Biocarbon composition having optimized compositional parameters and process for producing same

Abstract

In some variations, the disclosure provides a renewable biocarbon composition comprising 50% to 99% total carbon by weight, characterized by a base-acid ratio selected from 0.1 to 10, an iron-calcium ratio selected from 0.05 to 5, an iron+calcium parameter selected from 5 to 50% by weight, a slagging coefficient selected from 0.001 to 1, and / or a fouling coefficient or modified fouling coefficient selected from 0.1 to 10. Some variations include providing a biomass feedstock, pyrolyzing the biomass feedstock to produce an intermediate biocarbon stream, pyrolyzing the intermediate biocarbon stream with an acid, base, salt, metal, H, or other suitable additives, such as nitrate, ... 2 , H 2 O, CO, CO 2 or a combination thereof, and / or introducing additives in the process to adjust the base-acid ratio or other compositional parameters, and recovering a bio-carbon composition comprising 50% to 99% total carbon by weight and optimized for compositional parameters.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 278,573, filed November 12, 2021, which is incorporated herein by reference in its entirety.

[0002] The present invention generally relates to biocarbon compositions having optimized compositional parameters and processes for producing such biocarbon compositions. [Background technology]

[0003] Biomass is a term used to describe biologically produced or living matter. The chemical energy contained in biomass comes from solar energy using the natural process of photosynthesis, a process in which plants take carbon dioxide and water from their surroundings and convert them into sugars, starch, cellulose, hemicellulose, and lignin using energy from sunlight. Of all renewable energy sources, biomass is unique in that it is effectively stored solar energy. Furthermore, biomass is the only renewable source of carbon.

[0004] Carbonaceous materials generally include fossil resources such as natural gas, petroleum, coal, and lignite, or renewable resources such as lignocellulosic biomass and various carbon-enriched wastes. Due to the rising economic, environmental, and societal costs associated with fossil resources, there is growing interest in using renewable biomass to produce carbon-based reagents.

[0005] There is a need for biocarbon compositions with optimized compositional parameters, and processes for producing the optimized biocarbon compositions. The biocarbon compositional parameters should be optimized for various commercial applications. Summary of the Invention

[0006] In some variations, the present invention provides a biocarbon composition comprising about 50% to about 99% total carbon by weight, wherein the total carbon is 14 C / 12 is at least 50% renewable as determined from C isotope ratio measurements, and the biocarbon composition has the following formula:

number

[0007] In some embodiments, the base-acid ratio is selected from about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the base-acid ratio is at most 0.4 or at least 0.7.

[0008] In some embodiments, the biocarbon compositions are further characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, the iron-calcium ratio being selected from about 0.05 to about 5.

[0009] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12Provided is a biocarbon composition that is at least 50% renewable as determined from C isotope ratio measurements, wherein the biocarbon composition is characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, and the iron-calcium ratio is selected from about 0.05 to about 5.

[0010] In some embodiments, the iron-calcium ratio is selected from about 0.1 to about 2, or from about 0.3 to about 1. In certain embodiments, the iron-calcium ratio is at most 0.3 or at least 3.

[0011] In some embodiments, the biocarbon composition is further characterized by an iron plus calcium parameter, defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the iron plus calcium parameter is selected from about 5% to about 50% by weight.

[0012] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 Provided is a biocarbon composition that is at least 50% renewable as determined from C isotope ratio measurements, wherein the biocarbon composition is characterized by an iron + calcium parameter defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, and the iron + calcium parameter is selected from about 5% by weight to about 50% by weight.

[0013] In some embodiments, the iron + calcium parameter is selected from about 10% to about 40% by weight, or from about 20% to about 50% by weight. In certain embodiments, the iron + calcium parameter is at most 10% by weight. In other embodiments, the iron + calcium parameter is at least 10% by weight.

[0014] In some embodiments, the biocarbon composition is further characterized by a slagging factor, defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, where the base-acid ratio is determined by the following formula:

number

[0015] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 The biocarbon composition is at least 50% renewable as determined from a measurement of C isotope ratio, and the biocarbon composition is characterized by a slagging factor defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, wherein the base-acid ratio satisfies the following formula:

number

[0016] In some embodiments, the slagging factor is selected from about 0.01 to about 0.5, or from about 0.01 to about 0.1, hi certain embodiments, the slagging factor is at most 0.6.

[0017] In some embodiments, the biocarbon composition is further characterized by a fouling factor, defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, where the base-acid ratio is determined by the following formula:

number

[0018] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 and the biocarbon composition is at least 50% renewable as determined from a C isotope ratio measurement, and the biocarbon composition is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the base-acid ratio satisfies the following formula:

number

[0019] In some embodiments, the fouling factor is at most 2. In certain embodiments, the fouling factor is at most 1. Typically, a low fouling factor is desirable. However, in certain embodiments, a moderate or even higher fouling factor is beneficial to form alkali-bonded deposits, such as when fabricating composites containing alkali.

[0020] In some embodiments, the biocarbon composition is further characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble NaO, where water soluble NaO is the weight percentage of NaO leached in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the base-acid ratio is determined by the following formula:

number

[0021] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 and the biocarbon composition is at least 50% renewable as determined from C isotope ratio measurements, and the biocarbon composition is characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble NaO, where water soluble NaO is the weight percentage of NaO that leaches in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the base-acid ratio satisfies the following formula:

number

[0022] In some embodiments, the modified soiling factor is at most 2. In certain embodiments, the modified soiling factor is at most 1.

[0023] In some embodiments, the biocarbon composition is further characterized by a silica percentage, defined as the weight percentage of SiO2 in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. In certain embodiments, the silica percentage is selected from about 10% to about 30% by weight.

[0024] In some embodiments, the biocarbon compositions are further characterized by low mercury content: They may contain at most 100 ppm mercury (ppm = parts per million by weight), or at most 10 ppm mercury, or may be essentially mercury-free.

[0025] In some embodiments, the biocarbon composition is further characterized by an equilibrium moisture content according to ASTM D 1412. The equilibrium moisture can be about 0.1% to about 10% by weight, e.g., about, at least about, or at most about 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 2, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10% by weight, inclusive of all intervening ranges.

[0026] The biocarbon composition can contain from about 50% to about 99% fixed carbon by weight on a dry basis. In some embodiments, the biocarbon composition contains at least about 75% fixed carbon or at least about 90% fixed carbon by weight on a dry basis.

[0027] In some embodiments, the total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 The total carbon in the biocarbon composition can be at least 99% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0028] In some embodiments, the fixed carbon in the biocarbon composition is 14 C / 12 The fixed carbon in the biocarbon composition is at least 80% renewable, as determined by measurements of the C isotope ratio. 14 C / 12 The fixed carbon in the biocarbon composition can be at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It can be at least 95% renewable as determined from C isotope ratio measurements.

[0029] The biocarbon composition may be in the form of pellets. The pellets may include a binder. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof. In some embodiments, the biocarbon pellets do not contain an exogenously added binder.

[0030] The biocarbon composition may be in the form of a powder, which may be a loose powder, a compressed powder, a granulated powder, or other form.

[0031] In some embodiments, the biocarbon composition has the following formula:

number

[0032] Some variations of the invention provide biocarbon compositions comprising about 50% to about 99% total carbon by weight, wherein the total carbon is 14 C / 12 is at least 50% renewable as determined from C isotope ratio measurements, and the biocarbon composition has the following formula:

number

[0033] In some embodiments, the extended base-acid ratio is selected from about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the extended base-acid ratio is at most 0.4 or at least 0.7.

[0034] In some embodiments of biocarbon compositions having an optimized extended base-acid ratio, the biocarbon compositions are characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, selected from about 0.05 to about 5. The iron-calcium ratio can be selected, for example, from about 0.1 to about 2, or from about 0.3 to about 1. In certain embodiments, the iron-calcium ratio is at most 0.3 or at least 3.

[0035] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by an iron + calcium parameter, defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. The iron + calcium parameter can be selected, for example, from about 10% to about 40% by weight, or from about 20% to about 50% by weight. In certain embodiments, the iron + calcium parameter is at most 10% by weight. In other embodiments, the iron + calcium parameter is at least 10% by weight.

[0036] In some embodiments of biocarbon compositions having an optimized enhanced base-acid ratio, the biocarbon composition is characterized by a slagging factor, defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, the slagging factor being selected from about 0.001 to about 1. The slagging factor can be selected, for example, from about 0.01 to about 0.5, or from about 0.01 to about 0.1. In certain embodiments, the slagging factor is at most 0.6.

[0037] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, the fouling factor being selected from about 0.1 to about 10. The fouling factor can be, for example, at most 2 or at most 1.

[0038] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble Na2O, where water soluble Na2O is the weight percentage of Na2O leached in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the modified fouling factor is selected from about 0.1 to about 10. The modified fouling factor can be, for example, at most 2 or at most 1.

[0039] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by a silica percentage, defined as the weight percentage of SiO2 in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. The silica percentage can be selected, for example, from about 10% to about 30% by weight.

[0040] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition may contain at most 100 ppm mercury, or at most 10 ppm mercury, or may be essentially mercury-free.

[0041] In some embodiments of biocarbon compositions having an optimized extended base-acid ratio, the biocarbon composition comprises, on a dry basis, about 50% to about 99% fixed carbon by weight. In certain embodiments, the biocarbon composition comprises, on a dry basis, at least about 75% fixed carbon or at least about 90% fixed carbon by weight.

[0042] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 The total carbon in the biocarbon composition can be at least 99% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0043] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is in the form of pellets. The pellets optionally include a binder.

[0044] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is in the form of a powder, which can be a loose powder, a compacted powder, a granulated powder, or another form of powder.

[0045] Any of the disclosed biocarbon compositions can further include an additive, which can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0046] Some variations of the present invention are directed to a process for producing a biocarbon composition having an optimized base-acid ratio, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, wherein the intermediate biocarbon stream is a carbon-carbon mixture of the following formula:

number

[0047] In some processes, biomass can be softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit husks, The waste material is selected from fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper trimmings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0048] In some embodiments, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0049] In some embodiments, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step performed prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0050] In some embodiments, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0051] In some embodiments, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0052] In some embodiments, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0053] In some processes, step (c) is performed. In some processes, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0054] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0055] In some processes, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0056] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0057] In some processes, the base-acid ratio is optimized to be about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the base-acid ratio is optimized to be at most 0.4 or at least 0.7.

[0058] Some variations of the present invention are directed to a process for producing a biocarbon composition having an optimized extended base-acid ratio, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, wherein the intermediate biocarbon stream is a carbon-carbon mixture of the following formula:

number

[0059] In some processes where the extended base-acid ratio is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0060] In some processes where the extended base-acid ratio is optimized, step (c) utilizes acid water obtained from step (a), from step (b), or from another process step performed prior to step (c). For example, the acid water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0061] In some processes where the extended base-acid ratio is optimized, step (c) selectively removes the acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0062] In some processes where the extended base-acid ratio is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step performed prior to step (c).

[0063] In some processes where the extended base-acid ratio is optimized, step (c) utilizes a steam wash of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize a steam wash of the biocarbon composition.

[0064] In some processes where the extended base-acid ratio is optimized, step (c) is performed. In some processes where the extended base-acid ratio is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0065] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0066] In some processes where the extended base-acid ratio is optimized, the biocarbon composition has a higher calorific value of at least about 25 MJ / kg on a dry basis.

[0067] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization.

[0068] In some processes, the extended base-acid ratio is optimized to be about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the extended base-acid ratio is optimized to be at most 0.4 or at least 0.7.

[0069] In any of the disclosed processes, the biocarbon composition can be characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the iron-calcium ratio of the biocarbon composition is selected from about 0.05 to about 5.

[0070] Some variations include a process for producing a biocarbon composition having an optimized iron-calcium ratio, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, each characterized by an iron-to-calcium ratio, defined as Fe2O3 divided by CaO, as a weight percentage in a biocarbon composition according to ASTM D4326; (c) washing or treating the intermediate biocarbon stream with an acid, a base, a salt, a metal, H2, HO, CO2, CO2, or a combination thereof to adjust the iron-to-calcium ratio, and / or introducing an additive during step (a) or step (b) to adjust the iron-to-calcium ratio; (d) recovering a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12and recovering the biocarbon composition, wherein the iron-calcium ratio is at least 50% renewable as determined from measurements of C isotope ratios, and the iron-calcium ratio of the biocarbon composition is selected from about 0.05 to about 5.

[0071] In some processes in which the iron-calcium ratio is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, KO, or Na2O.

[0072] In some processes in which the iron-to-calcium ratio is optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0073] In some processes in which the iron-calcium ratio is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0074] In some processes in which the iron-calcium ratio is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0075] In some processes where the iron-calcium ratio is optimized, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0076] In some processes where the iron-calcium ratio is optimized, step (c) is performed. In some processes where the iron-calcium ratio is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0077] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0078] In some processes where the iron-calcium ratio is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0079] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization.

[0080] In some processes, the iron + calcium parameter is optimized to be between about 10% and about 40% by weight, or between about 20% and about 50% by weight. In certain embodiments, the iron + calcium parameter is optimized to be at most 10% by weight. In other embodiments, the iron + calcium parameter is optimized to be at least 10% by weight.

[0081] In any of the previously disclosed processes, the biocarbon composition can be characterized by an iron plus calcium parameter defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the iron plus calcium parameter of the biocarbon composition is selected from 5 wt% to about 50 wt%.

[0082] Some variations include a process for producing a biocarbon composition with optimized iron plus calcium parameters, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, the intermediate biocarbon stream being characterized by an iron plus calcium parameter defined as the sum of Fe2O3 and CaO, each as a weight percentage in a biocarbon composition according to ASTM D4326; (c) washing or treating the intermediate biocarbon stream with an acid, a base, a salt, a metal, H2, HO, CO2, CO2, or a combination thereof to adjust the iron plus calcium parameters, and / or introducing an additive during step (a) or step (b) to adjust the iron plus calcium parameters; (d) recovering a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 and recovering the biocarbon composition, wherein the biocarbon composition is at least 50% renewable as determined from a measurement of the C isotope ratio, and the iron plus calcium parameter of the biocarbon composition is selected from 5% by weight to about 50% by weight.

[0083] In some processes where the iron plus calcium parameters are optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, KO, or Na2O.

[0084] In some processes in which the iron plus calcium parameters are optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0085] In some processes where the iron plus calcium parameters are optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0086] In some processes where the iron plus calcium parameters are optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0087] In some processes where the iron plus calcium parameters are optimized, step (c) utilizes a steam wash of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize a steam wash of the biocarbon composition.

[0088] In some processes where iron + calcium parameters are optimized, step (c) is performed. In some processes where iron + calcium parameters are optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0089] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0090] In some processes where the iron plus calcium parameters are optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0091] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization.

[0092] In some processes, the iron + calcium parameter is optimized to be between about 10% and about 40% by weight, or between about 20% and about 50% by weight. In certain embodiments, the iron + calcium parameter is optimized to be at most 10% by weight. In other embodiments, the iron + calcium parameter is optimized to be at least 10% by weight.

[0093] In any of the previously disclosed processes, the biocarbon composition can be characterized by a slagging factor defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, the base-acid ratio being calculated using the following formula:

number

[0094] Some variations include a process for producing a biocarbon composition with an optimized slagging coefficient, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapors, the intermediate biocarbon stream being characterized by a slagging coefficient defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis; The base-acid ratio is determined by the following formula:

number

[0095] In some processes in which the slagging factor is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0096] In some processes in which the slagging factor is optimized, step (c) utilizes acid water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acid water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0097] In some processes in which the slagging factor is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0098] In some processes in which the slagging factor is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0099] In some processes in which the slagging factor is optimized, step (c) utilizes a steam wash of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize a steam wash of the biocarbon composition.

[0100] In some processes where the slugging factor is optimized, step (c) is performed. In some processes where the slugging factor is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0101] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0102] In some processes where the slagging factor is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0103] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization.

[0104] In some processes, the slugging factor is optimized to be between about 0.01 and about 0.5, or between about 0.01 and about 0.1. In certain embodiments, the slugging factor is optimized to be at most 0.6, e.g., about 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.04, 0.03, 0.02, 0.01, 0.005, 0.002, or 0.001, or less.

[0105] In any of the previously disclosed processes, the biocarbon composition can be characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, the base-acid ratio being calculated using the following formula:

number

[0106] Some variations include a process for producing a biocarbon composition with an optimized fouling coefficient, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapors, wherein the intermediate biocarbon stream is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326; The base-acid ratio is determined by the following formula:

number

[0107] In some processes in which the fouling factor is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0108] In some processes where the fouling factor is optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0109] In some processes where the fouling factor is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0110] In some processes where the fouling factor is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0111] In some processes where the fouling factor is optimized, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0112] In some processes where the fouling factor is optimized, step (c) is performed. In some processes where the fouling factor is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0113] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0114] In some processes where the fouling factor is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0115] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization.

[0116] In some processes, the fouling factor is optimized to be at most 2. In certain embodiments, the fouling factor is optimized to be at most 1, such as about 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, or less.

[0117] In any of the previously disclosed processes, the biocarbon composition can be characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble NaO, where water soluble NaO is the weight percentage of NaO leached in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the base-acid ratio is calculated according to the following formula:

number

[0118] Some variations include a process for producing a bio-carbon composition having an optimized modified fouling factor, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapors, wherein the intermediate biocarbon stream is characterized by a modified fouling factor that is a base-acid ratio multiplied by water soluble Na2O, where water soluble Na2O is the weight percentage of Na2O leached in the presence of water from ash derived from a biocarbon composition in accordance with ASTM D4326; The base-acid ratio is determined by the following formula:

number

[0119] In some processes in which the modified fouling factor is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0120] In some processes in which the modified fouling factor is optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0121] In some processes in which the modified fouling factor is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0122] In some processes in which the modified fouling factor is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0123] In some processes in which the modified fouling factor is optimized, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0124] In some processes where the modified fouling factor is optimized, step (c) is performed. In some processes where the modified fouling factor is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0125] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0126] In some processes where the modified fouling factor is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0127] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization.

[0128] In some processes, the modified fouling factor is optimized to be at most 2. In certain embodiments, the modified fouling factor is optimized to be at most 1, such as about 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, or less. [Brief explanation of the drawings]

[0129] [Figure 1] 1 is a photograph of an exemplary biocarbon composition having an optimized base-acid ratio in the form of biocarbon pellets.

[0130] [Figure 2] 1 is a photograph of an exemplary biocarbon composition having an optimized base-acid ratio in the form of a biocarbon powder.

[0131] [Figure 3] 1 is a simplified block flow diagram of a process for converting biomass feedstock into a biocarbon composition with an optimized base-acid ratio, according to some embodiments. Dotted lines indicate optional flows and units.

[0132] [Figure 4] 1 is a simplified block flow diagram of a process for converting biomass feedstock into a biocarbon composition with an optimized increased base-acid ratio, according to some embodiments. Dotted lines indicate optional flows and units.

[0133] [Figure 5] 1 is a data sheet showing the composition, base-acid ratio, and other properties for the biocarbon composition of Example 1.

[0134] [Figure 6] 1 is a data sheet showing the composition, base-acid ratio, and other properties for the biocarbon composition of Example 2.

[0135] [Figure 7] 1 is a data sheet showing the composition, base-acid ratio, and other properties for the biocarbon composition of Example 3.

[0136] [Figure 8]1 is a data sheet showing the composition, base-acid ratio, and other properties for the biocarbon composition of Example 4.

[0137] [Figure 9] 1 is a data sheet showing the composition (from which the base-acid ratio can be calculated) and other properties for the biocarbon composition of Example 5.

[0138] [Figure 10] 1 is a data sheet showing the composition, base-acid ratio, and other properties for the biocarbon composition of Example 6. DETAILED DESCRIPTION OF THE INVENTION

[0139] This description enables one skilled in the art to make and use the invention and describes several embodiments, adaptations, variations, alternatives, and uses of the invention. These and other embodiments, features, and advantages of the invention will become more apparent to those skilled in the art upon review of the following detailed description of the disclosure in conjunction with the accompanying drawings.

[0140] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0141] Unless otherwise indicated, all numbers expressing reaction conditions, stoichiometries, concentrations of ingredients, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending, at least in part, on particular analytical techniques.

[0142] The term "comprising," which is synonymous with "including," "comprising," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. "Comprising" is a term of art used in claim language to mean that a specified claim element is essential, but that other claim elements may be added and still form a construct within the scope of the claim.

[0143] As used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase "consists of" (or variations thereof) appears in a section of the body of a claim rather than immediately following the preamble, the phrase limits only the elements recited in that section and does not exclude other elements from the claim as a whole. As used herein, the phrase "consisting essentially of" limits the scope of the claim to those specified elements or method steps, in addition to those that do not materially affect the basic and novel characteristics of the claimed subject matter.

[0144] For the purpose of enabling technical disclosure, various explanations, hypotheses, theories, speculations, assumptions, etc. are disclosed. The present invention does not depend on any of these being actually true. None of the explanations, hypotheses, theories, speculations, or assumptions in this detailed description should be construed as limiting the scope of the present invention in any way.

[0145] For the present purposes, "biogenic" is intended to mean a material (feedstock, product, or intermediate) that contains elements such as carbon that are renewable on time scales of months, years, or decades. Non-biological materials can be non-renewable or renewable on time scales of centuries, millennia, millions of years, or even longer geological time scales. Biological materials can include a mixture of living and non-biological sources.

[0146] For the present purposes, "reagent" is intended to mean a material in its broadest sense, and a reagent may be a fuel, a chemical, a material, a compound, an additive, a blend component, a solvent, etc. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. In some embodiments, a reagent is a chemical reactant, and in some embodiments, a reagent is consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in adjusting the mechanical, physical, or hydrodynamic properties of a material to which it may be added. For example, a reagent may be introduced into a metal to impart certain strength properties to the metal. A reagent may be a substance of sufficient purity (typically carbon purity in the present context) to be used in chemical analysis or physical testing.

[0147] In this disclosure, a "product" can be, for example, a composition, a material, an object, or a structure. The term "product" is not intended to be limited by its commercial fate, such as whether it is sold, stored, traded, further processed, sold, or the like, to another party as an intermediate for further processing.

[0148] As used herein, "high carbon" as a description of a bioreagent means that the bioreagent has a high carbon content compared to the initial feedstock utilized to generate the high carbon bioreagent. A high carbon bioreagent may contain at least about half of its weight as carbon. More typically, a high carbon bioreagent will contain at least 55%, 60%, 65%, or 70% carbon by weight.

[0149] As used herein, the term "high-carbon bio-reagent" describes, in various embodiments, materials that can be produced by the processes and systems disclosed herein. Any limitations on carbon content or any other concentration are to be implied only by reference to specific embodiments and their equivalents, and not by the term itself. For example, it will be understood that starting materials with very low carbon content that are subjected to the disclosed processes may produce high-carbon bio-reagents that are highly enriched in carbon relative to the starting material (high carbon yield), but that are nevertheless relatively low in carbon (low carbon purity), such as at most 50% carbon by weight.

[0150] Various conversion technologies exist for converting biomass feedstocks into high-carbon materials. Pyrolysis is a process for thermally converting solid materials in the complete absence of oxidizing agents (e.g., air or oxygen) and with a limited supply of oxidizing agents such that no appreciable oxidation occurs. Depending on process conditions and additives, biomass pyrolysis can be adjusted to produce widely varying amounts of gas, liquids, and solids. Lower process temperatures and longer steam residence times favor the production of solids. High temperatures and longer residence times increase biomass conversion to syngas, while moderate temperatures and short steam residence times are generally optimal for producing liquids. Historically, slow pyrolysis of wood has been carried out in large piles in simple batch processes without emission controls. Traditional charcoal production techniques are not only energy inefficient but also highly polluting.

[0151] In many industrial applications, it is desirable to replace coal by providing biocarbon compositions obtained from biomass pyrolysis. Like coal, biocarbon products are rarely pure carbon; many other components, including various metals, are typically present. References to "ash" actually refer to the material remaining after combustion, which itself contains many individual components.

[0152] In this disclosure, a "compositional parameter" is any parameter that is a function of or correlates with biocarbon composition. In some embodiments, the compositional parameter is determined by ASTM D4326 and an equation with input from the ASTM D4326 results.

[0153] The prior art does not teach biocarbon compositions with compositional parameters optimized for specific applications, nor does it teach which compositional parameters may be important for various applications. An important compositional parameter is the base-acid ratio, which is described in more detail below.

[0154] In some variations, the present invention provides a biocarbon composition comprising about 50% to about 99% total carbon by weight, wherein the total carbon is 14 C / 12 is at least 50% renewable as determined from C isotope ratio measurements, and the biocarbon composition has the following formula:

number

[0155] In some embodiments, the base-acid ratio is selected from about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the base-acid ratio is at most 0.4 or at least 0.7.

[0156] It should be noted that the FeO, CaO, MgO, KO, NaO, SiO, AlO, and TiO concentrations are within the ash content after sample combustion according to ASTM D4326-13 "Standard Test Method for Major and Minor Elements by XRF," which is incorporated herein by reference in its entirety and is referred to herein as "ASTM D4326."

[0157] It is not necessary for all of Fe2O3, CaO, MgO, KO, Na2O, SiO2, Al2O3, and TiO2 to be present in the ash of a biocarbon composition, however, to have a non-zero and finite base-acid ratio, there must be detectable amounts (per ASTM D4326) of at least one of Fe2O3, CaO, MgO, KO, Na2O, and at least one of SiO2, Al2O3, and TiO2.

[0158] ASTM D4326 is a test method for analyzing major and minor elements commonly determined in ash from carbon samples using X-ray fluorescence (XRF) techniques. The carbon to be analyzed is ashed under standard conditions and ignited to a constant weight. The previously ashed material is ignited under standard conditions to a constant weight. The ash is fused with lithium tetraborate (Li2B4O7) or other suitable flux, crushed and pressed into pellets, or cast into glass disks. The pellets or disks are then irradiated with a short-wavelength X-ray beam. Characteristic X-rays emitted or fluoresced upon absorption of the primary or incident X-rays are dispersed, and their intensity at selected wavelengths is measured by a highly sensitive detector. The detector output is related to concentration by a calibration curve or computer algorithm. The K spectral line is used for all elements determined by this procedure. All elements are determined as elements and reported as oxides. Elements analyzed include Si, Al, Fe, Ca, Mg, Na, K, P, Ti, Mn, Sr, and Ba. Compositional analysis of ash is used in describing the quality of biocarbon due to its complete characterization. Ash composition is useful for predicting slagging and fouling characteristics, as well as evaluating potential uses in various commercial applications.

[0159] Importantly, the determination of a component in the formula for base-acid ratio by ASTM D4326 does not mean that such component is actually present as a specific oxide in the biocarbon composition, although its presence as a specific oxide is not excluded. For example, in the case of CaO returned from an ASTM D4326 analysis, the final calcium atom may be pure calcium atom (Ca), calcium oxide (CaO), calcium carbonate (CaCO), calcium hydroxide (Ca(OH)), calcium carbide (CaC), calcium hydride (CaH), free or loosely bound calcium cations (Ca 2+ ), ionic cross-linking with other components, etc. 2+), other forms of calcium, or a combination thereof, may have actually been present in the starting biocarbon composition. During the ASTM D4326 testing protocol, Ca may be oxidized to CaO or CaCO3 may be thermally decomposed to CaO.

[0160] Optionally, a separate analysis of the biocarbon composition may be performed to determine the exact atoms and molecules in the biocarbon composition, which may use, for example, atomic absorption spectroscopy, atomic emission spectroscopy, inductively coupled plasma mass spectroscopy, inductively coupled plasma optical emission spectroscopy, or X-ray absorption fine structure spectroscopy.

[0161] In some embodiments, the biocarbon compositions are further characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, the iron-calcium ratio being selected from about 0.05 to about 5.

[0162] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 Provided is a biocarbon composition that is at least 50% renewable as determined from C isotope ratio measurements, wherein the biocarbon composition is characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, and the iron-calcium ratio is selected from about 0.05 to about 5.

[0163] In some embodiments, the iron-calcium ratio is selected from about 0.1 to about 2, or from about 0.3 to about 1. In certain embodiments, the iron-calcium ratio is at most 0.3 or at least 3. In various embodiments, the iron-calcium ratio is about, at least about, or at most about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, or 5, including all intervening ranges.

[0164] In some embodiments, the biocarbon composition is further characterized by an iron + calcium parameter, defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. In various embodiments, the iron + calcium parameter is about, at least about, or at most about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, inclusive of all intervening ranges.

[0165] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 Provided is a biocarbon composition that is at least 50% renewable as determined from C isotope ratio measurements, wherein the biocarbon composition is characterized by an iron + calcium parameter defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, and the iron + calcium parameter is selected from about 5% by weight to about 50% by weight.

[0166] In some embodiments, the iron + calcium parameter is selected from about 10% to about 40% by weight, or from about 20% to about 50% by weight. In certain embodiments, the iron + calcium parameter is at most 10% by weight. In other embodiments, the iron + calcium parameter is at least 10% by weight.

[0167] In some embodiments, the biocarbon composition is further characterized by a slagging factor, defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, where the base-acid ratio is determined by the following formula:

number

[0168] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 The biocarbon composition is at least 50% renewable as determined from a measurement of C isotope ratio, and the biocarbon composition is characterized by a slagging factor defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, wherein the base-acid ratio satisfies the following formula:

number

[0169] In some embodiments, the slugging factor is selected from about 0.01 to about 0.5, or from about 0.01 to about 0.1. In certain embodiments, the slugging factor is at most 0.6. In various embodiments, the slugging factor is about, at least about, or at most about 0.001, 0.002, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 0.95, or 1, inclusive of all intervening ranges.

[0170] In some embodiments, the biocarbon composition is further characterized by a fouling factor, defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, where the base-acid ratio is determined by the following formula:

number

[0171] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 and the biocarbon composition is at least 50% renewable as determined from a C isotope ratio measurement, and the biocarbon composition is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the base-acid ratio satisfies the following formula:

number

[0172] In some embodiments, the fouling factor is at most 2. In certain embodiments, the fouling factor is at most 1. Typically, a low fouling factor is desirable. However, in certain embodiments, a moderate or even higher fouling factor is beneficial to form alkali-bonded deposits, such as when fabricating composites containing alkali. In various embodiments, the fouling factor is about, at least about, or at most about 0.1, 0.2, 0.5, 0.6, 0.7, 0.75, 0.8, 0.85, 0.9, 1, 1.2, 1.5, 1.8, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 9, or 10, including all intervening ranges.

[0173] In some embodiments, the biocarbon composition is further characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble NaO, where water soluble NaO is the weight percentage of NaO leached in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the base-acid ratio is determined by the following formula:

number

[0174] The present invention also provides a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12and the biocarbon composition is at least 50% renewable as determined from C isotope ratio measurements, and the biocarbon composition is characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble NaO, where water soluble NaO is the weight percentage of NaO that leaches in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the base-acid ratio satisfies the following formula:

number

[0175] In some embodiments, the modified soiling factor is at most 2. In certain embodiments, the modified soiling factor is at most 1. In various embodiments, the modified soiling factor is about, at least about, or at most about 0.1, 0.2, 0.5, 0.6, 0.7, 0.75, 0.8, 0.85, 0.9, 1, 1.2, 1.5, 1.8, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 9, or 10, including all intervening ranges.

[0176] In some embodiments, the biocarbon composition is further characterized by an equilibrium moisture content according to ASTM D 1412. The equilibrium moisture can be about 0.1% to about 10% by weight, e.g., about, at least about, or at most about 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 2, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10% by weight, inclusive of all intervening ranges.

[0177] In some embodiments, the biocarbon composition is further characterized by a silica percentage, defined as the weight percentage of SiO2 in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. Note that the silica percentage is the SiO2 concentration in the ash (ashing test per ASTM D4326), not in the original biocarbon composition. In certain embodiments, the silica percentage is selected from about 10% to about 30% by weight. In various embodiments, the silica percentage is about, at least about, or at most about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, inclusive of all intervening ranges.

[0178] In some embodiments, the biocarbon composition is further characterized by low mercury content. The biocarbon composition may contain at most 100 ppm mercury (ppm = parts per million by weight), at most 10 ppm mercury, or be essentially mercury-free. "Essentially mercury-free" means that Hg or Hg-containing compounds are either absolutely zero (absent) or below the detection limit for mercury when a sample is analyzed according to ASTM D6414-14, which is incorporated herein by reference. In various embodiments, the biocarbon composition contains at most about 200, 150, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 4, 3, 2, 1, 0.5, 0.2, or 0.1 ppm mercury.

[0179] The biocarbon composition can contain from about 50% to about 99% fixed carbon by weight on a dry basis. In some embodiments, the biocarbon composition contains at least about 75% fixed carbon or at least about 90% fixed carbon by weight on a dry basis.

[0180] In some embodiments, the total carbon in the biocarbon composition is 14 C / 12The total carbon in the biocarbon composition is at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 The total carbon in the biocarbon composition can be at least 99% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It may be fully renewable, as determined from measurements of C isotope ratios. Note that the total carbon in a biocarbon composition includes not only the carbon derived from cellulose, hemicellulose, and lignin, but also the carbon contained in other components present, such as metal carbonates (e.g., calcium carbonate), if present.

[0181] In some embodiments, the fixed carbon in the biocarbon composition is 14 C / 12 The fixed carbon in the biocarbon composition is at least 80% renewable, as determined by measurements of the C isotope ratio. 14 C / 12 The fixed carbon in the biocarbon composition can be at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It can be at least 95% renewable as determined from C isotope ratio measurements.

[0182] In certain embodiments, the biocarbon composition is in the form of a pellet with a binder, where the binder comprises non-renewable carbon and the remainder of the pellet comprises at least 50%, at least 90%, at least 95%, or 100% renewable carbon.

[0183] The biocarbon composition can be in the form of pellets. Figure 1 is a photograph of an exemplary biocarbon composition with an optimized base-acid ratio in the form of biocarbon pellets.

[0184] In certain embodiments, the biocarbon composition is in the form of pellets with a binder, and the binder comprises carbon that is at least 50%, at least 90%, at least 95%, or 100% renewable carbon. The remainder of the pellets (i.e., not the binder) comprises at least 50%, at least 90%, at least 95%, or 100% renewable carbon. In some embodiments, all of the carbon is fully renewable.

[0185] In certain embodiments, the biocarbon composition includes an additive, where the additive comprises non-renewable carbon, while the remainder of the pellet comprises at least 50%, at least 90%, at least 95%, or 100% renewable carbon.

[0186] In certain embodiments, the biocarbon composition includes an additive, and the additive comprises carbon that is at least 50%, at least 90%, at least 95%, or 100% renewable carbon. The remainder of the composition (i.e., not the additive) comprises at least 50%, at least 90%, at least 95%, or 100% renewable carbon. In some embodiments, all of the carbon is fully renewable.

[0187] In this disclosure, 100% or "fully" renewable carbon allows for very small amounts of adsorbed atmospheric CO2 molecules that may come from fossil fuels.

[0188] The biocarbon composition may be in the form of pellets. The pellets may include a binder. The binder may be starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof. In some embodiments, the biocarbon pellets do not contain an externally added binder.

[0189] If an organic or inorganic binder is present, the base-acid ratio and other compositional parameters are based on the total material including the binder. For example, if the compositional parameters are derived from ASTM D4326, the entire pellet is ashed.

[0190] The biocarbon composition can be in the form of a powder, which can be a loose powder, a compacted powder, a granulated powder, or other form. Figure 2 is a photograph of an exemplary biocarbon composition having an optimized base-acid ratio in the form of a biocarbon powder.

[0191] If there are organic or inorganic additives in the biocarbon composition, the base-acid ratio and other compositional parameters are based on the total material including the additives. For example, if the compositional parameters are derived from ASTM D4326, the entire sample is ashed.

[0192] In some embodiments, the biocarbon composition has the following formula:

number

[0193] Some variations of the invention provide biocarbon compositions comprising about 50% to about 99% total carbon by weight, wherein the total carbon is 14 C / 12 is at least 50% renewable as determined from C isotope ratio measurements, and the biocarbon composition has the following formula:

number

[0194] It is not necessary for all of Fe2O3, CaO, MgO, KO, Na2O, MnO, SrO, BaO, SiO2, Al2O3, TiO2, PO5, and SO3 to be present in the ash of a biocarbon composition. However, to have a non-zero and finite extended base-acid ratio, there must be detectable amounts (per ASTM D4326) of at least one of Fe2O3, CaO, MgO, KO, Na2O, MnO, SrO, BaO, and at least one of SiO2, Al2O3, TiO2, PO5, and SO3.

[0195] In some embodiments, the extended base-acid ratio is selected from about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the extended base-acid ratio is at most 0.4 or at least 0.7.

[0196] In some embodiments of biocarbon compositions having an optimized extended base-acid ratio, the biocarbon compositions are characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, selected from about 0.05 to about 5. The iron-calcium ratio can be selected, for example, from about 0.1 to about 2, or from about 0.3 to about 1. In certain embodiments, the iron-calcium ratio is at most 0.3 or at least 3.

[0197] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by an iron + calcium parameter, defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. The iron + calcium parameter can be selected, for example, from about 10% to about 40% by weight, or from about 20% to about 50% by weight. In certain embodiments, the iron + calcium parameter is at most 10% by weight. In other embodiments, the iron + calcium parameter is at least 10% by weight.

[0198] In some embodiments of biocarbon compositions having an optimized enhanced base-acid ratio, the biocarbon composition is characterized by a slagging factor, defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, the slagging factor being selected from about 0.001 to about 1. The slagging factor can be selected, for example, from about 0.01 to about 0.5, or from about 0.01 to about 0.1. In certain embodiments, the slagging factor is at most 0.6.

[0199] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, the fouling factor being selected from about 0.1 to about 10. The fouling factor can be, for example, at most 2 or at most 1.

[0200] In some embodiments of a biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble Na2O, where water soluble Na2O is the weight percentage of Na2O leached in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the modified fouling factor is selected from about 0.1 to about 10. The modified fouling factor can be, for example, at most 2 or at most 1.

[0201] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is characterized by a silica percentage, defined as the weight percentage of SiO2 in the biocarbon composition according to ASTM D4326, selected from about 5% to about 50% by weight. The silica percentage can be selected, for example, from about 10% to about 30% by weight.

[0202] In some embodiments of biocarbon compositions having an optimized extended base-acid ratio, the biocarbon composition is further characterized by an equilibrium moisture content according to ASTM D 1412. The equilibrium moisture can be from about 0.1% to about 10% by weight, e.g., about, at least about, or at most about 0.1, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 2, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10% by weight, inclusive of all intervening ranges.

[0203] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition contains at most about 100 ppm mercury, at most about 10 ppm mercury, or is essentially mercury-free.

[0204] In some embodiments of biocarbon compositions having an optimized extended base-acid ratio, the biocarbon composition comprises, on a dry basis, about 50% to about 99% fixed carbon by weight. In certain embodiments, the biocarbon composition comprises, on a dry basis, at least about 75% fixed carbon or at least about 90% fixed carbon by weight.

[0205] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the total carbon in the biocarbon composition is 14 C / 12 The total carbon in the biocarbon composition is at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 The total carbon in the biocarbon composition can be at least 99% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It can be determined from measurements of C isotope ratios and is fully reproducible.

[0206] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is in the form of pellets. The pellets optionally include a binder. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof.

[0207] In some embodiments of the biocarbon composition having an optimized extended base-acid ratio, the biocarbon composition is in the form of a powder, which can be a loose powder, a compacted powder, a granulated powder, or another form of powder.

[0208] Any of the disclosed biocarbon compositions may further comprise additives such as, but not limited to, additives selected from calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicates, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or combinations or derivatives thereof.

[0209] When an additive is present, the additive can be selected to adjust any of the compositional parameters disclosed herein (e.g., base-acid ratio, slagging coefficient, etc.). The additive can directly adjust the base-acid ratio, and the additive itself contains one or more of the metals used in the formula for the base-acid ratio. For example, if the additive is pure alumina, the base-acid ratio will be reduced to an extent determined by the concentration of the additive in the biocarbon composition.

[0210] Some variations of the present invention are directed to a process for producing a biocarbon composition having an optimized base-acid ratio, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, wherein the intermediate biocarbon stream is a carbon-carbon mixture of the following formula:

number

[0211] 3 is a simplified block flow diagram of a process for converting biomass feedstock into a biocarbon composition with an optimized base-acid ratio, according to some embodiments. Dotted lines indicate optional flows and units.

[0212] In some processes, biomass can be softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper trimmings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations or derivatives thereof.

[0213] In some embodiments, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0214] In some embodiments, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step performed prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0215] In some embodiments, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0216] In some embodiments, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0217] In some embodiments, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0218] In some processes, the intermediate biocarbon stream is washed or treated with an acid, a base, a salt, a metal, H2, HO, CO2, CO2, or a combination thereof. In some processes, an additive is introduced during step (a) or step (b). In certain processes, both of these options are used, i.e., the intermediate biocarbon stream is washed or treated with an acid, a base, a salt, a metal, H2, HO, CO2, CO2, or a combination thereof, and an additive (excluding any components from the washing or treatment) is introduced during step (a) or step (b).

[0219] In step (c), the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0220] When treating the intermediate biocarbon stream with H2, HO, CO2, CO2, or a combination thereof, the chemical reaction to adjust the base-acid ratio may add hydrogen, oxygen, and / or carbon to one or more metals present in the intermediate biocarbon stream. Alternatively, or additionally, treatment with H2, HO, CO2, CO2, or a combination thereof may remove hydrogen, oxygen, and / or carbon from one or more metals present in the intermediate biocarbon stream. It will be recognized that treatment with H2, HO, CO2, and / or CO2 does not necessarily change the base-acid ratio, even if the actual form of the metal is altered, due to the ashing protocol of ASTM D4326. However, if treatment with H2, HO, CO2, and / or CO2 is followed by removal of a portion of the intermediate biocarbon stream, the base-acid ratio may be adjusted. For example, liquid water or compressed CO2 may be used to wash the intermediate biocarbon stream, changing the base-acid ratio, for example, depending on the pH of the liquid. In certain embodiments, treatment with H, H0, CO, and / or CO creates compounds that are more or less susceptible to forming ash under the ASTM D4326 test, where the base-acid ratio is adjusted.

[0221] In some processes, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0222] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof.

[0223] In some processes, the base-acid ratio is optimized to be about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the base-acid ratio is optimized to be at most 0.4 or at least 0.7.

[0224] Some variations of the present invention are directed to a process for producing a biocarbon composition having an optimized extended base-acid ratio, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, wherein the intermediate biocarbon stream is a carbon-carbon mixture of the following formula:

number

[0225] 4 is a simplified block flow diagram of a process for converting biomass feedstock into a biocarbon composition with an optimized increased base-acid ratio, according to some embodiments. Dotted lines indicate optional flows and units.

[0226] In some processes where the enhanced base-acid ratio is optimized, the biomass can be softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit. , fruit shells, fruit stems, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper trimmings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations or derivatives thereof.

[0227] In some processes where the extended base-acid ratio is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0228] In some processes where the extended base-acid ratio is optimized, step (c) utilizes acid water obtained from step (a), from step (b), or from another process step performed prior to step (c). For example, the acid water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0229] In some processes where the extended base-acid ratio is optimized, step (c) selectively removes the acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0230] In some processes where the extended base-acid ratio is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step performed prior to step (c).

[0231] In some processes where the extended base-acid ratio is optimized, step (c) utilizes a steam wash of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize a steam wash of the biocarbon composition.

[0232] In some processes where the extended base-acid ratio is optimized, step (c) is performed. In some processes where the extended base-acid ratio is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0233] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0234] In some processes where the extended base-acid ratio is optimized, the biocarbon composition has a higher calorific value of at least about 25 MJ / kg on a dry basis.

[0235] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0236] In some processes, the extended base-acid ratio is optimized to be about 0.1 to about 0.4, or about 0.5 to about 10, or about 0.8 to about 10, or about 1.5 to about 5, or about 0.4 to about 0.7. In certain embodiments, the extended base-acid ratio is optimized to be at most 0.4 or at least 0.7.

[0237] In any of the previously disclosed processes, the biocarbon composition can be characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the iron-calcium ratio of the biocarbon composition is selected from about 0.05 to about 5.

[0238] Some variations include a process for producing a biocarbon composition having an optimized iron-calcium ratio, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, each characterized by an iron-to-calcium ratio, defined as Fe2O3 divided by CaO, as a weight percentage in a biocarbon composition according to ASTM D4326; (c) washing or treating the intermediate biocarbon stream with an acid, a base, a salt, a metal, H2, HO, CO2, CO2, or a combination thereof to adjust the iron-to-calcium ratio, and / or introducing an additive during step (a) or step (b) to adjust the iron-to-calcium ratio; (d) recovering a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 and recovering the biocarbon composition, wherein the iron-calcium ratio is at least 50% renewable as determined from measurements of C isotope ratios, and the iron-calcium ratio of the biocarbon composition is selected from about 0.05 to about 5.

[0239] In some processes in which the iron-calcium ratio is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, KO, or Na2O.

[0240] In some processes in which the iron-to-calcium ratio is optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0241] In some processes in which the iron-calcium ratio is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0242] In some processes in which the iron-calcium ratio is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0243] In some processes where the iron-calcium ratio is optimized, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0244] In some processes where the iron-calcium ratio is optimized, step (c) is performed. In some processes where the iron-calcium ratio is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0245] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0246] In some processes where the iron-calcium ratio is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0247] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0248] In some processes, the iron + calcium parameter is optimized to be between about 10% and about 40% by weight, or between about 20% and about 50% by weight. In certain embodiments, the iron + calcium parameter is optimized to be at most 10% by weight. In other embodiments, the iron + calcium parameter is optimized to be at least 10% by weight.

[0249] In any of the previously disclosed processes, the biocarbon composition can be characterized by an iron plus calcium parameter defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biocarbon composition according to ASTM D4326, wherein the iron plus calcium parameter of the biocarbon composition is selected from 5 wt% to about 50 wt%.

[0250] Some variations include a process for producing a biocarbon composition with optimized iron plus calcium parameters, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor, the intermediate biocarbon stream being characterized by an iron plus calcium parameter defined as the sum of Fe2O3 and CaO, each as a weight percentage in a biocarbon composition according to ASTM D4326; (c) washing or treating the intermediate biocarbon stream with an acid, a base, a salt, a metal, H2, HO, CO2, CO2, or a combination thereof to adjust the iron plus calcium parameters, and / or introducing an additive during step (a) or step (b) to adjust the iron plus calcium parameters; (d) recovering a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is 14 C / 12 and recovering the biocarbon composition, wherein the biocarbon composition is at least 50% renewable as determined from a measurement of the C isotope ratio, and the iron plus calcium parameter of the biocarbon composition is selected from 5% by weight to about 50% by weight.

[0251] In some processes where the iron plus calcium parameters are optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, KO, or Na2O.

[0252] In some processes in which the iron plus calcium parameters are optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0253] In some processes where the iron plus calcium parameters are optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0254] In some processes where the iron plus calcium parameters are optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0255] In some processes where the iron plus calcium parameters are optimized, step (c) utilizes a steam wash of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize a steam wash of the biocarbon composition.

[0256] In some processes where iron + calcium parameters are optimized, step (c) is performed. In some processes where iron + calcium parameters are optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0257] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0258] In some processes where the iron plus calcium parameters are optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0259] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0260] In some processes, the iron + calcium parameter is optimized to be between about 10% and about 40% by weight, or between about 20% and about 50% by weight. In certain embodiments, the iron + calcium parameter is optimized to be at most 10% by weight. In other embodiments, the iron + calcium parameter is optimized to be at least 10% by weight.

[0261] In any of the previously disclosed processes, the biocarbon composition can be characterized by a slagging factor defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, the base-acid ratio being calculated using the following formula:

number

[0262] Some variations include a process for producing a biocarbon composition with an optimized slagging coefficient, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapors, the intermediate biocarbon stream being characterized by a slagging coefficient defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis; The base-acid ratio is determined by the following formula:

number

[0263] In some processes in which the slagging factor is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0264] In some processes in which the slagging factor is optimized, step (c) utilizes acid water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acid water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0265] In some processes in which the slagging factor is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0266] In some processes in which the slagging factor is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0267] In some processes in which the slagging factor is optimized, step (c) utilizes a steam wash of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize a steam wash of the biocarbon composition.

[0268] In some processes where the slugging factor is optimized, step (c) is performed. In some processes where the slugging factor is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0269] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0270] In some processes where the slagging factor is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0271] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0272] In some processes, the slugging factor is optimized to be between about 0.01 and about 0.5, or between about 0.01 and about 0.1, and in certain embodiments, the slugging factor is optimized to be at most 0.6.

[0273] In any of the previously disclosed processes, the biocarbon composition can be characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326, the base-acid ratio being calculated using the following formula:

number

[0274] Some variations include a process for producing a biocarbon composition with an optimized fouling coefficient, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapors, wherein the intermediate biocarbon stream is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biocarbon composition according to ASTM D4326; The base-acid ratio is determined by the following formula:

number

[0275] In some processes in which the fouling factor is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0276] In some processes where the fouling factor is optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0277] In some processes where the fouling factor is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0278] In some processes where the fouling factor is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0279] In some processes where the fouling factor is optimized, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0280] In some processes where the fouling factor is optimized, step (c) is performed. In some processes where the fouling factor is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0281] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0282] In some processes where the fouling factor is optimized, the biocarbon composition has a higher heating value of at least about 25, 26, 27, 28, 29, 30, 31, 32, or 33 MJ / kg on a dry basis.

[0283] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0284] In some processes, the fouling factor is optimized to be at most 2. In one particular embodiment, the fouling factor is optimized to be at most 1.

[0285] In any of the previously disclosed processes, the biocarbon composition can be characterized by a modified fouling factor defined as the base-acid ratio multiplied by water soluble NaO, where water soluble NaO is the weight percentage of NaO leached in the presence of water from ash derived from the biocarbon composition according to ASTM D4326, and the base-acid ratio is calculated according to the following formula:

number

[0286] Some variations include a process for producing a bio-carbon composition having an optimized modified fouling factor, the process comprising: (a) providing a starting material comprising biomass, the starting material optionally being dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapors, wherein the intermediate biocarbon stream is characterized by a modified fouling factor that is a base-acid ratio multiplied by water soluble Na2O, where water soluble Na2O is the weight percentage of Na2O leached in the presence of water from ash derived from a biocarbon composition in accordance with ASTM D4326; The base-acid ratio is determined by the following formula:

number

[0287] In some processes in which the modified fouling factor is optimized, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, K2O, or Na2O.

[0288] In some processes in which the modified fouling factor is optimized, step (c) utilizes acidic water obtained from step (a), from step (b), or from another process step that occurs prior to step (c). For example, the acidic water can be obtained from the condensation of pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

[0289] In some processes in which the modified fouling factor is optimized, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, or TiO2.

[0290] In some processes in which the modified fouling factor is optimized, step (c) utilizes alkaline water obtained from step (a), from step (b), or from another process step that occurs prior to step (c).

[0291] In some processes in which the modified fouling factor is optimized, step (c) utilizes steam washing of the intermediate biocarbon stream. Alternatively or additionally, step (d) can utilize steam washing of the biocarbon composition.

[0292] In some processes where the modified fouling factor is optimized, step (c) is performed. In some processes where the modified fouling factor is optimized, step (d) is performed. In certain processes, both steps (c) and (d) are performed.

[0293] When step (d) is used, the additive can be calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

[0294] In some processes where the modified fouling factor is optimized, the biocarbon composition has a higher heating value of at least about 25 MJ / kg on a dry basis.

[0295] The biocarbon composition can be pelletized to produce biocarbon pellets. A binder can be utilized to aid in the pelletization. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof.

[0296] In some processes, the modified fouling factor is optimized to be at most 2. In one particular embodiment, the modified fouling factor is optimized to be at most 1.

[0297] Any of the processes disclosed herein may be optimized to achieve preselected values ​​or ranges for the compositional parameters previously discussed. Any discussion of properties for biocarbon compositions is incorporated by reference herein in each instance of the process discussion.

[0298] A process can be optimized to target a single compositional parameter (e.g., base-acid ratio) or more than one compositional parameter, e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more. It will be recognized that there is some covariance between certain compositional parameters, so optimizing one will affect the others. For example, optimizing the base-acid ratio to achieve a selected value will affect the extended base-acid ratio, since many of the coefficients are the same (Fe2O3, SiO2, etc.). Another example is the fouling coefficient, which is a linear function of the base-acid ratio, meaning that a change in the base-acid ratio will cause a change in the fouling coefficient unless Na2O is adjusted in the other direction.

[0299] As will be appreciated by those skilled in the art, various process optimization methodologies can be implemented, including, but not limited to, linear optimization, non-linear optimization, weighted optimization where certain compositional parameters are designated as more important, design and analysis of experiments, statistical process control, artificial intelligence, machine learning, and other techniques.

[0300] In some embodiments, compositional parameters are preselected based on the intended use of the biocarbon composition. The process for making the biocarbon composition is then optimized using process controls to achieve the preselected compositional parameters within predetermined tolerances. Process optimization can utilize results from previous experiments or production campaigns, simulations, calculations, and analyses. For example, if the preselected base-acid ratio is 2.2, the process can be designed using cleaning treatments or additives (or both) to target a continuous base-acid ratio setpoint of 2.2 ± 0.2 (with a tolerance of approximately 10%). The controlled base-acid ratio can be biased so that higher values ​​are tolerated more than lower values; for example, the process can be designed using cleaning treatments or additives (or both) to target a continuous base-acid ratio setpoint of 2.2 + 0.4 / - 0.1. In the present disclosure, compositional parameters can be "preselected" if such parameters are selected to optimize the process to actually achieve the setpoint via process control. Process control can also employ process control principles such as feedback loops and proportional-integral-differential logic programs.

[0301] The intended uses of biocarbon compositions can vary widely, such as solid fuel, solid gasifier feedstock, metallurgical process input (for energy, reduction chemistry, or carbon content), agricultural carbon, activated carbon, electrodes, batteries (e.g., lithium-ion batteries), carbon composites, and carbon precursors for other materials. If the biocarbon composition is ultimately to be combusted or oxidized for energy production or as part of a metal fabrication process, compositional parameters can be optimized to avoid problems such as slagging and fouling in reactors, for example, by using a relatively low base-acid ratio, slagging coefficient, and / or fouling coefficient. If the biocarbon composition is used as a filtration medium to remove acidic components, compositional parameters can be optimized to enhance acid neutralization, for example, by using a relatively high base-acid ratio and, consequently, a relatively high value for any parameter that is a linear function of the base-acid ratio (e.g., fouling coefficient). When the biocarbon composition is used as a reducing agent in a metals production process, the composition parameters can be optimized to balance the acid and base content to achieve a desired pH for reduction chemistry, such as the production of Fe from FeO, for example, by using a moderate base-acid ratio. When the biocarbon composition is used as agricultural carbon, the composition parameters can be optimized to consider the soil in which the carbon is placed to select the base-acid ratio and other parameters.

[0302] Some embodiments relate to the combustion of biocarbon compositions. When a biocarbon composition is combusted to convert C and O (usually from air) to CO and HO, metal oxides (and sometimes pure metals) are left behind unless the starting biocarbon composition essentially contains pure carbon. The residual metal oxides and other non-combustible components form what is commonly referred to as ash. The initial biomass feedstock may contain metals that oxidize to metal oxides during oxidation with air or oxygen, or the initial biomass feedstock may contain metal oxides that are not further oxidized during carbon oxidation. For example, in the case of silicon, Si may exist in the biomass feedstock as pure Si, as silica (SiO), and / or as various other compounds, such as silicic acid (silicon bonded to oxides and hydroxyl groups).

[0303] During combustion of biocarbon compositions in a reactor, fine particle ash that rises with the flue gas is called fly ash or flue ash, while heavier ash that does not rise is called bottom ash. Ash that neither rises nor falls but accumulates on the reactor walls or other heat transfer surfaces poses significant problems. Slagging is the accumulation of molten ash, which may be accompanied by partially molten deposits, on the walls of a furnace, gasifier, or boiler. Slagging is harmful because it reduces the heat transfer necessary for steam generation. Fouling is the accumulation of solid ash on heat transfer surfaces, which may be, for example, reactor walls or the reheater / superheater area of ​​a boiler. Clean boiler tube surfaces provide maximum heat transfer for steam generation and, consequently, power generation in a power plant. Both slagging and fouling reduce the effectiveness of the combustion process to generate energy / electricity.

[0304] In some embodiments relating to the use of a biocarbon composition as a coal replacement product for the production of steam or electricity, the base-acid ratio is adjusted to be about 0.1 to about 1.5, including any intervening range (e.g., 0.4 to 0.7), such as about, at least about, or at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5.

[0305] In some embodiments relating to the use of a biocarbon composition as a coal replacement product for the production of steam or electricity, the extended base-acid ratio is adjusted to be about 0.05 to about 1.2, e.g., about, at least about, or at most about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, or 1.2, including any intervening range.

[0306] In some embodiments relating to the use of a biocarbon composition as a coal replacement product for the production of steam or electricity, the fouling coefficient and / or modified fouling coefficient is about or less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, inclusive of all intervening ranges. In some embodiments relating to the use of a biocarbon composition as a coal replacement product for the production of steam or electricity, the slagging coefficient is about, at least about, or at most about 0.001, 0.002, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 0.95, or 1, inclusive of all intervening ranges.

[0307] Some embodiments relate to the gasification of biocarbon compositions to produce syngas (CO and H) rather than the sole combustion products (CO and H0). The slag and fouling problems that can occur during combustion can also occur during gasification. In the gasifier, the carbon in the biocarbon composition is converted to syngas, and the minerals in the biocarbon composition are converted to ash. Most of the ash melts, deposits on the walls of the gasifier (i.e., refractory or membrane), and forms a liquid slag that flows out the bottom of the gasifier. For example, in an entrained-flow gasifier for an integrated gasification combined cycle (IGCC) plant, most of the minerals convert to liquid slag on the walls of the gasifier and flow out the bottom, where it is typically solidified in a water bath. The accumulation of slag in the gasifier reduces syngas production. Additionally, a small portion of the minerals is entrained as fly ash with the crude syngas from the gasifier to downstream processing. This molten / sticky fly ash can cause fouling of the syngas cooler, which can also cause problematic plugging of the slurry feed to the IGCC plant. Other concerns with ash slagging and fouling in gasification include large amounts of unconverted carbon from the gasifier and material failure of the refractory lining within the gasifier.

[0308] In some embodiments relating to the use of a biocarbon composition for gasification, the base-acid ratio is adjusted to be about 0.1 to about 2.0, including any intervening range (e.g., 0.5 to 1.5), such as about, at least about, or at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.

[0309] In some embodiments relating to the use of a biocarbon composition for gasification, the extended base-acid ratio is adjusted to be about 0.05 to about 1.6, including any intervening range, such as about, at least about, or at most about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, or 1.6.

[0310] In some embodiments relating to the use of a biocarbon composition for gasification, the fouling coefficient and / or modified fouling coefficient is about or less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, inclusive of all intervening ranges. In some embodiments relating to the use of a biocarbon composition for gasification, the slagging coefficient is about, at least about, or at most about 0.001, 0.002, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 0.95, or 1, inclusive of all intervening ranges.

[0311] Some embodiments relate to the use of biocarbon compositions as metallurgical carbon to produce metals or reduced metal oxides. The optimal base-acid ratio (and extended base-acid ratio) for metallurgical carbon may depend on the particular metal or metal alloy being produced and the raw material (metal ore) composition.

[0312] The optimal base-acid ratio (and extended base-acid ratio) for metallurgical carbon may also depend on the nature of the slag produced during metallurgical processing. In this context, it should be noted that there may be slag derived from the starting metal ore and slag derived from a biocarbon composition. In metallurgical processes, the slag components are typically thoroughly mixed to form a single slag. To distinguish between slag sources, reference may be made to metal ore slags and biocarbon composition slags. Many metal ore slags can be described as either basic slags, as is typical in iron and steelmaking, or acidic slags, as is typical in non-ferrous smelting. If the metal ore slag tends to be acidic, a higher base-acid ratio for metallurgical biocarbon is preferred, such that biocarbon composition slags are comparable to acidic metal ore slags. If the metal ore slag tends to be basic, a lower base-acid ratio for metallurgical biocarbon is preferred, such that biocarbon composition slags are comparable to basic metal ore slags. For example, many iron ores contain FeO, which is melted into a metal ore slag. x It contains significant amounts of SiO2 and Al2O3 with iron oxides. An optimized base-acid ratio can counteract these acidic components.

[0313] In some embodiments relating to the use of the biocarbon composition as metallurgical carbon in the production of iron or iron alloys, the base-acid ratio is adjusted to be about 0.1 to about 10, e.g., about, at least about, or at most about 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10, including any intervening range (e.g., 0.5 to 3).

[0314] In some embodiments relating to the use of the biocarbon composition as a metallurgical carbon in the production of iron or iron alloys, the extended base-acid ratio is adjusted to be from about 0.05 to about 8, e.g., about, at least about, or at most about 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 8, including any intervening range.

[0315] In some embodiments relating to the use of biocarbon compositions as metallurgical carbon in the production of non-ferrous alloys, the base-acid ratio is adjusted to be about 0.1 to about 10, e.g., about, at least about, or at most about 0.2, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, or 10, including any intervening range (e.g., 1.5 to 6).

[0316] In some embodiments relating to the use of biocarbon compositions as metallurgical carbon in the production of non-ferrous alloys, the extended base-acid ratio is adjusted to be from about 0.05 to about 8, e.g., about, at least about, or at most about 0.1, 0.2, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, or 8, including any intervening range.

[0317] In some embodiments relating to the use of the biocarbon composition as metallurgical carbon in the production of iron, iron alloys, or non-ferrous alloys, the fouling factor and / or modified fouling factor is about or less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1, inclusive of all intervening ranges. In some embodiments relating to the use of the biocarbon composition as metallurgical carbon in the production of iron, iron alloys, or non-ferrous alloys, the slagging factor is about, at least about, or at most about 0.001, 0.002, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 0.95, or 1, inclusive of all intervening ranges.

[0318] Some embodiments relate to the use of biocarbon compositions as agricultural carbon. Agricultural carbon includes use in various agricultural media, such as soil, soilless media, or hydroponic media. For various uses of biocarbon compositions as agricultural carbon, see U.S. Patent No. 10,640,429, which is incorporated herein by reference.

[0319] For agricultural carbon applications, the base-acid ratio of the biocarbon composition can be adjusted to control the pH in the desired medium. For example, a soil pH below about 5.6 is considered low for most crops. Generally, the ideal soil pH range is 6.0 to 7.0. Most plant nutrients reach their peak availability at a near-neutral soil pH.

[0320] In some embodiments relating to the use of a biocarbon composition as an agricultural carbon, the base-acid ratio is adjusted to be about 0.5 to about 2.0, including any intervening range (e.g., 0.8 to 1.2), such as about, at least about, or at most about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.

[0321] In some embodiments relating to the use of biocarbon compositions as agricultural carbon, the extended base-acid ratio is adjusted to be about 0.25 to about 1.6, e.g., about, at least about, or at most about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, or 1.6, including any intervening range.

[0322] In certain embodiments, the base-acid ratio (or extended base-acid ratio) is selected in conjunction with the selection of additives intended to be added to the agricultural medium when the biocarbon composition is incorporated into the agricultural medium. In these embodiments, the additive (e.g., ammonia) will not necessarily be present in the biocarbon composition itself, but will be present in the agricultural medium along with the biocarbon composition.

[0323] Some embodiments relate to the use of biocarbon compositions in battery electrodes. The use of carbon in battery electrodes, such as in lithium-ion batteries, is well known. See Togonon et al., "Pure carbon-based electrodes for metal-ion batteries," Carbon Trends 3, 100035, 2021, which is incorporated herein by reference. Biocarbon compositions can be used as conductive additives in electrodes or as Li-ion electrodes in lithium-ion batteries. + The base-acid ratio of the biocarbon composition for use as or in a battery electrode (anode or cathode) can be selected based on the active metal ions in the battery, as well as other materials present in the electrode.

[0324] In some embodiments relating to the use of biocarbon compositions in battery electrodes, the base-acid ratio is adjusted to be about 0.2 to about 2.0, including any intervening range (e.g., 0.4 to 1.5), such as about, at least about, or at most about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.

[0325] In some embodiments relating to the use of biocarbon compositions in battery electrodes, the extended base-acid ratio is adjusted to be about 0.1 to about 1.6, including any intervening range, such as about, at least about, or at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, or 1.6.

[0326] Some embodiments relate to the use of a biocarbon composition as an activated carbon or as a precursor to making activated carbon. The base-acid ratio of a biocarbon composition for use as activated carbon can be selected based on the components to be removed via adsorption onto the activated carbon, such as, for example, whether the components are acidic, basic, or neutral pH.

[0327] In some embodiments relating to the use of a biocarbon composition as activated carbon or as a precursor to making activated carbon, the base-acid ratio is adjusted to be about 0.2 to about 2.0, including any intervening range (e.g., 0.8 to 1.7), such as about, at least about, or at most about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.

[0328] In some embodiments relating to the use of a biocarbon composition as activated carbon or as a precursor to making activated carbon, the extended base-acid ratio is adjusted to be about 0.1 to about 1.6, including any intervening range, such as about, at least about, or at most about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, or 1.6.

[0329] In some embodiments, an acidic water wash is utilized to optimize compositional parameters. Biocarbon is produced by a non-combustion thermal process (typically pyrolysis) that converts starting biomass into biochar, gas, steam, or liquid. The process can be configured so that both the water that comes with the starting feedstock and the water that is produced during the pyrolysis reaction are utilized in a manner that replaces some or all of the need for an external source of water.

[0330] In some variations, the process for producing the biocarbon composition comprises: (a) providing a starting material comprising biomass and about 0% to about 75% by weight of water; (b) drying the starting material to produce a dry material containing 0% to about 50% water by weight, and a first steam; (c) pyrolyzing the dry feedstock to produce a high temperature solid and a second vapor; (d) condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of about 1 to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of about 1 to about 7; (f) forming an acidic water containing at least a portion of the first condensed liquid, at least a portion of the second condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solids using at least a portion of the acidic water to produce washed cooled solids, wherein at least one compositional parameter is adjusted; (h) recovering the washed, cooled solids as a biocarbon composition comprising at least about 50% carbon by weight.

[0331] In some embodiments, the dry ingredients contain from 0% to about 25% water by weight. In various embodiments, the dry ingredients contain at most about 10% water by weight.

[0332] Process step (b) can utilize, for example, a steam-driven dryer or an air-driven dryer.

[0333] The produced vapor from the dryer, which comprises primarily water and light acids, is condensed from the dryer flue gas stream in step (d).

[0334] The acidity of the first condensed liquid can vary depending on the dryer operating conditions and the type of feedstock. In more severe dryer environments, non-water components will tend to outgas from the feed, allowing them to collect during condensation.

[0335] In some embodiments, the first pH is, for example, about 2 to about 7, or about 3 to about 6.5, or about 4 to about 6.5. In some embodiments, the second pH is, for example, about 2 to about 7, or about 3 to about 6.5, or about 4 to about 6.5. In some embodiments, the first pH is at most 7 and the second pH is at most 7. In other embodiments, the first pH is at most 7 and the second pH is about 7. In other embodiments, the second pH is at most 7 and the first pH is about 7.

[0336] In some embodiments, in step (f), the acidic water comprises only the first condensed liquid. In other embodiments, in step (f), the acidic water comprises only the second condensed liquid. In still other embodiments, in step (f), the acidic water comprises both the first condensed liquid and the second condensed liquid. The acidic water may comprise some or all of the first condensed liquid and some or all of the second condensed liquid. In certain embodiments, the acidic water comprises all of the first condensed liquid and all of the second condensed liquid. When the acidic water comprises a combination of the first condensed liquid and the second condensed liquid, the pH of the combined acidic water will be the logarithmic average of the pH of each condensed liquid.

[0337] The acidic water in step (f) can be formed in an amount of about 1 to about 500 gallons per dry metric ton of starting material, for example, about 50 to about 100 gallons per dry metric ton of starting material (depending on the original moisture content of the feed).

[0338] In some embodiments, a portion of the acidic water produced in step (f) is not used in step (g) and is recovered as a water co-product that is sold or transported to another party.

[0339] In some embodiments, no other water source (e.g., well water) is used to wash or cool the hot solids during step (g).

[0340] In some embodiments, in step (g), the hot solid is initially at a substrate temperature of about 300°C to about 800°C, and the acidic water cools the hot solid to a cooled substrate temperature below the substrate temperature. The cooled substrate temperature can be, for example, at most 300°C, at most 200°C, at most 100°C, at most 50°C, or about 20-30°C.

[0341] In some embodiments, washing in step (g) removes ash from the hot solids, which may generally contain high levels of ash (e.g., up to 50% ash by weight). The washed, cooled solids may contain, for example, at most about 5% total ash by weight, at most about 1% total ash by weight, or at most about 0.2% total ash by weight. The degree of ash reduction in step (g) may be, for example, at least about 25%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%.

[0342] In some embodiments, washing in step (g) removes impurities from the hot solid, including iron, aluminum, titanium, boron, silicon, calcium, potassium, zinc, lead, cadmium, manganese, chromium, arsenic, mercury, nickel, cobalt, copper, tin, antimony, vanadium, molybdenum, oxides of any of these elements, or combinations or derivatives thereof. The compositional parameters adjusted in the process can be individual concentrations, such as chromium content, or can be a function of multiple components either naturally present in the biocarbon composition or present in the ash, for example, according to ASTM D4326.

[0343] Other elements or compounds may be present in the hot solid as impurities. The washed, cooled solid may contain a total concentration of impurities of at most about 1000 ppm, at most about 100 ppm, or at most about 50 ppm. The degree of impurity reduction in step (g) may be, for example, at least about 25%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%. For example, the hot solid may contain impurity levels of up to 20,000 ppm, with a reduction to 50 ppm translating to a degree of impurity reduction of 99.7%.

[0344] In some embodiments, washing in step (g) produces washed cooled solids having a higher heating value (HHV) of at least about 22 MJ / kg on a dry basis, e.g., at least about 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, or 33 MJ / kg on a dry basis. The degree of HHV increase in step (g) can be, for example, at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. Note that ash removal, as discussed above, results in a higher HHV for the washed cooled solids, and thus the biocarbon composition.

[0345] The washed cooled solids may be pelletized after step (g), or optionally integrated with step (g), to produce biocarbon pellets. As used herein, "biocarbon pellets" means pellets containing biocarbon. The geometry of the pellets may vary widely, as taught later. In some embodiments, no external binder is introduced into the washed cooled solids during pelletization. A binder may be introduced into the washed cooled solids to aid in the production of biocarbon pellets. The binder can be starch, thermoplastic starch, crosslinked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof.

[0346] The water strength of the process can be at most about −10 kg HO per metric ton of biocarbon composition, for example, the water strength can be at most about −100, −200, −500, or −1000 kg HO per metric ton of biocarbon composition. In some embodiments of the process, no external water is utilized.

[0347] If the starting material is biomass, which contains both biological and renewable carbon, the carbon obtained by pyrolysis is also biological. This can be done, for example, using ASTM D6866 to determine the carbon content. 14 C / 12The total carbon in the biocarbon composition can be shown by measuring the C isotope ratio. 14 C / 12 In some embodiments, the total carbon in the biocarbon composition may be at least 90% renewable, as determined from measurements of C isotope ratios. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0348] Any biogenic carbon that is oxidized to carbon dioxide creates biogenic CO2. This also reduces the amount of carbon in a sample of produced CO2. 14 C / 12 This can also be shown by measuring C isotope ratios. This biogenic CO2 coming from biomass is returned to the environment and reabsorbed by growing biomass via photosynthesis. In this way, net CO2 emissions are significantly reduced.

[0349] In the above or other embodiments, the biocarbon composition is characterized by a carbon intensity of at most 0 kg CO2e per metric ton of biocarbon composition, for example, at most about -100, -200, -300, -400, or -500 kg CO2e per metric ton of biocarbon composition. The process may be simultaneously characterized by a negative carbon intensity and a negative water intensity.

[0350] The "carbon intensity" of a product (or process) is the net amount of carbon dioxide by weight produced per ton of product, or per ton of raw materials processed to make the product, as the case may be. CO2-equivalent carbon intensity can also be defined as the net amount of carbon dioxide equivalent produced per ton of product. A "carbon dioxide equivalent" or "CO2e" represents the amount of CO2 that would have an equivalent global warming effect. A typical unit of carbon intensity is kilograms of carbon dioxide equivalent per metric ton (1000 kg) of product.

[0351] A greenhouse gas (or "GHG") is any gas in the atmosphere that absorbs and re-emits heat, thereby keeping the planet's atmosphere warmer than it would otherwise be. The primary GHGs in Earth's atmosphere are water vapor, carbon dioxide, methane, nitrous oxide, and ozone. By convention, the global warming potential of CO2 is defined as 1. The global warming potential of CH4 is about 30, i.e., methane is 30 times more potent as a greenhouse gas than CO2. See "IPCC Fourth Assessment Report: Climate Change 2007," Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge (2007) (incorporated herein by reference).

[0352] Generally, to calculate the carbon intensity of products and processes, it is necessary to estimate the carbon intensity of the starting materials, the carbon intensities associated with the conversion of the starting materials to intermediates, and the carbon intensities associated with the conversion of the intermediates to the final product. These calculations can be performed by those skilled in the art of chemical engineering, and can be assisted by software such as life cycle analysis software (e.g., GREET® or SimaPro® software).

[0353] Known principles of life cycle analysis can be used to calculate carbon intensity and water intensity. Life cycle assessment (LCA) is a known method used to evaluate the environmental impact of a product over its entire life cycle, including raw material processing, manufacturing, distribution, use, recycling, and final disposal. When conducting an LCA, the fate of the final product must usually be identified. For example, in the case of steel, steel is often installed to be left in place for an extended period of time. In some embodiments, end-of-life options for the steel are considered, including industrial recycling options (steel is the most recycled material on earth).

[0354] LCA can also consider current conditions regarding environmental inputs and outputs associated with specific materials. For example, unharvested forest residues release large amounts of methane as they decompose, causing a severe GHG penalty. If these forest residues are instead directed toward the production of biocarbon and subsequently metals, the avoided methane emissions can be factored into the overall carbon intensity. Because so many possibilities exist and the current conditions themselves are evolving, databases within LCA software can be utilized to ensure appropriate industry averages are adopted.

[0355] In some variations, the process for producing the biocarbon composition comprises: (a) providing a starting material comprising biomass and about 0% to about 75% by weight of water; (b) optionally drying the starting material to produce a dry material containing 0% to about 50% water by weight, and a first steam; (c) pyrolyzing the dry feedstock (or starting material if step (b) is not performed) to produce a hot solid and a second vapor; (d) if step (b) is performed, condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of about 1 to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of about 1 to about 7; (f) forming acidic water containing at least a portion of the second condensed liquid, or if step (b) is performed, at least a portion of the first condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solids using at least a portion of the acidic water to produce washed cooled solids, wherein at least one compositional parameter is adjusted; (h) recovering the washed, cooled solids as a biocarbon composition comprising at least about 50% carbon by weight.

[0356] The water strength of the process can be at most about 1000 kg of HO per metric ton of biocarbon composition, for example, the water strength can be at most about 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 25, 10, 0, -10, -25, -50, -100, -200, -500, or -1000 kg of HO per metric ton of biocarbon composition.

[0357] The water strength of the low water strength process may be reduced by about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 100%, or more compared to an otherwise comparable process that does not use acid water recovery and reuse in steps (f) and (g).

[0358] The biocarbon composition produced according to the present disclosure may be metallurgical carbon. In this disclosure, "metallurgical carbon" refers to carbon intended for use in processes involving metals. Metallurgical carbon may be, for example, a feedstock in processes for converting metal ores to metals, refining metals, adding carbon as an alloying element to metals, creating carbon-metal composites, or a combination thereof. It will be recognized that metallurgical carbon has other uses that do not require addition to a metal-making process. Thus, the adjective metallurgical, in some (but not all) embodiments, limits the carbon to its intended use in metallurgical processing. Where the metallurgical carbon disclosed herein is not actually utilized in metallurgy, the adjective metallurgical should not be construed as otherwise limiting the carbon in terms of its physical structure, chemical composition, or material properties. Any embodiment providing metallurgical carbon should be understood to also refer to embodiments providing non-metallurgical carbon for use in non-metallurgical applications. Accordingly, various embodiments provide non-metallurgical carbon products.

[0359] In some embodiments, the biocarbon composition comprises, on a dry basis, at least about 60%, at least about 70%, at least about 80%, or at least about 90% carbon by weight. In some embodiments, the biocarbon composition comprises, on a dry basis, at least about 50%, at least about 75%, or at least about 90% fixed carbon by weight. Note that removal of ash during washing with acidic water results in a higher fixed carbon content in the washed, cooled solids, and therefore in the biocarbon composition.

[0360] The biocarbon composition can contain about 1% to about 30% by weight of water, e.g., about 5% to about 15% by weight of water, about 2% to about 10% by weight of water, or about 0.1% to about 1% by weight of water. Total water content can be measured, for example, by ASTM D3302 or ASTM D3173.

[0361] The biocarbon composition may contain 0 to about 30% ash (or more) by weight, e.g., about 2% to about 25% ash, about 5% to about 20% ash, or about 8% to about 15% ash by weight. "Ash" refers to non-carbon components that do not evaporate during pyrolysis. Ash content can be measured by ASTM D3175 or other techniques. Ash compositions can be analyzed by ASTM D4326 or other techniques.

[0362] In some embodiments, the biocarbon composition further comprises an additive. The concentration of the additive can be about 0.2% to about 25% by weight, about 2% to about 25% by weight, about 5% to about 20% by weight, or about 1% to about 5% by weight, based on the total weight of the biocarbon composition. In certain embodiments, the concentration of the additive is at most about 1% by weight, e.g., about, or at most about 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.10, 0.05, 0.02, or 0.01% by weight. Because the additive is optional, in some embodiments, the additive concentration is zero.

[0363] In some embodiments, the additive can be partially oxidized or combusted. In certain embodiments, the additive is a renewable material. In certain embodiments, the additive is a carbon-neutral or carbon-negative additive. An example of a carbon-neutral or carbon-negative additive is starch produced by photosynthesis. Specifically, solar energy can be stored by biomass as starch.

[0364] In some embodiments, the additive is a binder for the biocarbon composition. The binder can be an organic binder, an inorganic binder, or a combination thereof. In some embodiments, the additive is a binder selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof.

[0365] In certain embodiments, the additive is a binder selected from starch, thermoplastic starch, crosslinked starch, starch polymers, or combinations or derivatives thereof. The binder can be a thermoplastic starch that can be crosslinked. The thermoplastic starch can be a reaction product of starch and a polyol, where the polyol can be ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations or derivatives thereof, and the reaction product can be formed from a reaction catalyzed by an acid or a base. When the reaction is acid catalyzed, the acid can be formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations or derivatives thereof.

[0366] In some embodiments, the additive reduces the reactivity of the bio-carbon composition compared to an otherwise equivalent bio-carbon composition without the additive.

[0367] The reactivity can be thermal reactivity. For example, the biocarbon composition can have lower self-heating compared to an otherwise equivalent biocarbon composition without the additive. The reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron or iron oxide), or more than one of these species.

[0368] In some embodiments, the additive fills pores within the biocarbon composition. In these or other embodiments, the additive is disposed on the surface of the biocarbon composition.

[0369] The biocarbon composition may be in powder form. Alternatively or additionally, the biocarbon composition may be in agglomerated form.

[0370] For example, the biocarbon composition, optionally with a binder, can be in agglomerated form as biocarbon pellets. The biocarbon pellets can be characterized, for example, by a Hardgrove Crushability Index of at least 30. The biocarbon pellets can be characterized by a Pellet Durability Index of at least 80%.

[0371] The biocarbon composition can be used in metal processing to produce base metals selected from iron, copper, nickel, magnesium, manganese, aluminum, tin, zinc, cobalt, chromium, tungsten, molybdenum, silicon, or combinations or derivatives thereof. The metal product can be produced with alloying elements such as elements selected from Al, Bi, B, C, Ce, Cr, Cu, Fe, H, Mg, Mn, Mo, N, Nb, Ni, P, Pb, Si, Sn, S, Ta, Ti, W, V, Zr, Zn, oxides, carbides, hydrides, nitrides, or sulfides of any of the foregoing elements, or combinations or derivatives thereof. The metal product can include other elements, which may or may not function as alloying elements.

[0372] In some embodiments, the alloying element includes carbon. When carbon is present in a metal product, it may be present at an equilibrium concentration within the metal. Alternatively, it may be present at a non-equilibrium concentration within the metal, which may be less than or greater than the equilibrium concentration of carbon.

[0373] In some embodiments, the alloying element comprises carbon derived from the biocarbon composition disclosed herein. Other elements can be derived from the biocarbon composition and utilized as alloying elements, including, but not limited to, hydrogen, nitrogen, oxygen, sulfur, or phosphorus.

[0374] When low water strength biocarbon compositions are used in metal fabrication processes, the final metal product may similarly be characterized as having reduced water strength. Some embodiments provide reduced water strength metal products that are carbon negative ("carbon negative" is synonymous with negative carbon strength).

[0375] In certain embodiments, the alloying element includes hydrogen. When the hydrogen is derived from a biocarbon composition that is itself derived from a biomass feedstock, the hydrogen can be carbon-neutral or carbon-negative because it is added to the growing biomass from atmospheric water via photosynthesis. As with carbon, the reduced water strength associated with hydrogen carries over to the final metal product from an LCA perspective.

[0376] Carbon 14 C / 12 Measuring C isotope ratios (in solid carbon or in vapor forms such as CO, CO2, or CH4) is a proven technique. Similar concepts can be applied to hydrogen, 2 H / 1 H isotope ratios are measured ( 2 (H is also known as deuterium D). Fossil sources tend to be depleted in deuterium compared to biomass. See Schiegl et al., "Deuterium content of organic matter," Earth and Planetary Science Letters, Volume 7, Issue 4, 1970, Pages 307-313, and Hayes, "Fractionation of the Isotopes of Carbon and Hydrogen in Biosynthetic Processes," Mineralogical Society of America, National Meeting of the Geological Society of America, Boston, MA, 2001 (incorporated herein by reference).

[0377] Renewable hydrogen may be recognized in the marketplace in a variety of ways, such as through renewable energy standards, renewable energy credits, renewable identification numbers, etc. By way of example only, refineries that utilize renewable hydrogen in producing gasoline may receive renewable energy credits for such H content. In metal products such as steel, renewable hydrogen may be utilized during the production of the metal (e.g., reduction of metal ores with H), or renewable hydrogen may be a measurable alloying element in the final product.

[0378] In certain embodiments, the alloying element includes nitrogen. High-strength austenitic stainless steels can benefit from nitrogen. Nitrogen has a higher solid solubility than carbon, is a strong austenite stabilizer, a good interstitial solid solution strengthener, and improves pitting corrosion resistance. When nitrogen comes from a biocarbon composition that is itself derived from a biomass feedstock, it can be carbon-neutral or carbon-negative when added to growing biomass from atmospheric N2 via the nitrogen cycle. On the other hand, when alloying nitrogen ultimately comes from NH3-based fertilizer, and the NH3 comes from the energy-intensive Haber synthesis, such nitrogen will generally not be carbon-neutral or carbon-negative. If either is present, its contribution to the overall carbon and water strength of the metal product may be very low, since the nitrogen content is typically at most 1% by weight. Even the Haber process can be reduced in energy intensity, for example, by splitting water for H2 production using renewable energy or by employing renewable hydrogen.

[0379] In certain embodiments, the alloying element comprises oxygen. Oxygen is not a commonly utilized alloying element where metal oxides are avoided. However, certain alloys, particularly non-ferrous alloys, can use oxygen (as O atoms) as an interstitial alloying element to strengthen the metal through interstitial solid solution strengthening. It is recognized that when the oxygen is derived from a biocarbon composition that is itself derived from a biomass feedstock, the oxygen is derived from atmospheric CO via photosynthesis, which has O as an output.

[0380] In certain embodiments, the alloying element comprises sulfur. When the sulfur is derived from a biocarbon composition that is itself derived from a biomass feedstock, the carbon intensity of the sulfur depends on the source of the sulfur (e.g., soil vs. added fertilizer).

[0381] In certain embodiments, the alloying element comprises phosphorus. When the phosphorus is derived from a biocarbon composition that is itself derived from a biomass feedstock, the carbon intensity of the phosphorus depends on the source of the phosphorus (e.g., soil vs. added fertilizer).

[0382] In various embodiments, the metal product is in a form selected from a powder, pellet, sheet, rod, bar, wire, coil, pipe, plate, wall, tank, cast structure, engineered structure, electromagnet, permanent magnet, or combinations thereof. The metal product can be a final structure or can be a feedstock for making metal-containing structures via traditional subtractive manufacturing, additive manufacturing, or other techniques.

[0383] In some embodiments, carbon-negative low water strength steel products may contain at least about 80% iron by weight, at least about 90% iron by weight, or at least about 95% iron by weight. Carbon-negative low water strength steel products may comprise about 0.01% to about 10% by weight of alloying elements. The alloying elements may be Al, Bi, B, C, Ce, Cr, Cu, H, Mg, Mn, Mo, N, Nb, Ni, P, Pb, Si, Sn, S, Ta, Ti, W, V, Zr, Zn, oxides, carbides, hydrides, nitrides, or sulfides of any of the foregoing elements, or combinations or derivatives thereof.

[0384] A variation of the present invention employs optimized pyrolysis of biomass to produce a carbon substrate, mechanical size reduction of the carbon substrate, and the optional use of a binder to agglomerate the carbon substrate to form biocarbon pellets with an adjustable Hardgrove Grindability Index (HGI). The moisture level of the biocarbon pellets can be optimized to vary the density within the pellets. The ability to adjust the HGI of the biocarbon pellets is highly beneficial because downstream applications (e.g., use in blast furnaces) have varying HGI requirements. HGI is at least somewhat dependent on composition, and for that reason, HGI can be considered a compositional parameter.

[0385] Particle size reduction is necessary in the context of a wide variety of biorefinery processes for converting biomass (e.g., wood chips) into products. The size reduction step is essential but very energy intensive due to the strong bonds present in naturally occurring cellulose, hemicellulose, and lignin polymers. This problem is particularly acute when small particles are involved. For example, the energy consumption of hammer milling biomass increases exponentially as a function of decreasing screen mesh size.

[0386] Raw biomass is inferior to pyrolyzed forms of biomass (many of which are described in this patent application) for a wide variety of commercial applications. Once biomass is pyrolyzed into bioreagents, its mechanical properties often do not lend themselves to downstream applications, such as blast furnaces or pulverized coal boilers. Therefore, it is often preferable to pelletize the bioreagents into biocarbon pellets. However, once pelletized, the problematic grinding energy noted above for raw biomass also makes it difficult, and often even worse, to convert the pellets into industrial powders. While this can potentially be overcome by creating loose agglomerates, which are inherently weak pellets, these agglomerates defeat the purpose of pelletization in many cases where durability of the pellets is required during transportation and plant processing, and sometimes within the reactor itself (e.g., to support a metal bed). This problem is difficult to solve because, on the one hand, pellet durability is desirable, but, on the other hand, pellet grindability is also desirable. However, the present disclosure provides biocarbon pellets and processes for making them that have good grindability and adequate durability.

[0387] Furthermore, since there are so many downstream uses for biocarbon pellets, each with its own unique requirements, being able to control the grindability of the pellets is highly advantageous. The inventors have designed a process and composition that is well suited for controllably grindable biocarbon pellets.

[0388] In some variations, the present technology provides biocarbon pellets, (a) about 35% to about 99% by weight of a bioreagent, the bioreagent comprising at least about 60% by weight of carbon on a dry basis; (b) about 0% to about 35% by weight of water; (c) about 1% by weight to about 30% by weight of a binder; The biocarbon pellets are characterized by a hardgrove grindability index of at least 30.

[0389] In some embodiments, the bio-reagent comprises at least about 70%, at least about 80%, or at least about 90% carbon by weight on a dry basis. In various embodiments, the bio-reagent comprises about or at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% carbon by weight on a dry basis. These percentages refer to the concentration of total carbon (fixed carbon and volatile carbon) relative to the total bio-reagent.

[0390] In some embodiments, the bio-reagent comprises, on a dry basis, at least about 50% fixed carbon, at least about 75% fixed carbon, or at least about 90% fixed carbon by weight. In various embodiments, the bio-reagent comprises, on a dry basis, about or at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% fixed carbon by weight. These percentages refer to the concentration of fixed carbon relative to the entire bio-reagent (excluding water), not to total carbon. Fixed carbon is total carbon minus volatile carbon.

[0391] In some biocarbon pellets, the carbon is 14 C / 12 is at least 50% renewable, as determined from measurements of the C isotope ratio. 14 C / 12 It may be at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or at least 99.9% renewable, as determined from C isotope ratio measurements. 14 C / 12 It is determined from measurements of the C isotope ratio and is fully reproducible. 14 C / 12 The C isotope ratio can be measured using ASTM D6866.

[0392] In certain embodiments, the biological reagent comprises, on a dry basis, about 75% to about 94% by weight carbon, about 3% to about 15% by weight oxygen, and about 1% to about 10% by weight hydrogen.

[0393] The moisture present in the biocarbon pellets can be water chemically bound to the carbon or binder, water physically bound (absorbed or adsorbed) to the carbon or binder, free water present in the water phase that is not chemically or physically bound to the carbon or binder, or a combination thereof. When moisture is desired during the binding process, it is preferred that such moisture be chemically or physically bound to the carbon or binder rather than being free water.

[0394] Various moisture levels can be present in the pellet product. For example, biocarbon pellets can contain about 1% to about 30% (e.g., 32%) by weight of moisture, such as about 5% to about 15% by weight of moisture, about 2% to about 10% by weight of moisture, or about 0.1% to about 1% by weight of moisture. In some embodiments, biocarbon pellets contain about 4-8% by weight of moisture. In various embodiments, biocarbon pellets contain 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, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% by weight of moisture, including all intervening ranges.

[0395] Water is present during the process of making biocarbon pellets, but the pellets are then optionally dried. This means that the final biocarbon pellets are not necessarily moisture-free. In some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. In other market applications, lower moisture levels may be desirable (e.g., 1% moisture by weight, or even lower). In some metallurgical applications, low moisture is desirable, while in other metallurgical applications, some moisture is tolerable or even desirable to aid in the overall chemical reaction.

[0396] In some biocarbon pellets, the biocarbon pellets comprise about 2% to about 25% binder by weight, about 5% to about 20% binder by weight, or about 1% to about 5% binder by weight. In various embodiments, the biocarbon pellets 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% binder by weight, including all intervening ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0397] The binder may be pore-filled within the bio-reagent of the bio-carbon pellet. Alternatively or additionally, the binder may be disposed on the surface of the bio-carbon pellet.

[0398] The binder can be an organic binder or an inorganic binder. In some embodiments, the binder is or comprises a renewable material. In some embodiments, the binder is or comprises a biodegradable material. In some embodiments, the binder is capable of being partially oxidized or burned.

[0399] In various embodiments, the binder is selected from starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations or derivatives thereof. The binder may be or may include a grindable plasticizer.

[0400] In some embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), or combinations or derivatives thereof. The starch can be a nonionic starch, anionic starch, cationic starch, or zwitterionic starch.

[0401] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and easily chemically modified. The cyclic structure of starch molecules, along with strong hydrogen bonds, gives starch a rigid structure, resulting in highly ordered crystalline and granular regions. Starch in its granular state is generally not suitable for thermoplastic processing. To obtain thermoplastic starch, semicrystalline starch granules can be decomposed by thermal and mechanical forces. Because the melting point of pure starch is significantly higher than its decomposition temperature, plasticizers such as water or glycol can be added. The native crystallinity can then be destroyed by vigorous mixing (shearing) at high temperatures, resulting in thermoplastic starch. Starch can be plasticized with relatively low levels of molecules capable of hydrogen bonding with starch hydroxyl groups, such as water, glycerol, or sorbitol.

[0402] Thermoplastic starch can be chemically modified or blended with other biopolymers to produce stronger, more ductile, and resilient bioplastics. For example, starch can be blended with natural and synthetic (biodegradable) polyesters such as polylactic acid, polycaprolactone, or polyhydroxybutyrate. To improve the compatibility of starch / polyester blends, suitable compatibilizers such as poly(ethylene-co-vinyl alcohol) or polyvinyl alcohol can be added. The hydrophilic hydroxyl groups (-OH) of starch can be replaced with hydrophobic reactive groups, such as by esterification or etherification.

[0403] In some embodiments, the starch-containing binder is or comprises cross-linked starch. Various methods for cross-linking starch are known in the art. Starch materials can be cross-linked, for example, under acidic or alkaline conditions after dissolving or dispersing in an aqueous medium. Starch can be cross-linked using aldehydes (e.g., glutaraldehyde or formaldehyde).

[0404] An example of a cross-linked starch is the reaction product of starch with glycerol or another polyol, such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination thereof. The reaction product can be formed from a cross-linking reaction catalyzed by an acid, such as (but not limited to) formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof. Inorganic acids, such as sulfuric acid, can also be utilized to catalyze the cross-linking reaction. In some embodiments, the thermoplastic or cross-linked reaction product can alternatively be formed from a cross-linking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0405] In some embodiments, the binder is designed to be a water-resistant binder, for example, in the case of starch, the hydrophilic groups can be replaced by hydrophobic groups that better resist water.

[0406] In some embodiments, the binder serves other purposes such as (but not limited to) moisture retention within the biocarbon pellets and a food source for microorganisms.

[0407] In some embodiments, the binder reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the binder, which reactivity can refer to thermal reactivity or chemical reactivity (or both).

[0408] When thermally reactive, biocarbon pellets can have reduced self-heating compared to otherwise equivalent biocarbon pellets that do not contain a binder. "Self-heating" refers to biocarbon pellets that undergo a spontaneous exothermic reaction in the absence of any external ignition, at relatively low temperatures, and in an oxidizing atmosphere, to increase the internal temperature of the biocarbon pellets. In some embodiments, biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances."

[0409] The chemical reactivity can be with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. The chemical reactivity can be associated with, for example, a reaction to CO, CO2, HO, pyrolysis oil, and heat.

[0410] Optionally, the carbon-containing pellets include additives (not necessarily binders), such as inorganic bentonite clay, limestone, starch, cellulose, lignin, or acrylamide. When lignin is used as a binder or other additive, the lignin can be obtained from the same biomass feedstock used in the pyrolysis process. For example, the starting biomass feedstock can be subjected to a lignin extraction step to remove some amount of lignin for use as a binder or additive.

[0411] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additive is selected from an acid, a base, or a salt thereof. In some embodiments, at least one additive is selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination or derivative thereof. For example, the additive may be selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorite, bentonite, calcium oxide, lime, titanium, titanium compounds, or a combination or derivative thereof.

[0412] The additives can be introduced 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 the feedstock is harvested. However, the time at which the additive is introduced during the process is important and can be critical depending on the desired product. For example, if the additive is added before pyrolysis, the final product will contain a derivative of the additive or the additive itself, depending on how the additive behaves under pyrolysis conditions.

[0413] The Hardgrove Grindability Index of the biocarbon pellets can be at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. In some embodiments, the Hardgrove Grindability Index is from about 30 to about 50, or from about 50 to about 70. ASTM Standard D409 / D409M for "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method" is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to Hardgrove Grindability Index or HGI in this disclosure refer to ASTM Standard D409 / D409M.

[0414] In various embodiments, the Hard Glove Crushability 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, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 13 9, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0415] Biocarbon pellets (e.g., carbon negative and negative water strength biocarbon pellets) can be characterized by a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. Biocarbon pellets can be characterized by a pellet durability index of at most 99%, at most 95%, at most 90%, at most 85%, or at most 80%. Unless otherwise indicated, all references to pellet durability index in this disclosure refer to ISO 17831-1:2015 "Solid biofuels - Determination of mechanical durability of pellets and briquettes - Part 1: Pellets," which is incorporated herein by reference in its entirety.

[0416] The size and geometry of biocarbon pellets can vary. As used herein, "pellets" refers to agglomerated bodies rather than loose powder. The geometry of pellets is not limited to spherical or near-spherical shapes. Also, in this disclosure, "pellets" is synonymous with "briquettes," "granules," and "prills." The geometry of pellets can be spherical (round or ball-shaped), cubic (square), octagonal, hexagonal, honeycomb / honeycomb, elliptical, oval, cylindrical, rod-shaped, disc-shaped, pillow-shaped, random, or a combination thereof. For convenience of disclosure, the term "pellets" is used generally for any body comprising agglomerated powder, optionally using a binder.

[0417] Biocarbon pellets can be characterized by an average pellet diameter, which is the true diameter in the case of a sphere, or an equivalent diameter in the case of any other 3D geometric shape. The equivalent diameter of a non-spherical pellet is the diameter of a sphere with an equivalent volume to the actual pellet. In some embodiments, the average pellet diameter is about or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters, inclusive of all intervening ranges. In some embodiments, the average pellet diameter is about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns, inclusive of all intervening ranges.

[0418] In some embodiments, there are a plurality of biocarbon pellets that are relatively uniform in size, such as with a standard deviation of at most ±100%, at most ±50%, at most ±25%, at most ±10%, or at most ±5% of the average pellet diameter. In other embodiments, there are biocarbon pellets in a wide range of sizes, as this may be advantageous in some applications.

[0419] Some variations of the present technology are biocarbon pellets, (a) about 35% to about 99% by weight of a bioreagent, the bioreagent comprising at least about 60% by weight of carbon on a dry basis; (b) about 0% to about 35% by weight of water; (c) about 1% by weight to about 30% by weight of a reactivity moderator; To provide a bio-carbon pellet in which a reactivity mitigating agent reduces the reactivity of the bio-carbon pellet compared to an otherwise identical bio-carbon pellet that does not contain the reactivity mitigating agent.

[0420] In some embodiments, the bio-reagent comprises at least 70% carbon by weight on a dry basis. The bio-reagent may comprise at least about 50% fixed carbon by weight.

[0421] The bioreagent may contain, on a dry basis, about 75% to about 94% by weight carbon, about 3% to about 15% by weight oxygen, and about 1% to about 10% by weight hydrogen.

[0422] In some embodiments, the biocarbon pellets contain between about 1% and about 30% moisture by weight.

[0423] In some embodiments, the carbon is 14 C / 12 In certain embodiments, the carbon is at least 50% renewable as determined from measurements of the C isotope ratio. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0424] In some biocarbon pellets, the biocarbon pellets include about 2% to about 25% by weight of the reactivity mitigating agent. The biocarbon pellets can include, for example, about 5% to about 20% by weight, or about 1% to about 5% by weight of the reactivity mitigating agent.

[0425] The reactive mitigation agent can be organic or inorganic. The reactive mitigation agent can be a renewable material. In some embodiments, the reactive mitigation agent can be partially oxidized or combusted. The reactive mitigation agent preferably allows for adjustment of compositional parameters.

[0426] The reactive modifier may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof.

[0427] In some embodiments, the reactive modifier is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, or combinations or derivatives thereof.

[0428] In certain embodiments, the reactive modifier is an optionally crosslinked thermoplastic starch. For example, the thermoplastic starch can be the reaction product of starch and a polyol. The polyol can be selected from ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations or derivatives thereof. The reaction product can be formed from a reaction catalyzed by an acid, such as (but not limited to) formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof, or by a base.

[0429] In some biocarbon pellets, where the reactivity mitigating agent reduces the reactivity of the biocarbon pellet, the reactivity is thermal reactivity. For example, the biocarbon pellets may be characterized by lower self-heating compared to otherwise equivalent biocarbon pellets that do not contain the reactivity mitigating agent.

[0430] Reactivity mitigating agents reduce the reactivity of biocarbon pellets. For some biocarbon pellets, the reactivity is chemical reactivity with oxygen, water, hydrogen, carbon monoxide, metals (such as iron), or combinations thereof.

[0431] In some biocarbon pellets, the reactivity mitigating agent is loaded into pores within the bioreagent of the biocarbon pellet. In other biocarbon pellets, the reactivity mitigating agent is disposed on the surface of the biocarbon pellet. In still other biocarbon pellets, the reactivity mitigating agent is loaded into pores within the bioreagent of the biocarbon pellet and disposed on the surface thereof.

[0432] The reactive mitigating agent can function as a binder to adjustably control the Hard Grove Grindability Index of the biocarbon pellets. In some embodiments, the biocarbon pellets are characterized by a Hard Grove Grindability Index of at least 30, e.g., from about 30 to about 50, or from about 50 to about 70. Other HGI ranges are disclosed elsewhere herein and are equally applicable to embodiments in which a reactive mitigating agent is used and functions as a binder.

[0433] For example, a binder can be selected that both controllably adjusts HGI and functions as a reactivity mitigator. In these cases, it may be desirable to ensure that the binder is not only located on the surface of the biocarbon pellet, but is also dispersed throughout the biocarbon (filling the pores of the biocarbon pellet). The concentration of the binder may be different on the surface compared to the bulk (interior) of the pellet. In some cases, a higher concentration of binder is present in the pellet bulk relative to the surface, while in other cases (e.g., certain embodiments for reduced self-heating pellets), a higher binder concentration at the surface is desired. It is also possible to have two different binders (chemical species), one in the pellet bulk and one on the surface. In such cases, the bulk binder may be referred to as the binder, and the pellet surface agent may be referred to as the pellet reactivity mitigator. Even in such embodiments, if the binder is added during the pellet production process, it will be understood that some amount of binder will be present on the pellet surface. Similarly, if the reactive mitigation agent is coated onto the pellet after formation, some amount of the reactive mitigation agent can be expected to diffuse into the pellet pores.

[0434] Another variation of the present technology is a process for producing biocarbon pellets, the process comprising: (a) drying a biomass feedstock; (b) pyrolyzing the biomass feedstock to produce a bio-reagent, the bio-reagent comprising at least about 50% by weight carbon and at least about 5% by weight moisture; (c) mechanically treating the biological reagent to produce a plurality of carbon-containing particles; (d) combining the carbon-containing particles with a binder to form a carbon-binder mixture; (e) after or simultaneously with step (d), pelletizing the carbon-binder mixture to produce biocarbon pellets; (f) optionally, at least partially drying the biocarbon pellets; (g) condensing at least a portion of the first vapor collected in step (a) to produce a first condensed liquid having a first pH of about 1 to about 7; (h) condensing at least a portion of the second vapor collected in step (b) or step (f) to produce a second condensed liquid having a second pH of about 1 to about 7; (i) forming an acidic water containing at least a portion of a first condensed liquid, at least a portion of a second condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (j) washing and cooling the hot solids using at least a portion of the acidic water to produce washed cooled solids, wherein at least one compositional parameter is adjusted; (k) recovering the biocarbon pellets, the biocarbon pellets comprising at least about 50% carbon by weight.

[0435] In some process embodiments, the bioreagent comprises, on a dry basis, at least about 70%, at least about 80%, or at least about 90% carbon by weight.

[0436] In some process embodiments, the bioreagent comprises at least about 50% by weight fixed carbon, at least about 75% by weight fixed carbon, or at least about 90% by weight fixed carbon.

[0437] Carbon is carbon 14 C / 12It may be at least 50%, at least 90%, at least 95%, or completely renewable, as determined from C isotope ratio measurements. 14 C / 12 The C isotope ratio is measured using ASTM D6866.

[0438] In one particular process, the bioreagent comprises, on a dry basis, about 75% to about 94% by weight carbon, about 3% to about 15% by weight oxygen, and about 1% to about 10% by weight hydrogen.

[0439] In some processes, the bioreagent in step (b) contains at least about 10%, 15%, 20%, 25%, 30%, 35%, or 40% moisture by weight. Even when the moisture content is at least 40% by weight, biocarbon pellets can be produced, but the pellet density is expected to be low (too low for many applications). In some embodiments, step (c), step (d), or step (e) is performed at a moisture content lower than that of step (b). For example, when step (f) is performed, drying may result in a moisture content lower than that in step (b), and optionally lower than that in step (c), step (d), or step (e).

[0440] In some embodiments, step (f) occurs after step (e). In these or other embodiments, step (f) is integrated with step (e). For example, the pelletizing unit can allow water to escape from the pellets as they are formed. That is, the pelletizing unit can also act as a dryer. In certain embodiments, some drying occurs during pelletizing, and additional drying occurs after pelletizing, for example, in a drying unit or under ambient conditions.

[0441] In some embodiments, the biological reagents are not dried during step (c). In these or other embodiments, the biological reagents are not dried during step (d). In these or other embodiments, the biological reagents are not dried during step (e).

[0442] The biocarbon pellets may contain about 1% to about 30% by weight of moisture, e.g., about 5% to about 15% by weight of moisture, about 2% to about 10% by weight of moisture, or about 0.1% to about 1% by weight of moisture.

[0443] In some processes, step (b) is carried out at a pyrolysis temperature selected from about 250°C to about 1250°C, e.g., about 300°C to about 700°C. In some processes, step (b) is carried out for a pyrolysis time selected from about 10 seconds to about 24 hours. Other possible pyrolysis conditions are described later in this specification.

[0444] Step (c) may utilize a mechanical processing device selected from a hammer mill, an extruder, an attrition mill, a disc mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or a combination thereof.

[0445] In some processes, steps (c) and (d) are integrated. For example, the binder can be fed directly into a hammer mill or extruder, or other mechanical processing device.

[0446] The biocarbon pellets may contain about 2% to about 25% by weight of binder, such as about 5% to about 20% by weight of binder, or about 1% to about 5% by weight of binder. The binder may be organic or inorganic.

[0447] The binder may be selected from starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof. In certain processes, the binder is selected from starch, cross-linked starch, starch polymers, or combinations or derivatives thereof.

[0448] Step (e) can utilize a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquette, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0449] In some processes, steps (d) and (e) are integrated. For example, the binder can be introduced directly into the pelletizing unit. When steps (d) and (e) are performed separately, the binder is mixed with the carbon-containing particles to form a carbon-binder mixture before introducing such mixture into a unit configured to pelletize the carbon-binder mixture.

[0450] In some embodiments of the present invention, biocarbon pellets are utilized as starting materials for making smaller objects, and may also be referred to as biocarbon pellets because "pellets" does not limit the geometric shape. For example, initial biocarbon pellets having an average pellet diameter of 10 mm can be produced. These initial biocarbon pellets can then be crushed using various mechanical means (e.g., using a hammer mill). The crushed pellets can be separated according to size, such as by screening. In this manner, smaller biocarbon pellets can be produced having an average pellet 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 microns. The average pellet diameter of the smaller biocarbon pellets may be larger than the average particle diameter of the initial carbon-containing particles used to make the pellets with the binder.

[0451] When the biocarbon pellets are crushed to produce smaller biocarbon pellets, the crushing (and optionally screening) step can be integrated with step (e), can occur after step (e), can be integrated with step (f), or can occur after step (f), potentially including at an industrial location. The optional step to produce smaller biocarbon pellets can utilize a crushing device selected from a hammer mill, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, rock crusher, or combinations thereof.

[0452] In various process embodiments, the Hard Glove Crushability Index is at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. For example, the Hard Glove Crushability Index can be from about 30 to about 50, or from about 50 to about 70.

[0453] In various processes, the process conditions may range from 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, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 96, 97, 98, 99, 100.

[0454] In some processes, the biocarbon pellets are characterized by a pellet durability index of at least 80%, at least 90%, or at least 95%.

[0455] In some embodiments, the process includes preselecting a Hard Grove Grindability Index, adjusting process conditions based on the preselected Hard Grove Grindability Index, and achieving within ±20% of the preselected Hard Grove Grindability Index for the biocarbon pellets, where the adjusted process conditions include adjusting one or more of pyrolysis temperature, pyrolysis time, mechanical processing conditions, pelletizing conditions, binder type, binder concentration, binding conditions, and drying. Certain embodiment processes may achieve within ±10% or ±5% of the preselected Hard Grove Grindability Index for the biocarbon pellets.

[0456] The biocarbon pellets disclosed herein have a wide variety of downstream applications. They can be stored, sold, distributed, and converted into other products. They can be pulverized, crushed, or milled for feeding into furnaces, such as blast furnaces, in metal production. They can be fed directly into furnaces, such as Tecnored furnaces in metal production. They can be pulverized for use in boilers to burn carbon and generate electrical energy or heat. They can be pulverized, crushed, or milled for feeding into gasifiers to create syngas from the biocarbon pellets.

[0457] In certain embodiments, the biocarbon pellets are negative water strength and carbon negative metallurgical carbon pellets that are fed directly or after a pulverizing, crushing, grinding, or other particle size reduction step into a furnace. The furnace can be a blast furnace, a top gas recirculation blast furnace, a shaft furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a silencer furnace, a retort furnace, a flash furnace, a Tecnored furnace, an Ausmelt furnace, an ISASMELT furnace, a puddle furnace, a bogie hearth furnace, a continuous chain furnace, a pusher furnace, a rotary hearth furnace, a walking beam furnace, an electric arc furnace, an induction furnace, a basic oxygen furnace, a puddle furnace, a Bessemer furnace, a direct reduction metal furnace, or a combination or derivative thereof.

[0458] It should be noted that despite the Hardgrove Crushability Index of biocarbon pellets, they do not necessarily subsequently undergo a crushing process. For example, biocarbon pellets can be used directly in agricultural applications. As another example, biocarbon pellets can be directly incorporated into engineered structures, such as landscape walls. Then, at the end of the life of the structure containing the biocarbon pellets, the pellets can be crushed, burned, gasified, or otherwise reused or reclaimed.

[0459] Pyrolysis Processes and Systems Suitable processes and systems for pyrolyzing biomass feedstocks to produce carbon-containing bioreagents are now described in further detail.

[0460] "Pyrolysis" and "pyrolyzing" generally refer to the thermal decomposition of a carbonaceous material. In pyrolysis, less oxygen is present than is required for complete combustion of the material, such as at most 10%, 5%, 1%, 0.5%, 0.1%, or 0.01% of the oxygen (O molar basis) required for complete combustion. In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0461] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from the heat source increases the temperature within the feedstock; (ii) the initiation of primary pyrolysis reactions at this higher temperature liberates volatiles and forms char; (iii) the flow of hot volatiles toward the cooler solids results in heat transfer between the hot volatiles and the cooler, non-pyrolyzed feedstock; (iv) some of the volatiles in the cooler portions of the feedstock may condense, followed by secondary reactions to produce tar; (v) autocatalytic secondary pyrolysis reactions proceed while competing primary pyrolysis reactions occur simultaneously; and (vi) further pyrolysis, reforming, water-gas shift reaction, free-radical recombination, or dehydration may also occur, which are functions of residence time, temperature, and pressure profiles.

[0462] Pyrolysis can at least partially dewater the starting material (e.g., lignocellulosic biomass). In various embodiments, pyrolysis removes at least about 50%, 75%, 90%, 95%, 99%, or more of the water from the starting material.

[0463] In various embodiments, the starting biomass feedstock is softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugarbeet, sugarbeet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit The biomass feedstock may be selected from the group consisting of: stalks, fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper trimmings, food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal sewage, or combinations or derivatives thereof. The biomass feedstock comprises at least carbon, hydrogen, and oxygen.

[0464] The bioreagent may contain at least about 50%, at least about 75%, or at least about 90% carbon by weight (total carbon). In various embodiments, the bioreagent contains about, at least about, or at most about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% carbon by weight. Total carbon is the sum of fixed and non-fixed carbon present in the volatile materials. In some embodiments, component weight percentages are on an absolute basis, which is assumed unless otherwise stated. In other embodiments, component weight percentages are on a dry and ash-free basis.

[0465] The bioreagent may comprise at least about 50%, at least about 75%, or at least about 90% by weight fixed carbon. In various embodiments, the bioreagent comprises about, at least about, or at most about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% by weight fixed carbon.

[0466] The carbon (within the bioreagent) can be, for example, at least about 50%, at least about 75%, or at least about 90% by weight fixed carbon, with the remainder of the carbon being volatile carbon. In various embodiments, the carbon comprises about, at least about, or at most about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100% by weight fixed carbon.

[0467] Pyrolysis conditions can vary widely depending on the desired composition of the bioreagent and pyrolysis exhaust gas, the starting materials, the reactor configuration, and other factors.

[0468] In some embodiments, multiple reactor zones are designed and operated to optimize carbon yield and product quality from pyrolysis while maintaining flexibility and adjustability to feedstock variations and product requirements.

[0469] In some embodiments, temperatures and residence times are selected to achieve relatively slow pyrolysis chemical reactions. An advantage can be substantial preservation of the cell walls contained in the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, equipment that does not mechanically disrupt cell walls or otherwise convert biomass particles into small fines may be utilized. Various reactor configurations are considered in accordance with the process description below.

[0470] Additionally, if the feedstock is a milled or sized feedstock, such as wood chips or pellets, it may be desirable to carefully mill or size the feedstock. Careful initial processing tends to preserve the strength and cell wall integrity present in the natural feedstock source (e.g., wood). This may also be important if the final product is to retain some, most, or all of the shape and strength of the starting biomass.

[0471] In some embodiments, the first zone of the pyrolysis reactor is configured to feed biomass (or another carbon-containing feedstock) in a manner that does not "shock" the biomass, which ruptures cell walls and initiates rapid decomposition of the solid phase into steam and gas. This first zone can be considered mild pyrolysis.

[0472] In some embodiments, the second zone of the pyrolysis reactor is configured as a primary reaction zone, where preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, leaving behind a significant amount of solid material that is a high-carbon reaction intermediate. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to create vapors that escape by penetrating pores or by creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0473] In some embodiments, the third zone of the pyrolysis reactor is configured to receive the high-carbon reaction intermediates and provide some cooling of the solids. Typically, the third zone is at a lower temperature than the second zone. In the third zone, chemical reactions and mass transfer can be surprisingly complex. Without being limited by a particular theory or proposed mechanism, it is believed that secondary reactions can occur in the third zone. Essentially, carbon-containing components in the gas phase can decompose to form additional fixed carbon or become adsorbed onto carbon. Thus, in some embodiments, the final carbonaceous material is not simply the solid, degassed residue of the processing step, but includes additional carbon deposited from the gas phase, such as by the decomposition of organic vapors (e.g., tars) that can form carbon.

[0474] Certain embodiments extend the concept of additional carbon formation by including a separate unit in which the cooled carbon is subjected to an environment containing carbon-containing species to enhance the carbon content of the product. If the temperature of this unit is below the pyrolysis temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0475] There are many options with regard to intermediate input and output (purge or probe) streams of one or more phases present in any particular zone, various mass and energy recycle schemes, various additives that can be introduced anywhere in the process, adjustability of process conditions, including both reaction and separation conditions to tailor product distribution, etc. Zone-specific input and output streams allow for better process monitoring and control, such as by FTIR sampling and dynamic process adjustment.

[0476] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis. Surprisingly, high quality carbon materials, including compositions with very high percentages of fixed carbon, can be obtained from the disclosed processes and systems.

[0477] In some embodiments, the pyrolysis process for producing high carbon bio-reagents comprises the following steps: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in the presence of a substantially inert gas phase at at least one temperature selected from about 250°C to about 700°C for at least 10 minutes to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the high temperature pyrolysis solid to produce a cooled pyrolysis solid; (g) recovering the high-carbon biological reagent comprising at least a portion of the cooled pyrolysis solids.

[0478] "Biomass," for purposes of this disclosure, shall be construed as any living material or a mixture of living and non-living materials. Essentially, biomass comprises at least carbon, hydrogen, and oxygen. The methods and apparatus of the present invention are adaptable to a wide range of materials of various types, sizes, and moisture contents.

[0479] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal waste, poultry waste, and municipal solid waste. In various embodiments of the present invention utilizing biomass, the biomass feedstock can include materials selected from timber harvest residues, softwood chips, hardwood chips, tree branches, tree stumps, wood knots, leaves, bark, sawdust, off-spec paper pulp, cellulose, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal waste, municipal sewage, commercial waste, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, carbohydrates, plastic, or fabric. One skilled in the art will readily appreciate that the raw material options are virtually limitless.

[0480] The present invention can also be used with mixtures of biomass and fossil fuels (e.g., biomass / coal blends), recognizing that the carbon intensity of the final product, while not as low as with pure biomass feedstock, will be lower than if pure fossil fuel feedstock were used. In some embodiments, the feedstock comprises coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Feedstocks can include scrap tires, recycled plastics, recycled paper, construction and demolition waste, and other waste or recycled materials.

[0481] The selection of the particular feedstock(s) is not considered technically critical, but is carried out in a manner that tends to favor an economical process. Typically, regardless of the feedstock selected, there may (in some embodiments) be screening to remove undesirable materials. The feedstock may optionally be dried before processing. The carbon-containing feedstock may be transportable by any known means, such as truck, train, ship, barge, tractor-trailer, or any other vehicle or conveyance.

[0482] The raw materials used can be provided or processed into a wide variety of particle sizes or shapes. For example, the feed material can be a fine powder or a mixture of fine and coarse particles. The feed material can be in the form of larger pieces of material, such as wood chips or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the feed material comprises pellets or other agglomerated forms of particles that are pressed together or otherwise bound, for example, with a binder.

[0483] It should be noted that size reduction is an expensive and energy-intensive process. Pyrolyzed material can be sized with significantly less energy input. Therefore, it may be desirable to reduce the particle size of the product rather than the feedstock. This is an option in the present invention because the process does not require fine starting material and there is not necessarily any significant particle size reduction during processing. The ability to process very large feedstock pieces is an important economic advantage of the present invention. In particular, some market applications of high-carbon products actually require large sizes (e.g., on the order of centimeters), and therefore in some embodiments, large pieces are sourced, produced, and sold.

[0484] If it is desired to produce a final carbonaceous bio-reagent with structural integrity, such as a cylindrical shape, there are at least two options in the context of the present invention. First, the material produced from the process can be collected and then further mechanically processed into the desired form. For example, the product can be pressed or pelletized with a binder. A second option is to utilize a feed material that generally has the desired size or shape for the final product and use processing steps that do not destroy the basic structure of the feed material. In some embodiments, the feed and product have similar geometric shapes, such as spheres, cylinders, or cubes.

[0485] The ability to maintain the approximate size of the feed material throughout the process is beneficial when product strength is important, and it avoids the difficulty and cost of pelletizing high fixed carbon materials.

[0486] The starting feedstock may be provided at a range of moisture levels, as will be appreciated. In some embodiments, the feedstock may already be sufficiently dry that further drying prior to pyrolysis is not necessary. Typically, it is desirable to utilize commercial sources of biomass that normally contain moisture and to feed the biomass through a drying step before introducing it into the pyrolysis reactor. However, in some embodiments, dry feedstock may be utilized.

[0487] It is desirable to provide a relatively low oxygen environment in the pyrolysis reactor, such as about, 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% O in the gas phase. First, uncontrolled combustion should be avoided in the pyrolysis reactor for safety reasons. Some amount of total carbon oxidation to CO may occur, and the heat released from the exothermic oxidation may support the endothermic pyrolysis chemical reaction. Large amounts of carbon oxidation, including partial oxidation to syngas, reduce the carbon yield to solids.

[0488] In practice, achieving a strictly oxygen-free environment in the reactor can be difficult. This limit can be approached, and in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that little or no oxygen is present in the pyrolysis reactor, it may be desirable to remove air from the feed before it is introduced into the reactor. There are various methods for removing or reducing air in the feed.

[0489] In some embodiments, a degassing unit is utilized before or after drying, in which the feedstock is conveyed in the presence of another gas that can remove adsorbed oxygen and penetrate the feedstock pores to remove oxygen from the pores. Essentially, any gas with less than 21% O by volume can be used with varying effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO or CO is used. Mixtures can be used, such as a mixture of nitrogen and small amounts of oxygen. Water vapor may be present in the degassing gas, but adding significant moisture back to the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or an effluent treatment unit) or recycled.

[0490] In principle, the effluent from the degassing unit (or a portion thereof) could be introduced into the pyrolysis reactor itself, since the oxygen removed from the solids would be highly diluted. In this embodiment, it may be advantageous to introduce the degassed effluent gas into the last zone of the reactor if the reactor is operated in a countercurrent configuration.

[0491] Various types of degassing units can be used. If drying is performed, it can occur before degassing due to the inefficiency of scrubbing soluble oxygen from the moisture present. In certain embodiments, the drying and degassing steps are combined into a single unit, or some amount of degassing is achieved during drying.

[0492] The optionally dried and optionally degassed feedstock is introduced into a pyrolysis reactor or multiple reactors in series or parallel. The feedstock can be introduced using any known means, including, for example, a screw feeder or a lock hopper. In some embodiments, the feed system incorporates an air knife.

[0493] When a single reactor is used, there can be multiple zones, such as two, three, four, or more zones, which can allow for separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, or pressure to adjust overall process performance.

[0494] References to "zones" shall be interpreted broadly to include regions of space within a single physical unit, physically separated units, or any combination thereof. With respect to continuous reactors, zone boundaries may relate to structures such as the presence of flights within the reactor or separate heating elements for providing heat to separate zones. Alternatively or additionally, zone boundaries in continuous reactors may relate to functions such as, for example, separate temperatures, fluid flow patterns, solids flow patterns, extent of reaction, etc. In single batch reactors, a "zone" is an operating regime in time rather than space. Multiple batch reactors may also be used.

[0495] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary, and some amount of pyrolysis may occur in part of the preheat zone, while some amount of "preheating" may continue to occur in the pyrolysis zone. The temperature profile in the reactor is typically continuous, including at zone boundaries within the reactor.

[0496] Some embodiments employ a first zone operated under preheat or mild pyrolysis conditions. The temperature of the first zone can be selected from about 150° C. to about 500° C., e.g., about 300° C. to about 400° C. The temperature of the first zone is not so high as to bombard the biomass material, rupturing cell walls and initiating rapid decomposition of the solid phase into steam and gas.

[0497] All references to zone temperatures herein should be interpreted non-limitingly to include temperatures that may be applied to the bulk solids present, or the gas phase, or the reactor wall (process side). It will be understood that temperature gradients exist in each zone, both axially and radially, and over time (i.e., after start-up or due to transients). Thus, references to zone temperatures may be to average temperatures or other effective temperatures that may affect actual kinetics. Temperatures may be measured directly by thermocouples or other temperature probes, or may be measured or estimated indirectly by other means.

[0498] The second zone, or generally the primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone can be selected from about 250°C to about 700°C, e.g., about, or as low as about, or as high as about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemical reactions, releasing gases and condensable vapors, leaving behind a significant amount of solid material as a high-carbon reaction intermediate. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or creating new pores. The temperature depends at least on the residence time in the second zone, as well as the nature of the feedstock and the desired product characteristics.

[0499] The third zone, or cooling zone, is operated to cool the high-carbon reaction intermediate to various degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone can be selected from about 100°C to about 550°C, for example, from about 150°C to about 350°C.

[0500] Chemical reactions can continue to occur in the cooling zone. Without being limited to a particular theory, it is believed that a secondary pyrolysis reaction can be initiated in the third zone. Carbonaceous components that are in the gas phase can condense (due to the decrease in temperature in the third zone). However, the temperature remains high enough to promote reactions that can form additional fixed carbon from the condensed liquid (secondary pyrolysis), or at least reactions that can form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that can occur is the Boudouin reaction to convert carbon monoxide to carbon dioxide and fixed carbon.

[0501] The residence time of the reactor zones can vary. There is an interaction of time and temperature, such that for a desired amount of pyrolysis, higher temperatures can allow for shorter reaction times, and vice versa. The residence time in a continuous reactor (zone) is the volume divided by the volumetric flow rate. The residence time in a batch reactor is the batch reaction time after heating to the reaction temperature.

[0502] It should be recognized that in a multiphase reactor, multiple residence times exist. In the present context, there are residence times (and residence time distributions) for both the solid and vapor phases in each zone. For a given apparatus using multiple zones, at a given throughput, the residence times across the zones are generally coupled on the solid side, but if multiple inlet and outlet ports are utilized in the individual zones, the residence times may not be coupled on the vapor side. The solid and vapor residence times are not coupled.

[0503] The solids residence time in the preheat zone can be selected from about 5 minutes to about 60 minutes, e.g., about 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a time sufficient to allow the biomass to reach the desired preheat temperature is desirable. Heat transfer rates, which depend on particle type and size, physical equipment, and heating parameters, dictate the minimum residence time required to allow the solids to reach the desired preheat temperature. Additional time is usually undesirable, as it contributes to higher capital costs, unless some amount of mild pyrolysis is intended in the preheat zone.

[0504] The solids residence time in the pyrolysis zone can be selected from about 10 minutes to about 120 minutes, for example, about 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be sufficient time for the necessary heat transfer followed by the carbonization chemical reaction. For times less than about 10 minutes, the temperature needs to be very high, such as above 700°C, to remove a significant amount of non-carbon elements. This temperature promotes fast pyrolysis and the production of vapors and gases derived from the carbon itself, but should be avoided if the intended product is solid carbon.

[0505] In a static system, there will be an equilibrium conversion that can be substantially reached at a certain time. When, as in certain embodiments, steam is continuously flowing over the solids with continuous devolatilization, the equilibrium constraint can be removed to allow pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times tend not to substantially change the remaining refractory solids.

[0506] The residence time of the solids in the cooling zone can be selected from about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be sufficient time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature dictate the minimum residence time required to allow the carbon to cool. Additional time is not preferred unless some amount of secondary pyrolysis is desired.

[0507] As discussed above, the vapor phase residence times can be independently selected and controlled. The vapor residence time in the preheating zone can be selected from about 0.1 minutes to about 15 minutes, e.g., 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, e.g., 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, e.g., about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. A short vapor residence time promotes rapid clearing of volatiles from the system, while a longer vapor residence time promotes reaction of components in the vapor phase with the solid phase.

[0508] The mode of operation of the reactor, and the overall system, can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the reactor is a continuous countercurrent reactor, in which solids and vapor flow in substantially opposite directions. The reactor can also be operated in batch, but with simulated countercurrent flow of vapor, for example, by periodically introducing and removing the vapor phase from the batch vessel.

[0509] A variety of flow patterns may be desired or observed. In chemical reactions and simultaneous separations involving multiple phases in multiple reactor zones, the fluid dynamics can become very complex. Typically, solids flow can approach plug flow (well mixed in the radial dimension), while vapor flow can approach perfectly mixed flow (high velocity transport in both the radial and axial dimensions). Multiple inlet and outlet ports for vapor can contribute to overall mixing.

[0510] The pressure in each zone can be selected and controlled separately. The pressure in each zone can be independently selected from about 1 kPa to about 3000 kPa, for example, about 101.3 kPa (standard atmospheric pressure). Independent zone control of pressure is possible when multiple gas inlets and outlets are used, including vacuum ports for withdrawing gas when subatmospheric zone pressures are desired.

[0511] The process can, in some embodiments, be conveniently operated at atmospheric pressure. Operation at atmospheric pressure has many advantages, ranging from mechanical simplicity to improved safety. In certain embodiments, the pyrolysis zone is operated at a pressure of about 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute).

[0512] Vacuum operation (e.g., 10-100 kPa) promotes rapid sweeping of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) can be useful when exhaust gas is fed to high-pressure operation. Higher pressures can also be useful to promote heat transfer, chemical reactions, or separations.

[0513] The step of separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high-temperature pyrolysis solids can be accomplished in the reactor itself or using a separate separation unit. A substantially inert sweep gas can be introduced into one or more zones. The condensable vapors and non-condensable gases are then carried away from the zones in the sweep gas and exit the reactor.

[0514] The sweep gas may be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweep gas may be initially preheated before introduction, or may be cooled if obtained from a heated source.

[0515] The sweep gas more completely removes volatile components by removing them from the system before they can condense or further react. The sweep gas allows volatiles to be removed at a higher rate than would be possible from volatilization alone at a given process temperature. Alternatively, the use of a sweep gas allows more moderate temperatures to be used to remove a given amount of volatiles. The reason the sweep gas improves volatile removal is because the mechanism of separation is not simply relative volatility, but rather liquid / vapor phase separation assisted by the sweep gas. The sweep gas can reduce the mass transfer limitation of volatilization as well as the thermodynamic limitation by continuously depleting a given volatile species, allowing more volatile species to evaporate and achieve thermodynamic equilibrium.

[0516] Some embodiments remove gases full of volatile organic carbon from subsequent processing stages to produce products with high fixed carbon. Otherwise, the volatile carbon may be adsorbed or absorbed onto the pyrolyzed solids, thereby requiring additional energy (cost) to achieve a purer form of carbon that may be desired. It is also speculated that rapid removal of vapors can increase porosity in the pyrolysis solids. Higher porosity is desirable for some products.

[0517] In certain embodiments, the sweep gas, in conjunction with a relatively low process pressure, such as atmospheric pressure, provides rapid vapor removal without requiring large amounts of inert gas.

[0518] In some embodiments, the sweep gas flows countercurrently to the feed flow direction. In other embodiments, the sweep gas flows cocurrently to the feed flow direction. In some embodiments, the flow pattern of the solids approaches plug flow, while the flow patterns of the sweep gas and vapor phase generally approach perfectly mixed flow in one or more zones.

[0519] Sweeping can be performed in any one or more of the reactor zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted (along with generated volatiles) from the cooling or pyrolysis zone. In some embodiments, the sweep gas is introduced into the pyrolysis zone and extracted from the pyrolysis or preheating zone. In some embodiments, the sweep gas is introduced into the preheating zone and extracted from the pyrolysis zone. In these or other embodiments, the sweep gas can be introduced into each of the preheating zone, pyrolysis zone, and cooling zone, and can also be extracted from each of the zones.

[0520] In some embodiments, the zone or zones in which separation is performed are units physically separate from the reactor. Separation units or zones can be located between reactor zones, if desired. For example, a separation unit can be located between a pyrolysis unit and a cooling unit.

[0521] The sweep gas can be introduced continuously, especially when the solids flow is continuous. If the pyrolysis reaction is operated as a batch process, the sweep gas can be introduced after a certain amount of time or periodically to remove volatiles. Even if the pyrolysis reaction is operated continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, using suitable valves and controls.

[0522] The volatile sweep gas can exit one or more reactor zones or can be combined if obtained from multiple zones. The resulting gas stream containing various vapors can then be fed to a thermal oxidizer for controlled air emissions. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are fed to the thermal oxidizer to reach a temperature sufficient to substantially destroy the volatiles contained therein.

[0523] The effluent of the thermal oxidizer is a hot gas stream containing water, carbon dioxide, and nitrogen. This effluent stream can be purged directly to the air exhaust, if desired. The energy content of the thermal oxidizer effluent can be recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (such as a sweep gas). The energy content can be utilized by directly or indirectly heating or assisting in heating units elsewhere in the process, such as a dryer or reactor. In some embodiments, essentially all of the thermal oxidizer effluent is used to indirectly heat (the utility side) the dryer. The thermal oxidizer can use fuels other than natural gas.

[0524] The yield of carbonaceous materials can vary depending on the factors mentioned above, including the type of feedstock and process conditions. In some embodiments, the net yield of solids as a percentage of the starting material on a dry basis is at least 25%, 30%, 35%, 40%, 45%, 50%, or more. The remainder is divided between condensable vapors, such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases, such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on process conditions, including the presence of water.

[0525] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or more. For example, in some embodiments, the carbonaceous material comprises from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon forms, to varying degrees, methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones.

[0526] In alternative embodiments, some portion of these compounds are combined with carbon-rich solids to enrich the carbon and energy content of the product. In these embodiments, some or all of the gas stream resulting from the reactor, including various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids originating from a cooling zone or a separate cooling unit. These embodiments are described in more detail below.

[0527] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids may be introduced into a separate cooling unit. In some embodiments, the solids are recovered and simply cooled at a slow rate. If the carbonaceous solids are reactive or unstable in air, it may be desirable to maintain an inert atmosphere or to rapidly cool the solids, for example, to a temperature of at most 40° C., such as ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. "Cooling unit" should be interpreted broadly to include vessels, tanks, pipes, or portions thereof.

[0528] In some embodiments, the process further includes operating a cooling unit to cool the warm pyrolyzed solids with steam, thereby producing cooler pyrolyzed solids and superheated steam, and drying is performed at least in part using superheated steam obtained from an external cooler. Optionally, the cooling unit can be operated to first cool the warm pyrolyzed solids with steam to reach a first cooling unit temperature, and then with air to reach a second cooling unit temperature, the second cooling unit temperature being lower than the first cooling unit temperature and associated with a reduced risk of combustion of the warm pyrolyzed solids in the presence of air.

[0529] Following cooling to ambient conditions, the carbonaceous solids may be collected and stored, conveyed to another on-site operation, transported to another site, or otherwise disposed of, traded, or sold. The solids may be fed to a unit to reduce particle size. A variety of size reduction units are known in the art, including crushers, shredders, grinders, pulverizers, jet mills, pin mills, and ball mills.

[0530] Screening or some other means for particle size-based separation may be included. Grinding, if present, may be upstream or downstream of the grinding. A portion of the screened material (e.g., large chunks) may be returned to the grinding unit. Small and large particles may be recovered for separate downstream uses. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as a finely divided carbon or activated carbon product.

[0531] Various additives can be introduced throughout the process before, during, or after any step disclosed herein. Additives can be broadly categorized as process additives selected to improve process performance, such as carbon yield or pyrolysis time / temperature to achieve a desired carbon purity, and product additives selected to improve the properties of downstream products incorporating the high-carbon bioreagent or reagents. Certain additives can provide enhanced process and product (bioreagent or bioreagent-containing products) properties.

[0532] The 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 the feedstock is harvested. The additive treatment can be incorporated before, during, or after sizing, drying, or other preparation of the feedstock. The additives can be incorporated into or on the feedstock supply facility, transport truck, unloading equipment, storage bin, conveyor (including open or closed conveyors), dryer, process heater, or any other unit. The additives can be added anywhere in the pyrolysis process itself, using a suitable means for introducing the additive. If desired, the additives can be added after carbonization or even after pulverization.

[0533] In some embodiments, the additive is selected from a metal, a metal oxide, a metal hydroxide, or a combination thereof. For example, the additive may be selected from, but is in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0534] In some embodiments, the additive is selected from an acid, a base, or a salt thereof. For example, the additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof.

[0535] In some embodiments, the additive is selected from metal halides. Metal halides are compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are generally obtained by direct combination of a basic metal salt with a hydrohalic acid, or more commonly, by neutralization. In some embodiments, the additive is selected from iron chloride (FeCl2 or FeCl3), iron bromide (FeBr2 or FeBr3), or hydrates thereof, and any combination thereof.

[0536] The additives can result in a final product with a higher energy content (energy density). The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content can result from the removal of non-combustible materials or materials with a lower energy density than carbon. In some embodiments, the additives reduce the degree of liquid formation in favor of solid and gas formation, or in favor of solid formation.

[0537] Without being limited to any particular hypothesis, the additives can chemically modify the starting biomass or treated biomass prior to pyrolysis to reduce cell wall breakdown for greater strength / integrity. In some embodiments, the additives can increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0538] Additives can result in bioreagents with improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. Additives can improve mechanical properties simply by their presence (e.g., the additive itself imparts strength to the mixture) or by some transformation that occurs within the additive phase or the resulting mixture. For example, a reaction such as vitrification can occur within a portion of the bioreagent that contains the additive, thereby improving the final strength.

[0539] Chemical additives can be applied to wet or dry biomass feedstock. The additives can be applied as a solid powder, spray, mist, liquid, or vapor. In some embodiments, the additives can be introduced by spraying from a liquid solution (such as in an aqueous solution or solvent) or by immersion in a tank, bin, bag, or other container.

[0540] In certain embodiments, an immersion pretreatment is used, in which the solid feedstock is immersed, either batchwise or continuously, in a bath containing the additive for a time sufficient to impregnate the additive into the solid feed material.

[0541] In some embodiments, additives applied to the feedstock can reduce the energy requirements for pyrolysis or increase the yield of the carbonaceous product. In these or other embodiments, additives applied to the feedstock can provide desirable functionality for the intended use of the carbonaceous product.

[0542] Throughput or process capacity can vary widely from small laboratory-scale units to full operations, including any pilot-, demonstration-, or semi-commercial-scale. In various embodiments, process capacities (of 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 ton / day, 100 ton / day, 500 ton / day, 1000 ton / day, 2000 ton / day, or more.

[0543] In some embodiments, a portion of the solids produced may be recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the reactor. By returning to the front end and passing through the process again, the treated solids may be higher in fixed carbon. The solids, liquids, and gas streams produced or present in the process may be independently recycled, passed to subsequent steps, or removed / purged from the process at any point.

[0544] In some embodiments, the pyrolyzed material is recovered and then fed to a separate unit for further pyrolysis to create a product with higher carbon purity. In some embodiments, the secondary process can be carried out in a simple container, such as a steel drum, through which a heated inert gas (such as heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas containing volatiles can be sent, for example, to a thermal oxidizer or returned to the main process reactor. To cool the product, another stream of inert gas, initially at, for example, ambient temperature, can be passed through the solids to cool them and then returned to the inert gas preheat system.

[0545] Some variations of this technology include: (a) a feeder configured to introduce a carbonaceous feedstock; (b) an optional dryer disposed in operable communication with the supply apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solids cooler disposed in operable communication with the multi-zone reactor; (e) utilizing a high-carbon biological reagent production system comprising a high-carbon biological reagent recovery unit disposed in operable communication with the solid-state cooler;

[0546] Some variations are: (a) a feeder configured to introduce a carbonaceous feedstock; (b) an optional dryer disposed in operable communication with the supply apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) an optional preheater disposed in operable communication with the dryer and configured to heat or gently pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operable communication with the preheater and configured to pyrolyze the feedstock; (e) a cooler disposed in operable communication with the pyrolysis reactor and configured to cool the pyrolysis solids; (f) a high-carbon biological reagent recovery unit disposed in operative communication with the cooler, The system utilizes a bioreagent production system configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solid.

[0547] The feed system can be physically integrated with the multi-zone reactor, such as through the use of a screw feed system or auger mechanism to introduce the feed solids into the first reaction zone.

[0548] In some embodiments, the system further comprises a preheating zone disposed in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) can be located within a single unit or can be located in separate units.

[0549] Optionally, the dryer can be configured as a drying zone within a multi-zone reactor. Optionally, a solids cooler can be located within the multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0550] The system may include a purging means for removing oxygen from the system. For example, the purging means may comprise one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the system. In some embodiments, the purging means is a degasser disposed in operative communication between the dryer and the multi-zone reactor.

[0551] The multi-zone reactor can be configured with at least a first gas inlet and a first gas outlet, which can be disposed in communication with different zones or the same zone.

[0552] In some embodiments, the multi-zone reactor is configured with a second gas inlet or a second gas outlet. In some embodiments, the multi-zone reactor is configured with a third gas inlet or a third gas outlet. In some embodiments, the multi-zone reactor is configured with a fourth gas inlet or a fourth gas outlet. In some embodiments, each zone present in the multi-zone reactor is configured with a gas inlet and a gas outlet.

[0553] The gas inlets and outlets not only allow for the introduction and removal of vapors, but the gas outlets (probes) in particular allow for accurate process monitoring and control over various stages of the process, up to and potentially including all stages of the process. Accurate process monitoring is expected to result in improved yield and efficiency, both dynamically and over time, when operating history can be utilized to adjust process conditions.

[0554] In some embodiments, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful for sampling and analyzing gases to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as by adjusting the feed rate, the rate of inert gas sweep, the temperature (in one or more zones), the pressure (in one or more zones), additives, etc.

[0555] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more sampling via the reactive gas probe, and optionally, if deemed necessary or desirable, making process or equipment adjustments based on the measurements using well-known principles of process control (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0556] The reaction gas probe can be configured to extract a gas sample in many ways. For example, the sampling line can have a pressure lower than the pyrolysis reactor pressure, so that when the sampling line is opened, a quantity of gas can be easily extracted from the pyrolysis zone. The sampling line can be under vacuum, such as when the pyrolysis zone is at near atmospheric pressure. Typically, the reaction gas probe is associated with one gas output or a portion thereof (e.g., a line branching off from the gas output line).

[0557] In some embodiments, both the gas input and gas output are utilized as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with a process sample (a "sample sweep"). Such a configuration can be used in zones that do not have a gas inlet / outlet for a substantially inert gas for processing, or the reactive gas probe can be associated with a separate gas inlet / outlet in addition to the process inlet and outlet. The sampling inert gas that is periodically introduced and withdrawn for sampling (in embodiments utilizing a sample sweep) can be different from the process inert gas, as desired, either for analytical accuracy reasons or to introduce an analytical tracer.

[0558] For example, the acetic acid concentration in the gas phase of the pyrolysis zone can be measured using a gas probe to extract a sample, which is then analyzed using a suitable technique (gas chromatography, GC; mass spectrometry, MS; GC-MS, or Fourier transform infrared spectroscopy, FTIR, etc.). The CO or CO2 concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity to gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity to liquid.

[0559] In some embodiments, the system further comprises at least one additional gas probe disposed in operative communication with the cooling zone, or the drying zone (if present) or the preheating zone (if present).

[0560] A gas probe for the cooling zone can be useful, for example, to determine the extent of any additional chemical reactions occurring in the cooling zone. A gas probe in the cooling zone can also be useful as an independent measurement of temperature (e.g., in addition to a thermocouple located in the cooling zone). This independent measurement can be a correlation between cooling temperature and a measured quantity of a particular species. The correlation can be developed separately or can be established after a period of process operation.

[0561] A gas probe for the drying zone can be useful to determine the degree of drying, for example by measuring moisture content. A gas probe in the preheat zone can be useful, for example, to determine the extent of any mild pyrolysis that occurs.

[0562] In certain embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the preheating zone (if present) can be configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively or additionally, the drying zone can be configured with a gas outlet to generate a substantially countercurrent flow.

[0563] The one or more pyrolysis reactors may be selected from any suitable reactor configuration capable of carrying out a pyrolysis process. Exemplary reactor configurations include, but are not limited to, a fixed bed reactor, a fluidized bed reactor, an entrained bed reactor, an auger, an ablation reactor, a rotating cone, a rotating drum kiln, a calciner, a roaster, a moving bed reactor, a transport bed reactor, an ablation reactor, a rotating cone, or a microwave-assisted pyrolysis reactor.

[0564] In some embodiments where an auger is used, sand or another heat carrier can optionally be used. For example, the feedstock and sand can be fed at one end of a screw. The screw mixes the sand and feedstock and conveys them through the reactor. The screw can provide good control of feedstock residence time and does not dilute the pyrolysis products with carrier or fluidizing gas. The sand can be reheated in a separate vessel.

[0565] In some embodiments where an ablation process is used, the feedstock is moved at high velocity relative to the hot metal surface. Ablation of any char that forms on the surface can maintain a high heat transfer rate. Such an arrangement can prevent dilution of the product. Alternatively, the feedstock particles can be suspended in a carrier gas and introduced at high velocity through a cyclone with heated walls.

[0566] In some embodiments where a fluidized bed reactor is used, the feedstock may be introduced into a bed of hot sand fluidized by a gas, typically a recycled product gas. References herein to "sand" also include similar substantially inert materials such as glass particles, recovered ash particles, and the like. The high heat transfer rate from the fluidized sand can result in rapid heating of the feedstock. There may be some abrasion due to friction with the sand particles. Heat is typically provided by heat exchanger tubes through which the hot combustion gases flow.

[0567] A circulating fluidized bed reactor can be used, in which gas, sand, and feedstock move together. Exemplary transport gases include recycled product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the feedstock, and ablation is expected to be stronger than in a conventional fluidized bed. A separator can be used to separate the product gas from the sand and char particles. The sand particles can be reheated in a fluidized burner vessel and recycled to the reactor.

[0568] In some embodiments, the multi-zone reactor is a continuous reactor comprising a feedstock inlet, a plurality of spatially separated reaction zones configured to separately control the temperature and mixing within each of the reaction zones, and a carbonaceous solids outlet, one of the reaction zones configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the reaction zones configured with a first gas outlet.

[0569] In various embodiments, the reactor comprises at least two, three, four, or more reaction zones. Each of the reaction zones is disposed in communication with separately adjustable heating means independently selected from electrical heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat heat transfer, or combinations thereof. In some embodiments, at least one reactor zone is heated with an effluent stream from a thermal oxidizer, if present.

[0570] The reactor can be configured to separately adjust the gas phase composition and gas phase residence time of at least two reaction zones up to all reaction zones present in the reactor.

[0571] The reactor can be equipped with a second gas inlet or a second gas outlet. In some embodiments, the reactor is configured with a gas inlet for each reaction zone. In these or other embodiments, the reactor is configured with a gas outlet for each reaction zone. The reactor can be a co-current or counter-current reactor.

[0572] In some embodiments, the feedstock inlet comprises a screw or auger feed mechanism, hi some embodiments, the carbonaceous solids outlet comprises a screw or auger output mechanism.

[0573] Certain embodiments utilize a rotary calciner equipped with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotational speed affects solids flow patterns and heat and mass transfer. Each reaction zone can be configured with flights disposed on the interior walls to provide agitation of the solids. The flights can be independently adjustable in each reaction zone.

[0574] Other means of agitating the solids can be used, such as an auger, screw, or paddle conveyor. In some embodiments, the reactor contains a single continuous auger positioned throughout each of the reaction zones. In other embodiments, the reactor contains twin screws positioned throughout each of the reaction zones.

[0575] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., to process biomass feedstock without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not include augers, screws, or rakes, which tend to significantly reduce the size of the feedstock being pyrolyzed.

[0576] In some embodiments of the present invention, the system further includes a thermal oxidizer disposed in operable communication with the outlet through which the condensable vapors and non-condensable gases are removed. The thermal oxidizer may be configured to receive separate fuel (such as natural gas) and oxidant (such as air) into a combustion chamber adapted to combust the fuel and at least some of the condensable vapors. Certain non-condensable gases, such as CO or CH4, may also be oxidized to CO2.

[0577] When a thermal oxidizer is used, the system may include a heat exchanger disposed between the thermal oxidizer and the dryer and configured to utilize at least a portion of the heat of combustion for the dryer. This embodiment can significantly contribute to the overall energy efficiency of the process.

[0578] In some embodiments, the system further comprises a carbon enrichment unit disposed in operative communication with the solids cooler and configured to combine the condensable vapor in at least partially condensed form with the solids, the carbon enrichment unit being capable of increasing the carbon content of the high-carbon biological reagent obtained from the recovery unit.

[0579] The system may further include a separate pyrolysis unit adapted to further pyrolyze the high-carbon bio-reagent to further increase its carbon content. The separate pyrolysis unit may be a relatively simple container, unit, or device, such as a tank, barrel, bin, drum, tote, sack, or roll-off.

[0580] The entire system may be at a fixed location or may be distributed over several locations. The system may be constructed using modules that can be easily replicated for practical scale-up. The system may also be constructed using economy of scale principles, as is well known in the process industries.

[0581] Some variations on carbon enrichment of solids will now be further described. In some embodiments, the process for producing a high-carbon bio-reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) optionally cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; (h) then passing at least a portion of the condensable vapors or at least a portion of the non-condensable gases from step (e) through a warm or cold pyrolysis solid to form an enhanced pyrolysis solid having an increased carbon content; (i) recovering a high-carbon biological reagent comprising at least a portion of the enhanced pyrolysis solids.

[0582] In some embodiments, step (h) comprises passing at least a portion of the condensable vapors from step (e), in vapor or condensed form, through warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gases from step (e) through warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content.

[0583] Alternatively or additionally, the vapor or gas can be contacted with the low temperature pyrolytic solid. In some embodiments, step (h) comprises passing at least a portion of the condensable vapor from step (e), in vapor or condensed form, through the low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gas from step (e) through the low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0584] In certain embodiments, step (h) comprises passing substantially all of the condensable vapors from step (e), in vapor or condensed form, through a low-temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content. In certain embodiments, step (h) comprises passing substantially all of the non-condensable gases from step (e) through a low-temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0585] The process may include various methods of treating or separating the steam or gas prior to using the steam or gas for carbon enrichment. For example, the intermediate feed stream, consisting essentially of at least a portion of the condensable steam and at least a portion of the non-condensable gas obtained from step (e), may be fed to a separation unit configured to produce at least first and second output streams. In certain embodiments, the intermediate feed stream includes all of the condensable steam, all of the non-condensable gas, or both.

[0586] Separation techniques can include or use distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separations can be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and can exploit differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to a stationary phase, and any combination thereof.

[0587] In some embodiments, the first and second output streams are separated from the intermediate feed stream based on relative volatility. For example, the separation unit can be a distillation column, a flash tank, or a condenser.

[0588] Thus, in some embodiments, the first output stream includes condensable vapors and the second output stream includes non-condensable gases. The condensable vapors may include at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapors from pyrolysis may include aromatic compounds such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic compounds such as refractory tars may be present in the vapors. The non-condensable gases may include at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, or methane.

[0589] In some embodiments, the first and second output streams are intermediate feed streams that have been separated based on their relative polarity. For example, the separation unit can be a stripping column, a packed bed, a chromatography column, or a membrane.

[0590] Thus, in some embodiments, the first output stream comprises polar compounds and the second output stream comprises non-polar compounds. The polar compounds may comprise at least one carbon-containing molecule selected from methanol, furfural, or acetic acid. The non-polar compounds may comprise at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, methane, terpene, or terpene derivatives.

[0591] Step (h) can increase the total carbon content of the high-carbon biological reagent relative to an otherwise identical process that does not include step (h). The degree of increase in carbon content can be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more in various embodiments.

[0592] In some embodiments, step (h) increases the fixed carbon content of the high-carbon bioreagent. In these or other embodiments, step (h) increases the volatile carbon content of the high-carbon bioreagent. The volatile carbon content is carbon attributable to volatile materials in the reagent. Volatile materials can be, but are not limited to, aliphatic or aromatic compounds (e.g., terpenes); oxygenates, including alcohols, aldehydes, or ketones; and hydrocarbons, including various tars. Volatile carbon typically remains bound or adsorbed to solids at ambient conditions, but is released upon heating before the fixed carbon is oxidized, gasified, or otherwise released as vapor.

[0593] Depending on the conditions associated with step (h), it is possible for some amount of volatile carbon to become fixed carbon (e.g., via Boudoir carbon formation from CO). Typically, volatiles enter the micropores of the fixed carbon and exist as condensed / adsorbed species, but remain relatively volatile. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0594] Step (h) can increase the energy content (i.e., energy density) of the high-carbon biological reagent. The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. The degree of increase in energy content can be, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher in various embodiments.

[0595] Further separation can be used to recover non-condensable gases or condensable vapors for use within the process or further processing, for example, further processing can be included to produce purified carbon monoxide or hydrogen.

[0596] As another example, separation of acetic acid can be performed followed by reduction of the acetic acid to ethanol, which can be achieved, at least in part, using hydrogen derived from the non-condensable gases produced.

[0597] Condensable vapors can be used for energy in the process (such as by thermal oxidation) or for carbon enrichment to increase the carbon content of the high-carbon bioreagent. Certain non-condensable gases, such as CO or CH4, can be utilized for energy in the process or as part of the substantially inert gas for the pyrolysis step. Any combination of the foregoing is also possible.

[0598] A potential advantage of including step (h) is that the gas stream is scrubbed and the resulting gas stream is enriched in CO and CO. The resulting gas stream can be utilized for energy recovery, recycled for carbon enrichment of solids, or used as an inert gas in the reactor. Similarly, by separating non-condensable gases from condensable vapors, a CO / CO stream is prepared for use as an inert gas in, for example, a reactor system or a cooling system.

[0599] Other variations are premised on the recognition that the principles of the carbon enrichment step can be applied to any feedstock to which it is desired to add carbon.

[0600] In some embodiments, a batch or continuous process for producing a high carbon bio-reagent comprises: (a) providing a solids stream comprising a carbon-containing material; (b) providing a gas stream comprising a condensable carbonaceous vapor, a non-condensable carbonaceous gas, or a mixture of a condensable carbonaceous vapor and a non-condensable carbonaceous gas; (c) passing the gas stream through the solid stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0601] In some embodiments, the starting carbon-containing material is pyrolyzed biomass or torrefied biomass. The gas stream can be obtained during an integrated process to provide the carbon-containing material. Alternatively, the gas stream can be obtained from a separate processing of the carbon-containing material. The gas stream, or a portion thereof, can be obtained from an external source (e.g., a sawmill oven). Mixtures of gas streams from various sources are possible, as well as mixtures of carbon-containing materials.

[0602] In some embodiments, the process further comprises repeating the process to recycle or reuse the gas stream to further increase the carbon or energy content of the carbon-containing product. In some embodiments, the process further comprises performing the process to recycle or reuse the gas stream to increase the carbon or energy content of another feedstock different from the carbon-containing material.

[0603] In some embodiments, the process further includes introducing the gas stream into a separation unit configured to produce at least first and second output streams, the gas streams comprising a mixture of condensable carbonaceous vapors and non-condensable carbonaceous gases. The first and second output streams can be separated based on relative volatility, relative polarity, or any other characteristic. The gas streams can be obtained from separate processing of carbonaceous materials.

[0604] In some embodiments, the process further comprises repeating the process to recycle or reuse the gas stream to further increase the carbon content of the carbon-containing product. In some embodiments, the process further comprises performing the process to recycle or reuse the gas stream to increase the carbon content of another feedstock.

[0605] The carbon-containing product can have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, relative to the starting carbon-containing material.

[0606] In a related variation, the high carbon bio-reagent production system comprises: (a) a feeder configured to introduce a carbonaceous feedstock; (b) an optional dryer disposed in operable communication with the supply apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solids cooler disposed in operable communication with the multi-zone reactor; (e) a material enrichment unit disposed in operable communication with the solids cooler and configured to pass a condensable vapor or a non-condensable gas through the solids to form an enriched solid having an increased carbon content; (f) a high-carbon biological reagent recovery unit disposed in operable communication with the material concentration unit.

[0607] The system may further include a preheating zone disposed in operable communication with the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within the multi-zone reactor. Each of the zones may be located within a single unit or in separate units. Additionally, a solids cooler may be disposed within the multi-zone reactor.

[0608] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet, thereby creating a substantially countercurrent flow of the gas phase relative to the solid phase. In these or other embodiments, the preheating zone or drying zone (or dryer) is configured with a gas outlet, thereby creating a substantially countercurrent flow of the gas phase relative to the solid phase.

[0609] In certain embodiments, the system incorporates a material enrichment unit, the material enrichment unit comprising: (i) a housing having an upper portion and a lower portion; (ii) an inlet at the bottom of the lower portion of the housing configured to carry condensable vapors and non-condensable gases; (iii) an outlet at the top of the upper portion of the housing configured to carry a concentrated gas stream derived from the condensable vapors and non-condensable gases; (iv) a passageway defined between the upper and lower portions of the housing; (v) a transport system following the pathway, the transport system configured to transport the solid, the housing shaped such that the solid adsorbs at least a portion of the condensable vapor or at least a portion of the non-condensable gas.

[0610] The present invention is capable of producing a variety of compositions useful as high-carbon biological reagents, and products incorporating such reagents. In some variations, the high-carbon biological reagents can be prepared using any of the processes disclosed herein, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 250°C to about 700°C to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; and (h) recovering a high-carbon biological reagent comprising at least a portion of the cold pyrolysis solids.

[0611] In some embodiments, the reagent comprises, on a dry basis, about at least 70%, at least 80%, at least 90%, or at least 95% total carbon by weight. Total carbon includes at least fixed carbon and may further include carbon from volatile materials. In some embodiments, carbon from volatile materials is about at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the high-carbon biological reagent. For example, fixed carbon can be measured using ASTM D3172, and volatile carbon can be measured using ASTM D3175.

[0612] The high-carbon bio-reagent may contain, on a dry basis, about 10% by weight or less, e.g., about 5% by weight or less, hydrogen. The bio-reagent may contain, on a dry basis, about 1% by weight or less, e.g., about 0.5% by weight or less, nitrogen. The bio-reagent may contain, on a dry basis, about 0.5% by weight or less, e.g., about 0.2% by weight or less, phosphorus. The bio-reagent may contain, on a dry basis, about 0.2% by weight or less, e.g., about 0.1% by weight or less, sulfur.

[0613] Carbon, hydrogen, and nitrogen can be measured, for example, using ASTM D5373 for elemental analysis. Oxygen can be measured, for example, using ASTM D3176. Sulfur can be measured, for example, using ASTM D3177.

[0614] Certain embodiments provide reagents that are substantially free of hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture that may be present. Thus, some embodiments provide bioreagents that have 100% or less carbon on a dry / ash-free (DAF) basis.

[0615] Generally speaking, feedstocks such as biomass contain non-volatile species, including silica and various metals, that are not readily released during pyrolysis. Of course, ashless feedstocks can also be utilized, in which case there should be no substantial amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0616] Varying amounts of non-combustible materials, such as ash, may be present. The high-carbon bioreagent may contain about 10% or less, e.g., about 5%, about 2%, about 1% or less, by weight of non-combustible materials on a dry basis. In certain embodiments, the reagent contains little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon containing 100% carbon on a dry basis.

[0617] Varying amounts of moisture may be present. Based on total mass, the high-carbon bioreagent may contain at least 1%, 2%, 5%, 10%, 15%, 25%, 35%, 50%, or more by weight of moisture. As intended herein, "moisture" should be interpreted to include any form of water present in the bioreagent, including absorbed moisture, adsorbed water molecules, chemical hydrates, and physical hydrates. The equilibrium moisture content may vary depending on at least the local environment, such as relative humidity. Moisture may also vary during transportation, preparation for use, and other logistics. Moisture can be measured, for example, using ASTM D3173.

[0618] High-carbon bioreagents can have a variety of energy contents, which for the present purposes refers to energy density based on the higher calorific value associated with the total combustion of the bone-dry reagent. For example, high-carbon bioreagents can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In certain embodiments, the energy content is about 14,000-15,000 Btu / lb. Energy content can be measured, for example, using ASTM D5865.

[0619] The high-carbon biological reagent can be formed into a powder, such as a coarse or fine powder. For example, the reagent can, in embodiments, be formed into a powder having an average mesh size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0620] In some embodiments, the high-carbon biological reagent is formed into a structure comprising compressed, bonded, or agglomerated particles. The starting material for forming these bodies can be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The bodies can be formed by mechanical pressing or other forces, optionally with the use of binders or other means to agglomerate the particles together.

[0621] In some embodiments, the high-carbon bio-reagent is produced in the form of a structure whose structure is substantially derived from the source material. For example, a source chip can produce a product chip of high-carbon bio-reagent. Or, a source cylinder can produce a high-carbon bio-reagent cylinder, which can be somewhat smaller but otherwise maintain the basic structure and geometry of the starting material.

[0622] High carbon biological reagents according to the present invention can be produced or formed into objects having a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or more. In various embodiments, the minimum or maximum dimension can be a length, width, or diameter.

[0623] Other variations of the invention relate to the incorporation of additives into the process, into the product, or both. In some embodiments, the high-carbon biological reagent includes at least one process additive that is incorporated during the process. In these or other embodiments, the reagent includes at least one product additive that is introduced into the reagent after the process.

[0624] In some embodiments, the high-carbon biological reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5 wt. % or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

[0625] The additives may be selected from, but are in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0626] In some embodiments, the high-carbon biological reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5 wt. % or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from an acid, a base, or a salt thereof.

[0627] The additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0628] In certain embodiments, the high-carbon biological reagent, on a dry basis, comprises: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5 wt. % or less of phosphorus; 0.2% by weight or less of sulfur; a first additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; a second additive selected from an acid, a base, or a salt thereof; The first additive is different from the second additive.

[0629] The first additive may be selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof, and the second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0630] Certain high-carbon biological reagents consist essentially, on a dry basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, a non-combustible material, and an additive selected from magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof.

[0631] Certain high-carbon biological reagents consist essentially, on a dry basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, a non-combustible material, and an additive selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, or combinations thereof.

[0632] The amount of additive (or total additives) can vary widely, such as from about 0.01% to about 25% by weight, including about 0.1%, about 1%, about 5%, about 10%, or about 20% by weight. It will be appreciated, therefore, that when relatively large amounts of additive, such as greater than about 1% by weight, are incorporated, the energy content calculated based on the total reagent weight (including additives) will be reduced. Furthermore, in various embodiments, the high-carbon biological reagent with additives can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0633] The above discussion regarding product form also applies to embodiments incorporating additives, and indeed certain embodiments incorporate additives as binders, fluxing agents, or other modifiers to improve final properties for particular applications.

[0634] In some embodiments, the majority of the carbon contained in the high-carbon bio-reagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. There may be certain market mechanisms (e.g., renewable identification numbers, tax credits, etc.) where value is attributed to the renewable carbon content in the high-carbon bio-reagent.

[0635] In certain embodiments, the fixed carbon can be classified as non-renewable carbon (e.g., from coal), while the volatile carbon, which can be added separately, can be renewable carbon to increase not only the energy content but also the renewable carbon value.

[0636] The high-carbon bioreagents produced as described herein are useful for a wide variety of carbonaceous products. They may themselves be desirable market products. The high-carbon bioreagents provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including higher renewable carbon content) compared to the state of the art.

[0637] In variations, the product comprises any of the high-carbon biological reagents obtainable by the disclosed processes or described in the compositions set forth herein, or any portion, combination, or derivative thereof.

[0638] Generally speaking, high-carbon bioreagents can be combusted to produce energy (including electricity and heat); partially oxidized, gasified, or steam reformed to produce syngas; utilized for their adsorption or absorption properties; utilized for their reactive properties in metal refining (such as reduction of metal oxides) or other industrial processes; or utilized for their material properties in carbon steel and various other metal alloys. Essentially, high-carbon bioreagents can be utilized in any market application of carbon-based commodities or advanced materials, including specialized uses to be developed.

[0639] Prior to suitability or actual use in any product application, the disclosed high-carbon bioreagents can be analyzed, measured, and optionally modified (such as by additives) in a variety of ways. Some potentially important properties beyond chemical composition and energy content include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, and basicity, to name a few. 【0...

Claims

1. 1. A method for producing a biocarbon composition having an optimized base-acid ratio, the method comprising: (a) providing a starting material comprising biomass, wherein the starting material is optionally dried; (b) pyrolyzing the starting material to produce an intermediate biocarbon stream and pyrolysis vapor, wherein the intermediate biocarbon stream has a carbon-carbon bond represented by the following formula: [Equation 1] wherein Fe is a base-acid ratio defined by ２ O ３ , CaO, MgO, K ２ O, Na ２ O, SiO ２ , Al ２ O ３ , and TiO ２ each of which corresponds to a weight percentage according to ASTM D4326, (c) treating the intermediate biocarbon stream with a solution of an acid, a base, a salt, a metal, H ２ , H ２ O, CO, CO ２ or a combination thereof to adjust the base-acid ratio, and / or introducing an additive during step (a) or step (b) to adjust the base-acid ratio; (d) recovering a biocarbon composition comprising about 50% to about 99% by weight of total carbon, wherein the total carbon is １４ C / １２ wherein the recovering is at least 50% renewable as determined from C isotope ratio measurements, and the base-acid ratio of the biocarbon composition is selected from about 0.1 to about 10.

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

3. Step (c) selectively removes basic components, thereby ２ O ３ , the CaO, the MgO, the K ２ O, or the Na ２ The method of claim 1, wherein O is reduced.

4. 10. The method of claim 1, wherein step (c) utilizes acidic water obtained from step (a), from step (b), or from another method step performed prior to step (c).

5. 5. The method of claim 4, wherein the acidic water is obtained from condensation of the pyrolysis vapors to produce a condensed liquid having a pH of about 1 to about 7.

6. Step (c) selectively removes the acidic components, thereby removing the SiO ２ , the Al ２ O ３ or the TiO ２ The method of claim 1, wherein

7. 10. The method of claim 1, wherein step (c) utilizes alkaline water obtained from step (a), from step (b), or from another method step performed prior to step (c).

8. 10. The method of claim 1, wherein step (c) utilizes steam scrubbing of the intermediate biocarbon stream.

9. 10. The method of claim 1, wherein step (d) utilizes steam washing of the biocarbon composition.

10. 10. The method of claim 1, wherein the additive in step (c) comprises calcium, calcium oxide, calcium carbonate, magnesium oxide, magnesium carbonate, limestone, lime, dolomite, dolomitic lime, bentonite, gypsum, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, iron ore concentrate, fluorspar, fluorospar, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, borax, silica, alumina, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or a combination or derivative thereof.

11. Step (c) treating the intermediate biocarbon stream with an acid, base, salt, metal, H ２ , H ２ O, CO, CO ２ or a combination thereof to adjust the base-acid ratio, and introducing an additive during step (a) or step (b) to adjust the base-acid ratio.

12. 10. The method of claim 1, wherein the biocarbon composition has a higher calorific value of at least about 25 MJ / kg on a dry basis.

13. 10. The method of claim 1, wherein the biocarbon composition is pelletized, thereby producing biocarbon pellets, and wherein a binder is optionally utilized to aid in pelletizing, the binder being selected from the group consisting of starch, thermoplastic starch, cross-linked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metco tungsten, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, or combinations or derivatives thereof.

14. 14. The method of any one of claims 1 to 13, wherein the base-acid ratio is at least about 1.5 to at most about 5.

15. The biocarbon composition comprises: the Fe, each as a weight percentage in the biocarbon composition according to ASTM D4326; ２ O ３ 14. The method of claim 1, wherein the biocarbon composition is characterized by an iron-calcium ratio defined as:

16. The biocarbon composition comprises: the Fe, each as a weight percentage in the biocarbon composition according to ASTM D4326; ２ O ３ and CaO, and the iron + calcium parameter of the biocarbon composition is selected from 5 wt% to about 50 wt%.

17. 14. The method of any one of claims 1 to 13, wherein the biocarbon composition is characterized by a slagging factor defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biocarbon composition on a dry basis, and wherein the slagging factor of the biocarbon composition is selected from about 0.001 to about 1.

18. The biocarbon composition may have a base-acid ratio of Na as a weight percentage in the biocarbon composition according to ASTM D4326. ２ 14. The method of any one of claims 1 to 13, characterized by a fouling factor defined as multiplied by O, and wherein the fouling factor of the biocarbon composition is selected from about 0.1 to about 10.

19. The biocarbon composition has a base-acid ratio of 0.01 to 0.

01. ２ characterized by a modified soiling factor defined as the sum of the water-soluble Na ２ O is leached from ash derived from the biocarbon composition in the presence of water according to ASTM D4326. ２ 0, and the modified soiling factor is selected from about 0.1 to about 10.

20. The biocarbon composition comprises, on a dry basis, about 50% to about 99% by weight of fixed carbon, and the total carbon in the biocarbon composition is about 50% to about 99% by weight of the total carbon. １４ C / １２ 14. The method of any one of claims 1 to 13, which is at least 90% reproducible as determined from measurements of C isotope ratios.

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