Biomedia compositions for peat replacement products and processes for producing biomedia compositions

Abstract

Some variations include a biomedia composition that is 50% to 75% by weight total carbon, on a dry basis, according to ASTM D5373, and the total carbon is 50% to 75% by weight total carbon, according to ASTM D6866 ( 14 C / 1 2 The biomedia composition comprises total carbon that is renewable according to the carbon isotope ratio (C isotope ratio), 20% to 40% by weight, on a dry basis, of oxygen according to ASTM D5373, 3% to 10% by weight, on a dry basis, of hydrogen according to ASTM D5373, and 0.1% to 2% by weight, on a dry basis, of nitrogen according to ASTM D5373, the biomedia composition characterized by a volatile matter content of 50% to 75% by weight according to ASTM D3175, the biomedia composition characterized by an ash content of 1% to 25% by weight according to ASTM D3174, and the biomedia composition characterized by a moisture content of 0 to 75% by weight according to ASTM D3173. Processes for making and using the biomedia composition are also described.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 418,305, filed October 21, 2022, which is incorporated herein by reference in its entirety.

[0002] The present invention relates generally to peat replacement products. [Background technology]

[0003] Peat is an accumulation of partially decayed vegetation or organic matter. It is composed of organic matter, minerals, and water. Peat is traditionally harvested from natural areas, peatlands, which can take specific forms, such as bogs, mires, heaths, marshes, fens, pocosins, or peat swamp forests. Summary of the Invention

[0004] Some variations of the present invention are biomedia compositions comprising: About 50% to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, 14 C / 12 total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% by weight hydrogen on a dry basis according to ASTM D5373 elemental analysis of the biomedia composition; and about 0.1% to about 2% nitrogen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; A biomedia composition is provided, wherein the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0005] In some embodiments, the biomedia composition comprises, on a dry basis, about 55% to about 70% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition. In certain embodiments, the biomedia composition comprises, on a dry basis, about 60% to about 65% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0006] In some embodiments, the total carbon is 14 C / 12 In certain embodiments, the total carbon is at least 80% renewable according to ASTM D6866 measurement of C isotope ratio. 14 C / 12 It is at least 90% (e.g., 100%) renewable according to ASTM D6866 measurement of C isotope ratio.

[0007] In some embodiments, the biomedia composition comprises, on a dry basis, about 25% oxygen by weight to about 35% oxygen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0008] In some embodiments, the biomedia composition comprises, on a dry basis, about 5% to about 8% hydrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0009] In some embodiments, the biomedia composition comprises, on a dry basis, about 0.5% to about 1% by weight of nitrogen according to ASTM D5373 elemental analysis of the biomedia composition. Nitrogen is an important nutrient for plant growth.

[0010] In some embodiments, the biomedia composition includes phosphorus, potassium, sulfur, or a combination thereof. Phosphorus, potassium, and sulfur are important nutrients for plant growth.

[0011] In some embodiments, the biomedia composition contains less than 1 ppm of mercury. The biomedia composition may be essentially mercury-free.

[0012] In some embodiments, the biomedia composition further comprises one or more additives. Additives may be introduced for a variety of reasons, including both functional (e.g., for pH optimization) and decorative (e.g., color). For example, additives may be used to improve the water absorption, nutrient absorption, or breathability of the biomedia composition.

[0013] In some embodiments, the biomedia composition is characterized by a volatile matter content of about 60% to about 70% by weight according to ASTM D3175 proximate analysis of the biomedia composition.

[0014] In some embodiments, the biomedia composition is characterized by an ash content of about 2% to about 20% by weight according to ASTM D3174 proximate analysis of the biomedia composition.

[0015] In some embodiments, the biomedia composition is characterized by a moisture content of 10% to about 50% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0016] In some embodiments, the biomedia composition is hydrophilic. In other embodiments, the biomedia composition is hydrophobic. In certain embodiments, the biomedia composition is amphiphilic.

[0017] The biomedia composition may be characterized by an equilibrium moisture content, as defined in accordance with ASTM D1412. The equilibrium moisture content may be from 0 to about 90% water by weight, such as from about 25% to about 75% by weight. A higher equilibrium moisture content typically means that the biomedia composition has a high water absorption capacity.

[0018] In some embodiments, the biomedia composition is in the form of fine particles. In some embodiments, the biomedia composition is in the form of fibrous particles. In certain embodiments, the biomedia composition is in the form of a mixture of fine particles and fibrous particles.

[0019] In some embodiments, the biomedia composition is in the form of a densified body, such as a pellet or brick of the biomedia composition.

[0020] In some embodiments, the biomedia composition has a biomedia pH selected from about 4 to about 8. In certain embodiments, the biomedia composition has a biomedia pH selected from about 5 to about 7.

[0021] In some embodiments, the biomedia composition has a cation exchange capacity selected from about 50 to about 200 meq / 100 g, such as about 80 to about 150 meq / 100 g, or about 100 to about 125 meq / 100 g.

[0022] In some embodiments, the biomedia composition has the following formula:

number

[0023] In some embodiments, the biomedia composition has the following formula:

number

[0024] In some embodiments, the biomedia composition is biologically sterile.

[0025] In some embodiments, the biomedia composition is biodegradable.

[0026] In some embodiments, the biomedia composition is compostable.

[0027] In some embodiments, the biomedia composition has low fine particle / particulate levels to avoid dust hazards.

[0028] Another variation of the present invention is a process for producing a biomedia composition, the process comprising: (a) providing a starting material containing biomass, the starting material being optionally dried; (b) mildly pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor; (c) optionally 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 acidity of the intermediate biocarbon stream; (d) about 50% by weight to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is 14 C / 12 total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% by weight hydrogen on a dry basis according to ASTM D5373 elemental analysis of the biomedia composition; and recovering a biomedia composition containing, on a dry basis, about 0.1% to about 2% nitrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The process provides that the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0029] Some variations of the present invention are processes for producing a biomedia composition, the process comprising: (a) providing a starting material containing biomass, the starting material being optionally dried; (b) mildly pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor; (c) optionally introducing one or more additives during step (a) or step (b) to adjust the acidity of the intermediate biocarbon stream; (d) about 50% by weight to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is 14C / 12 total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% by weight hydrogen on a dry basis according to ASTM D5373 elemental analysis of the biomedia composition; and recovering a biomedia composition containing, on a dry basis, about 0.1% to about 2% nitrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The process provides that the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0030] 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.

[0031] In some processes, the intermediate biocarbon stream or biomedia composition is mechanically shredded.

[0032] In some processes, the intermediate biocarbon stream or biomedia composition is mechanically disaggregated.

[0033] In some processes, the intermediate biocarbon stream or biomedia composition is further processed.

[0034] In some processes, the intermediate biocarbon stream or biomedia composition is treated to alter the porosity of the biomedia composition.

[0035] In some processes, the intermediate biocarbon stream or biomedia composition is treated to alter the solids flow properties of the biomedia composition.

[0036] In some processes, the biomedia composition is treated to adjust the chemical oxygen demand of the biomedia composition.

[0037] In some processes, the biomedia composition is treated to adjust the color of the biomedia composition.

[0038] In some processes, the biomedia composition is treated to control the odor of the biomedia composition.

[0039] In some processes, the biomedia composition is treated to adjust the texture of the biomedia composition.

[0040] In various processes, the biomedia composition comprises, on a dry basis, about 55% to about 70% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition. In one particular process, the biomedia composition comprises, on a dry basis, about 60% to about 65% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0041] In some processes, the total carbon is 14 C / 12 At least 80% renewable according to ASTM D6866 measurement of C isotope ratio. In certain processes, total carbon is 14 C / 12 At least 90%, at least 95%, or 100% renewable according to ASTM D6866 measurement of C isotope ratio.

[0042] In some processes, the biomedia composition comprises, on a dry basis, about 25% oxygen to about 35% oxygen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0043] In some processes, the biomedia composition comprises, on a dry basis, about 5% to about 8% hydrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0044] In some processes, the biomedia composition comprises, on a dry basis, about 0.5% to about 1% by weight nitrogen according to ASTM D5373 elemental analysis of the biomedia composition.

[0045] In some processes, the biomedia composition includes phosphorus, potassium, sulfur, or a combination thereof.

[0046] In some processes, the biomedia composition contains less than 1 ppm mercury. In certain processes, the biomedia composition is essentially mercury-free.

[0047] In some processes, the biomedia composition is characterized by a volatile matter content of about 60% to about 70% by weight according to ASTM D3175 proximate analysis of the biomedia composition.

[0048] In some processes, the biomedia composition is characterized by an ash content of about 2% to about 20% by weight according to ASTM D3174 proximate analysis of the biomedia composition.

[0049] In some processes, the biomedia composition is characterized by a moisture content of 10% to about 50% by weight according to ASTM D3173 Proximate Analysis of the Biomedia Composition.

[0050] In some processes, the biomedia composition is hydrophilic. In other processes, the biomedia composition is hydrophobic. In certain processes, the biomedia composition is amphiphilic.

[0051] In some processes, the biomedia composition is in the form of fine particles. In other processes, the biomedia composition is in the form of fibrous particles or a mixture of fibrous particles and fine particles. In still other processes, the biomedia composition is in the form of a densified body.

[0052] In some processes, step (c) is not performed. In other processes, step (c) is performed. If step (c) is performed, it may include 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 acidity of the intermediate biocarbon stream, as well as introducing one or more additives into step (a) or step (b) to adjust the acidity of the intermediate biocarbon stream, as needed.

[0053] In some processes, the biomedia composition has a biomedia pH selected from about 4 to about 8, such as a biomedia pH selected from about 5 to about 7.

[0054] In some processes, the biomedia composition has a cation exchange capacity selected from about 50 to about 200 meq / 100g, such as about 80 to about 150 meq / 100g, or about 100 to about 125 meq / 100g.

[0055] In some processes, the biomedia composition comprises a compound having the following formula:

number

[0056] In some processes, the biomedia composition comprises a compound having the following formula:

number

[0057] In some processes, the biomedia composition is biologically sterile. In some processes, the biomedia composition is biodegradable. In some processes, the biomedia composition is compostable.

[0058] The process can be a continuous, semi-continuous, or batch process. [Brief explanation of the drawings]

[0059] [Figure 1] FIG. 1 is a schematic diagram (not to scale) of an exemplary biomedia composition in the form of fine particles.

[0060] [Figure 2] FIG. 1 is a schematic diagram (not to scale) of an exemplary biomedia composition in the form of fibrous particles.

[0061] [Figure 3] 1 is a simplified block flow diagram of a process for converting biomass feedstock into a biomedia composition according to some embodiments. Dotted lines indicate optional flows and units.

[0062] [Figure 4] 1 is a simplified block flow diagram of a process for converting biomass feedstock into a biomedia composition according to some embodiments. Dotted lines indicate optional flows and units. DETAILED DESCRIPTION OF THE INVENTION

[0063] Globally, peat stores approximately 40% of all soil carbon on Earth, more than the carbon stored in all other vegetation types, even though peat covers only 3% of the Earth's land surface. See Dunne, “Climate change and deforestation threaten world's largest tropical peatland,” Carbon Brief, January 2018, www.carbonbrief.org / climate-change-and-deforestation-threaten-worlds-largest-tropical-peatland retrieved April 18, 2022.

[0064] Peatlands typically take thousands of years to develop. Therefore, peat is generally not considered a renewable source of energy or biomaterials. Peat formation is often the first step in the geological formation of fossil fuels such as coal, especially low-grade coals such as lignite. The rate of peat extraction in industrialized countries far exceeds its slow regrowth rate, which is on the order of 1 mm per year. Centuries of human peat burning and emissions have released significant amounts of CO2 into the atmosphere. Peatland restoration is being sought in some areas.

[0065] Sphagnum is a genus of 151–350 species of moss commonly referred to as “peat moss” due to its dominance in wetland habitats, where it contributes to the formation of peat bogs and mires. “Sphagnum” refers to the living moss that grows on top of peat bogs. “Sphagnum peat moss” (American usage) and “sphagnum peat” (British usage) refer to the moss that slowly decays beneath the sphagnum. While peat moss is a common component of peat, it should be noted that many other decaying plant materials can also be present in peat.

[0066] Peat is used in horticulture and agriculture in certain parts of the world. Peat, such as peat moss, is used as a primary growing medium and soil conditioner for cultivating plants by increasing the soil's ability to retain moisture and nutrients, primarily by increasing capillary action and cation exchange capacity. As a result of heavy harvesting and flooding and ecosystem destruction associated with environmental changes, the annual production capacity of peat has decreased in recent years, resulting in an increase in peat market prices. Furthermore, natural sphagnum moss often becomes infected with the fungus Fusarium oxysporum or is a carrier of disease. As a result, the quality of plants cultivated on natural sphagnum moss deteriorates.

[0067] Research into peat substitutes began in the 1970s, as the environmental impacts of peatland destruction began to attract concern in some parts of the world. First-generation substitutes were often made from composted waste materials such as grass and tree prunings, food processing by-products such as spent brewer's grain, and animal manure. None of these substitutes were as successful as peat.

[0068] It is known that polymers such as polyesters or polyamides can function as peat replacement products, however, their use as soil amendments leads to the accumulation of polymer waste that does not biodegrade over a significant time scale.

[0069] What remains desirable are natural and sustainable peat alternatives that are of uniform quality, do not cause infections and are less susceptible to disease.

[0070] Some variations of the present invention are premised on the recognition that while peat harvesting is not sustainable, biomass harvesting and biomass pyrolysis can be carried out in a sustainable manner. Peat-like products in the form of biomedia compositions are described in this disclosure, and it is understood that biomedia compositions have numerous other uses. Peat-like products can be formed in minutes or hours, rather than thousands of years. Biomedia compositions can also have certain superior properties compared to traditional peat.

[0071] As used herein, 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.

[0072] 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.

[0073] As used herein, the term "about" means ±20% of a given range, value, or structure, unless otherwise indicated.

[0074] As used herein, any concentration range, percentage range, ratio range, or integer range should be understood to include any integer value within the recited range, and fractions thereof (such as integer tenths and hundredths), where appropriate, unless otherwise indicated. Also, any numerical range recited herein should be understood to include any integer within the recited range, unless otherwise indicated.

[0075] As used herein, "about X to about Y," "a range from about to or therebetween," and "a range from about X, Y, or Z or therebetween" include "at least X and at most Z."

[0076] As used herein, "comprising," which is synonymous with "including," "containing," 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 that means that a specified claim element is essential, but that other claim elements can be added and still form a construct within the scope of the claim.

[0077] 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.

[0078] With respect to the terms "comprising," "consisting of," and "consisting essentially of," when one of these three terms is used herein, the subject matter disclosed and claimed herein may include use of either of the other two terms. Thus, in some embodiments not otherwise explicitly recited, any instance of "comprising" can be replaced by "consisting of," or alternatively, by "consisting essentially of."

[0079] As used herein, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." Unless the word "or" is expressly limited in reference to a list of two or more items to mean only one item exclusively of the other items, the use of "or" in such a list should be interpreted to include (a) any one item in the list, (b) all items in the list, or (c) any combination of items in the list. As used herein, a phrase "and / or," such as "A and / or B," refers to A alone, B alone, and both A and B. Where the context allows, singular or plural terms may also include the plural or singular terms, respectively.

[0080] As used herein, "biological" refers to materials (either feedstocks, products, or intermediates) containing elements such as carbon that are renewable over time scales of months, years, or decades. Non-biological materials can be non-renewable or renewable over time scales of centuries, millennia, millions of years, or even longer geological time scales. For example, traditional fuel sources of coal and petroleum are non-renewable and non-biological. Biological materials can consist essentially of biological sources. It will be understood by those skilled in the art that naturally sourced or derived biological materials can contain trace amounts of non-biological materials. Furthermore, the processes disclosed herein can be used with non-biological materials, although the beneficial environmental impact may be less significant.

[0081] The three naturally occurring isotopes of carbon, 12 C. 13 C, and 14 C exists. 12 C and 13 C is stable and occurs in a natural ratio of approximately 93:1. 14 C is produced by thermal neutrons from cosmic radiation in the upper atmosphere and transported to Earth where it is absorbed by living biological material. 14Although C constitutes a small fraction, it is radioactive with a half-life of 5,700 years and is therefore detectable radiometrically. 14 Because it does not absorb C, 14 The amount of C is one of the methods used for radiometric dating of biological materials.

[0082] Plants fix atmospheric carbon through photosynthesis 14 C. Then, when animals consume the plants, or other animals that consume the plants, 14 Therefore, living plants and animals absorb atmospheric CO 2 Same as 14 C vs. 12 When an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer produces new carbon. 14 C is not incorporated. Radioactive decay then occurs in living organisms. 14 It gradually depletes C. This effect is the basis of radiocarbon dating.

[0083] Fossil fuels such as coal are primarily made from plant material deposited millions of years ago. 14 This is equivalent to thousands of half-lives of C, so essentially all of the carbon in fossil fuels 14 C is decaying. Also, fossil fuels were originally formed from living organisms, so compared to the atmosphere, 13 C is depleted. Therefore, carbon from fossil fuels is 13 C and 14 Both C are depleted.

[0084] This difference between the carbon isotopes of recently depleted organic matter, such as from renewable sources, and the carbon isotopes of fossil fuels, such as coal, allows for the determination of the source of carbon in a composition, specifically whether the carbon in the composition is derived from a renewable resource or a fossil fuel, or in other words, whether a renewable resource or a fossil fuel was used to produce the composition.

[0085] Biomass is a term used to describe biologically produced or living matter. Biomass refers to the mass of living organisms, including plants, animals, and microorganisms, or, from a biochemical perspective, cellulose, lignin, sugars, fats, and proteins. Biomass includes both above-ground and below-ground plant tissues, such as leaves, twigs, branches, and trunks, as well as the roots of trees and the rhizomes of grasses. The chemical energy contained in biomass comes from solar energy using the natural process of photosynthesis. This is the process by which plants take in carbon dioxide and water from their surroundings and convert them into sugars, starch, cellulose, hemicellulose, and lignin using energy from sunlight. Biomass is useful in that it is effectively stored solar energy. Biomass is the only renewable carbon source.

[0086] As used herein, "total carbon" is the sum of fixed and non-fixed carbon present in the volatile matter. 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.

[0087] As used herein, a "zone" is a region of space within a single physical unit, physically separated units, or any combination thereof. With respect to continuous reactors, zone boundaries may be related to structures such as the presence of flights within the reactor or separate heating elements for providing heat to separate zones. Alternatively or additionally, zone boundaries within a continuous reactor may be related to functions such as distinct temperatures, fluid flow patterns, solid flow patterns, or extent of reaction. In single batch reactors, "zones" are operating regimes in time rather than space. There is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary; some amount of pyrolysis may occur in a portion of the preheat zone, and some amount of "preheating" may continue to occur in the pyrolysis zone. The temperature profile within the reactor is typically continuous, including the zone boundaries within the reactor.

[0088] As used herein, a "reagent" is a material in its broadest sense; a reagent can be a fuel, a chemical, a material, a compound, an additive, a blend component, a solvent, etc. A reagent does not necessarily have to be a chemical reagent that causes or participates in a chemical reaction. A reagent may or may not be a chemical reactant and may or may not be consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in 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.

[0089] As used herein, a "derivative" is a compound, molecule, or ion derived from another substance by chemical reaction. The substance from which the derivative is derived is an additive. A derivative is also an additive.

[0090] As used herein, the term "substantially" refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, an object that is "substantially" enclosed would mean that the object is completely enclosed or nearly completely enclosed. The precise degree of acceptable deviation from absolute completeness may, in some cases, depend on the particular context. Generally speaking, however, near completeness would be such that one would have the same overall result as if absolute and total completeness had been achieved. The use of "substantially" is equally applicable when used in a negative sense to refer to the complete or nearly complete absence of an action, characteristic, property, state, structure, item, or result.

[0091] As used herein, 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 consequences, such as whether it is sold as an intermediate for further processing, stored, traded, further processed, sold to another party, etc.

[0092] As used herein, "high carbon" refers to a relatively high carbon content compared to the initial feedstock utilized to generate the high carbon bioreagent. Typically, 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%, 70%, or more by weight of carbon.

[0093] Notwithstanding the foregoing, as used herein, the term "high-carbon bio-reagent" refers, in various embodiments, to materials that can be produced by the disclosed processes and systems. 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 less than about 50% carbon by weight.

[0094] 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.

[0095] 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.

[0096] Some variations of the present invention are biomedia compositions comprising: About 50% to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, 14 C / 12 total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% by weight hydrogen on a dry basis according to ASTM D5373 elemental analysis of the biomedia composition; and about 0.1% to about 2% nitrogen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; A biomedia composition is provided, wherein the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0097] In some embodiments, the biomedia composition comprises, on a dry basis, about 55% to about 70% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition. In certain embodiments, the biomedia composition comprises, on a dry basis, about 60% to about 65% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0098] In some embodiments, the total carbon is 14 C / 12 In certain embodiments, the total carbon is at least 80% renewable according to ASTM D6866 measurement of C isotope ratio. 14 C / 12 It is at least 90% (e.g., 100%) renewable according to ASTM D6866 measurement of C isotope ratio.

[0099] In some embodiments, the biomedia composition comprises, on a dry basis, about 25% oxygen by weight to about 35% oxygen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0100] In some embodiments, the biomedia composition comprises, on a dry basis, about 5% to about 8% hydrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0101] In some embodiments, the biomedia composition comprises, on a dry basis, about 0.5% to about 1% by weight of nitrogen according to ASTM D5373 elemental analysis of the biomedia composition. Additionally or alternatively, the biomedia composition may include phosphorus, potassium, sulfur, or a combination thereof.

[0102] Nitrogen is an important nutrient for plant growth. It is part of the chlorophyll molecule, which gives plants their green color and is involved in producing plant food through photosynthesis. Nitrogen is also a major component of plant protoplasm, the translucent substance that is the living material in cells. It is necessary, for example, for flower differentiation, rapid bud growth, and healthy flower buds.

[0103] Phosphorus, potassium, and sulfur are also important nutrients for plant growth. Phosphorus is an essential nutrient for several plant structural compounds and functions as a catalyst for numerous biochemical reactions in plants, including photosynthesis. Phosphorus is also an important component of DNA and RNA, the structures of both being linked together by phosphorus bonds. Potassium is classified as a macronutrient because plants take up large amounts of potassium during their life cycle. Potassium-deficient plants are less tolerant of drought, excess water, and high and low temperatures. Potassium-deficient plants are also less tolerant of pests, diseases, and nematode attacks. Sulfur is another essential nutrient required for proper plant growth and development. Sulfur is a structural component of protein disulfide bonds, amino acids, vitamins, and cofactors.

[0104] If the biomedia composition contains nitrogen, phosphorus, potassium, or sulfur, the biomedia composition may act as a fertilizer for the soil or another habitat in which it is placed.

[0105] In some embodiments, the biomedia composition contains less than 1 ppm of mercury. The biomedia composition may be essentially mercury-free.

[0106] In some embodiments, the biomedia composition further comprises one or more additives. Additives may be introduced for a variety of reasons, including both functional (e.g., for pH optimization) and decorative (e.g., color). For example, additives may be used to improve the water absorption, nutrient absorption, or breathability of the biomedia composition.

[0107] In some embodiments, the biomedia composition is characterized by a volatile matter content of about 55% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition. In various embodiments, the biomedia composition is characterized by a volatile matter content of about, at least about, or at most about 50, 55, 60, 65, 70, or 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition.

[0108] In some embodiments, the biomedia composition is characterized by an ash content of about 2% to about 20% by weight according to ASTM D3174 Proximate Analysis of the biomedia composition. In various embodiments, the biomedia composition is characterized by an ash content of about, at least about, or at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25% by weight, including any intervening range, according to ASTM D3174 Proximate Analysis of the biomedia composition.

[0109] In some embodiments, the biomedia composition is characterized by a moisture content of 10% to about 50% by weight according to ASTM D3173 Proximate Analysis of the biomedia composition. In various embodiments, the biomedia composition is characterized by an ash content of about, at least about, or at most about 0, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75% by weight, including any intervening range, according to ASTM D3173 Proximate Analysis of the biomedia composition.

[0110] Generally speaking, the fixed carbon content of a biomedia composition is defined as 100% by weight minus the sum of volatile matter, ash, and moisture. As an example, a biomedia composition containing 50% by weight volatile matter, 10% by weight moisture, and 5% by weight ash has a fixed carbon content of 100-50-10-5 = 35% by weight.

[0111] In some embodiments, the biomedia composition is hydrophilic. In other embodiments, the biomedia composition is hydrophobic or moderately hydrophobic.

[0112] In certain embodiments, the biomedia composition is amphiphilic. An amphiphilic biomedia composition has hydrophilic and hydrophobic regions. For example, there may be regions with a relatively high concentration of hydrophilic -OH, -COOH, or -CHO groups, as well as hydrophobic carbon-rich regions. Without being limited by theory, amphiphilic biomedia compositions may result when mild pyrolysis, such as through the conversion of -OH and -COOH groups to aliphatic and aromatic groups, partially converts hydrophilic biomass to hydrophobic materials. Pyrolysis conditions can be adjusted to tailor the degree of hydrophilicity or hydrophobicity of the biomedia composition.

[0113] Biomedia compositions can be characterized by an equilibrium moisture content, as defined in accordance with ASTM D1412. The equilibrium moisture content can be from 0 to about 90% water by weight, such as from about 25% to about 75% by weight. A higher equilibrium moisture content typically means that the biomedia composition has a high water absorption capacity. In many commercial applications of biomedia compositions, a high water absorption capacity is desirable, for example, to allow for better penetration of soil nutrients.

[0114] In some embodiments, the biomedia composition is in the form of fine particles. The fine particles can have an average particle size of about 10 microns to about 1000 microns, such as about, at least about, or at most about 10, 20, 30, 40, 50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, including any intervening range. The fine particles can be spherical or non-spherical. In the case of spheres, particle size refers to the diameter; in the case of other shapes of fine particles, particle size refers to the equivalent diameter, which is the diameter of a sphere with an equivalent volume as the non-spherical particulate.

[0115] In some embodiments, the biomedia composition is in the form of fibrous particles. In some applications, fibrous biomedia compositions are preferred over fine particles. For example, a biomedia composition with low fine / fine particle levels may be desirable to avoid dust-related health and safety (e.g., fire) hazards.

[0116] When the biomedia composition is in the form of fibrous particles, it can have an average fiber length of about 100 microns to about 100 millimeters, such as about, at least about, or at most about 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, or about, at least about, or at most about 1, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 millimeters, including any intervening range. The fibrous particles can have an average fiber diameter of from about 1 micron to about 1000 microns, such as about, at least about, or at most about 1, 2, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, including any intervening range.

[0117] In some embodiments, the biomedia composition is in the form of a mixture of fine particles and fibrous particles. When a mixture is present, the fine particles can have an average particle size of about 10 microns to about 1000 microns, such as about, at least about, or at most about 10, 20, 30, 40, 50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, including any intervening range, and the fibrous particles can have an average particle size of about, at least about, or at most about 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, including any intervening range. The fibrous particles may have an average fiber length of from about 100 microns to about 100 millimeters, such as about, at least about, or at most about 1, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 millimeters, and the fibrous particles may have an average fiber diameter of from about 1 micron to about 1000 microns, such as about, at least about, or at most about 1, 2, 5, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, including any intervening range. The biomedia composition in the form of a mixture can contain a weight ratio of fine particles to fibrous particles of about 0.01 to about 100, such as about, at least about, or at most about 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100, including any intervening range.

[0118] When a biomedia composition contains fibrous particles, the fibrous particles may contain multiple length scales in a hierarchical structure. For example, a fibrous particle may be characterized by a fiber having a primary length and diameter, where the fiber contains smaller, finer fibrils attached to the main fiber that are structurally arranged, typically at random angles relative to the surface of the fiber. In materials science, this type of hierarchical morphology is known as a "hairy" structure. In such hierarchical structures, the primary fibers may have an average primary fiber length of about 100 microns to about 100 millimeters, such as about, at least about, or at most about 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 microns, or about, at least about, or at most about 1, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 millimeters, including any intervening range; The fibers may have an average primary fiber diameter of about 1 micron to about 1000 microns, such as 300, 400, 500, 600, 700, 800, 900, or 1000 microns, while the microfibrils (attached to the primary fibers) may have an average microfibril length of about 100 nanometers to about 100 microns, such as about, at least about, or at most about 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 nanometers, or about, at least about, or at most about 1, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 microns.

[0119] In some embodiments, the biomedia composition is in the form of a densified body. Exemplary densified bodies include pellets, sheets, mats, bricks, blocks, blankets, and sponges. The bulk density of a densified body containing the biomedia composition is about, at least about, or at most about 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 g / cm, including any intervening range.3 etc., approximately 1.0 g / cm 3 ~Approx. 2.0g / cm 3 The characteristic length scale (e.g., diameter or effective diameter, or length) of the densified object can be from about 1 millimeter to about 1 meter, such as from about 1 centimeter to about 100 centimeters. An exemplary densified object having a length scale on the order of 1 meter is a package of biomedia composition, such as for storage or transportation.

[0120] There are many embodiments in which the biomedia composition in the form of a densified body is transported, stored, and potentially used directly or mechanically unraveled and then used. In one embodiment, loose pellets of the biomedia composition are applied to a field, and then under normal weather (e.g., wind and rain), the pellets break down to form fine or fibrous particles that then penetrate the soil matrix. In another application, with respect to replacing traditional feedstock in a peat boiler, strong pellets (such as pellets containing a binder) can be made and then fed to the peat boiler. A similar embodiment could utilize the biomedia composition in the form of pellets or other densified bodies to feed a peat gasifier.

[0121] When the biomedia composition is in the form of biomedia pellets, the size and geometry of the biomedia pellets can vary. As used herein, "pellets" refers to agglomerated bodies rather than loose powders. The geometric shape of pellets is not limited to spherical or nearly spherical. Also, in this disclosure, "pellets" is synonymous with "briquettes," "granules," and "prills." The geometric shape 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 "pellet" is used generically for any body containing powder agglomerated, optionally with a binder.

[0122] Biomedia pellets may be characterized by an average pellet diameter, which is the true diameter if spherical, or an equivalent diameter if any other 3D geometric shape. The equivalent diameter of a non-spherical pellet is the diameter of a sphere of equivalent volume to the actual pellet. In some embodiments, the average pellet diameter is about or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters, 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.

[0123] In some embodiments, there are multiple biomedia pellets that are relatively uniform in size, such as a standard deviation of less than ±100%, less than ±50%, less than ±25%, less than ±10%, or less than ±5% of the average pellet diameter. In other embodiments, there are biomedia pellets in a wide range of sizes, as this can be advantageous in some applications.

[0124] In some embodiments, the biomedia composition has a biomedia pH selected from about 4 to about 8. In certain embodiments, the biomedia composition has a biomedia pH selected from about 5 to about 7. In various processes, the biomedia pH is about, at least about, or at most about 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, including any intervening range (e.g., 4.8-7.2, 5.3-6.9, etc.). Biomedia pH can be measured by adding 2 volumes of water to 1 volume of biomedia composition and then measuring the pH of the liquid solution after extraction from the solid biomedia composition for 10 minutes at 25° C. An alkaline additive can be added to the biomedia composition to raise the pH to a desired range, such as about 6.5 to about 7.5.

[0125] Cation exchange capacity (CEC) has historically been used to describe the buffering capacity of soil. Buffers provide resistance to changes in pH or nutrient concentration in the soil solution. Media with a high CEC help growers maintain a stable pH or nutrient concentration over time. Biomedia particles with negatively charged "exchange sites" allow the particles to absorb, e.g., H + , NH4 + , Ca 2+ , Mg 2+ , K. + , and Na + Biomedia particles with a high CEC have the ability to absorb and release large amounts of cations from soil (or other matrix) solution. In some embodiments, the biomedia composition has a cation exchange capacity selected from about 50 to about 200 meq / 100g, such as about 80 to about 150 meq / 100g, or about 100 to about 125 meq / 100g.

[0126] In some embodiments, the biomedia composition has the following formula:

number

[0127] In some embodiments, the biomedia composition has the following formula:

number

[0128] In some embodiments, the biomedia composition itself is biologically sterile. A biologically sterile biomedia composition is substantially free of bacteria, fungi, and weed seeds that may harm plants. Other organic materials (e.g., compost) carry the risk of contaminating the soil with various pathogens.

[0129] In some embodiments, the biomedia composition is biodegradable. As used herein, a biodegradable biomedia composition is capable of being broken down under normal environmental conditions by the action of naturally available microorganisms into environmentally acceptable products such as water, carbon dioxide, and humus.

[0130] In some embodiments, the biomedia composition is compostable. As used herein, a compostable biomedia composition meets the compostability specifications defined in ASTM D6400, which is incorporated herein by reference.

[0131] Another variation of the present invention is a process for producing a biomedia composition, the process comprising: (a) providing a starting material containing biomass, the starting material being optionally dried; (b) mildly pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor; (c) optionally 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 acidity of the intermediate biocarbon stream; (d) about 50% by weight to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is 14 C / 12 total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% by weight hydrogen on a dry basis according to ASTM D5373 elemental analysis of the biomedia composition; and recovering a biomedia composition containing, on a dry basis, about 0.1% to about 2% nitrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The process provides that the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0132] Some variations of the present invention are processes for producing a biomedia composition, the process comprising: (a) providing a starting material containing biomass, the starting material being optionally dried; (b) mildly pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor; (c) optionally introducing one or more additives during step (a) or step (b) to adjust the acidity of the intermediate biocarbon stream; (d) about 50% by weight to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is 14 C / 12 total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% by weight hydrogen on a dry basis according to ASTM D5373 elemental analysis of the biomedia composition; and recovering a biomedia composition containing, on a dry basis, about 0.1% to about 2% nitrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The process provides that the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

[0133] 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.

[0134] In some processes, the intermediate biocarbon stream is mechanically shredded. Alternatively or additionally, the biomedia composition may be mechanically shredded. In these or other processes, the intermediate biocarbon stream may be mechanically defiberized. Alternatively or additionally, the biomedia composition may be mechanically defiberized.

[0135] Mechanical processing can be useful for adding porosity, surface area, or hierarchical particle size to biomedia compositions. Mechanical devices such as shredders can be utilized to form fibrous strands. Other mechanical devices include, but are not limited to, hammer mills, extruders, attrition mills, disk mills (e.g., with a single disk or double disks), pin mills, ball mills, cone crushers, jaw crushers, pulp refiners, defibrillators, and combinations thereof.

[0136] Generally, an intermediate biocarbon stream or biomedia composition may be treated. As used herein, "treatment," "treated," and the like refer to chemical modification, physical modification, the use of additives, or a combination thereof.

[0137] In some processes, the intermediate biocarbon stream or biomedia composition is treated to change the porosity of the biomedia composition. For example, injecting a gas through a bed of the biomedia composition can be used to create porosity.

[0138] In some processes, the intermediate biocarbon stream or biomedia composition is treated to change the solid flowability of the biomedia composition, which can be a practical feature of the biomedia composition, allowing it to be easily packaged in containers for transport and storage, and then easily applied to soil or other matrices.

[0139] In some processes, the biomedia composition is treated to adjust the chemical oxygen demand of the biomedia composition. For example, organic chemical substrates (e.g., glycerol, ethanol, or monomeric sugars) can be introduced as additives to the biomedia composition.

[0140] In some processes, the biomedia composition is treated to adjust the color of the biomedia composition. For example, organic dyes may be incorporated into the biomedia composition. In certain embodiments, the organic dyes themselves are plant extracts, such as madder extract (red), indigo (blue), and weld (yellow).

[0141] In some processes, the biomedia composition is treated to adjust the odor of the biomedia composition. Additives that impart a desirable odor, such as botanical extracts that function as fragrances, may be incorporated. Alternatively or additionally, additives that eliminate or mask odors associated with the biomedia composition may be incorporated.

[0142] In some processes, the biomedia composition is treated to adjust the texture of the biomedia composition. For example, the biomedia composition may be mechanically treated to improve the texture of the product. Alternatively or additionally, additives (e.g., cellulose fiber, straw, sand, or silt) may be incorporated to adjust the texture of the biomedia composition.

[0143] In various processes, the biomedia composition comprises, on a dry basis, about 55% to about 70% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition. In one particular process, the biomedia composition comprises, on a dry basis, about 60% to about 65% total carbon by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0144] In some processes, the total carbon is 14 C / 12 At least 80% renewable according to ASTM D6866 measurement of C isotope ratio. In certain processes, total carbon is 14 C / 12 At least 90%, at least 95%, or 100% renewable according to ASTM D6866 measurement of C isotope ratio.

[0145] In some processes, the biomedia composition comprises, on a dry basis, about 25% oxygen to about 35% oxygen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0146] In some processes, the biomedia composition comprises, on a dry basis, about 5% to about 8% hydrogen by weight according to ASTM D5373 elemental analysis of the biomedia composition.

[0147] In some processes, the biomedia composition comprises, on a dry basis, about 0.5% to about 1% by weight nitrogen according to ASTM D5373 elemental analysis of the biomedia composition.

[0148] In some processes, the biomedia composition includes phosphorus, potassium, sulfur, or a combination thereof.

[0149] In some processes, the biomedia composition contains less than 1 ppm mercury. In certain processes, the biomedia composition is essentially mercury-free.

[0150] In some processes, the biomedia composition is characterized by a volatile matter content of about 60% to about 70% by weight according to ASTM D3175 proximate analysis of the biomedia composition.

[0151] In some processes, the biomedia composition is characterized by an ash content of about 2% to about 20% by weight according to ASTM D3174 proximate analysis of the biomedia composition.

[0152] In some processes, the biomedia composition is characterized by a moisture content of 10% to about 50% by weight according to ASTM D3173 Proximate Analysis of the Biomedia Composition.

[0153] In some processes, the biomedia composition is hydrophilic. In other processes, the biomedia composition is hydrophobic. In certain processes, the biomedia composition is amphiphilic.

[0154] In some processes, the biomedia composition is in the form of fine particles. In other processes, the biomedia composition is in the form of fibrous particles or a mixture of fibrous particles and fine particles. In still other processes, the biomedia composition is in the form of a densified body.

[0155] In some processes, step (c) is not performed. For example, if the pH of the final biomedia composition is already within an acceptable range for the intended product use, step (c) can be omitted.

[0156] In other processes, step (c) is performed, such as for pH optimization, and may include 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 acidity of the intermediate biocarbon stream, as well as introducing one or more additives into step (a) or step (b) to adjust the acidity of the intermediate biocarbon stream, as needed.

[0157] In some processes, the biomedia composition has a biomedia pH selected from about 4 to about 8, such as a biomedia pH selected from about 5 to about 7. In various processes, the selected biomedia pH is about, at least about, or at most about 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, including any intervening range (e.g., 4.5-7.0, 5.5-6.8, etc.).

[0158] In some processes, the biomedia composition has a cation exchange capacity selected from about 50 to about 200 meq / 100g, such as about 80 to about 150 meq / 100g, or about 100 to about 125 meq / 100g.

[0159] In some processes, the biomedia composition comprises a compound having the following formula:

number

[0160] In some processes, the biomedia composition comprises a compound having the following formula:

number

[0161] In some processes, the biomedia composition is biologically sterile. In some processes, the biomedia composition is biodegradable. In some processes, the biomedia composition is compostable.

[0162] The process can be continuous, semi-continuous, or batch. In some processes, for example, mild pyrolysis of the starting material is carried out in a continuous pyrolysis reactor to produce an intermediate biocarbon stream, which is recovered. The intermediate biocarbon stream is then washed or treated in a batch process to produce a biomedia composition, which is recovered.

[0163] With respect to base-acid ratios, Fe2O3, CaO, MgO, KO, Na2O, SiO2, Al2O3, and TiO2 concentrations are those in the ash 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."

[0164] ASTM D4326 is a test method covering the analysis of commonly determined major and minor elements 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 of atoms emitted or fluoresced upon absorption of the primary or incident X-rays are dispersed, and their intensities at selected wavelengths are measured by a sensitive detector. The detector output is related to concentrations by calibration curves or computerized data handling equipment. The K spectral line is used for all elements determined by this procedure. All elements were determined as elements and reported as oxides, including Si, Al, Fe, Ca, Mg, Na, K, P, Ti, Mn, Sr, and Ba. Ash composition analysis is used in describing the quality of biocarbon for its complete characterization. Ash composition is useful for predicting the slagging and fouling characteristics of the burned material, as well as its potential use in various commercial applications.

[0165] In this disclosure, a "compositional parameter" is any parameter that is a function of or correlates with biomedia composition. In some embodiments, the compositional parameter is determined according to ASTM D4326 and by an equation with input from ASTM D4326 results.

[0166] In some embodiments, the biomedia compositions are further characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biomedia composition according to ASTM D4326, selected from about 0.05 to about 5. 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 less than 0.3 or greater than 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, inclusive of all intervening ranges.

[0167] In some embodiments, the biomedia composition is further characterized by an iron + calcium parameter, defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biomedia 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, including all intervening ranges. 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 less than 10% by weight. In other embodiments, the iron + calcium parameter is greater than 10% by weight.

[0168] In some embodiments, the biomedia composition is further characterized by a slagging factor defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biomedia composition on a dry basis, wherein the base-acid ratio satisfies the following formula:

number

[0169] In some embodiments, the biomedia 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, wherein the base-acid ratio satisfies the following formula:

number

[0170] In some embodiments, the biomedia composition is further characterized by a modified soiling 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 biomedia composition according to ASTM D4326, and the base-acid ratio satisfies the following formula:

number

[0171] In some embodiments, the biomedia compositions described above are further characterized by an equilibrium moisture content according to ASTM D 1412. The equilibrium moisture can be from about 1% to about 50% by weight, such as about, at least about, or at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, inclusive of all intervening ranges.

[0172] In some embodiments, the biomedia composition is further characterized by a silica percentage, defined as the weight percentage of SiO2 in the biocarbon composition according to ASTM D4326. The silica percentage can be selected, for example, from about 5% to about 50% by weight. Note that the silica percentage is the SiO2 concentration in the ash (ASTM D4326 ashing test), not in the original biomedia 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, including all intervening ranges.

[0173] In some embodiments, the biomedia compositions are characterized by low mercury content. The biomedia compositions may contain less than 100 ppm mercury (ppm = parts per million by weight), less than 10 ppm mercury, or may 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 less than 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.

[0174] The biomedia composition may contain, on a substantial basis, about 10% to about 50% fixed carbon by weight (along with any moisture). In various embodiments, the biomedia composition contains, on a substantial basis, about, at least about, or at most about 10, 15, 20, 25, 30, 35, 40, 45, or 50% fixed carbon by weight, including any intervening range.

[0175] The total carbon in the biomedia composition is 14 C / 12 The total carbon in the biomedia composition can be at least 90% renewable as determined from measurements of C isotope ratios. 14 C / 12 The total carbon in the biomedia 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.

[0176] In certain embodiments, the biomedia composition is in the form of pellets that include 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.

[0177] In certain embodiments, the biomedia composition is in the form of pellets that include a binder, the binder comprising carbon that is at least 50%, at least 90%, at least 95%, or 100% renewable carbon, and the remainder of the pellets (i.e., not the binder) comprising at least 50%, at least 90%, at least 95%, or 100% renewable carbon. In some embodiments, essentially all of the carbon in the biomedia composition is fully renewable.

[0178] In certain embodiments, the biomedia composition includes an additive, the additive includes non-renewable carbon, and the remainder of the biomedia composition includes at least 50%, at least 90%, at least 95%, or 100% renewable carbon.

[0179] In certain embodiments, the biomedia 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 biomedia composition (i.e., not the additive) can comprise at least 50%, at least 90%, at least 95%, or 100% renewable carbon. In certain biomedia compositions that include an additive, essentially all of the carbon in the biomedia composition is fully renewable.

[0180] In this disclosure, 100% or "fully" renewable carbon allows for very small amounts of adsorbed atmospheric CO2 molecules that may come from fossil fuels.

[0181] The biomedia composition can be in the form of pellets, which optionally contain a binder. The binder can be chosen from, for example, 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 any combination of the foregoing. In some embodiments, the pellets do not contain an externally added binder.

[0182] 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.

[0183] The biomedia composition can be in the form of a powder, which can be a loose powder, a compacted powder, a granulated powder, or other form. In some embodiments, the powder is free-flowing.

[0184] The biomedia composition can be in the form of fibers, which can be loose fibers, compressed fibers, or other forms. In some embodiments, the fiber-containing biomedia composition is flowable.

[0185] If organic or inorganic additives are present in the biomedia 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.

[0186] In some embodiments of biomedia compositions having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia compositions are characterized by an iron-calcium ratio, defined as Fe2O3 divided by CaO, each as a weight percentage in the biomedia 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 less than 0.3 or greater than 3.

[0187] In some embodiments of a biomedia composition having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition is characterized by an iron + calcium parameter, defined as the sum of Fe2O3 and CaO, each as a weight percentage in the biomedia 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 less than 10% by weight. In other embodiments, the iron + calcium parameter is greater than 10% by weight.

[0188] In some embodiments of biomedia compositions having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition is characterized by a slagging factor, defined as the base-acid ratio multiplied by the weight percentage of sulfur present in the biomedia composition on a dry basis, 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 less than 0.6.

[0189] In some embodiments of a biomedia composition having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition is characterized by a fouling factor defined as the base-acid ratio multiplied by the NaO as a weight percentage in the biomedia composition according to ASTM D4326, the fouling factor being selected from about 0.1 to about 10. The fouling factor can be, for example, less than 2 or less than 1.

[0190] In some embodiments of a biomedia composition having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition is characterized by a modified soiling 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 the ash derived from the biomedia composition according to ASTM D4326, and the modified soiling factor is selected from about 0.1 to about 10. The modified soiling factor can be, for example, less than 2 or less than 1.

[0191] In some embodiments of biomedia compositions having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition is characterized by a silica percentage, defined as the weight percentage of SiO2 in the biomedia 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.

[0192] In some embodiments of biomedia compositions having an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition is further characterized by an equilibrium moisture content according to ASTM D 1412. The equilibrium moisture can be from about 1% to about 50% by weight, such as about, at least about, or at most about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, including all intervening ranges.

[0193] In certain embodiments of a biomedia composition comprising an optimized base-acid ratio or an optimized extended base-acid ratio, the biomedia composition contains less than 100 ppm mercury, less than 10 ppm mercury, or is essentially mercury-free.

[0194] Any of the disclosed biomedia compositions may further contain one or more 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, aluminosilicate, titanium, titanium dioxide, titanium carbide, titanium hydride, titanium nitride, or combinations thereof. When additives are present, the additives may be selected to adjust any of the compositional parameters disclosed herein (e.g., biomedia pH, base-acid ratio, etc.). In some process embodiments, the additive is introduced in step (c). Alternatively or additionally, the additive may be introduced elsewhere in the process, such as directly into the starting biomass, or may be injected into the mild pyrolysis reactor.

[0195] In some process embodiments, step (c) selectively removes basic components, thereby reducing Fe2O3, CaO, MgO, KO, Na2O, or any other basic components present.

[0196] In some process 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.

[0197] In some embodiments, step (c) selectively removes acidic components, thereby reducing SiO2, Al2O3, TiO2, or any acidic components present.

[0198] 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).

[0199] In some embodiments, step (c) utilizes steam scrubbing of the intermediate biocarbon stream as a type of scrubbing.

[0200] Any of the processes disclosed herein can be optimized to achieve preselected values ​​or ranges for one or more of the compositional parameters previously discussed, where any discussion of biomedia composition properties is incorporated by reference in each instance of the process discussion.

[0201] 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 degree of covariance between certain compositional parameters, so optimizing one will often affect another. 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.

[0202] 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.

[0203] In certain embodiments, one or more compositional parameters are preselected based on the intended use of the biomedia composition. The process for making the biomedia composition is then optimized using process controls to achieve the preselected compositional parameters within predetermined tolerances. Process optimization can utilize the results of 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 also 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, a compositional parameter can be "preselected" if such a parameter is selected to optimize the process via process controls to actually achieve the setpoint. In turn, the process control preferably uses process control principles such as feedback loops and ratio, integral, differential, and logic programs.

[0204] The intended uses of the biomedia composition can vary widely beyond peat-like products. For example, the biomedia composition can be, for example, a solid fuel, a solid gasifier feedstock, a metallurgical process input (for energy, for reduction chemistry, or for carbon content), a filtration medium, an agricultural product (e.g., to support crop growth), a landscaping product (e.g., to improve grass growth), an animal care product (e.g., animal bedding), or a precursor for another material.

[0205] If the biomedia composition is ultimately combusted or oxidized, either for energy production or as part of a metal production process, it may be desirable to optimize the compositional parameters to avoid issues such as slagging and fouling in the reactor (e.g., lower base-acid ratio, slagging coefficient, and / or fouling coefficient). If the biomedia composition is used as a filtration medium to remove acidic components, it may be desirable to optimize the compositional parameters to improve acid neutralization, e.g., a higher base-acid ratio and, consequently, a higher parameter (e.g., fouling coefficient) that is a linear function of the base-acid ratio. If the biomedia composition is used as a reducing agent in a metal production process, it may be desirable to optimize the compositional parameters to balance the acid and base content to achieve a desired pH for reduction chemistry (such as the production of Fe from FeO), e.g., a moderate base-acid ratio. If the biomedia composition is used as an agricultural medium, it may be desirable to optimize the compositional parameters, taking into account the soil in which the carbon will be placed, in order to select the base-acid ratio and other parameters.

[0206] In some embodiments, an acidic water wash is utilized to optimize one or more compositional parameters. Biomedia is produced by a non-combustion thermal process (e.g., pyrolysis) that converts starting biomass into biochar, gas, steam, or liquid. The process can be configured so that incoming water with the starting feedstock, as well as water produced during the pyrolysis reaction, is utilized in a manner that replaces some or all of the need for an external source of water.

[0207] If the starting material is biomass, which contains renewable carbon of biological origin, the carbon obtained from mild pyrolysis is also of biological origin. This can be done, for example, using ASTM D6866 to determine the carbon content. 14 C / 12 The total carbon in the biomedia composition can be shown by measuring the C isotope ratio. 14 C / 12In some embodiments, the total carbon in the biomedia 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.

[0208] Any biogenic carbon that is oxidized to carbon dioxide creates biogenic CO2. This also creates CO 2 of carbon in the sample 14 C / 12 This can also be shown by measuring C isotope ratios. This biogenic CO2 from biomass is returned to the environment and reabsorbed by new biomass growing via photosynthesis. In this way, net CO2 emissions are significantly reduced.

[0209] In the above or other embodiments, the biocarbon biomedia is characterized by a carbon intensity of less than 0 kg CO2e per metric ton of biocarbon composition, such as a carbon intensity of less than about -100, -200, -300, -400, or -500 kg CO2e per metric ton of biocarbon composition. 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 material processed to make the product, as the case may be. "CO2 intensity carbon intensity" can also be defined as the net amount of carbon dioxide intensity produced per ton of product. "Carbon dioxide intensity" or "CO2e" represents the amount of CO2 that would have a strong global warming effect. A typical unit of carbon intensity is kilograms of carbon dioxide intensity per metric ton (1000 kg) of product.

[0210] A greenhouse gas (or "GHG") is any gas in the atmosphere that absorbs and re-emits heat, thereby keeping the Earth's atmosphere warmer than it would otherwise be. The primary GHGs in the 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.

[0211] 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).

[0212] It may be desirable to use known principles of life cycle analysis to calculate the carbon and water intensities. Life cycle assessment (LCA) is a known method used to assess 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, it is usually necessary to identify the fate of the final product. 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).

[0213] 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 numerous possibilities exist and the current conditions themselves are evolving, it may be preferable to utilize a database within the LCA software to ensure appropriate industry averages are used.

[0214] Pyrolysis Processes and Systems Suitable processes and systems for the mild pyrolysis of biomass feedstocks to produce carbon-containing bioreagents (i.e., intermediate biocarbon streams) are now described in further detail.

[0215] "Pyrolysis" and "pyrolyzing" generally refer to the thermal decomposition of a carbonaceous material. In pyrolysis, less oxygen is present than is required for complete combustion of the material, such as less than 10%, 5%, 1%, 0.5%, 0.1%, or 0.01% of the oxygen (on an O molar basis) required for complete combustion. In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0216] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the temperature within the feedstock; (ii) the initiation of primary pyrolysis reactions at this higher temperature liberates volatiles and forms char; (iii) the flow of hot volatiles toward the cooler solids results in heat transfer between the hot volatiles and the cooler, non-pyrolyzed feedstock; (iv) some of the volatiles in the cooler portions of the feedstock may condense, 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 (which are functions of residence time, temperature, and pressure profiles) may also occur.

[0217] Pyrolysis can at least partially dewater the starting material (e.g., lignocellulosic biomass). In various embodiments, pyrolysis removes greater than about 10%, 25%, 50%, 75%, 90%, 95%, or more of the water from the starting material.

[0218] As mentioned above, mild pyrolysis is preferred when producing biomedia compositions intended for peat replacement products and similar uses. Exemplary pyrolysis conditions for mild pyrolysis include pyrolysis temperatures of about 150°C to about 600°C, such as about, at least about, or at most about 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, 350°C, 400°C, 450°C, 500°C, 550°C, or 600°C, including any intervening range. Exemplary pyrolysis conditions for mild pyrolysis include pyrolysis times of about 10 minutes to about 8 hours, such as about, at least about, or at most about 15 minutes, 30 minutes, 45 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 6 hours, or 8 hours, including any intervening range.

[0219] In some embodiments of the present invention, mild pyrolysis can be classified as torrefaction. In biomass torrefaction, the starting biomass feedstock is heated to about 200-300°C in a substantially inert environment. Residence times for biomass torrefaction are typically from about 30 minutes to about 2 hours.

[0220] In some embodiments, the starting biomass feedstock is 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 extracts, and the like. The biomass feedstock may be selected from the group consisting of 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, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. Note that biomass feedstocks typically contain at least carbon, hydrogen, and oxygen.

[0221] The bioreagent may comprise 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.

[0222] 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 contains about, at least about, or at most about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% by weight total carbon.

[0223] 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 contains 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.

[0224] Mild pyrolysis conditions can vary widely depending on the desired composition of the bioreagent and pyrolysis off-gas, the starting materials, the reactor configuration, and other factors.

[0225] 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.

[0226] In some non-limiting embodiments, the temperature and residence time are preferably selected to achieve a relatively slow pyrolysis chemical reaction. An advantage can be substantial preservation of the cell walls contained in the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, it is preferable to utilize equipment that does not mechanically disrupt cell walls or otherwise convert biomass particles into small fines. Certain suitable reactor configurations are discussed in accordance with the process description below.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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, the final carbonaceous material may not simply be the solid, degassed residue of the processing step, but may include additional carbon that has been deposited from the gas phase, such as by the decomposition of organic vapors (e.g., tars) that can form carbon.

[0231] Certain embodiments extend the concept of additional carbon formation by including a separate unit in which the cooled carbon is subjected to an environment containing carbon-containing species to enhance the carbon content of the final product. If the temperature of this unit is below the pyrolysis temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0232] There are numerous options with regard to intermediate input and output (purge or probe) streams of one or more phases present in any particular zone, various mass and energy recycle schemes, various additives that can be introduced anywhere in the process, adjustability of process conditions, including both reaction and separation conditions to tailor product distribution, etc. Zone-specific input and output streams allow for better process monitoring and control, such as by FTIR sampling and dynamic process adjustment.

[0233] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis. Surprisingly, high quality biomedia compositions can be obtained from the disclosed processes and systems.

[0234] 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 in the feedstock; (d) pyrolyzing the feedstock in the presence of a substantially inert gas phase at at least one temperature selected from about 150°C to about 600°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.

[0235] "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.

[0236] Biomass can include, 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 one or more 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, plastics, and textiles. Those skilled in the art will readily appreciate that the raw material options are virtually limitless.

[0237] The present invention can also be used with mixtures of biomass and fossil fuels (such as biomass / coal blends), recognizing that the carbon intensity of the final product will not be as low as with pure biomass feedstocks, but will be lower than if pure fossil fuel feedstocks were used. In some embodiments, the feedstocks include 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.

[0238] 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.

[0239] 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.

[0240] It should be noted that size reduction is an expensive and energy-intensive process. Pyrolyzed materials can be sized with significantly less energy input, i.e., it may be preferable to reduce the particle size of the product rather than the feedstock. This is an option in the present invention 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 a significant 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.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] In a mild pyrolysis reactor, it is desirable to provide a relatively low-oxygen environment, 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 partial or complete oxidation of carbon will reduce the carbon yield to solids.

[0245] In practice, it can be difficult to achieve a strictly oxygen-free environment in the reactor. This limit can be approached, and in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that 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 ways to remove or reduce air in the feed.

[0246] 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.

[0247] 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.

[0248] Various types of degassing units can be used. If drying is performed, it may be inefficient to scrub soluble oxygen from the moisture present, so drying and then degassing may be preferred. In certain embodiments, the drying and degassing steps are combined in a single unit, or some amount of degassing is achieved during drying, etc.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] 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 a portion 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.

[0253] 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., such as about 300° C. to about 400° C. Preferably, the temperature of the first zone is not so high as to bombard the biomass material and rupture cell walls, initiating rapid decomposition of the solid phase into vapors and gases.

[0254] 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.

[0255] The second zone, or generally the primary pyrolysis zone, is operated under pyrolysis conditions. The temperature of the second zone can be selected from about 150°C to about 700°C, such as about, or at least about, or at most about 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, or 600°C. Within this zone, the preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, leaving behind a significant amount of solid material as a high-carbon reaction intermediate. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or creating new pores. The preferred temperature depends at least on the residence time in the second zone, as well as the nature of the feedstock and the desired product characteristics.

[0256] 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, such as from about 150°C to about 350°C.

[0257] Chemical reactions can continue to occur in the cooling zone. Without being limited to a particular theory, it is believed that a secondary pyrolysis reaction can be initiated in the third zone. Carbon-containing components that are in the gas phase can condense (due to the 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.

[0258] 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.

[0259] 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.

[0260] The solids residence time in the preheat zone can be selected from about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the temperature, a sufficient time is desirable to allow the biomass to reach the desired preheat temperature. The heat transfer rate, which depends on the particle type and size, physical equipment, and heating parameters, dictates the minimum residence time required to allow the solids to reach the desired preheat temperature. Additional time may be undesirable unless some amount of mild pyrolysis is intended in the preheat zone, as it contributes to higher capital costs.

[0261] The solids residence time in the pyrolysis zone can be selected from about 10 minutes to about 120 minutes, e.g., 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 would need to be very high, such as above 700°C, to remove significant amounts 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.

[0262] 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.

[0263] 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. Unless some amount of secondary pyrolysis is desired, additional time may not be desirable.

[0264] As discussed above, the vapor phase residence times can be selected and controlled separately. The vapor residence time in the preheating zone can be selected from about 0.1 minutes to about 15 minutes, such as about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time in the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, such as about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time in the cooling zone can be selected from about 0.1 minutes to about 15 minutes, such as about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. A short vapor residence time promotes rapid sweep of volatiles out of the system, while a longer vapor residence time promotes reaction of components in the vapor phase with the solid phase.

[0265] 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.

[0266] 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.

[0267] 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, such as 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.

[0268] 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).

[0269] 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.

[0270] 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.

[0271] The sweep gas can be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweep gas can be initially preheated before introduction, or can be cooled if obtained from a heated source.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] In some embodiments, the zone or zones in which separation is carried out are units physically separate from the reactor. Separation units or zones can be located between reactor zones as needed. For example, there can be a separation unit located between a pyrolysis unit and a cooling unit.

[0278] 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, as needed, using suitable valves and controls.

[0279] The volatile-containing sweep gas can exit one or more reactor zones or can be combined if obtained from multiple zones. The resulting gas stream containing various vapors can then be fed to a thermal oxidizer for controlled air emissions. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are fed to the thermal oxidizer to reach a temperature sufficient to substantially destroy the volatiles contained therein.

[0280] 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. Preferably, the energy content of the thermal oxidizer effluent is 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.

[0281] 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 higher. The remainder is divided between condensable vapors, such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases, such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on process conditions, including the presence of water.

[0282] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80%, or higher. For example, in some embodiments, the carbonaceous material contains from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon leads to varying degrees of formation of methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones.

[0283] 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 obtained from the reactor containing various vapors can be at least partially condensed and then passed over cooled pyrolysis solids from a cooling zone or a separate cooling unit. These embodiments are described in more detail below.

[0284] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids can be introduced into a separate cooling unit. In some embodiments, the solids are collected and simply cooled slowly. 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 to a temperature below 40°C, e.g., 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.

[0285] 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.

[0286] 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.

[0287] Some other means for screening or 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 pulverized carbon or activated carbon product.

[0288] 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 one or more properties of the high-carbon bioreagent or downstream products incorporating the reagent. Certain additives can provide enhanced process and product (bioreagent or products containing bioreagent) characteristics.

[0289] 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.

[0290] 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.

[0291] 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.

[0292] 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.

[0293] 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.

[0294] 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.

[0295] The additive may result in the bioreagent having improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. The additive may improve mechanical properties simply by its presence (e.g., the additive itself imparts strength to the mixture) or due to some transformation that occurs in the additive phase or within the resulting mixture. For example, a reaction such as vitrification may occur within a portion of the bioreagent that contains the additive, thereby improving the final strength.

[0296] 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.

[0297] 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.

[0298] 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.

[0299] 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 higher.

[0300] 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.

[0301] 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 final product, for example, another stream of inert gas at ambient temperature can be passed through the solids to cool them, and then returned to the inert gas preheat system.

[0302] Some variations of the present invention include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the supplying apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor configured to contain at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone and having an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solids cooler disposed in operable communication with the multi-zone reactor; (e) utilizing a bioreagent production system comprising: a high-carbon bioreagent recovery unit disposed in operable communication with the solid-state cooler;

[0303] Some variations are: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the supplying 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) utilizing a bioreagent production system comprising: a high-carbon bioreagent recovery unit disposed in operative communication with the cooler; The system is configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0304] 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.

[0305] 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) may be located within a single unit or may be located in separate units.

[0306] 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).

[0307] 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.

[0308] 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.

[0309] 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.

[0310] Gas inlets and outlets not only allow for the introduction and removal of vapors, but the gas outlets (probes) in particular allow for accurate process monitoring and control over various stages of the process, up to and potentially including all stages of the process. Accurate process monitoring is expected to result in improved yields and efficiencies, both dynamically and over time, when operating history can be utilized to adjust process conditions.

[0311] In certain embodiments, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful for 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.

[0312] 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.).

[0313] 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).

[0314] 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 an arrangement may be used in zones that do not have a gas inlet / outlet for a substantially inert gas for processing, or the reactive gas probe may be associated with a separate gas inlet / outlet in addition to the process inlet and outlet. The sampling inert gas that is periodically introduced and withdrawn for sampling (in embodiments utilizing a sample sweep) may be different from the process inert gas, as desired, either for reasons of analytical accuracy or to introduce an analytical tracer.

[0315] 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.

[0316] 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).

[0317] 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.

[0318] 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 degree of any mild pyrolysis that occurs.

[0319] 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.

[0320] 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.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] 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.

[0327] 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.

[0328] 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.

[0329] 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.

[0330] 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.

[0331] 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.

[0332] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., the ability to process biomass feedstock without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not contain augers, screws, or rakes, which tend to significantly reduce the size of the feedstock being pyrolyzed.

[0333] 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 a separate fuel (such as natural gas) and an oxidant (such as air) into a combustion chamber adapted to combust the fuel and at least a portion of the condensable vapors. Certain non-condensable gases, such as CO or CH4, may also be oxidized to CO2.

[0334] 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.

[0335] 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.

[0336] 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.

[0337] The entire system may be at a fixed location or may be distributed over several locations. The system may be built using modules that can be easily replicated for practical scale-up. The system may also be built using economy of scale principles, as is well known in the process industries.

[0338] Some variations on solid carbon enrichment will now be further described. In some embodiments, the process for producing a bio-reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 150°C to about 600°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 enriched pyrolysis solid.

[0339] 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.

[0340] Alternatively or additionally, the vapor or gas can be contacted with a 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 a 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 a low-temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0341] 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.

[0342] The process may include various methods of treating or separating the steam or gas prior to using the steam or gas for carbon enrichment. For example, the intermediate feed stream comprising or 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 comprises all of the condensable steam, all of the non-condensable gas, or both.

[0343] 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.

[0344] 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.

[0345] 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.

[0346] 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.

[0347] 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.

[0348] 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.

[0349] 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.

[0350] 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.

[0351] 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.

[0352] Further separation can be used to recover one or more non-condensable gases or condensable vapors for use within the process or further processing, for example, to produce purified carbon monoxide or hydrogen.

[0353] 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.

[0354] 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 either for energy in the process or as part of the substantially inert gas in the pyrolysis step. Any combination of the foregoing is also possible.

[0355] 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.

[0356] 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.

[0357] In some embodiments, a batch or continuous process for producing a bioreagent comprises: (a) providing a solids stream comprising a carbon-containing material; (b) providing a gas stream comprising a condensable carbon-containing vapor, a non-condensable carbon-containing gas, or a mixture of a condensable carbon-containing vapor and a non-condensable carbon-containing gas; (c) passing the gas stream through the solid stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0358] In some embodiments, the starting carbon-containing material is pyrolyzed biomass or torrefied biomass. The gas stream can be obtained during an integrated process that provides 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.

[0359] 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.

[0360] 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 carbon-containing vapors and non-condensable carbon-containing gases. The first and second output streams can be separated based on relative volatility, relative polarity, or any other characteristic. The gas streams can be obtained from separate processing of carbon-containing materials.

[0361] 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.

[0362] 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, compared to the starting carbon-containing material.

[0363] In a related variation, the bioreagent production system comprises: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the supplying apparatus and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor configured to contain at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone and having an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a 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.

[0364] 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.

[0365] 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.

[0366] 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.

[0367] The present invention is capable of producing a variety of compositions useful as bioreagents, and products incorporating such reagents. In some variations, the bioreagents can be prepared using any of the processes disclosed herein, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes at a pyrolysis temperature selected from about 150°C to about 600°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.

[0368] 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.

[0369] The high-carbon bio-reagent may contain about 10% by weight or less, e.g., about 5% by weight or less, hydrogen on a dry basis. The bio-reagent may contain about 1% by weight or less, such as about 0.5% by weight or less, nitrogen on a dry basis. The bio-reagent may contain about 0.5% by weight or less, phosphorus on a dry basis, such as about 0.2% by weight or less. The bio-reagent may contain about 0.2% by weight or less, such as about 0.1% by weight or less, sulfur on a dry basis.

[0370] 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.

[0371] Certain embodiments provide reagents that contain little or essentially no hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture that is present. Thus, some embodiments provide bioreagents that have 100% or less carbon on a dry / ash-free (DAF) basis.

[0372] 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 content can be measured, for example, using ASTM D3174.

[0373] Varying amounts of non-combustible materials, such as ash, may be present. The high-carbon bioreagent may contain about 10% by weight or less, e.g., about 5%, about 2%, about 1% by weight or less, of non-combustible materials on a dry basis. In certain embodiments, the reagent contains little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon, including 100% carbon on a dry basis.

[0374] 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.

[0375] 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 bone-dry reagent. For example, a high-carbon bioreagent 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.

[0376] The biological reagents can be formed into a powder, such as a coarse or fine powder. For example, the reagents can, in embodiments, be formed into a powder having an average mesh size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0377] In some embodiments, the biological reagents are formed into structural objects comprising compressed, bonded, or aggregated particles. The starting material for forming these objects can be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The objects can be formed by mechanical pressing or other forces, optionally with the use of binders or other means to aggregate the particles together.

[0378] In some embodiments, the bio-reagent is produced in the form of a structural object whose structure is substantially derived from the source material. For example, a source chip can produce a bio-reagent product chip. 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.

[0379] Bioreagents 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.

[0380] 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.

[0381] In some embodiments, the 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; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

[0382] 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.

[0383] 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.

[0384] 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.

[0385] 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.

[0386] 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.

[0387] 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.

[0388] 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.

[0389] 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, then, that when a relatively large amount of additive, such as greater than about 1% by weight, is incorporated, the energy content calculated based on the total reagent weight (including additives) will be reduced. Note that in various embodiments, the high-carbon biological reagent including 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.

[0390] 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.

[0391] In certain 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.

[0392] 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.

[0393] 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.

[0394] 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.

[0395] 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.

[0396] 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 various 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.

[0397] Products or materials into which these high carbon bioreagents can be incorporated include, but are in no way limited to, carbon-based blast furnace additive products, carbon-based taconite pellet additive products, ladle additive carbon-based products, metcoke carbon-based products, coal replacement products, carbon-based coking products, carbon breeze products, fluidized bed carbon-based feedstocks, carbon-based furnace additive products, injectable carbon-based products, pulverized carbon-based products, stoker carbon-based products, carbon electrodes, or activated carbon products.

[0398] Certain uses of the disclosed bio-reagents in metal production can reduce slag, increase overall efficiency, and reduce life cycle environmental impact.

[0399] Some variations of the present invention utilize high-carbon bioreagents as carbon-based blast furnace addition products. A blast furnace is a type of metallurgical furnace used in smelting to produce industrial metals, such as (but not limited to) iron. Smelting is a form of extractive metallurgy, and its primary use is to produce metals from their ores. Smelting uses heat and chemical reducing agents to break down the ore. Carbon, or carbon monoxide derived from the carbon, removes oxygen from the ore, leaving behind the elemental metal.

[0400] The reducing agent may comprise or consist essentially of a high-carbon bioreagent. In a blast furnace, the high-carbon bioreagent, ore, and typically limestone may be continuously fed through the top of the furnace, while air (optionally oxygen-enriched) is blown into the bottom of the chamber, resulting in a chemical reaction occurring throughout the furnace as the material moves downward. The end products are typically molten metal and slag phases removed from the bottom, and flue gases exiting the top of the furnace. The downward flow of ore in contact with the upward flow of hot, carbon monoxide-enriched gas is a countercurrent process.

[0401] Carbon quality in a blast furnace is measured by its resistance to degradation. The role of carbon as a permeable medium is important for economic blast furnace operation. Carbon decomposition varies with location in the blast furnace and involves a combination of reaction with CO, H, or O, and attrition of carbon particles to each other and to other components of the charge. Decomposed carbon particles can cause clogging and reduced performance.

[0402] The coke reactivity test is a highly regarded measure of the performance of carbon in a blast furnace. This test has two components: coke reactivity index (CRI) and reacted coke strength (CSR). Carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​are preferred for better blast furnace performance. CRI can be determined as received according to any suitable method known in the art, for example, by ASTM method DS341.

[0403] In some embodiments, the high carbon bioreagent provides a carbon product with properties suitable for direct introduction into a blast furnace.

[0404] The strength of the high-carbon bio-reagent can be determined by any suitable method known in the art, for example, by drop crush test or CSR test. In some embodiments, the high-carbon bio-reagent, when optionally blended with another carbon source, provides a final carbon product having a CSR of at least about 50%, 60%, or 70%. The composite product can also provide a final coke product with a reactivity suitable for combustion in a blast furnace. In some embodiments, the product has a CRI such that the high-carbon bio-reagent is suitable for use as an additive or substitute for metcoal, metcoke, coke breeze, foundry coke, or injectable coal.

[0405] Some embodiments use one or more additives in an amount sufficient to provide a high-carbon bio-reagent that, when added to another carbon source (e.g., coke) that has insufficient CRI or CSR for use as a blast furnace product, provides a composite product with sufficient CRI or CSR for use in a blast furnace. In some embodiments, the one or more additives are present in an amount sufficient to provide a high-carbon bio-reagent with a CRI of about 40%, 30%, or 20% or less.

[0406] In some embodiments, one or more additives selected from alkaline earth metals, or their oxides or carbonates, are introduced during or after the process of producing the high-carbon bioreagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate can be introduced as additives. Adding these compounds before, during, or after pyrolysis can increase the reactivity of the high-carbon bioreagent in the blast furnace. These compounds can result in stronger materials, i.e., higher CSR, thereby improving blast furnace efficiency. In addition, additives such as those selected from alkaline earth metals, or their oxides or carbonates, can result in lower emissions (e.g., SO2).

[0407] In some embodiments, the blast furnace replacement product is a high-carbon bioreagent according to the present invention, comprising at least about 55% by weight carbon, not more than about 0.5% by weight sulfur, not more than about 8% by weight non-combustible materials, and a calorific value of at least about 11,000 Btu / lb. In some embodiments, the blast furnace replacement product further comprises not more than about 0.035% by weight phosphorus, about 0.5% to about 50% by weight volatile materials, and optionally one or more additives. In some embodiments, the blast furnace replacement product comprises about 2% to about 15% by weight dolomite, about 2% to about 15% by weight dolomitic lime, about 2% to about 15% by weight bentonite, or about 2% to about 15% by weight calcium oxide. In some embodiments, the blast furnace replacement product has dimensions substantially in the range of about 1 cm to about 10 cm.

[0408] In some embodiments, the high carbon bioreagent according to the present invention is useful as a foundry coke replacement product. Foundry coke is generally characterized as having a carbon content of at least about 85% by weight, a sulfur content of about 0.6% by weight, not more than about 1.5% by weight volatile matter, not more than about 13% by weight ash, not more than about 8% by weight moisture, not more than about 0.035% by weight phosphorus, a CRI value of about 30, and dimensions ranging from about 5 cm to about 25 cm.

[0409] Some variations of the present invention utilize high-carbon bioreagents as carbon-based taconite pellet addition products. The ores used in iron and steel production are iron oxides. The primary iron oxide ores include hematite, limonite (also known as brown ore), taconite, and magnetite, a black ore. Taconite is a low-grade but important ore that contains both magnetite and hematite. The iron content of taconite is generally between 25% and 30% by weight. Blast furnaces typically require ores with at least 50% iron by weight for efficient operation. Iron ore can undergo beneficiation processes, including crushing, screening, tumbling, flotation, and magnetic separation. Refined ores are often concentrated to greater than 60% iron and formed into pellets before transport.

[0410] For example, taconite can be crushed into a fine powder and combined with a binder such as bentonite clay and limestone. For example, pellets about one centimeter in diameter containing about 65% iron by weight can be formed. The pellets are calcined to oxidize the magnetite to hematite. The pellets are durable and ensure that the blast furnace charge remains porous enough to allow heated gases to pass through and react with the pelletized ore.

[0411] The taconite pellets can be fed into a blast furnace to produce iron, as described above with respect to blast furnace adducts. In some embodiments, a high-carbon bioreagent is introduced into the blast furnace. In these or other embodiments, the high-carbon bioreagent is incorporated into the taconite pellets themselves. For example, beneficiated taconite ore powder can be mixed with a high-carbon bioreagent and a binder, rolled into small bodies, and then fired until hard. In such embodiments, taconite-carbon pellets having the appropriate composition can be conveniently introduced into a blast furnace without the need for a separate carbon source.

[0412] Some variations of the present invention utilize high carbon bioreagents as ladle-added carbon-based products. A ladle is a vessel used to transport and pour out molten metal. A casting ladle is used to pour molten metal into a mold to produce a casting. A transfer ladle is used to transfer large quantities of molten metal from one process to another. A processing ladle is used for processes that occur in a ladle to change some aspect of the molten metal, such as converting cast iron to ductile iron by adding various elements to the ladle.

[0413] The high-carbon bio-reagent can be introduced into any type of ladle, but typically, carbon is added to a treatment ladle in a suitable amount based on the target carbon content. The carbon injected into the ladle can be in the form of a fine powder for good mass transfer of the carbon into the final composition. In some embodiments, the high-carbon bio-reagent according to the present invention, when used as a ladle-added product, has a minimum dimension of about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or greater.

[0414] In some embodiments, the high carbon bio-reagents according to the present invention are useful as ladle added carbon additives, for example, in basic oxygen furnace or electric arc furnace facilities where ladle addition of carbon is used (e.g., added to ladle carbon during steel production).

[0415] In some embodiments, the ladle-added carbon additive further comprises up to about 5% by weight manganese, up to about 5% by weight calcium oxide, or up to about 5% by weight dolomitic lime.

[0416] Direct reduced iron (DRI), also known as sponge iron, is produced from the direct reduction of iron ore (in lump, pellet, or fine form) with a reducing gas traditionally produced from natural gas or coal. The reducing gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide, which acts as a reducing agent. The high-carbon bioreagents provided herein can be converted into a gas stream containing CO to act as a reducing agent to produce direct reduced iron.

[0417] Iron nuggets are a high-quality steelmaking and iron casting feed material. Iron nuggets are essentially all iron and carbon, with little gangue (slag) and low levels of metallic residues. They are a premium grade pig iron product with excellent transportation and handling characteristics. The carbon contained in the iron nuggets or any portion thereof can be the high-carbon bioreagent provided herein. Iron nuggets can be produced by reducing iron ore in a rotary hearth furnace using the high-carbon bioreagent as a reducing agent and energy source.

[0418] Some variations of the present invention utilize high-carbon bioreagents as the metallurgical coke carbonaceous product. Metallurgical coke, also known as "met" coke, is a carbonaceous material typically produced by destructive distillation of various blends of bituminous coal. The final solid is unfused carbon, referred to as metallurgical coke. As a result of the loss of volatile gases and partial melting, met coke has an open-porous morphology. Met coke has a very low volatile content. However, ash components that were part of the original bituminous coal feedstock remain encapsulated in the resulting coke. Met coke feedstock is available in a wide range of sizes, from fine powder to basketball-sized chunks. Typical purity ranges from 86 to 92% fixed carbon by weight.

[0419] Metallurgical coke is used wherever high quality, tough, and resilient wear carbon is required. Applications include, but are not limited to, conductive flooring, friction materials (e.g., carbon linings), foundry coatings, foundry carbon lazers, corrosion materials, drilling applications, reducing agents, heat treatment agents, ceramic packing media, electrolytic processes, and oxygen scavenging.

[0420] Metcoke can be characterized as having a calorific value of about 10,000 to 14,000 Btu / lb and an ash content of about 10% by weight or greater. Thus, in some embodiments, a metcoke replacement product comprises a high-carbon bioreagent (e.g., carbon-negative pellets) according to the present invention, comprising at least about 80%, 85%, or 90% by weight carbon, about 0.8% or less sulfur, about 3% or less volatiles, about 15% or less ash, about 13% or less moisture, and about 0.035% or less phosphorus. When used as a metcoke replacement product, the high-carbon bioreagent according to the present invention can have a size range of, for example, about 2 cm to about 15 cm.

[0421] In some embodiments, the metcoke substitute product further comprises additives such as chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorospar, calcium oxide, lime, dolomitic lime, bentonite, and combinations thereof.

[0422] Some variations of the present invention utilize high-carbon bio-reagents as coal replacement products. Any process or system that uses coal can, in principle, be adapted to use high-carbon bio-reagents.

[0423] In some embodiments, a high-carbon bioreagent is combined with one or more coal-based products to form a composite product that has a higher rank than the coal-based product or that has fewer emissions when combusted than the pure coal-based product.

[0424] For example, low-rank coal, such as sub-bituminous coal, can be used in applications that normally require high-rank coal products, such as bituminous coal, by combining a selected amount of a high-carbon bio-reagent according to the present invention with the low-rank coal product. In other embodiments, the rank of a blended coal product (e.g., a combination of multiple coals of different ranks) can be improved by combining the blended coal with an amount of high-carbon bio-reagent. The amount of high-carbon bio-reagent blended with the coal product can vary depending on the rank of the coal product, the properties of the high-carbon bio-reagent (e.g., carbon content, calorific value, etc.), and the desired rank of the final combined product.

[0425] For example, anthracite coal is generally characterized as having at least about 80% by weight carbon, about 0.6% by weight sulfur, about 5% by weight volatile matter, a maximum of about 15% by weight ash, a maximum of about 10% by weight moisture, and a heating value of about 12,494 Btu / lb. In some embodiments, anthracite substitute products are high-carbon bioreagents comprising at least about 80% by weight carbon, no more than about 0.6% by weight sulfur, no more than about 15% by weight ash, and a heating value of at least about 12,000 Btu / lb.

[0426] In some embodiments, the high-carbon bioreagent is useful as a thermal coal replacement product. Thermal coal products are generally characterized by high sulfur levels, high phosphorus levels, high ash content, and a heating value of up to about 15,000 Btu / lb. In some embodiments, the thermal coal replacement product is a high-carbon bioreagent containing about 0.5% by weight or less sulfur, about 4% by weight or less ash, and a heating value of at least about 12,000 Btu / lb.

[0427] Some variations of the present invention utilize a high-carbon bioreagent as a carbon-based coking product. Any coking process or system can be adapted to use a high-carbon bioreagent to produce coke or use it as a coke feedstock.

[0428] In some embodiments, the high-carbon bioreagent is useful as a thermal coal or coke substitute product. For example, the thermal coal or coke substitute product can consist essentially of the high-carbon bioreagent comprising at least about 50% by weight carbon, not more than about 8% by weight ash, not more than about 0.5% by weight sulfur, and a heating value of at least about 11,000 Btu / lb. In other embodiments, the thermal coke substitute product further comprises from about 0.5% by weight to about 50% by weight volatile matter. The thermal coal or coke substitute product can comprise from about 0.4% by weight to about 15% by weight moisture.

[0429] In some embodiments, the high-carbon bioreagent is useful as a petroleum (pet) coke or calcined pet coke replacement product. Calcined pet coke is generally characterized by having at least about 66% by weight carbon, up to 4.6% by weight sulfur, up to about 5.5% by weight volatiles, up to about 19.5% by weight ash, and up to about 2% by weight moisture, and is typically about 3 mesh or smaller in size. In some embodiments, the calcined pet coke replacement product is a high-carbon bioreagent containing at least about 66% by weight carbon, up to about 4.6% by weight sulfur, up to about 19.5% by weight ash, and up to about 2% by weight moisture, and is about 3 mesh or smaller in size.

[0430] In some embodiments, the high-carbon bioreagent is useful as a coking carbon substitute (e.g., co-fired with metallurgical coal in a coking furnace). In one embodiment, the coking carbon substitute product is a high-carbon bioreagent containing at least about 55% by weight carbon, not more than about 0.5% by weight sulfur, not more than about 8% by weight non-combustible materials, and a heating value of at least about 11,000 Btu / lb. In some embodiments, the coking carbon substitute product contains from about 0.5% by weight to about 50% by weight volatile materials or one or more additives.

[0431] Some variations of the present invention utilize a high-carbon bioreagent as a carbon breeze product, which typically has a very fine particle size, such as 6 mm, 3 mm, 2 mm, 1 mm, or less. In some embodiments, the high-carbon bioreagent of the present invention is useful as a coke breeze replacement product. Coke breeze is generally characterized as having a maximum dimension of about 6 mm or less, a carbon content of at least about 80% by weight, 0.6-0.8% by weight sulfur, 1%-20% by weight volatile matter, up to about 13% by weight ash, and up to about 13% by weight moisture. In some embodiments, the coke breeze replacement product is a high-carbon bioreagent of the present invention comprising at least about 80% by weight carbon, up to about 0.8% by weight sulfur, up to about 20% by weight volatile matter, up to about 13% by weight ash, up to about 13% by weight moisture, and a maximum dimension of about 6 mm.

[0432] In some embodiments, the high carbon bioreagent is useful as a carbon breeze replacement product, for example, during taconite pellet production or in steelmaking processes.

[0433] Some variations utilize high-carbon bioreagents as feedstock for various fluidized beds or as a fluidized bed carbonaceous feedstock replacement product. The carbon can be used in fluidized beds for total combustion, partial oxidation, gasification, steam reforming, etc. The carbon can be converted primarily to synthesis gas for various downstream uses, including the production of energy (e.g., combined heat and power) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel).

[0434] In some embodiments, high carbon bio-reagents according to the present invention are useful, for example, as fluidized bed coal replacement products in fluidized bed furnaces where coal is used (eg, for process heat or energy generation).

[0435] Some variations utilize high-carbon bioreagent as a carbon-based furnace additive product. Coal-based carbon furnace additive products are generally characterized as having high sulfur levels, high phosphorus levels, and high ash content, which contribute to the degradation of metal products and cause air pollution. In some embodiments, a carbon furnace additive replacement product containing high-carbon bioreagent contains about 0.5% or less by weight sulfur, about 4% or less by weight ash, about 0.03% or less by weight phosphorus, and a maximum dimension of about 7.5 cm. In some embodiments, the carbon furnace additive replacement product contains about 0.5% to about 50% by weight volatiles and about 0.4% to about 15% by weight moisture.

[0436] In some embodiments, the high carbon bio-reagent is useful as a furnace additive wherever furnace additive carbon is used, for example, in basic oxygen furnaces or electric arc furnace facilities. For example, furnace additive carbon can be added to scrap steel during steel production in electric arc furnace facilities. In electric arc furnace applications, high purity carbon is desirable so that impurities are not returned to the process after early removal.

[0437] In some embodiments, the furnace-added carbon additive is a high-carbon bioreagent containing at least about 80% by weight carbon, not more than about 0.5% by weight sulfur, not more than about 8% by weight non-combustible material, and a heating value of at least about 11,000 Btu / lb. In some embodiments, the furnace-added carbon additive further contains up to about 5% by weight manganese, up to about 5% by weight fluorospar, about 5% to about 10% by weight dolomite, about 5% to about 10% by weight dolomitic lime, or about 5% to about 10% by weight calcium oxide.

[0438] Some variations utilize high-carbon bio-reagent as a stoker furnace carbon-based product. In some embodiments, the high-carbon bio-reagent according to the present invention is useful, for example, as a stoker coal replacement product in stoker furnace facilities where coal is used (e.g., for process heat or energy generation).

[0439] Some variations utilize a high-carbon bio-reagent as the injectable (e.g., finely divided) carbon-based material. In some embodiments, the high-carbon bio-reagent is useful as an injection-grade calcined pet coke replacement product. Injection-grade calcined pet coke is generally characterized by having at least about 66% by weight carbon, about 0.55 to about 3% by weight sulfur, up to about 5.5% by weight volatiles, up to about 10% by weight ash, and up to about 2% by weight moisture, and is about 6 mesh or smaller in size. In some embodiments, the calcined pet coke replacement product is a high-carbon bio-reagent containing at least about 66% by weight carbon, up to about 3% by weight sulfur, up to about 10% by weight ash, and up to about 2% by weight moisture, and is about 6 mesh or smaller in size.

[0440] In some embodiments, the high carbon bio-reagent is useful as an injectable carbon replacement product in any application where injectable carbon is used (e.g., injected into slag or ladles during steel production), for example, in basic oxygen furnace or electric arc furnace facilities.

[0441] In some embodiments, the high-carbon bio-reagent is useful, for example, as a pulverized carbon replacement product whenever pulverized coal is used (e.g., for process heat or energy generation). In some embodiments, the pulverized coal replacement product comprises up to about 10 percent calcium oxide.

[0442] Some variations utilize high-carbon bioreagent as a carbon addition product for metal production. In some embodiments, the high-carbon bioreagent according to the present invention is useful as a carbon addition product for the production of carbon steel or another metal alloy containing carbon. Coal-based late-stage carbon addition products are generally characterized as having high sulfur levels, high phosphorus levels, and high ash content, as well as high mercury levels that degrade metal quality and contribute to air pollution. In some embodiments of the present invention, the carbon addition product comprises about 0.5% by weight or less sulfur, about 4% by weight or less ash, about 0.03% by weight or less phosphorus, a minimum dimension of about 1-5 mm, and a maximum dimension of about 8-12 mm.

[0443] Some variations utilize high-carbon bio-reagents within carbon electrodes. In some embodiments, the high-carbon bio-reagents are useful as electrode (e.g., anode) materials suitable for use in, for example, aluminum production.

[0444] Other applications of high-carbon bio-reagents in carbon electrodes include batteries, fuel cells, capacitors, and other energy storage or energy delivery devices. For example, in lithium-ion batteries, high-carbon bio-reagents can be used on the anode side to intercalate lithium. In these applications, carbon purity and low ash content can be very important.

[0445] Some variations of the present invention utilize high-carbon bioreagents as catalyst supports. Carbon is a known catalyst support in a wide range of catalytic chemical reactions, such as the synthesis of mixed alcohols from syngas using sulfided cobalt-molybdenum metal catalysts supported on a carbon phase, or iron-based catalysts supported on carbon for the Fischer-Tropsch synthesis of higher hydrocarbons from syngas.

[0446] Some variations utilize the high-carbon bioreagent as an activated carbon product. Activated carbon is used in a wide variety of liquid- and gas-phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, and pharmaceuticals. For activated carbon, the porosity and surface area of ​​the material are generally important. The high-carbon bioreagent provided herein, in various embodiments, can provide a superior activated carbon product due to: (i) a larger surface area than fossil-fuel-based activated carbon; (ii) carbon renewable potential; (iii) the vascularity of the biomass feedstock in combination with additives allows for better penetration / distribution of additives to enhance pollutant control; and (iv) less inert material (ash content), resulting in greater reactivity.

[0447] In the foregoing description of market applications for bioreagents, it should be recognized that the applications described are not exclusive or exhaustive. Thus, a bioreagent described as suitable for one type of carbon product may, in various embodiments, be suitable for any of the other applications described. These applications are exemplary only, and other applications for bioreagents or their derivatives exist.

[0448] Additionally, in some embodiments, the same physical material may be used in multiple market processes, either in an integrated manner or sequentially. Thus, for example, a high-carbon bioreagent used as a carbon electrode or activated carbon may, at the end of its useful life as a performance material, be introduced into a combustion process for energy value or into a metal fabrication (e.g., reduction of metal ores) process, etc.

[0449] Some embodiments may use bio-reagents for their reactive or adsorption properties, as well as fuels. For example, bio-reagents injected into the exhaust stream may be suitable for removing contaminants and subsequently combusting the bio-reagent particles and possibly the contaminants to generate energy and thermally destroy or chemically oxidize the contaminants.

[0450] Compared to traditional fossil fuel-based products, high-carbon bio-reagents can be associated with significant environmental and product use advantages. High-carbon bio-reagents can be not only environmentally superior, but also functionally superior from a processing standpoint, for example, due to higher purity.

[0451] For some embodiments of metal production, production of bioreagents by the disclosed process produces significantly less CO, CO, NO compared to the coking of coal-based products required to prepare them for use in metal production. x , SO2, and hazardous air pollutant emissions.

[0452] The use of high carbon bioreagents instead of coal or coke also significantly reduces environmental emissions of SO2, hazardous air pollutants, and mercury.

[0453] Additionally, due to the purity of these high carbon bio-reagents (including low ash content), the disclosed bio-reagents have the potential to reduce slag and increase production capacity in batch metal fabrication processes.

[0454] In some embodiments, the bio-reagent functions as activated carbon or other filtration media. In certain embodiments, a portion of the bio-reagent is recovered as an activated carbon product or filtration media product, and another portion (e.g., the remainder) of the bio-reagent is pelletized with a binder to produce bio-carbon pellets. In other embodiments, the bio-reagent is pelletized with a binder to produce bio-carbon pellets, and the bio-carbon pellets are shipped for subsequent conversion to activated carbon products. Subsequent conversion may include pulverization back to a powder or chemical treatment, for example, with steam, acid, or base. In these embodiments, the bio-carbon pellets may be considered activated carbon or filtration media precursor pellets.

[0455] When produced, activated carbon can be characterized, for example, by an iodine number of at least about 500, 750, 800, 1000, 1500, or 2000. 14 C / 12 The activated carbon may be characterized by a renewable carbon content of at least 50%, 60%, 70%, 80%, 90%, or 95% as determined from C isotope ratio measurements. 14 C / 12 It can be characterized as a (fully) renewable activated carbon, as determined from measurements of the C isotope ratio.

[0456] In some embodiments, the pyrolysis reactor is configured to optimize the production of different types of activated carbon. For example, reaction conditions (e.g., time, temperature, and steam concentration) can be selected for activated carbon products with certain attributes, such as iodine value. Different reaction conditions can be selected for different activated carbon products, such as those with higher iodine values. The pyrolysis reactor can operate in a campaign mode to produce one product and then switch to another mode for a different product. The first product can be removed continuously or periodically during the first campaign, or can be removed before switching the reaction conditions of the pyrolysis reactor.

[0457] The activated carbon can be characterized, for example, by an iodine number of at least about 500, 750, 1000, 1500, or 2000. 14 C / 12 In some embodiments, the activated carbon may be characterized by a renewable carbon content of at least 90% as determined from C isotope ratio measurements. 14 C / 12 It can be characterized as a (fully) renewable activated carbon, as determined from measurements of the C isotope ratio.

[0458] The activated carbon or filtration media produced by the processes disclosed herein can be used in many ways.

[0459] In some embodiments, activated carbon or filtration media is utilized internally at a processing site to purify one or more primary products. In some embodiments, activated carbon is utilized on-site to purify water. In these or other embodiments, activated carbon or filtration media is utilized on-site to treat liquid waste streams to reduce liquid-phase emissions or to treat steam waste streams to reduce air emissions. In some embodiments, activated carbon or filtration media is utilized as a soil amendment to aid in the generation of new biomass, which may be the same type of biomass utilized on-site as local feedstock.

[0460] Activated carbon or filtration media prepared according to the processes disclosed herein can have the same or better characteristics as conventional fossil-fuel-based activated carbon. In some embodiments, the activated carbon or filtration media has a surface area comparable to, equal to, or greater than that associated with fossil-fuel-based activated carbon. In some embodiments, the activated carbon or filtration media can control contaminants as well as or better than conventional activated carbon products. In some embodiments, the activated carbon or filtration media has an inert material (e.g., ash) level comparable to, equal to, or less than that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration media has a particle size or particle size distribution comparable to, equal to, greater than, or less than that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration media has a particle shape comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration media has a particle shape that is substantially different from that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration medium has a pore volume comparable to, equal to, or greater than that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration medium has a pore size comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration medium has a particle abrasion resistance value comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration medium has a hardness value comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon or filtration medium has a bulk density value comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon product or filtration medium has an adsorption capacity comparable to, substantially similar to, or the same as that associated with conventional activated carbon products.

[0461] Prior to suitability or actual use in any product application, the disclosed activated carbon or filtration media can be analyzed, measured, and optionally modified (such as with additives) in various ways. Some potentially important properties include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, basicity, hardness, and iodine number.

[0462] Activated carbon is used commercially in a wide variety of liquid and gas phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, sugar and sweetener refining, automotive applications, and pharmaceuticals. For activated carbon, key product attributes can include particle size, shape, composition, surface area, pore volume, pore dimensions, particle size distribution, carbon surface and internal chemistry, particle attrition resistance, hardness, bulk density, and adsorption capacity.

[0463] The bulk density of the bioactivated carbon or filtration media can be, for example, from about 50 g / liter to about 650 g / liter.

[0464] The surface area of ​​the bioactivated carbon or filtration media can vary widely. An exemplary surface area (e.g., BET surface area) is about 500 m 2 / g, 600m 2 / g, 800m 2 / g, 1000m 2 / g, 1200m 2 / g, 1400m 2 / g, 1600m 2 / g, or 1800m 2 / g, approximately 400m 2 / g~about 2000m 2 / g or greater. Surface area generally correlates with adsorption capacity.

[0465] Pore ​​size distribution can be important in determining the ultimate performance of the activated carbon. Pore size measurements can include micropore content, mesopore content, and macropore content.

[0466] Iodine number is a parameter used to characterize activated carbon performance. Iodine number measures the degree of activation of the carbon and is a measure of the micropore (e.g., 0-20 Å) content. This is an important measurement for liquid-phase applications. Exemplary iodine numbers for activated carbon products or filtration media produced by embodiments of the present disclosure include approximately 500, 600, 750, 900, 1000, 1100, 1200, 1300, 1500, 1600, 1750, 1900, 2000, 2100, and 2200, including all intervening ranges. Iodine number units are milligrams of iodine per gram of carbon.

[0467] Another pore-related measurement is the Methylene Blue Number, which measures mesopore content (e.g., 20-500 Å). Exemplary Methylene Blue Numbers for activated carbon products or filtration media produced by embodiments of the present disclosure include approximately 100, 150, 200, 250, 300, 350, 400, 450, and 500, including all intervening ranges. The Methylene Blue Number is measured in milligrams of methylene blue (methylthioninium chloride) per gram of carbon.

[0468] Another pore-related measurement is the Molasses Number, which measures macropore content (e.g., greater than 500 Å). Exemplary Molasses Numbers for activated carbon products or filtration media produced according to embodiments of the present disclosure include 100, 150, 200, 250, 300, 350, and 400, including all intervening ranges. The Molasses Number units are milligrams of molasses per gram of carbon.

[0469] In some embodiments, the activated carbon or filtration medium is at least about 1 cm 3 / g, at least about 0.5 cm 3 It is characterized by its mesopore volume in g / g.

[0470] Activated carbon or filtration media can be characterized by its water retention capacity. In various embodiments, activated carbon products or filtration media produced according to embodiments of the present disclosure have a water retention capacity at 25° C. of about 50% to about 100%, e.g., about 60% to about 80%, of about 10% to about 300% (weight of water divided by weight of dry activated carbon).

[0471] Hardness, or abrasion number, is a measure of the abrasion resistance of activated carbon. It is an indicator of the physical integrity of activated carbon to withstand frictional forces and mechanical stresses during handling or use. While a certain degree of hardness is desirable, too much hardness can result in excessive equipment wear. Exemplary abrasion numbers measured according to ASTM D3802 range from about 1% to greater than about 99%, e.g., about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or at least greater than about 99%.

[0472] In some embodiments, activated carbon can achieve an optimum range of hardness that is moderately resistant to wear but does not cause wear and tear on the capital equipment that processes the activated carbon. This optimum is possible in some embodiments of the present disclosure through the selection of raw materials and processing conditions. In some embodiments where downstream uses can handle high hardness, the processes of the present disclosure can be operated to increase or maximize hardness to produce bioactivated carbon or filtration media with an attrition number of about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or at least about 99%.

[0473] The bioactivated carbon or filtration media provided by the present disclosure have a wide range of commercial uses. For example, but not limited to, the bioactivated carbon or filtration media can be utilized in emission control, water purification, groundwater treatment, wastewater treatment, air stripper applications, PCB removal applications, odor removal applications, soil vapor extraction, product gas plants, industrial water filtration, industrial fumigation, tanks and process vents, pumps, blowers, filters, pre-filters, mist filters, piping, piping modules, adsorber, absorbers, and columns.

[0474] In one embodiment, a method of using activated carbon to reduce emissions comprises: (a) providing activated carbon particles comprising a bioactivated carbon composition recovered from a second reactor as disclosed herein; (b) providing a gas-phase effluent stream containing at least one selected contaminant; (c) providing an additive selected to assist in the removal of selected contaminants from the gas phase effluent stream; (d) introducing the activated carbon particles and the additive into the gas-phase effluent stream, thereby adsorbing at least a portion of the selected contaminants onto the activated carbon particles, thereby producing contaminant-adsorbed carbon particles within the gas-phase effluent stream; (e) separating at least a portion of the contaminant-adsorbed carbon particles from the gas-phase exhaust stream to produce a contaminant-reduced gas-phase exhaust stream.

[0475] The additive for the bioactivated carbon composition may be provided as part of the activated carbon particles. Alternatively or additionally, the additive may be introduced directly into the gas-phase exhaust stream, fuel bed, or combustion zone. As will be appreciated by those skilled in the art, other ways of introducing the additive directly or indirectly into the gas-phase exhaust stream for removal of selected contaminants are also possible.

[0476] The selected contaminant (in the gas-phase effluent stream) may be a metal, such as mercury, boron, selenium, arsenic, or any compound, salt, or mixture thereof. The selected contaminant may be, for example, a hazardous air pollutant, an organic compound (such as a VOC), or a non-condensable gas. In some embodiments, the biogenic activated carbon product adsorbs, absorbs, or chemisorbs the selected contaminant in a higher amount than a comparable non-biogenic activated carbon product. In some such embodiments, the selected contaminant is a metal, a hazardous air pollutant, an organic compound (such as a VOC), a non-condensable gas, or any combination thereof. In some embodiments, the selected contaminant comprises mercury. In some embodiments, the selected contaminant comprises one or more VOCs. In some embodiments, the biogenic activated carbon comprises at least about 1% hydrogen by weight or at least about 10% oxygen by weight.

[0477] Hazardous air pollutants are pollutants that cause or may cause cancer or other serious health effects (e.g., reproductive effects or birth defects, or adverse environmental and ecological effects). Section 112 of the Clean Air Act, as amended, is incorporated herein by reference in its entirety. Pursuant to Section 112 of the Clean Air Act, the United States Environmental Protection Agency (EPA) is mandated to control 189 hazardous air pollutants. Any current or future compound classified by the EPA as a hazardous air pollutant is included in the possible selected pollutants in this context.

[0478] Volatile organic compounds (some of which are also hazardous air pollutants) are organic chemicals that have high vapor pressures at normal room temperature. Examples include short-chain alkanes, olefins, alcohols, ketones, and aldehydes. Many volatile organic compounds are hazardous to human health or harmful to the environment. The EPA regulates volatile organic compounds in air, water, and land. The EPA's definition of volatile organic compounds is found in 40 CFR §51.100, which is incorporated herein by reference in its entirety.

[0479] Non-condensable gases are gases that do not condense under normal room temperature conditions and may include, but are not limited to, nitrogen oxides, carbon monoxide, carbon dioxide, hydrogen sulfide, sulfur dioxide, sulfur trioxide, methane, ethane, ethylene, ozone, ammonia, or combinations thereof.

[0480] The disclosed activated carbon particles can remove multiple contaminants. In some embodiments, the contaminant-adsorbed carbon particles include at least two contaminants, at least three contaminants, or more. The activated carbons disclosed herein can enable the control of multiple contaminants as well as the control of certain target contaminants (e.g., selenium).

[0481] In some embodiments, the pollutant-adsorbed carbon particles are treated to regenerate the activated carbon particles. In some embodiments, the method includes thermally oxidizing the pollutant-adsorbed carbon particles. The pollutant-adsorbed carbon particles, or a regenerated form thereof, can be combusted to provide energy.

[0482] In some embodiments, the additive for the activated carbon is selected from an acid, a base, a salt, a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. In certain embodiments, the additive is selected from magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, an organic acid (e.g., citric acid), or a combination thereof.

[0483] In some embodiments, the gas phase effluent stream is derived from metal processing, such as the processing of high sulfur content metal ores.

[0484] In an exemplary embodiment for mercury control, activated carbon can be injected (e.g., into piping) upstream of a particulate matter control device such as an electrostatic precipitator or fabric filter. In some cases, a flue gas desulfurization (dry or wet) system can be located downstream of the activated carbon injection point. The activated carbon can be injected pneumatically as a powder. The injection location can be determined by the existing plant configuration (unless this is a new site) and whether additional downstream particulate matter control equipment is being modified.

[0485] For boilers currently equipped with particulate matter control devices, implementing biogenic activated carbon injection for mercury control can involve (i) injecting powdered activated carbon upstream of the existing particulate matter control device (electrostatic precipitator or fabric filter), (ii) injecting powdered activated carbon downstream of the existing electrostatic precipitator and upstream of a retrofit fabric filter, or (iii) injecting powdered activated carbon between the fields of an electrostatic precipitator. The inclusion of iron or iron-containing compounds can dramatically improve the performance of electrostatic precipitators for mercury control. Furthermore, the inclusion of iron or iron-containing compounds can dramatically change end-of-life options by separating spent activated carbon solids from other ash.

[0486] In some embodiments, the powdered activated carbon injection approach can be used in combination with an existing SO2 control device. The activated carbon can be injected before the SO2 control device or after the SO2 control device, depending on the availability of a means to collect the activated carbon sorbent downstream of the injection point.

[0487] In some embodiments, the same physical material can be used in multiple processes, either in an integrated manner or sequentially. Thus, for example, activated carbon can be introduced at the end of its useful life as a performance material into a combustion process for its energy value, or into a metal fabrication process that requires carbon but does not require the properties of activated carbon, etc.

[0488] The bioactivated carbon or filtration media and principles of the present disclosure can be applied to liquid phase applications, including, for example, the processing of water, aqueous streams of various purities, solvents, liquid fuels, polymers, molten salts, and molten metals. As intended herein, "liquid phase" includes slurries, suspensions, emulsions, multi-phase systems, or any other material that has (or can be adjusted to have) at least some amount of a liquid state present.

[0489] In one embodiment, the present disclosure, in some variations, provides a method of using activated carbon or a filtration medium to purify a liquid, comprising: (a) providing activated carbon or filtration media particles; (b) providing a liquid containing at least one selected contaminant; (c) providing an additive selected to assist in the removal of selected contaminants from the liquid; (d) contacting the liquid with the activated carbon particles or filtration media and the additive to adsorb at least a portion of the at least one selected contaminant onto the activated carbon or filtration media particles, thereby producing the contaminant-adsorbing carbon particles and the contaminant-reducing liquid.

[0490] The additive may be provided as part of the activated carbon or filtration media particles, or the additive may be introduced directly into the liquid. In some embodiments, the additive (which may be the same or different) is introduced both as part of the activated carbon or filtration media particles and directly into the liquid.

[0491] In some embodiments for liquid-phase applications, the additive is selected from an acid, a base, a salt, a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof. For example, the additive can be selected from magnesium, manganese, aluminum, nickel, iron, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, an organic acid (e.g., citric acid), or a combination thereof.

[0492] In some embodiments, the selected contaminant (in the liquid being treated) is a metal, such as a metal selected from arsenic, boron, selenium, mercury, and any compound, salt, or mixture thereof. In some embodiments, the selected contaminant is an organic compound (such as a VOC), a halogen, a biological compound, a pesticide, or a herbicide. The contaminant-adsorbing carbon particles may contain two, three, or more contaminants. In some embodiments, the activated carbon product adsorbs, absorbs, or chemisorbs the selected contaminant in a higher amount than a comparable amount of a non-biological activated carbon product. In some such embodiments, the selected contaminant is a metal, a hazardous air pollutant, an organic compound (such as a VOC), a non-condensable gas, or any combination thereof. In some embodiments, the selected contaminant includes mercury. In some embodiments, the selected contaminant includes one or more VOCs. In some embodiments, the biogenic activated carbon or filtration medium contains at least about 1% hydrogen by weight or at least about 10% oxygen by weight.

[0493] The liquid to be treated may typically be aqueous, but this is not required by the principles of the present disclosure. In some embodiments, the liquid is treated with activated carbon or filtration media particles in a fixed bed. In other embodiments, the liquid is treated with activated carbon or filtration media particles in solution or in a moving bed.

[0494] In one embodiment, the present disclosure provides a method for removing at least a portion of sulfur-containing contaminants from a liquid using a biological activated carbon or filtration media composition, comprising: (a) providing activated carbon or filtration media particles; (b) providing a liquid containing sulfur-containing contaminants; (c) providing an additive selected to assist in the removal of sulfur-containing contaminants from the liquid; and (d) contacting the liquid with the activated carbon particles and the additive to adsorb or absorb at least a portion of the sulfur-containing contaminants onto or into the activated carbon or filtration media particles.

[0495] In some embodiments, the sulfur-containing contaminant is selected from elemental sulfur, sulfate, sulfite, sulfur dioxide, sulfur trioxide, sulfate anion, bisulfate anion, sulfite anion, bisulfite anion, thiol, sulfide, disulfide, polysulfide, thioether, thioester, thioacetal, sulfoxide, sulfone, thiosulfinate, sulfimide, sulfoximide, sulfondiimine, sulfur halide, thioketone, thioaldehyde, sulfur oxide, thiocarboxylic acid, thioamide, sulfonic acid, sulfinic acid, sulfenic acid, sulfonium, oxosulfonium, sulfurfuran, persulfuran, or a combination, salt, or derivative thereof. For example, the sulfur-containing contaminant can be sulfate in anionic or salt form.

[0496] The liquid can be an aqueous liquid such as water. In some embodiments, the water is wastewater associated with a process selected from metal mining, acid mine drainage, mineral processing, municipal sewage treatment, pulp and paper, ethanol, or any other industrial process that may produce sulfur-containing contaminants in the wastewater. The water can also be (or a portion thereof) of a natural body of water such as a lake, river, or stream.

[0497] In one embodiment, the present disclosure provides a process for reducing the concentration of sulfate in water, the process comprising: (a) providing recovered activated carbon or filtration media particles; (b) providing a volume or flow of water containing sulfate; (c) providing an additive selected to assist in the removal of sulfate from the water; (d) contacting the water with the activated carbon or filtration media particles and the additive to adsorb or absorb at least a portion of the sulfate onto or into the activated carbon particles or filtration media.

[0498] In some embodiments, sulfate is reduced to a concentration of about 50 mg / L or less in water, such as a concentration of about 10 mg / L or less in water. In some embodiments, sulfate is present primarily in the form of sulfate or bisulfate anions. Depending on the pH, sulfate can also be present in the form of sulfate salts.

[0499] The water can be derived from some or all of a wastewater stream. Exemplary wastewater streams may be associated with metal mining, acid mine drainage, mineral processing, municipal sewage treatment, pulp and paper, ethanol, or any other industrial process that may discharge sulfur-containing contaminants into the wastewater. The water may be a natural body of water, such as a lake, river, or stream. In some embodiments, the process is performed continuously. In other embodiments, the process is performed in batches.

[0500] When water is treated with activated carbon or filtration media, it can be water filtration, water permeation, or direct addition of activated carbon or filtration media particles to the water (with sedimentation, clarification, etc.). When permeation is used, activated carbon or filtration media can be used in several ways within the permeation device or to supplement the permeation device. In some embodiments, activated carbon or filtration media particles and additives are introduced directly into the water prior to permeation. Activated carbon or filtration media particles and additives are optionally used in pre-filtration prior to permeation. In certain embodiments, activated carbon or filtration media particles and additives are incorporated into a membrane for permeation.

[0501] The present disclosure also provides a method of using a bioactivated carbon or filtration media composition for removing sulfur-containing contaminants from a gas phase, comprising: (a) providing activated carbon or filtration media particles; (b) providing a gas-phase effluent stream comprising at least one sulfur-containing contaminant; (c) providing an additive selected to assist in the removal of sulfur-containing contaminants from the gas-phase effluent stream; (d) introducing activated carbon or filtration media particles and an additive into the gas-phase exhaust stream to adsorb or absorb at least a portion of the sulfur-containing contaminants onto the activated carbon particles; (e) separating at least a portion of the activated carbon or filtration media particles from the gas-phase exhaust stream.

[0502] In some embodiments, the sulfur-containing contaminant is selected from elemental sulfur, sulfate, sulfite, sulfur dioxide, sulfur trioxide, sulfate anion, bisulfate anion, sulfite anion, bisulfite anion, thiol, sulfide, disulfide, polysulfide, thioether, thioester, thioacetal, sulfoxide, sulfone, thiosulfinate, sulfimide, sulfoximide, sulfondiimine, sulfur halides, thioketone, thioaldehyde, sulfur oxide, thiocarboxylic acid, thioamide, sulfonic acid, sulfinic acid, sulfenic acid, sulfonium, oxosulfonium, sulfurane, persulfuranes, or combinations, salts, or derivatives thereof.

[0503] Generally speaking, the disclosed activated carbon or filtration media can be used in any application where conventional activated carbon can be used. In some embodiments, the activated carbon is used as a total (i.e., 100%) replacement for conventional activated carbon. In some embodiments, the activated carbon or filtration media is essentially all or substantially all of the activated carbon used in a particular application.

[0504] For example, but not limited to, activated carbon or filtration media can be used in filters, either alone or in combination with conventional activated carbon products. In some embodiments, a packed bed or packed column contains the disclosed activated carbon or filtration media. In such embodiments, the biogenic activated carbon or filtration media has size characteristics suitable for the particular packed bed or packed column. Injection of biogenic activated carbon or filtration media into gas streams can be useful for controlling pollutant emissions in gas or liquid streams from coal-fired power plants, biomass-fired power plants, metal processing plants, crude oil refineries, chemical plants, polymer plants, pulp and paper plants, cement plants, waste incinerators, food processing plants, gasification plants, and syngas plants.

[0505] This detailed description refers to multiple embodiments of the invention and non-limiting examples of how the invention may be realized and practiced. Other embodiments that do not provide all of the features and advantages set forth herein may be utilized without departing from the spirit and scope of the invention. The invention incorporates routine experimentation and optimization of the methods and systems described herein. Such modifications and variations are considered to be within the scope of the invention, as defined by the claims.

[0506] All publications, patents, and patent applications cited in this specification are herein incorporated by reference in their entirety, as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference herein.

[0507] While the above methods and steps indicate certain events occurring in a particular order, one skilled in the art will recognize that the order of certain steps can be varied and that such variations are in accordance with variations of the present invention. Additionally, some of the steps may be performed simultaneously in a parallel process where possible, or may be performed sequentially.

[0508] Therefore, to the extent there are variations of the present invention that are within the spirit of the disclosure or equivalents of the present invention found in the appended claims, it is intended that this patent cover those variations as well. The present invention is limited only by the claims.

Claims

1. A biomedia composition comprising: about 50% to about 75% by weight total carbon, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is １４ C / １２ total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% hydrogen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; about 0.1% to about 2% nitrogen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The biomedia composition, wherein the biomedia composition is characterized by a moisture content of 0% to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

2. 10. The biomedia composition of claim 1, wherein the biomedia composition comprises, on a dry basis, about 55% to about 70% total carbon by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

3. 10. The biomedia composition of claim 1, wherein the biomedia composition comprises, on a dry basis, about 60% to about 65% total carbon by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

4. The total carbon is １４ C / １２ The biomedia composition of any one of claims 1 to 3, which is at least 80% renewable according to the ASTM D6866 measurement of C isotope ratio.

5. The total carbon is １４ C / １２ The biomedia composition of any one of claims 1 to 3, which is at least 90% renewable according to the ASTM D6866 measurement of C isotope ratio.

6. The total carbon is １４ C / １２ The biomedia composition of any one of claims 1 to 3, which is 100% renewable according to the ASTM D6866 measurement of C isotope ratio.

7. 7. The biomedia composition of any one of claims 1-6, wherein the biomedia composition comprises, on a dry basis, about 25% oxygen by weight to about 35% oxygen by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

8. 8. The biomedia composition of any one of claims 1-7, wherein the biomedia composition comprises about 5% to about 8% hydrogen by weight on a dry basis according to the ASTM D5373 elemental analysis of the biomedia composition.

9. 9. The biomedia composition of any one of claims 1-8, wherein the biomedia composition comprises, on a dry basis, about 0.5% to about 1% by weight nitrogen according to the ASTM D5373 elemental analysis of the biomedia composition.

10. The biomedia composition according to any one of claims 1 to 9, wherein the biomedia composition contains phosphorus.

11. The biomedia composition according to any one of claims 1 to 10, wherein the biomedia composition contains potassium.

12. The biomedia composition according to any one of claims 1 to 11, wherein the biomedia composition comprises sulfur.

13. The biomedia composition of any one of claims 1 to 12, wherein the biomedia composition contains less than 1 ppm of mercury.

14. 14. The biomedia composition of claim 13, wherein the biocarbon composition is essentially mercury-free.

15. The biomedia composition of any one of claims 1 to 14, wherein the biomedia composition further comprises one or more additives.

16. 16. The biomedia composition of any one of claims 1-15, wherein the biomedia composition is characterized by a volatile matter content of about 60% to about 70% by weight according to the ASTM D3175 proximate analysis of the biomedia composition.

17. 17. The biomedia composition of any one of claims 1-16, wherein the biomedia composition is characterized by an ash content of about 2% to about 20% by weight according to the ASTM D3174 proximate analysis of the biomedia composition.

18. 18. The biomedia composition of any one of claims 1-17, wherein the biomedia composition is characterized by a moisture content of 10% to about 50% by weight according to the ASTM D3173 proximate analysis of the biomedia composition.

19. The biomedia composition according to any one of claims 1 to 18, wherein the biomedia composition is hydrophilic.

20. The biomedia composition of any one of claims 1 to 18, wherein the biomedia composition is hydrophobic.

21. The biomedia composition of any one of claims 1 to 18, wherein the biomedia composition is amphiphilic.

22. The biomedia composition according to any one of claims 1 to 21, wherein the biomedia composition is in the form of fine particles.

23. The biomedia composition according to any one of claims 1 to 21, wherein the biomedia composition is in the form of fibrous particles.

24. The biomedia composition of any one of claims 1 to 21, wherein the biomedia composition is in the form of a densified body.

25. 25. The biomedia composition of any one of claims 1 to 24, wherein the biomedia composition has a biomedia pH selected from about 4 to about 8.

26. 25. The biomedia composition of any one of claims 1 to 24, wherein the biomedia composition has a biomedia pH selected from about 5 to about 7.

27. 27. The biomedia composition of any one of claims 1 to 26, wherein the biomedia composition has a cation exchange capacity selected from about 50 to about 200 meq / 100g.

28. 27. The biomedia composition of any one of claims 1 to 26, wherein the biomedia composition has a cation exchange capacity selected from about 80 to about 150 meq / 100g.

29. 27. The biomedia composition of any one of claims 1 to 26, wherein the biomedia composition has a cation exchange capacity selected from about 100 to about 125 meq / 100g.

30. The biomedia composition comprises a compound having 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 corresponds to a weight percentage in the biomedia composition according to ASTM D4326, and the base-acid ratio is selected from about 0.5 to about 10.

31. 31. The biomedia composition of claim 30, wherein the base-acid ratio is selected from about 1 to about 10.

32. 31. The biomedia composition of claim 30, wherein the base-acid ratio is selected from about 1 to about 5.

33. 31. The biomedia composition of claim 30, wherein the base-acid ratio is selected from about 5 to about 10.

34. The biomedia composition comprises a compound having the following formula: [Equation 2] wherein Fe is an acid-base bond; ２ O ３ , CaO, MgO, K ２ O, Na ２ O, MnO, SrO, BaO, SiO ２ , Al ２ O ３ , TiO ２ , P ２ O ５ , and SO ３ each of which corresponds to a weight fraction in the biomedia composition according to ASTM D4326, and the extended base-acid ratio is selected from about 0.25 to about 8.

35. 35. The biomedia composition of claim 34, wherein the extended base-acid ratio is selected from about 0.5 to about 8.

36. 35. The biomedia composition of claim 34, wherein the extended base-acid ratio is selected from about 1 to about 4.

37. 35. The biomedia composition of claim 34, wherein the extended base-acid ratio is selected from about 4 to about 8.

38. The biomedia composition of any one of claims 1 to 37, wherein the biomedia composition is biologically sterile.

39. The biomedia composition according to any one of claims 1 to 38, wherein the biomedia composition is biodegradable.

40. The biomedia composition of any one of claims 1 to 39, wherein the biomedia composition is compostable.

41. 1. A process for producing a biomedia composition, the process comprising: (a) providing a starting material containing biomass, the starting material being optionally dried; (b) mildly pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor; (c) optionally 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 acidity of the intermediate biocarbon stream; (d) about 50% to about 75% total carbon by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is １４ C / １２ total carbon that is at least 50% renewable according to ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% hydrogen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; and recovering a biomedia composition containing, on a dry basis, about 0.1% to about 2% nitrogen by weight according to said ASTM D5373 elemental analysis of said biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The process wherein the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

42. 1. A process for producing a biomedia composition, the process comprising: (a) providing a starting material containing biomass, the starting material being optionally dried; (b) mildly pyrolyzing the starting material to produce an intermediate biocarbon stream and a pyrolysis vapor; (c) optionally introducing one or more additives during step (a) or step (b) to adjust the acidity of the intermediate biocarbon stream; (d) about 50% to about 75% total carbon by weight, on a dry basis, according to ASTM D5373 elemental analysis of the biomedia composition, wherein the total carbon is １４ C / １２ total carbon that is at least 50% renewable according to said ASTM D6866 measurement of C isotope ratio; about 20% to about 40% oxygen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; about 3% to about 10% hydrogen by weight, on a dry basis, according to the ASTM D5373 elemental analysis of the biomedia composition; and recovering the biomedia composition containing, on a dry basis, about 0.1% to about 2% nitrogen by weight according to the ASTM D5373 elemental analysis of the biomedia composition; the biomedia composition is characterized by a volatile matter content of about 50% to about 75% by weight according to ASTM D3175 proximate analysis of the biomedia composition; the biomedia composition is characterized by an ash content of about 1% to about 25% by weight according to ASTM D3174 proximate analysis of the biomedia composition; The process wherein the biomedia composition is characterized by a moisture content of 0 to about 75% by weight according to ASTM D3173 proximate analysis of the biomedia composition.

43. 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, fruit peels, fruit seeds, 43. The process of claim 41 or 42, wherein the waste material is selected from vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

44. 43. The process of claim 41 or 42, wherein the intermediate biocarbon stream or the biomedia composition is mechanically shredded.

45. 44. The process of any one of claims 41 to 43, wherein the intermediate biocarbon stream or the biomedia composition is mechanically defiberized.

46. 46. ​​The process of any one of claims 41-45, wherein the intermediate biocarbon stream or the biomedia composition is mechanically treated to alter the porosity of the biomedia composition.

47. 47. The process of any one of claims 41-46, wherein the intermediate biocarbon stream or the biomedia composition is mechanically treated to alter the solid flow properties of the biomedia composition.

48. 48. The process of any one of claims 41-47, wherein the biomedia composition is treated to adjust the chemical oxygen demand of the biomedia composition.

49. 49. The process of any one of claims 41-48, wherein the biomedia composition is treated to adjust the color of the biomedia composition.

50. 50. The process of any one of claims 41-49, wherein the biomedia composition is treated to control the odor of the biomedia composition.

51. 51. The process of any one of claims 41-50, wherein the biomedia composition is treated to adjust the texture of the biomedia composition.

52. 52. The process of any one of claims 41-51, wherein the biomedia composition comprises, on a dry basis, about 55% to about 70% total carbon by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

53. 53. The process of claim 52, wherein the biomedia composition comprises, on a dry basis, about 60% to about 65% total carbon by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

54. The total carbon is １４ C / １２ 54. The process of any one of claims 41 to 53, which is at least 80% reproducible according to the ASTM D6866 measurement of C isotope ratio.

55. The total carbon is １４ C / １２ 54. The process of any one of claims 41 to 53, which is at least 90% reproducible according to the ASTM D6866 measurement of C isotope ratio.

56. The total carbon is １４ C / １２ 54. The process of any one of claims 41 to 53, which is 100% renewable according to the ASTM D6866 measurement of C isotope ratio.

57. 57. The process of any one of claims 41-56, wherein the biomedia composition comprises, on a dry basis, about 25% oxygen by weight to about 35% oxygen by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

58. 58. The process of any one of claims 41-57, wherein the biomedia composition comprises, on a dry basis, about 5% to about 8% hydrogen by weight according to the ASTM D5373 elemental analysis of the biomedia composition.

59. 59. The process of any one of claims 41-58, wherein the biomedia composition comprises, on a dry basis, about 0.5% to about 1% by weight nitrogen according to the ASTM D5373 elemental analysis of the biomedia composition.

60. 60. The process of any one of claims 41-59, wherein the biomedia composition comprises phosphorus, potassium, sulfur, or a combination thereof.

61. 61. The process of any one of claims 41-60, wherein the biomedia composition contains less than 1 ppm mercury.

62. 62. The process of claim 61, wherein the biocarbon composition is essentially mercury-free.

63. 63. The process of any one of claims 41-62, wherein the biomedia composition is characterized by a volatile matter content of about 60% to about 70% by weight according to the ASTM D3175 proximate analysis of the biomedia composition.

64. 64. The process of any one of claims 41-63, wherein the biomedia composition is characterized by an ash content of about 2% to about 20% by weight according to the ASTM D3174 proximate analysis of the biomedia composition.

65. 65. The process of any one of claims 41-64, wherein the biomedia composition is characterized by a moisture content of 10% to about 50% by weight according to the ASTM D3173 proximate analysis of the biomedia composition.

66. 66. The process of any one of claims 41 to 65, wherein step (c) is carried out.

67. The process of any one of claims 41 to 65, wherein step (c) is not performed.

68. 68. The process of any one of claims 41 to 67, wherein the biomedia composition is hydrophilic.

69. 68. The process of any one of claims 41 to 67, wherein the biomedia composition is hydrophobic.

70. 68. The process of any one of claims 41 to 67, wherein the biomedia composition is amphiphilic.

71. 71. The process of any one of claims 41 to 70, wherein the biomedia composition is in the form of fine particles.

72. 71. The process of any one of claims 41 to 70, wherein the biomedia composition is in the form of fibrous particles.

73. 71. The process of any one of claims 41 to 70, wherein the biomedia composition is in the form of a densified body.

74. 74. The process of any one of claims 41-73, wherein the biomedia composition has a biomedia pH selected from about 4 to about 8.

75. 74. The process of any one of claims 41-73, wherein the biomedia composition has a biomedia pH selected from about 5 to about 7.

76. 76. The process of any one of claims 41-75, wherein the biomedia composition has a cation exchange capacity selected from about 50 to about 200 meq / 100g.

77. 76. The process of any one of claims 41-75, wherein the biomedia composition has a cation exchange capacity selected from about 80 to about 150 meq / 100g.

78. 76. The process of any one of claims 41-75, wherein the biomedia composition has a cation exchange capacity selected from about 100 to about 125 meq / 100g.

79. The biomedia composition comprises a compound having the following formula: [Equation 3] 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 corresponds to a weight percentage in the biomedia composition according to ASTM D4326, and the base-acid ratio is selected from about 0.5 to about 10.

80. 80. The process of claim 79, wherein the base-acid ratio is selected from about 1 to about 10.

81. 80. The process of claim 79, wherein the base-acid ratio is selected from about 1 to about 5.

82. 80. The process of claim 79, wherein the base-acid ratio is selected from about 5 to about 10.

83. The biomedia composition comprises a compound having the following formula: [Equation 4] wherein Fe is an acid-base bond; ２ O ３ , CaO, MgO, K ２ O, Na ２ O, MnO, SrO, BaO, SiO ２ , Al ２ O ３ , TiO ２ , P ２ O ５ , and SO ３ each corresponds to a weight fraction in the biomedia composition according to ASTM D4326, and the extended base-acid ratio is selected from about 0.25 to about 8.

84. 84. The process of claim 83, wherein the extended base-acid ratio is selected from about 0.5 to about 8.

85. 84. The process of claim 83, wherein the extended base-acid ratio is selected from about 1 to about 4.

86. 84. The process of claim 83, wherein the extended base-acid ratio is selected from about 4 to about 8.

87. 87. The process of any one of claims 41 to 86, wherein the biomedia composition is biologically sterile.

88. 88. The process of any one of claims 41 to 87, wherein the biomedia composition is biodegradable.

89. 89. The process of any one of claims 41 to 88, wherein the biomedia composition is compostable.

90. 90. The process of any one of claims 41 to 89, wherein the process is continuous or semi-continuous.

91. The process of any one of claims 41 to 89, wherein the process is a batch process.

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