to 3, wherein step (a) is carried out at a first pyrolysis temperature selected from 250°C to 1250°C.

17. The method of claim 16, wherein the first pyrolysis temperature is selected from 300°C to 700°C.

18. The method according to any one of claims 1 to 3, wherein step (b) is carried out at a second pyrolysis temperature selected from 250°C to 1250°C.

19. The method of claim 18, wherein the second pyrolysis temperature is selected from 300°C to 700°C.

20. The method according to any one of claims 1 to 3, wherein step (a) is performed for a first pyrolysis time selected from 10 seconds to 24 hours.

21. The method according to any one of claims 1 to 3, wherein step (b) is performed for a second pyrolysis time selected from 10 seconds to 24 hours.

22. The method according to any one of claims 1 to 3, wherein the first pyrolysis exhaust gas is at least partially oxidized to generate heat.

23. The method of claim 22, wherein the heat is used in the method.

24. The method according to any one of claims 1 to 3, wherein the second pyrolysis waste gas is at least partially oxidized to generate heat.

25. The method of claim 24, wherein the heat is used in the method.

26. The method according to any one of claims 1 to 3, wherein the first pyrolysis exhaust gas is at least partially oxidized to produce a reducing gas comprising hydrogen and / or carbon monoxide.

27. The method according to any one of claims 1 to 3, wherein the second pyrolysis waste gas is at least partially oxidized to produce a reducing gas comprising hydrogen and / or carbon monoxide.

28. The method according to any one of claims 1 to 3, wherein the low fixed carbon material is subjected to a first grinding prior to step (c), and wherein the first grinding utilizes a mechanical processing device selected from: hammer mill, extruder, grinding mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

29. The method according to any one of claims 1 to 3, wherein the high fixed carbon material is subjected to a second grinding prior to step (c), and wherein the second grinding utilizes a mechanical processing device selected from: hammer mill, extruder, grinding mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, or a combination thereof.

30. The method according to any one of claims 1 to 3, wherein step (c) utilizes a mechanical processing device selected from: a hammer mill, an extruder, a grinding mill, a disc mill, a needle mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

31. The method according to any one of claims 1 to 3, wherein the low-carbon-fixed material and the high-carbon-fixed material exist as a homogeneous physical blend in the biochar composition.

32. The method according to any one of claims 1 to 3, wherein the first fixed carbon concentration is uniform throughout the biochar composition.

33. The method according to any one of claims 1 to 3, wherein the second fixed carbon concentration is uniform throughout the biochar composition.

34. The method according to any one of claims 1 to 3, wherein both the first fixed carbon concentration and the second fixed carbon concentration are uniform throughout the biochar composition.

35. The method according to any one of claims 1 to 3, wherein the low-fixed carbon material and the high-fixed carbon material exist as heterogeneous physical blends in the biochar composition.

36. The method according to any one of claims 1 to 3, wherein the low-carbon-fixed material and the high-carbon-fixed material exist as different layers in the biochar composition.

37. The method according to any one of claims 1 to 3, wherein the low fixed carbon material is contained in a shell or coating surrounding a core comprising the high fixed carbon material.

38. The method according to any one of claims 1 to 3, wherein the high-fixed carbon material is contained in a shell or coating surrounding a core comprising the low-fixed carbon material.

39. The method according to any one of claims 1 to 3, wherein the high-fixed carbon material is in the form of particulate matter in the continuous phase of the low-fixed carbon material.

40. The method according to any one of claims 1 to 3, wherein the low-fixed carbon material is in the form of particles in the continuous phase of the high-fixed carbon material.

41. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 10 wt% to 90 wt% of the low-fixed carbon material.

42. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 10 wt% to 90 wt% of the highly fixed carbon material.

43. The method according to any one of claims 1 to 3, wherein the weight ratio of the low fixed carbon material to the high fixed carbon material is selected from 0.1 to 10.

44. The method according to any one of claims 1 to 3, wherein the weight ratio of the low fixed carbon material to the high fixed carbon material is selected from 0.2 to 5.

45. The method according to any one of claims 1 to 3, wherein the weight ratio of the low fixed carbon material to the high fixed carbon material is selected from 0.5 to 2.

46. ​​The method according to any one of claims 1 to 3, wherein the weight ratio of the low fixed carbon material to the high fixed carbon material is selected from 0.8 to 1.

2.

47. The method according to any one of claims 1 to 3, wherein the first fixed carbon concentration is 15 wt% to 40 wt%.

48. The method according to any one of claims 1 to 3, wherein the first fixed carbon concentration is 20 wt% to 50 wt%.

49. The method according to any one of claims 1 to 3, wherein the first fixed carbon concentration is 30 wt% to 55 wt%.

50. The method according to any one of claims 1 to 3, wherein the second fixed carbon concentration is 80 wt% to 100 wt%.

51. The method according to any one of claims 1 to 3, wherein the second fixed carbon concentration is 70 wt% to 95 wt%.

52. The method according to any one of claims 1 to 3, wherein the second fixed carbon concentration is 60 wt% to 90 wt%.

53. The method according to any one of claims 1 to 3, wherein the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is 30 wt% to 90 wt%.

54. The method according to any one of claims 1 to 3, wherein the unweighted average of the first fixed carbon concentration and the second fixed carbon concentration is 40 wt% to 80 wt%.

55. The method according to any one of claims 1 to 3, wherein, on an absolute basis, the biochar composition contains a total fixed carbon concentration of 25 wt% to 95 wt%.

56. The method according to any one of claims 1 to 3, wherein, on an absolute basis, the biochar composition contains a total fixed carbon concentration of 35 wt% to 85 wt%.

57. The method according to any one of claims 1 to 3, wherein, on an absolute basis, the low fixed carbon material contains 45 wt% to 80 wt% volatile carbon.

58. The method according to any one of claims 1 to 3, wherein, on an absolute basis, the high fixed carbon material contains 0 to 50 wt% volatile carbon.

59. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 0.1 wt% to 20 wt% water.

60. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 0.1 wt% to 10 wt% ash.

61. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 0.1 wt% to 10 wt% of the one or more additives.

62. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 1 wt% to 15 wt% of the one or more additives.

63. The method according to any one of claims 1 to 3, wherein the biochar composition comprises 3 wt% to 18 wt% of the one or more additives.

64. The method according to any one of claims 1 to 3, wherein the one or more additives comprise organic additives.

65. The method according to any one of claims 1 to 3, wherein the one or more additives comprise inorganic additives.

66. The method according to any one of claims 1 to 3, wherein the one or more additives comprise renewable materials.

67. The method according to any one of claims 1 to 3, wherein the one or more additives comprise a material capable of being partially oxidized and / or burned.

68. The method according to any one of claims 1 to 3, wherein the one or more additives comprise an adhesive.

69. The method of claim 68, wherein the method utilizes granulation equipment selected from: an extruder, a ring die granulator, a flat die granulator, a roller compactor, a roller briquetting machine, a wet agglomerating mill, a dry agglomerating mill, or a combination thereof.

70. The method of claim 68, wherein the adhesive is selected from starch, cellulose, hemicellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, soybean flour, corn flour, wood flour, coal tar, coal powder, metallurgical coke, asphalt, bentonite, borax, limestone, lime, wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, povidone, polyacrylamide, polylactic acid, phenolic resin, plant resin, recycled shingles, recycled tires, derivatives thereof, or any combination thereof.

71. The method of claim 70, wherein the adhesive is starch.

72. The method of claim 71, wherein the adhesive is a cross-linked thermoplastic starch.

73. The method according to claim 72, wherein the thermoplastic starch is a reaction product of starch and polyol.

74. The method according to claim 73, wherein the polyol is selected from ethylene glycol, propylene glycol, glycerol, butylene glycol, glycerol, erythritol, xylitol, sorbitol, or combinations thereof.

75. The method of claim 73, wherein the reaction product is formed by an acid-catalyzed reaction.

76. The method of claim 75, wherein the acid is selected from formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof.

77. The method of claim 73, wherein the reaction product is formed by a base-catalyzed reaction.

78. The method according to any one of claims 1 to 3, wherein the one or more additives reduce the reactivity of the biochar composition compared to a biochar composition that is otherwise equivalent without the one or more additives.

79. The method of claim 78, wherein the reactivity is thermal reactivity.

80. The method of claim 79, wherein the biochar composition has lower self-heating compared to the otherwise equivalent biochar composition without the one or more of the additives.

81. The method according to claim 78, wherein the reactivity is chemical reactivity with oxygen.

82. The method of claim 78, wherein the reactivity is chemical reactivity with water.

83. The method of claim 78, wherein the reactivity is chemical reactivity with hydrogen.

84. The method of claim 78, wherein the reactivity is chemical reactivity with carbon monoxide.

85. The method of claim 78, wherein the reactivity is chemical reactivity with metals.

86. The method of claim 85, wherein the metal comprises iron.

87. The method according to any one of claims 1 to 3, wherein step (d) is performed, and the one or more additives are pore fillers within the low fixed carbon material.

88. The method according to any one of claims 1 to 3, wherein step (d) is performed, and the one or more additives are pore fillers within the high-fixed carbon material.

89. The method according to any one of claims 1 to 3, wherein step (d) is performed, and the one or more additives are pore fillers within both the low-fixed carbon material and the high-fixed carbon material.

90. The method according to any one of claims 1 to 3, wherein step (d) is performed, and the one or more additives are disposed on the outer surface of the biochar composition.

91. The method according to any one of claims 1 to 3, wherein the biochar composition is in powder form.

92. The method according to any one of claims 1 to 3, wherein the biochar composition is in the form of granules.

93. The method of claim 92, wherein step (d) is performed, and the one or more additives comprise a binder for the granules.

94. The method of claim 92, wherein the agglomerates utilize the low-fixed carbon material as a binder within the agglomerates.

95. The method according to any one of claims 1 to 3, wherein step (d) is performed, and the one or more additives are located within one of the low-fixed carbon material or the high-fixed carbon material.

96. The method according to any one of claims 1 to 3, wherein when a self-heating test is performed according to the Manual of Tests and Standards, 7th Revision 2019, United Nations, page 375, 33.4.6 Test N.4: "Test Method for Self-Heating Substances", the biochar composition is characterized as non-self-heating.

97. The method according to any one of claims 1 to 3, wherein the total carbon in the biochar composition is at least 50% renewable, as determined by measuring the total carbon content. 14 C / 12 Determined by the C isotope ratio.

98. The method according to any one of claims 1 to 3, wherein the total carbon in the biochar composition is at least 90% renewable, as determined by measuring the total carbon content. 14 C / 12 Determined by the C isotope ratio.

99. The method according to any one of claims 1 to 3, wherein the total carbon in the biochar composition is fully renewable, as determined by measuring the total carbon content. 14 C / 12 Determined by the C isotope ratio.

100. A method for producing a biochar composition, the method comprising: (a) Providing a low fixed carbon material, wherein, on an absolute basis, the low fixed carbon material has a first fixed carbon concentration of 10 wt% to 55 wt% of fixed carbon; (b) Separate from step (a), providing a high fixed carbon material, wherein, on an absolute basis, the high fixed carbon material has a second fixed carbon concentration of 50 wt% to 100 wt% fixed carbon, and wherein the second fixed carbon concentration is higher than the first fixed carbon concentration; (c) Blending at least a portion of the low-carbon-fixed material with at least a portion of the high-carbon-fixed material to produce an intermediate material; (d) Blending one or more additives into the intermediate material; (e) Dry the intermediate material; as well as (f) Recover biochar compositions containing the intermediate material or its heat-treated form. Both the low-fixed carbon material and the high-fixed carbon material produced are solids.

101. The method of claim 100, wherein the low fixed carbon material is selected from unpyrolyzed biomass, pyrolyzed biomass, or a combination thereof.

102. The method according to any one of claims 100 or 101, wherein the high fixed carbon material is selected from pyrolytic biomass, coal, coke, activated carbon, carbon black, graphite, or combinations thereof.

103. The method according to any one of claims 100 or 101, wherein the total carbon in said biochar composition is at least 50% renewable, as determined by measuring the total carbon content. 14 C / 12 Determined by the C isotope ratio.

104. The method according to any one of claims 100 or 101, wherein the total carbon in said biochar composition is at least 90% renewable, as determined by measuring the total carbon content. 14 C / 12 Determined by the C isotope ratio.

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