Low water consumption biocarbon product and process for producing low water consumption biocarbon product

Abstract

The process disclosed herein is an environmentally friendly technology for producing a bio-carbon product with low water and carbon intensities. Some variations provide a low water intensities process for producing a bio-carbon product, comprising: providing a starting material comprising biomass and water; drying the starting material to produce a dried material and a first steam; pyrolyzing the dried material to produce a hot solid and a second steam; condensing the first steam to produce a first condensed liquid having a first pH of about 1 to about 7; condensing the second steam to produce a second condensed liquid having a second pH of about 1 to about 7; forming an acidic water comprising the first condensed liquid, the second condensed liquid, or a mixture thereof; washing and cooling the hot solid using the acidic water to produce a washed cooled solid; and recovering the washed cooled solid as a low water intensities bio-carbon product.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority benefit of U.S. Provisional Patent Application No. 63 / 219,267, filed July 7, 2021, and U.S. Provisional Patent Application No. 63 / 219,781, filed July 8, 2021, each of which is incorporated by reference in its entirety herein.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates generally to processes and systems for producing bio-carbon containing products having low water inputs. [Background technology]

[0003] Water is one of the most important molecules on Earth. It covers over two-thirds of the Earth's surface and is renewable globally, but there are frequent local shortages and quality problems. Water withdrawn for industrial processes contributes to the drying up of rivers and lakes and the falling water table if it is not returned to the same bodies of water in its original quantity and quality.

[0004] Water is often a large input into industrial processes for making chemicals or materials. Water can be consumed chemically in the manufacturing process, but more typically water is used for cooling, heating, or cleaning. Essentially every manufactured product uses water as part of the manufacturing process. Industrial water uses include water for purposes such as making, processing, cleaning, diluting, heating, cooling, or transporting products, incorporating water into products, or providing sanitation needs within manufacturing facilities.

[0005] Most water is released back into the environment after use in processes, either directly to surface waters (often of degraded quality) or by evaporation. Avoiding evaporation to the atmosphere reduces the amount of water that needs to be withdrawn from municipal, ground, or surface waters. Summary of the Invention

[0006] Some variations are water negative process for producing a biocarbon product, the process comprising: providing a feedstock, the feedstock comprising biomass and at least about 0% to at most about 75% by weight water; drying the feedstock, thereby producing a dried feedstock and a first steam, the dried feedstock comprising at least about 0% and up to about 50% water by weight; pyrolyzing the dried feedstock, thereby producing a hot solid and a second vapor; condensing at least a portion of the first vapor, thereby producing a first condensed liquid, the first condensed liquid having a first pH of at least about 1 and up to about 7; condensing at least a portion of the second vapor, thereby producing a second condensed liquid, the second condensed liquid having a second pH of at least about 1 and up to about 7; generating acidic water, the acidic water comprising at least a portion of the first condensed liquid, at least a portion of the second condensed liquid, or a mixture thereof; washing and cooling the hot solids, the washing and cooling being accomplished using acidic water, thereby producing washed and cooled solids; recovering the washed and cooled solids as a bio-carbon product, the bio-carbon product comprising at least about 50% by weight carbon; A negative water intensity process is provided in which the biocarbon product has a water intensity defined as kilograms of external water utilized divided by metric tons of biocarbon product.

[0007] Biomass can be, for example, softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, fruit husks, fruit stem ... The waste stream may be selected from peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable skins, vegetable seeds, grape pomace, almond shells, pecan shells, coconut shells, coffee grounds, food waste, commercial waste, grass pellets, hay pellets, wood pellets, cardboard, paper, paper pulp, paper packaging, paper shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0008] In some embodiments, the dry ingredients contain at least about 0% and up to about 25% water by weight. In certain embodiments, the dry ingredients contain up to about 10% water by weight.

[0009] In some embodiments, drying is accomplished using a steam driven dryer, hi some embodiments, drying is accomplished using an air driven dryer.

[0010] In some embodiments, the first pH is at least about 2 and up to about 7. In certain embodiments, the first pH is at least about 3 and up to about 6.5. In certain embodiments, the first pH is at least about 4 and up to about 6.5. In some embodiments, the second pH is at least about 2 and up to about 7. In certain embodiments, the second pH is at least about 3 and up to about 6.5. In certain embodiments, the second pH is at least about 4 and up to about 6.5. In some embodiments, the first pH is up to about 7 and the second pH is up to about 7. In certain embodiments, the first pH is up to about 7 and the second pH is about 7. In certain embodiments, the second pH is up to about 7 and the first pH is about 7.

[0011] In some embodiments, the acidic water comprises a first condensed liquid and does not comprise a second condensed liquid. In some embodiments, the acidic water comprises a second condensed liquid and does not comprise the first condensed liquid. In certain embodiments, the acidic water comprises a first condensed liquid and a second condensed liquid.

[0012] In some embodiments, the acidic water comprises the entirety of the first condensed liquid produced. In some embodiments, the acidic water comprises the entirety of the second condensed liquid produced. In certain embodiments, the acidic water comprises the entirety of the first condensed liquid produced and the entirety of the second condensed liquid produced.

[0013] In some embodiments, producing the acid water comprises producing at least about 1 and up to about 500 gallons of acid water per dry metric ton of feedstock. In certain embodiments, producing the acid water comprises producing at least about 50 and up to about 100 gallons of acid water per dry metric ton of feedstock.

[0014] The process may further include recovering a portion of the acid water as a water co-product. The portion of the acid water recovered as a water co-product may be some or all of the first condensed liquid, some or all of the second condensed liquid, or part of a combined stream including the first condensed liquid and the second condensed liquid.

[0015] In some embodiments, washing and cooling is accomplished using a water source consisting essentially of acidified water.

[0016] In some embodiments, the hot solid is generated at a substrate temperature of at least about 300° C. up to about 800° C., and cooling comprises cooling the hot solid to a cooled substrate temperature below the substrate temperature. In certain embodiments, the cooled substrate temperature is up to about 300° C., up to about 200° C., up to about 100° C., or up to about 50° C.

[0017] In some embodiments, washing includes removing ash from the hot solids. The washed and cooled solids may contain up to about 5% total ash by weight, up to about 1% total ash by weight, or up to about 0.2% total ash by weight after removal.

[0018] In some embodiments, washing comprises removing from the hot solid an impurity selected from aluminum, aluminum oxide, antimony, arsenic, barium, beryllium, boron, boron oxide, bromine, cadmium, calcium, chlorine, chromium, cobalt, copper, fluorine, gold, iron, iron oxide, lead, lithium, magnesium, manganese, mercury, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silicon oxide, silver, sodium, strontium, sulfur, tellurium, thallium, tin, titanium, titanium oxide, tungsten, vanadium, zinc, zirconium, or combinations thereof. The washed and cooled solid comprises up to about 1000 ppm impurities, up to about 100 ppm impurities, or up to about 50 ppm impurities after removal.

[0019] In some embodiments, the washed and cooled solids have a heating value of at least about 22 MJ / kg on a dry basis. In certain embodiments, the washed and cooled solids have a heating value of at least about 33 MJ / kg on a dry basis.

[0020] The process may further include pelletizing the washed and cooled solids, thereby producing biocarbon pellets. In some embodiments, the pelletizing does not include introducing an external binder to the washed and cooled solids. In other embodiments, the pelletizing includes introducing an external binder to the washed and cooled solids. In some embodiments, the pelletizing utilizes an in situ binder derived from the pyrolysis step, such as a condensed or precipitated form of pyrolysis vapors.

[0021] If a binder is used in the pelletizing, the binder can be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or any combination of the foregoing.

[0022] In some embodiments, the process does not utilize external water, which results in a negative water intensity of the process and the biocarbon product. "External water" refers to water that is not carried by the biomass (e.g., as moisture) and is not produced in the chemical reactions in converting the biomass to products. In some embodiments of the negative water intensity process, the water intensity is up to about -10 kgH2O per metric ton of biocarbon product. 2 In various embodiments, the water consumption is up to about -100, -200, -300, -400, -500, -600, -700, -800, -900, or -1000 kgH2O per metric ton of biocarbon product. 2 It is O.

[0023] In some embodiments, the biocarbon product has up to about 0 kg CO per metric ton of biocarbon product. 2 e of carbon intensity. In various embodiments, the bio-carbon product comprises up to about -100, -200, -300, -400, or -500 kg CO per metric ton of bio-carbon product. 2 Includes carbon intensity of e.

[0024] The total carbon of biocarbon products is 14 C / 12 It can be at least about 90%, such as about 95%, about 100%, or exactly 100% biogenic carbon as determined from C isotope ratio measurements.

[0025] Some variations include: providing a feedstock, the feedstock comprising biomass and at least about 0% to at most about 75% by weight water; drying the feedstock, thereby producing a dried feedstock and a first steam, the dried feedstock comprising at least about 0% and up to about 50% water by weight; pyrolyzing the dried feedstock, thereby producing a hot solid and a second vapor; condensing the first vapor, thereby producing a first condensed liquid, the first condensed liquid having a first pH of at least about 1 and up to about 7; condensing the second vapor, thereby producing a second condensed liquid, the second condensed liquid having a second pH of at least about 1 and up to about 7; generating acidic water, the acidic water comprising the first condensed liquid, the second condensed liquid, or a mixture thereof; washing and cooling the hot solids, the washing and cooling being accomplished using acidic water, thereby producing washed and cooled solids; recovering the washed and cooled solids as a biocarbon product; and Optionally, pelletizing the bio-carbon product; A bio-carbon product is provided that is produced by a process, wherein the bio-carbon product comprises at least about 50% carbon by weight.

[0026] In some embodiments, the biocarbon product comprises total carbon, the total carbon being 0.01% of the total carbon.14 C / 12 At least about 90% is biogenic carbon, as determined by measurements of C isotope ratios.

[0027] Some variations are low water intensity processes for producing biocarbon products, the process comprising: (a) providing a starting material comprising biomass and about 0% to about 75% by weight water; (b) optionally drying the starting material to produce a dried material comprising 0% to about 50% by weight water and the first steam; (c) pyrolyzing the dried feedstock (or starting material, if step (b) is not performed) to produce a high temperature solid and a second vapor; (d) when performing step (b), condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of at least about 1 and up to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of at least about 1 and up to about 7; (f) forming acidic water containing at least a portion of the second condensed liquid, or, if performing step (b), at least a portion of the first condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solid using acidic water to produce a washed cooled solid; (h) recovering the washed cooled solids as a bio-carbon product, the bio-carbon product comprising at least about 50% carbon by weight. A low water intensity process is provided in which the biocarbon product has a water intensity defined as kilograms of external water utilized divided by metric tons of biocarbon product.

[0028] In some embodiments, the biomass 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, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit husk ... The waste material is selected from plant 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 scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0029] If the starting material is dry or relatively dry, step (b) can be omitted. In some embodiments, step (b) is performed and the dried material contains at least about 0% to at most about 25% water by weight. In certain embodiments using step (b), the dried material contains at least about 0% to at most about 10% water by weight.

[0030] In some embodiments, the first pH is at least about 2 and up to about 7. In some embodiments, the first pH is at least about 3 and up to about 6.5. In some embodiments, the second pH is at least about 2 and up to about 7. In some embodiments, the second pH is at least about 3 and up to about 6.5. In some embodiments, the first pH is up to about 7 and the second pH is up to about 7.

[0031] In some embodiments, the acidic water comprises a first condensed liquid and does not comprise a second condensed liquid. In some embodiments, the acidic water comprises a second condensed liquid and does not comprise the first condensed liquid. In certain embodiments, the acidic water comprises a first condensed liquid and a second condensed liquid.

[0032] In some embodiments, the acidic water comprises the entirety of the first condensed liquid produced. In some embodiments, the acidic water comprises the entirety of the second condensed liquid produced. In certain embodiments, the acidic water comprises the entirety of the first condensed liquid produced and the entirety of the second condensed liquid produced.

[0033] In some embodiments, producing the acid water comprises producing at least about 1 and up to about 500 gallons of acid water per dry metric ton of feedstock. In certain embodiments, producing the acid water comprises producing at least about 50 and up to about 100 gallons of acid water per dry metric ton of feedstock.

[0034] The process may further include recovering a portion of the acid water as a water co-product. The portion of the acid water recovered as a water co-product may be some or all of the first condensed liquid (if step (d) is performed), some or all of the second condensed liquid, or part of a combined stream including the first condensed liquid and the second condensed liquid.

[0035] In some embodiments, the washing and cooling is accomplished using a water source, which consists essentially of acidified water.

[0036] In some embodiments, the hot solid is generated at a substrate temperature of at least about 300° C. up to about 800° C., and cooling comprises cooling the hot solid to a cooled substrate temperature below the substrate temperature. In certain embodiments, the cooled substrate temperature is up to about 100° C. or up to about 50° C.

[0037] In some embodiments, washing includes removing ash from the hot solids. The washed and cooled solids may contain up to about 1% or up to about 0.2% total ash by weight after removal.

[0038] In some embodiments, washing includes removing impurities from the hot solid selected from aluminum, aluminum oxide, antimony, arsenic, barium, beryllium, boron, boron oxide, bromine, cadmium, calcium, chlorine, chromium, cobalt, copper, fluorine, gold, iron, iron oxide, lead, lithium, magnesium, manganese, mercury, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silicon oxide, silver, sodium, strontium, sulfur, tellurium, thallium, tin, titanium, titanium oxide, tungsten, vanadium, zinc, zirconium, or combinations thereof. The washed and cooled solid may contain up to about 1000 ppm or up to about 100 ppm of impurities after removal.

[0039] The process may further include pelletizing the washed and cooled solids, thereby producing biocarbon pellets. In some embodiments, the pelletizing does not include introducing an external binder to the washed and cooled solids. In other embodiments, the pelletizing includes introducing an external binder to the washed and cooled solids. In these or other embodiments, the pelletizing includes introducing an in situ binder to the washed and cooled solids.

[0040] If an external binder is utilized, the binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing.

[0041] In some embodiments of the low water consumption process, the process does not utilize external water. In other embodiments of the low water consumption process, the process uses a relatively small amount of external water, resulting in a positive but small water consumption of the biocarbon product. In various embodiments, the water consumption is up to about 1000, 500, 200, 100, 50, 0, -50, or -100 kgH2O per metric ton of biocarbon product. 2 It is O.

[0042] In some embodiments of the low water intensity process, the biocarbon product has up to about 0 kg CO per metric ton of biocarbon product. 2 Includes carbon intensity of e.

[0043] In some embodiments of the low water intensity process, the biocarbon product comprises total carbon, the total carbon being: 14 C / 12 At least about 90%, at least about 95%, or about 100% is biogenic carbon as determined from C isotope ratio measurements.

[0044] Some variations include: (a) providing a starting material comprising biomass and about 0% to about 75% by weight water; (b) optionally drying the starting material to produce a dried material comprising 0% to about 50% by weight water and the first steam; (c) pyrolyzing the dried feedstock (or starting material, if step (b) is not performed) to produce a high temperature solid and a second vapor; (d) when performing step (b), condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of at least about 1 and up to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of at least about 1 and up to about 7; (f) forming acidic water containing at least a portion of the second condensed liquid, or, if performing step (b), at least a portion of the first condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solid using acidic water to produce a washed cooled solid; (h) recovering the washed cooled solids as a biocarbon product; the biocarbon product comprises at least about 50% by weight carbon; A biocarbon product contains total carbon, Total carbon is 14 C / 12 A biocarbon product is provided that is produced by the process and is at least about 90% biogenic carbon, as determined from C isotope ratio measurements. [Brief description of the drawings]

[0045] [Figure 1] FIG. 1 is a simplified block flow diagram for producing negative water intensity bio-carbon products (e.g., negative water intensity bio-carbon pellets) according to some embodiments.

[0046] [Diagram 2] FIG. 1 is a simplified block flow diagram for producing a low water input bio-carbon product (e.g., low water input bio-carbon pellets) according to some embodiments. Dotted lines indicate optional flows and optional unit operations. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] (Detailed Description) In general, it is desirable to use water sustainably to support healthy ecosystems that depend on a reliable water supply. Certain regions have taken water conservation measures or are at risk of localized water resource depletion. One such region is the state of California in the United States.

[0048] California has long been at the forefront of water conservation, becoming the first state to adopt urban water efficiency targets in its 2009 Water Conservation Act. California’s Water Conservation Act mandates a 20% reduction in per capita urban water use by 2020. However, as the effects of climate change become more evident (longer droughts, more destructive wildfires, more intense floods, and shrinking snowpack), California has committed to acting more aggressively. In 2018, a new landmark water conservation act was signed into law, establishing a new long-term water conservation framework for California. The first goal of the new framework is to use water more wisely. See https: / / water.ca.go, retrieved June 28, 2022.

[0049] Greenhouse gases (GHGs) are gases that absorb and emit radiant energy in the thermal infrared range. Greenhouse gases cause the greenhouse effect, trapping the sun's heat in the Earth's lower atmosphere because the atmosphere is more transparent to visible radiation from the sun than to the infrared radiation emitted by the Earth's surface. The main greenhouse gas in the Earth's atmosphere is carbon dioxide (CO 2), methane, nitrous oxide, ozone, and water vapor. Combustion of fossil fuels produces large amounts of CO 2 It is well known that atmospheric CO 2 absorbs heat, and this heat is converted into CO 2 Since the start of the Industrial Revolution (around 1750), human activities have led to a significant increase in atmospheric CO 2 Concentrations have increased by 45% from 280 ppm in 1750 to 414 ppm in 2020. 2 Emissions are estimated at 37 billion metric tons. 2 Emissions have fallen, but by 2022, CO 2 Emissions have returned to pre-pandemic levels.

[0050] With the 1992 United Nations Framework Convention on Climate Change, signatory countries committed to reducing GHG emissions based on evidence that anthropogenic emissions are the main cause of global warming (UNFCCC, 1992). Despite the agreement, between 1992 and 2019, global GHG emissions increased by about 40%. In 2015, the 21st Conference of the Parties (COP21) held in Paris reached a non-binding agreement in which about 200 countries committed to reducing carbon emissions and limiting global warming to a maximum of 1.5°C. See Rogelj et al., “Paris Agreement climate proposals need a boost to keep warming well below 2°C”, Nature 534, 7609, 2016. Numerous policies have been proposed, including carbon taxes, emissions trading schemes, and low-carbon fuel standards, some of which have been implemented.

[0051] Metal processing is a very important industry worldwide. For example, for steel (iron alloys), the global steel market size is expected to reach US$1 trillion by 2025, according to Steel Market Size, Share & Trends Analysis 2018-2025, Grand View Research, Inc. (2017). Metal processing is responsible for significant net CO2 emissions worldwide each year. 2 The growing trend towards sustainable, low-cost and durable building materials is driving the demand for steel in industrial infrastructure and residential projects. In pre-engineered metal buildings with high structural integrity, steel serves essential functions of stability, design flexibility and aesthetic appeal. Strict regulations promoting green and energy-efficient buildings are also contributing to the demand for steel, especially in industrial structures.

[0052] Today, steelmaking accounts for approximately 100% of the world’s CO emissions. 2 Oxygenated iron ore is one of the largest industrial contributors to CO2 emissions. Oxygenated iron ore is mined worldwide. Typically, iron ore is taken through a beneficiation process to crush and concentrate the iron fraction, then rolled into pellets (with a binder), heated in a hardening furnace that burns coal to generate heat to harden the pellets, and transported to a blast furnace where coke is used to reduce the oxygenated ore to metallic iron. The hardening and coking processes produce large amounts of CO2. 2 and other pollutants. Approximately 70% of all steel is made from pig iron, produced by reducing iron oxide in a blast furnace using coke or coal before reduction in a basic oxygen furnace. In addition to depleting fossil resources, the use of non-renewable coal or coal-derived coke releases non-renewable carbon dioxide into the atmosphere.

[0053] Today, CO 2In addition to stricter emission regulations, changing customer requirements tend to drive demand for environmentally friendly steel products. Also, investors and the public are increasingly paying attention to sustainability. For example, the Institutional Investors Group on Climate Change, a global network representing hundreds of investors and managing over US$50 trillion in assets, has high expectations for the steel industry to safeguard its future in the face of climate change.

[0054] There is a strong desire to make metal making processes more environmentally friendly, including reducing both water and carbon intensities. An attractive approach is to utilize biocarbon, such as from biomass pyrolysis, rather than fossil fuels, such as metallurgical coke. To that end, it is desirable to reduce the water and carbon intensities of the biocarbon production itself, so that the resulting benefits are passed on to the metal product, or to any other products derived from the biocarbon, or to any downstream uses of the biocarbon.

[0055] This description enables a person skilled in the art to make and use the disclosed technology and describes several embodiments, adaptations, variations, alternatives, and uses. These and other embodiments, features, and advantages of the present disclosure will become more apparent to those skilled in the art upon reference to the following detailed description in conjunction with the accompanying drawings.

[0056] definition As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0057] 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 on certain analytical techniques.

[0058] As used herein, the term "about" means ±20% of a given range, value, or structure, unless otherwise indicated.

[0059] 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, where appropriate (such as tenths and hundredths of integers), unless otherwise indicated. Also, any numerical range recited herein should be understood to include any integer within the recited range, unless otherwise indicated.

[0060] As used herein, "a range from about or between," e.g., "a range from about X, Y, or Z, between or between," includes "at least X up to Z."

[0061] The term "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 may be added and still form a construct within the scope of the claim.

[0062] As used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase "consist of" (or variations thereof) appears in a section in 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.

[0063] 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 the use of either of the other two terms. Thus, in some embodiments not expressly recited otherwise, any instance of "comprising" can be replaced by "consisting of," or alternatively, by "consisting essentially of."

[0064] As used herein, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." Unless the word "or" is expressly limited in reference to a list of two or more items to mean only one item exclusively from the other items, the use of "or" in such a list should be interpreted to include (a) any one item in the list, (b) all items in the list, or (c) any combination of items in the list. As used herein, a phrase "and / or," such as "A and / or B," refers to A alone, B alone, and both A and B. Where the context permits, singular or plural terms may also include the plural or singular terms, respectively.

[0065] As used herein, "biological" is a material (either a feedstock, product, or intermediate) that contains elements such as carbon that are renewable on time scales of months, years, or decades. Non-biological materials can be non-renewable or renewable on 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 biological materials as natural sources or derived from nature 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 not be as significant.

[0066] 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 is transported to Earth where it is absorbed by living biological material. 14C constitutes a negligible portion, but it is radioactive with a half-life of 5,700 years and is therefore detectable by radiometric measurements. 14 Because it does not absorb C, 14 The amount of C is one of the methods used for radiometric dating of biological materials.

[0067] Plants fix carbon from the atmosphere through photosynthesis. 14 C. The animals then, when they consume the plant, or consume other animals that consume the plant, 14 Living plants and animals therefore absorb atmospheric CO 2 Same as 14 C vs. 12 C ratio. When an organism dies, it stops exchanging carbon with the atmosphere and therefore no longer produces new 14 C is not incorporated. Radioactive decay then occurs in living organisms. 14 It gradually depletes C. This effect is the basis of radiocarbon dating.

[0068] Fossil fuels such as coal are derived primarily from plant material deposited millions of years ago. 14 This is equivalent to thousands of half-lives of C, so essentially all of the 14 C is decaying. Also, fossil fuels are not harmful to the atmosphere because they were originally formed from living organisms. 13 C is depleted. Therefore, carbon from fossil fuels is less efficient than biocarbon. 13 C and 14 Both C are depleted.

[0069] This difference between the carbon isotopes of recently depleted organic matter, such as from renewable sources, and the carbon isotopes of fossil fuels, such as coal, allows for the determination of the source of carbon in the composition, specifically, whether the carbon in the composition is derived from a renewable resource or from a fossil fuel, in other words, whether a renewable resource or a fossil fuel was used in the production of the composition.

[0070] 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 standpoint, cellulose, lignin, sugars, fats, and proteins. Biomass includes both above-ground and below-ground tissues of plants, such as leaves, twigs, branches, and stems, as well as the roots of trees and 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 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 source of carbon.

[0071] 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.

[0072] As used herein, a "zone" is a region of space within a single physical unit, physically separated units, or any combination thereof. For continuous reactors, the boundaries of the zones may relate to structures such as the presence of flights within the reactor or separate heating elements to provide heat to separate zones. Alternatively or additionally, the boundaries of the zones in a continuous reactor may relate to functions such as separate temperatures, fluid flow patterns, solid flow patterns, or extent of reaction. In a single batch reactor, the "zones" are operating regimes in time rather than space. There is not necessarily an abrupt transition from one zone to another. For example, the boundaries 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, and some amount of "preheat" may continue to occur in the pyrolysis zone. The temperature profile within the reactor is typically continuous, including the zone boundaries within the reactor.

[0073] For the present purposes, "reagent" is intended to mean a material in its broadest sense, and a reagent may be a fuel, a chemical, a material, a compound, an additive, a blend component, a solvent, etc. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. A reagent may 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.

[0074] 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.

[0075] Furthermore, as used herein, the term "substantially" refers to the complete or nearly complete extent or degree of an action, feature, characteristic, state, structure, item, or result. For example, an object being "substantially" surrounded would mean that the object is completely surrounded or nearly completely surrounded. The exact acceptable degree of deviation from absolute completeness may depend, in some cases, on the particular context. Generally speaking, however, approximating completeness would be such as to have the same overall result as if absolute and total completeness had been obtained. The use of "substantially" is equally applicable when used in a negative sense to refer to a complete or nearly complete lack of an action, feature, characteristic, state, structure, item, or result.

[0076] In this disclosure, a "product" can be, for example, a composition, a material, an object, or a structure. The term "product" is not intended to be limited by its commercial fate, such as whether it is sold to other parties as an intermediate for further processing, stored, traded, further processed, sold, etc.

[0077] As used in this application to describe preferred bioreagents, "high carbon" simply means that the bioreagent has a relatively high carbon content as compared to the initial feedstock utilized to make the high carbon bioreagent. Typically, a high carbon bioreagent will 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 carbon by weight.

[0078] Notwithstanding the above, the term "high carbon bio-reagent" is used herein for practical purposes in various embodiments to consistently describe materials that may be produced by the processes and systems as disclosed. Any limitations on carbon content or any other concentration should be imputed only by reference to specific embodiments and their equivalents, and not from 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 are nevertheless relatively low in carbon (low purity carbon), such as less than about 50% carbon by weight.

[0079] The processes disclosed herein are environmentally friendly technologies with low water intensity. In this disclosure, "water intensity" of a product or process means the mass in kilograms (kg) of external water used in the process to produce the product divided by the mass in metric tons of the product produced. "External water" refers to water that is not carried by the biomass (e.g., as moisture) and is not produced in chemical reactions in converting the biomass to a product.

[0080] Generally, external water may be introduced into the pyrolysis process from, for example, a supply line attached to a well, a body of water (e.g., a river, lake, or ocean), or a municipal water treatment plant. When an external source of water is used in the process and the process water is subsequently discharged to the atmosphere or returned to a body of water, the process water is counted as external water when calculating water unit consumption herein.

[0081] In biomass, there is typically free moisture that is physically associated with cellulose and hemicellulose but not chemically associated. There is also bound moisture (strong intermolecular hydrogen bonds) adsorbed within the cellulose and hemicellulose cell walls of the biomass. Free moisture (free water) and bound moisture (bound water) may be referred to herein as "transport water." Additionally, in pyrolysis, hydrogen and oxygen atoms in the starting materials may combine to form water that is produced by reaction. The reaction-formed water may be referred to herein as "reaction water." Free water, bound water, or reaction water may be collectively referred to as "biomass-derived water." Biomass-derived water is not external water (see above for definition of external water).

[0082] In some variations, the biomass-derived water can replace some or all of the external water that may otherwise be required for cooling or washing the biocarbon after its production. If the biomass-derived water is ultimately released from the process to the atmosphere, there is considered to be no water footprint. If the biomass-derived water is recovered as a co-product or fed back to a body of water, there is considered to be a net external water usage. The water footprint can be negative because water is being added to, not drawn from, an external source. The water footprint can also be negative if the water co-product replaces water that would have otherwise been drawn from an external source (e.g., a lake).

[0083] The disclosed technology is based, at least in part, on water generation for biocarbon product cooling and acid water washing. Biocarbon is produced by a non-combustion thermal process (e.g., pyrolysis) that converts starting biomass into biochar, gas, steam, or liquid. The process is configured to utilize incoming water with the starting material and water produced during the pyrolysis reaction in a manner that replaces some or all of the need for an external water source.

[0084] Some variations are water negative process for producing a biocarbon product, the process comprising: (a) providing a starting material comprising biomass and about 0% to about 75% by weight water; (b) drying the starting material to produce a dried material comprising 0% to about 50% by weight water and a first steam; (c) pyrolyzing the dried feedstock to produce a high temperature solid and a second vapor; (d) condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of about 1 to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of about 1 to about 7; (f) forming an acidic water containing at least a portion of the first condensed liquid, at least a portion of the second condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solids with at least a portion of the acidic water to produce washed cooled solids; (h) recovering the washed cooled solids as a bio-carbon product comprising at least about 50% by weight carbon; A negative water intensity process is provided in which the biocarbon product has a water intensity defined as kilograms of external water utilized divided by metric tons of biocarbon product.

[0085] In some embodiments, the biomass 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, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit husk ... The waste material is selected from plant 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 scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0086] In some embodiments, the dry ingredients contain at least about 0% and up to about 25% water by weight. In various embodiments, the dry ingredients contain up to about 10% water by weight. In various embodiments, the dry ingredients contain about or up to 0%, 5%, 10%, 15%, 20%, or 25% water by weight, including any intervening range.

[0087] Process step (b) can utilize various types of dryers. In some embodiments, drying is achieved using a steam-driven dryer. In some embodiments, drying is achieved using an air-driven dryer.

[0088] When using an air-driven dryer, dry air or air with a relatively low level of humidity (such as less than 40%, 30%, 20%, 10%, or 5% relative humidity) is injected directly into the drying unit. The air can be heated so that the latent heat of the biomass moisture is provided by the heating value of the heated air, thereby evaporating the moisture contained in the wet biomass. In other embodiments, the air is not necessarily heated, but has a humidity of 0% to about 20%, for example, air that absorbs moisture from the wet biomass to form moist air in the wet gas. The pressure of the air introduced into the air-driven dryer can vary, such as from about 1 bar (atmospheric pressure) to about 5 bar.

[0089] When using a steam-driven dryer, the drying gas can be superheated steam. The use of superheated steam injected directly into the drying unit allows for drying of the wet biomass by evaporating moisture and producing a wet gas containing water from both the drying gas and the wet biomass. The pressure of the steam introduced into the steam-driven dryer can vary, such as from about 1 bar (atmospheric pressure) to about 10 bar. In certain embodiments, the dryer utilizes a mixture of superheated steam and air.

[0090] The produced vapor from the dryer, which comprises primarily water and light acids (eg, acetic acid), is condensed from the dryer flue gas stream in step (d).

[0091] The acidity of the first condensed liquid can vary depending on the dryer operating conditions and the type of feedstock. A more severe dryer environment tends to off-gas non-water components from the feed, allowing them to be collected during condensation.

[0092] In some embodiments, the first pH is at least about 2 and up to about 7. In certain embodiments, the first pH is at least about 3 and up to about 6.5. In certain embodiments, the first pH is at least about 4 and up to about 6.5. In various embodiments, the first pH is about, at least about, or up to about 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7, including any intervening ranges.

[0093] In some embodiments, the second pH is at least about 2 and up to about 7. In certain embodiments, the second pH is at least about 3 and up to about 6.5. In certain embodiments, the second pH is at least about 4 and up to about 6.5. In various embodiments, the second pH is about, at least about, or up to about 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7, including any intervening ranges.

[0094] In some embodiments, the first pH is up to about 7 and the second pH is up to about 7. In certain embodiments, the first pH is up to about 7 and the second pH is about 7. In certain embodiments, the second pH is up to about 7 and the first pH is about 7.

[0095] In some embodiments, in step (f), the acidic water comprises only the first condensed liquid. In other embodiments, in step (f), the acidic water comprises only the second condensed liquid. In yet other embodiments, in step (f), the acidic water comprises both the first condensed liquid and the second condensed liquid. The acidic water may comprise some or all of the first condensed liquid and some or all of the second condensed liquid. In certain embodiments, the acidic water comprises all of the first condensed liquid and all of the second condensed liquid. When the acidic water comprises a combination of the first condensed liquid and the second condensed liquid, the pH of the combined acidic water is the logarithmic average of the pH of each condensed liquid.

[0096] In some embodiments, the acidic water comprises a first condensed liquid and does not comprise a second condensed liquid. In some embodiments, the acidic water comprises a second condensed liquid and does not comprise the first condensed liquid. In certain embodiments, the acidic water comprises a first condensed liquid and a second condensed liquid.

[0097] In some embodiments, the acidic water comprises the entirety of the first condensed liquid produced. In some embodiments, the acidic water comprises the entirety of the second condensed liquid produced. In certain embodiments, the acidic water comprises the entirety of the first condensed liquid produced and the entirety of the second condensed liquid produced.

[0098] The acid water of step (f) can be formed in an amount of about 1 to about 500 gallons per dry metric ton of starting material, for example, about 50 to about 100 gallons per dry metric ton of starting material (depending on the original moisture content of the feed). In various embodiments, the step of producing acid water includes producing about or at least about 1, 5, 10, 25, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450, or 500 gallons per dry metric ton of starting material, including any intervening range.

[0099] In some embodiments, a portion of the acidic water produced in step (f) is recovered as a water co-product that is sold or transferred to another party rather than being used in step (g).

[0100] The process may further include recovering a portion of the acid water as a water co-product. The portion of the acid water recovered as a water co-product may be some or all of the first condensed liquid, some or all of the second condensed liquid, or part of a combined stream including the first condensed liquid and the second condensed liquid.

[0101] In some embodiments, no other water source (e.g., well water) is used to wash or cool the hot solids during step (g), i.e., in some embodiments, washing and cooling can be accomplished using a water source consisting essentially of acidified water.

[0102] Step (g) typically co-produces water along with impurities, i.e., impurities contained in the hot solids from the pyrolysis. The water with impurities can be further processed or sold as a water co-product.

[0103] In some embodiments, step (g) generates a hot solid at a substrate temperature of at least about 300° C. up to about 800° C., and cooling with acidic water comprises cooling the hot solid to a cooled substrate temperature below the substrate temperature. In certain embodiments, the cooled substrate temperature is up to about 300° C., up to about 200° C., up to about 100° C., or up to about 50° C. In various embodiments, the cooled substrate temperature is about or less than about 300° C., 250° C., 200° C., 150° C., 100° C., 90° C., 80° C., 70° C., 60° C., 50° C., 40° C., 30° C., 25° C., or 20° C., including any intervening range (e.g., 20-30° C.).

[0104] In some embodiments, washing in step (g) removes ash from the hot solids, which may generally contain high levels of ash (such as up to 50% ash by weight). The washed cooled solids may contain, for example, up to about 5% total ash by weight, up to about 1% total ash by weight, or up to about 0.2% total ash by weight. The degree of ash reduction in step (g) may be, for example, at least about 25%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%.

[0105] In some embodiments, the washing in step (g) removes one or more impurities from the hot solid, for example, selected from iron, aluminum, titanium, boron, silicon, calcium silicon, potassium, zinc, lead, cadmium, manganese, chromium, arsenic, nickel, cobalt, copper, tin, antimony, vanadium, molybdenum, oxides of any of these elements, or combinations thereof. Other elements or compounds may be present as impurities in the hot solid. The washed cooled solid may include a total concentration of one or more impurities or a concentration of a single impurity of up to about 1000 ppm, up to about 100 ppm, or up to about 50 ppm. The degree of impurity reduction in step (g) may be, for example, at least about 25%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%. For example, hot solids may contain impurity levels of up to 20,000 ppm, and a reduction to 50 ppm translates to a degree of impurity reduction of 99.7%.

[0106] In some embodiments, washing in step (g) produces washed cooled solids having a higher heating value (HHV) of at least about 22 MJ / kg on a dry basis, e.g., an HHV of at least about 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, or 33 MJ / kg on a dry basis. The degree of HHV enhancement in step (g) can be, for example, at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. It is noted that the removal of ash discussed above results in a higher HHV for the washed cooled solids and thus a higher HHV for the biocarbon product.

[0107] The washed, cooled solids can be pelletized after step (g) or, optionally, integrated with step (g) to produce biocarbon pellets. As used herein, "biocarbon pellets" means pellets that contain biogenic carbon. The geometry of the pellets can vary widely, as taught below.

[0108] In some embodiments, no external binder is introduced to the washed cooled solids during pelletizing. A binder can be introduced to the washed cooled solids to aid in the production of biocarbon pellets. The binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or any combination of the foregoing. In some embodiments, pelletization utilizes an in situ binder derived from the pyrolysis step, such as a condensed or precipitated form of the pyrolysis vapors.

[0109] In some embodiments, the process does not utilize external water, which results in a negative water consumption of the process and the biocarbon product. In some embodiments of the negative water consumption process, the water consumption is up to about -10 kgH2O per metric ton of biocarbon product. 2 In various embodiments, the water consumption is up to about -100, -200, -300, -400, -500, -600, -700, -800, -900, or -1000 kgH2O per metric ton of biocarbon product, including any intervening ranges. 2 It is O.

[0110] As stated, external water does not include transport water and does not include reaction water. Thus, the water consumption of the process generally has a contribution from transport water and a contribution from reaction water. The percentage of water consumption from reaction water can be about 1% to about 100% (relative to reaction water + transport water). 100% water consumption from reaction water is possible when the process uses a completely dry starting biomass feedstock with no moisture. In various embodiments, the percentage of water consumption from reaction water is about or at least about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%, including any intervening range.

[0111] If the starting material is biomass, which contains both living and renewable carbon, the carbon obtained by pyrolysis is also living. This can be done, for example, using ASTM D6866 to determine the carbon content. 14 C / 12 The total carbon in the biocarbon product can be shown by measuring the C isotope ratio. 14 C / 12 The total carbon in the biocarbon product may be at least 90% renewable as determined from C isotope ratio measurements. In some embodiments, the total carbon in the biocarbon product may be at least 90% renewable as determined from C isotope ratio measurements. 14 C / 12 It is at least 95%, at least 99%, or 100% (fully) renewable, as determined from measurements of the C isotope ratio.

[0112] Any biogenic carbon that is oxidized to carbon dioxide is biogenic CO 2 This also reduces the amount of CO produced. 2 of carbon in the sample 14 C / 12 This can also be shown by measuring the C isotope ratio. 2 is returned to the environment and reabsorbed by the growing biomass via photosynthesis. In this way, net CO 2 Emissions are significantly reduced.

[0113] In the above or other embodiments, the bio-carbon product has a carbon content of 0 kg CO per metric ton of bio-carbon product. 2 e carbon intensity, e.g., about -100, -200, -300, -400, or -500 kg CO per metric ton of biocarbon product 2 In some embodiments, the negative water intensity process is simultaneously characterized by a negative carbon intensity and a negative water intensity.

[0114] The "carbon intensity" of a product (or process) is the net amount of carbon dioxide by weight produced per tonne of product, or, as the case may be, per tonne of raw material processed to make the product. 2 “Carbon dioxide equivalent” can also be defined as the net amount of carbon dioxide equivalent produced per tonne of product. 2 e” is the amount of CO that would have a comparable global warming impact. 2 A typical unit of carbon intensity is kilograms of carbon dioxide equivalent per metric ton (1000 kg) of product.

[0115] A greenhouse gas (or "GHG") is any gas in the atmosphere that absorbs and re-emits heat, thereby keeping the planet's atmosphere warmer than it would otherwise be. The primary GHGs in Earth's atmosphere are water vapor, carbon dioxide, methane, nitrous oxide, and ozone. By convention, CO 2 The global warming potential of CH is defined as 1. 4 The global warming potential of methane is about 30, meaning that methane is a greenhouse gas with a 100% 2 See "IPCC Fourth Assessment Report: Climate Change 2007," Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge (2007), incorporated herein by reference.

[0116] Generally, to calculate the carbon intensity of products and processes, it is necessary to estimate the carbon intensity of the starting material, the carbon intensity associated with the conversion of the starting material to an intermediate, and the carbon intensity associated with the conversion of the intermediate to the final product. A person skilled in the art of chemical engineering can perform these calculations, which can be assisted by software such as life cycle analysis software (e.g., GREET® or SimaPro® software).

[0117] The calculation of carbon and water intensity can use known principles of life cycle analysis. Life cycle assessment (LCA) is a known method used to evaluate the environmental impacts of a product throughout its life cycle, including raw material processing, manufacture, distribution, use, recycling, and final disposal. If multiple products are manufactured, allocation rules are used to calculate the LCA impacts attributable to each product.

[0118] When performing an LCA, one typically needs to identify the fate of the end product. For example, with steel, steel is often installed to remain in place for an extended period of time. In some embodiments, end-of-life options for steel are considered, including industrial recycling options (steel is the most recycled material on earth).

[0119] LCA can also take into account the current state regarding environmental inputs and outputs associated with a particular material. For example, unharvested forest residues release large amounts of methane as they undergo decomposition, causing severe GHG penalties. If these forest residues are instead directed towards the production of biocarbon and subsequently metals, the avoided methane emissions can be taken into account for the overall carbon intensity. As there are so many possibilities and the state of affairs itself is evolving, it is beneficial to utilize the database within the LCA software to ensure that appropriate industry averages are adopted.

[0120] Some aspects of the disclosure can be understood with reference to FIG. 1, which is a simplified block flow diagram of a negative water intensity pyrolysis process for converting wet biomass feedstock to biocarbon. In FIG. 1, wet biomass is fed to a drying unit driven using dry gas (e.g., dry air or superheated steam). The wet gas from the drying unit is fed to a first condenser to produce a first acid water and a first dry gas. The dried biomass is conveyed to a pyrolysis reactor to produce carbon-rich biocarbon solids and pyrolysis steam. The pyrolysis steam is sent to a second condenser to produce a second dry gas and a second acid water. In a carbon washing unit, the biocarbon solids or a portion thereof are fed along with the first acid water and the second acid water. Washed and cooled carbon is produced along with impure water.

[0121] 1 shows the acid water from each condenser being fed separately to the carbon scrubbing unit, it is understood that there can be a mixing step such that a combined stream (first acid water + second acid water) is fed to the carbon scrubbing unit. It will also be appreciated that a single condenser can be used instead of separate condensers.

[0122] The flow of the biocarbon solids and the acidic water may be co-current, counter-current, or cross-current. The exemplary configuration of Figure 1 provides that the flow of the biocarbon solids and the first acidic water stream may be substantially co-current, while the flow of the biocarbon solids and the second acidic water stream may be substantially counter-current.

[0123] Some variations include: providing a feedstock, the feedstock comprising biomass and at least about 0% to at most about 75% by weight water; drying the feedstock, thereby producing a dried feedstock and a first steam, the dried feedstock comprising at least about 0% and up to about 50% water by weight; pyrolyzing the dried feedstock, thereby producing a hot solid and a second vapor; condensing the first vapor, thereby producing a first condensed liquid, the first condensed liquid having a first pH of at least about 1 and up to about 7; condensing the second vapor, thereby producing a second condensed liquid, the second condensed liquid having a second pH of at least about 1 and up to about 7; generating acidic water, the acidic water comprising the first condensed liquid, the second condensed liquid, or a mixture thereof; washing and cooling the hot solids, the washing and cooling being accomplished using acidic water, thereby producing washed and cooled solids; recovering the washed and cooled solids as a biocarbon product; and Optionally, pelletizing the bio-carbon product; A bio-carbon product is provided that is produced by a process, wherein the bio-carbon product comprises at least about 50% carbon by weight.

[0124] In some embodiments, the biocarbon product comprises total carbon, the total carbon being 0.01% of the total carbon. 14 C / 12 At least about 90% is biogenic carbon, as determined by C isotope ratio measurements.

[0125] Some variations are directed to a low water intensity process for producing a biocarbon product, the process comprising: (a) providing a starting material comprising biomass and about 0% to about 75% by weight water; (b) optionally drying the starting material to produce a dried material comprising 0% to about 50% by weight water and the first steam; (c) pyrolyzing the dried feedstock (or starting material, if step (b) is not performed) to produce a high temperature solid and a second vapor; (d) when performing step (b), condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of about 1 to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of about 1 to about 7; (f) forming acidic water containing at least a portion of the second condensed liquid, or, if performing step (b), at least a portion of the first condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solids with at least a portion of the acidic water to produce washed cooled solids; (h) recovering the washed cooled solids as a bio-carbon product comprising at least about 50% by weight carbon; A low water intensity process is provided in which the biocarbon product has a water intensity defined as kilograms of external water utilized divided by metric tons of biocarbon product.

[0126] Some aspects of the disclosure can be understood with reference to FIG. 2, which is a simplified block flow diagram of a low water intensity pyrolysis process for converting biomass feedstock to biocarbon. The dotted lines indicate optional flows and optional unit operations. In FIG. 2, a biomass feed (which may be wet or dry) is provided. The biomass feed is optionally fed to a drying unit driven using a drying gas (e.g., dry air or superheated steam). The wet gas from the drying unit, if present, is fed to a first condenser to produce a first acid water and a first dry gas. The dried biomass is conveyed to a pyrolysis reactor to produce carbon-rich biocarbon solids and pyrolysis steam. The pyrolysis steam is sent to a second condenser to produce a second dry gas and a second acid water. In a carbon scrubbing unit, the biocarbon solids or a portion thereof are fed along with the first acid water (if present) and the second acid water. 2 shows the acid water from each condenser being fed separately to the carbon scrubbing unit, it being understood that there is a mixing step such that the combined stream (first acid water + second acid water) is fed to the carbon scrubbing unit. It will also be appreciated that a single integrated condenser (e.g., a multi-stage condenser) can be used in place of separate first and second condensers. Washed and cooled carbon is produced along with water containing impurities.

[0127] In some embodiments, the biomass 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, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit husk ... The waste material is selected from plant 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 scraps, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof.

[0128] If the starting material is dry or relatively dry, step (b) can be omitted. In some embodiments, step (b) is performed and the dried material contains at least about 0% to at most about 25% water by weight. In certain embodiments using step (b), the dried material contains at least about 0% to at most about 10% water by weight.

[0129] In general, the first condenser and the second condenser may be multi-stage condensers. It may be preferable to use a multi-stage second condenser to separate the various fractions of the pyrolysis vapor. The multi-stage second condenser may have two, three, four, five, or more stages. For example, the water-rich stream may be the condensed fraction of one stage of the multi-stage condenser, or of several, but less than all, stages. In some embodiments, the second acid water is the condensed product of the last stage of the multi-stage condenser. In these embodiments, the second acid water may be about or at least about 10, 15, 20, 25, 30, 35, 40, 45, or 50% water by weight, or even higher.

[0130] Optionally, there may be a purge stream of the first acid water, the second acid water, or the combined acid water that is recovered as a water co-product rather than being used for scrubbing and cooling. The split of the acid water used in the carbon scrubbing unit and the acid water co-product may be determined by economics or by the overall water balance. For example, a sufficiently low water consumption rate may be achieved to allow for recovery and sale of the water co-product.

[0131] Water with impurities from the carbon scrubbing unit may also be a co-product of the process. This stream may be recycled elsewhere in the process, elsewhere within the location where the process is operated, may be further treated, or may be recovered and sold.

[0132] Low water consumption The water consumption of the process is approximately 1000 kgH2 per metric ton of biocarbon product. 2 0, for example, the water consumption may be less than about 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 25, 10, 0, -10, -25, -50, -100, -200, -500, or -1000 kgH2O per metric ton of biocarbon product. 2 That is, the water consumption is at least reduced compared to a process that does not incorporate the disclosed technology, although in some embodiments the water consumption may be negative. In certain embodiments of the low water consumption process, the process does not utilize external water. In other embodiments of the low water consumption process, the process uses a relatively small amount of external water, resulting in a positive but small water consumption of the biocarbon product.

[0133] The water consumption of the low water consumption process can be reduced by about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 100% or more compared to an otherwise comparable process that does not use acid water recovery and reuse in steps (f) and (g).

[0134] The water consumption of a low water consumption process generally has a contribution from transport water and a contribution from reaction water. The percentage of water consumption from reaction water can be from about 1% to about 100% (relative to reaction water + transport water). 100% water consumption from reaction water is possible when the process uses a completely dry starting biomass feedstock with no moisture. In various embodiments, the percentage of water consumption from reaction water is about or at least about 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%, including any intervening ranges.

[0135] In some embodiments of the low water intensity process for producing biocarbon products, the first pH is at least about 2 and up to about 7. In some embodiments, the first pH is at least about 3 and up to about 6.5. In some embodiments, the second pH is at least about 2 and up to about 7. In some embodiments, the second pH is at least about 3 and up to about 6.5. In some embodiments, the first pH is up to about 7 and the second pH is up to about 7.

[0136] In some embodiments, the acidic water comprises a first condensed liquid and does not comprise a second condensed liquid. In some embodiments, the acidic water comprises a second condensed liquid and does not comprise the first condensed liquid. In certain embodiments, the acidic water comprises a first condensed liquid and a second condensed liquid.

[0137] In some embodiments, the acidic water comprises the entirety of the first condensed liquid produced. In some embodiments, the acidic water comprises the entirety of the second condensed liquid produced. In certain embodiments, the acidic water comprises the entirety of the first condensed liquid produced and the entirety of the second condensed liquid produced.

[0138] In some embodiments, producing the acid water comprises producing at least about 1 and up to about 500 gallons of acid water per dry metric ton of feedstock. In certain embodiments, producing the acid water comprises producing at least about 50 and up to about 100 gallons of acid water per dry metric ton of feedstock.

[0139] The process may further include recovering a portion of the acid water as a water co-product. The portion of the acid water recovered as a water co-product may be some or all of the first condensed liquid (if step (d) is performed), some or all of the second condensed liquid, or part of a combined stream including the first condensed liquid and the second condensed liquid.

[0140] In some embodiments, the washing and cooling is accomplished using a water source, which consists essentially of acidified water.

[0141] In some embodiments, the hot solid is generated at a substrate temperature of at least about 300° C. up to about 800° C., and cooling comprises cooling the hot solid to a cooled substrate temperature below the substrate temperature. In certain embodiments, the cooled substrate temperature is up to about 100° C. or up to about 50° C.

[0142] In some embodiments, washing includes removing ash from the hot solids. The washed and cooled solids may contain up to about 1% or up to about 0.2% total ash by weight after removal.

[0143] In some embodiments, washing includes removing impurities from the hot solid selected from aluminum, aluminum oxide, antimony, arsenic, barium, beryllium, boron, boron oxide, bromine, cadmium, calcium, chlorine, chromium, cobalt, copper, fluorine, gold, iron, iron oxide, lead, lithium, magnesium, manganese, mercury, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silicon oxide, silver, sodium, strontium, sulfur, tellurium, thallium, tin, titanium, titanium oxide, tungsten, vanadium, zinc, zirconium, or combinations thereof. The washed and cooled solid may contain up to about 1000 ppm or up to about 100 ppm of impurities after removal.

[0144] The process may further include pelletizing the washed and cooled solids, thereby producing biocarbon pellets. In some embodiments, the pelletizing does not include introducing an external binder to the washed and cooled solids. In other embodiments, the pelletizing includes introducing an external binder to the washed and cooled solids. In these or other embodiments, the pelletizing includes introducing an in situ binder to the washed and cooled solids.

[0145] If an external binder is utilized, the binder may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, xanthan gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations of the foregoing.

[0146] In some embodiments of the low water intensity process, the biocarbon product has up to about 0 kg CO per metric ton of biocarbon product. 2 Includes carbon intensity of e.

[0147] In some embodiments of the low water intensity process, the biocarbon product comprises total carbon, the total carbon being: 14 C / 12 At least about 90%, at least about 95%, or about 100% is biogenic carbon as determined from C isotope ratio measurements.

[0148] Some variations include: (a) providing a starting material comprising biomass and about 0% to about 75% by weight water; (b) optionally drying the starting material to produce a dried material comprising 0% to about 50% by weight water and the first steam; (c) pyrolyzing the dried feedstock (or starting material, if step (b) is not performed) to produce a high temperature solid and a second vapor; (d) when performing step (b), condensing at least a portion of the first vapor to produce a first condensed liquid having a first pH of at least about 1 and up to about 7; (e) condensing at least a portion of the second vapor to produce a second condensed liquid having a second pH of at least about 1 and up to about 7; (f) forming acidic water containing at least a portion of the second condensed liquid, or, if performing step (b), at least a portion of the first condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (g) washing and cooling the hot solid using acidic water to produce a washed cooled solid; (h) recovering the washed cooled solids as a biocarbon product; the biocarbon product comprises at least about 50% by weight carbon; A biocarbon product contains total carbon, Total carbon is 14 C / 12 A biocarbon product is provided that is produced by the process and is at least about 90% biogenic carbon, as determined from C isotope ratio measurements.

[0149] This technology provides biocarbon products produced by the disclosed low or negative water consumption processes.

[0150] For example, a biocarbon product produced by the present disclosure may be metallurgical carbon. In this disclosure, "metallurgical carbon" means carbon intended to be used in a process involving one or more metals. Metallurgical carbon may be, for example, a feedstock in a process for converting metal ores to metals, a process for refining metals, a process for adding carbon as an alloying element to metals, a process for making carbon-metal composites, or a combination thereof. It will be appreciated that metallurgical carbon has other uses that do not require addition to a metal manufacturing process. Thus, the adjective metallurgical in some (but not all) embodiments limits the carbon to its intended use in metallurgical processing. If the metallurgical carbons disclosed herein are not actually utilized in metallurgy, the adjective metallurgical is not to be construed as otherwise limiting the carbon in terms of its physical structure, chemical composition, or material properties. Any embodiment providing metallurgical carbon should be understood to also refer to an embodiment providing non-metallurgical carbon for use in one or more non-metallurgical applications. Thus, various embodiments provide non-metallurgical carbon products.

[0151] In some embodiments, the biocarbon product comprises at least about 60%, at least about 70%, at least about 80%, or at least about 90% carbon by weight. In some embodiments, the biocarbon product comprises at least about 50% fixed carbon, at least about 75% fixed carbon, or at least about 90% fixed carbon by weight. It is noted that removal of ash during washing with acid water results in a higher fixed carbon content in the washed cooled solids and thus in the biocarbon product.

[0152] In some embodiments, the biocarbon product is a carbon 14 C / 12 Contains at least 50%, at least 75%, at least 90%, at least 95%, or 100% renewable carbon as determined by C isotope ratio measurements.

[0153] The biocarbon product may contain from about 1% to about 30% moisture by weight, e.g., from about 5% to about 15% moisture by weight, from about 2% to about 10% moisture by weight, or from about 0.1% to about 1% moisture by weight.

[0154] Biocarbon products may contain 0 to about 30% ash (or more) by weight, e.g., about 2% to about 25% ash, about 5% to about 20% ash, or about 8% to about 15% ash by weight. "Ash" refers to non-carbon components that are not vaporized during pyrolysis. Ash content can be measured by ASTM D3175 or other techniques. Ash composition can be analyzed by ASTM D4326 or other techniques. Ash from pyrolysis of woody biomass typically contains primarily SiO 2 , CaO, K 2 O and Fe 2 O 3 Includes.

[0155] In some embodiments, the biocarbon product further comprises an additive. The concentration of the additive can be about 0.2% to about 25% by weight, about 2% to about 25% by weight, about 5% to about 20% by weight, or about 1% to about 5% by weight based on the total weight of the biocarbon product. In certain embodiments, the concentration of the additive is less than about 1% by weight, for example, about or up to about 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.10, 0.05, 0.02, 0.01% by weight. Because the additive is optional, in some embodiments, the additive concentration is zero.

[0156] In some embodiments, the additive can be partially oxidized or combusted. In certain embodiments, the additive is a renewable material. In certain embodiments, the additive is a carbon neutral or carbon negative additive. An example of a carbon neutral or carbon negative additive is starch produced by photosynthesis (specifically, solar energy can be stored by biomass as starch).

[0157] In some embodiments, the additive is a binder for the biocarbon product. The binder can be an organic binder, an inorganic binder, or a combination thereof. In various embodiments, the additive is a binder selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or any combination thereof.

[0158] In certain embodiments, the additive is a binder selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof. The binder can be a thermoplastic starch that can be crosslinked. The thermoplastic starch can be a reaction product of starch and a polyol, whereby the polyol can be selected from ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or a combination, and the reaction product can be formed, for example, from a reaction catalyzed by an acid or by a base. When the reaction is catalyzed by an acid, the acid can be selected, for example, from formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or a combination thereof.

[0159] In some embodiments, the additive reduces the reactivity of the bio-carbon product compared to an otherwise equivalent bio-carbon product without the additive.

[0160] The reactivity can be thermal reactivity. For example, a biocarbon product can have a lower self-heating tendency compared to an otherwise equivalent biocarbon product without the additive. The reactivity can be chemical reactivity with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron or iron oxide), or two or more of these species.

[0161] In some embodiments, the additive fills pores within the bio-carbon product. In these or other embodiments, the additive is disposed on the surface of the bio-carbon product.

[0162] The biocarbon product may be in powder form. Alternatively or additionally, the biocarbon product may be in agglomerated form.

[0163] For example, the bio-carbon product may be in an aggregate form as bio-carbon pellets, optionally with a binder.

[0164] When the bio-carbon product is a bio-carbon pellet, the bio-carbon pellet can be characterized, for example, by a Hard Grove Crushability Index of at least 30. In various embodiments, the bio-carbon pellet has a Hard Grove Crushability Index of about, at least about, or up to about 30, 40, 50, 60, 70, 80, 90, or 100, including any intervening ranges.

[0165] When the bio-carbon product is a bio-carbon pellet, the bio-carbon pellet can be characterized by a pellet durability index of at least 80%. In various embodiments, the bio-carbon pellet has a pellet durability index of about or at least about 50%, 60%, 70%, 75%, 80%, 85%, 90%, or 95%, including any intervening ranges.

[0166] The biocarbon products can be used in metal processing to produce one or more base metals selected from iron, copper, nickel, magnesium, manganese, aluminum, tin, zinc, cobalt, chromium, tungsten, molybdenum, silicon, or combinations thereof. Metal products can be produced with alloying elements such as one or more elements selected from Al, Bi, B, C, Ce, Cr, Cu, Fe, H, Mg, Mn, Mo, N, Nb, Ni, P, Pb, Si, Sn, S, Ta, Ti, W, V, Zr, Zn, oxides, carbides, hydrides, nitrides, or sulfides of any of the foregoing elements, or combinations thereof. Metal products can include other elements that may or may not function as alloying elements.

[0167] In some embodiments, the alloying element comprises carbon. When carbon is present in a metal product, it may be present in an equilibrium concentration within one or more metals. Alternatively, it may be present in a non-equilibrium concentration within one or more metals, which may be lower than or higher than the equilibrium concentration of carbon.

[0168] In some embodiments, the alloying element comprises carbon derived from a bio-carbon product as disclosed herein. Other elements may be derived from the bio-carbon product and may be utilized as alloying elements including, but not limited to, hydrogen, nitrogen, oxygen, sulfur, or phosphorus.

[0169] It should be noted that when negative water intensity bio-carbon products are used in metal fabrication processes, the final metal product may have reduced water intensity as well. Thus, some embodiments provide carbon negative reduced water intensity metal products ("carbon negative" is synonymous with negative carbon intensity).

[0170] In certain embodiments, the alloying element includes hydrogen. When the hydrogen is derived from a biocarbon product that is itself derived from a biomass feedstock, it can be carbon neutral or carbon negative, since it is added to the growing biomass from atmospheric water via photosynthesis. As with carbon, the reduced water intensity associated with hydrogen is carried over to the final metal product from an LCA perspective.

[0171] Carbon 14 C / 12 C isotope ratio (in solid carbon, or CO, CO 2 , or CH 4 Measuring the CO2 concentration in vapor form (such as in carbon) is a proven technique. Similar concepts can be applied to hydrogen, 2 H / 1 H isotope ratios are measured ( 2 H is also known as deuterium D). Fossil sources tend to be depleted in deuterium compared to biomass. See Schiegl et al., "Deuterium content of organic matter", Earth and Planetary Science Letters, Volume 7, Issue 4, 1970, Pages 307-313, and Hayes, "Fractionation of the Isotopes of Carbon and Hydrogen in Biosynthetic Processes", Mineralogical Society of America, National Meeting of the Geological Society of America, Boston, MA, 2001 (incorporated herein by reference).

[0172] Renewable hydrogen may be recognized in the market in a variety of ways, such as through renewable energy standards, renewable energy credits, renewable identification numbers, etc. As just one example, a refinery that utilizes renewable hydrogen in producing gasoline may be recognized as a renewable energy producer. 2You can receive renewable energy credits for the content. In metal products such as steel, renewable hydrogen is used in the production of metals (e.g., H 2 Hydrogen, which may be utilized during the reduction of metal ores by hydrogen peroxide or which is renewable, may be a measurable alloying element in the final product.

[0173] In certain embodiments, the alloying element includes nitrogen. High strength austenitic stainless steels can benefit from nitrogen. Nitrogen has a higher solid solubility than carbon, is a strong austenite stabilizer, is a good interstitial solid solution strengthener, and improves pitting corrosion resistance. When the nitrogen is derived from a biocarbon product that is itself derived from a biomass feedstock, it can be absorbed into the atmosphere via the nitrogen cycle. 2 When added to biomass growing from nitrogen, it can be carbon neutral or carbon negative. On the other hand, alloying nitrogen can eventually be NH 3 It is derived from the base fertilizer, NH 3 However, if derived from the energy-intensive Haber synthesis, such nitrogen will generally not be carbon neutral or carbon negative. If either is present, its contribution to the overall carbon and water intensity of the metal product may be very low, since the nitrogen content is typically less than 1 wt. %. Even the Haber process can be used to produce H using renewable energy, for example. 2 By splitting the water for production or employing renewable hydrogen, the energy intensity can be reduced.

[0174] In certain embodiments, the alloying element comprises oxygen. Oxygen is typically not a preferred alloying element, especially when metal oxides are to be avoided. However, certain alloys, particularly non-ferrous alloys, can use oxygen (as O atoms) as an interstitial alloying element that strengthens the metal through interstitial solid solution strengthening. When the oxygen is derived from a biocarbon product that is itself derived from a biomass feedstock, the oxygen can be used as an output of O 2 With atmospheric CO through photosynthesis 2 It is recognized that it originates from

[0175] In certain embodiments, the alloying element comprises sulfur. When the sulfur is derived from a biocarbon product that is itself derived from a biomass feedstock, the carbon intensity of the sulfur depends on the source of the sulfur (e.g., soil vs. added fertilizer).

[0176] In certain embodiments, the alloying element comprises phosphorus. When the phosphorus is derived from a biocarbon product that is itself derived from a biomass feedstock, the carbon intensity of the phosphorus depends on the source of the phosphorus (e.g., soil vs. added fertilizer).

[0177] In various embodiments, the metal product is in a form selected from a powder, pellet, sheet, rod, bar, wire, coil, pipe, plate, wall, tank, cast structure, engineered structure, electromagnet, permanent magnet, or combinations thereof. The metal product may be a final structure or may be a feedstock for making metal-containing structures via traditional subtractive manufacturing, additive manufacturing, or other techniques.

[0178] In some embodiments, the steel product with reduced carbon negative water consumption may include at least about 80% iron by weight, at least about 90% iron by weight, or at least about 95% iron by weight. The steel product with reduced carbon negative water consumption may include from about 0.01% to about 10% by weight of one or more alloying elements. The one or more alloying elements may be selected from Al, Bi, B, C, Ce, Cr, Cu, H, Mg, Mn, Mo, N, Nb, Ni, P, Pb, Si, Sn, S, Ta, Ti, W, V, Zr, Zn, oxides, carbides, hydrides, nitrides, or sulfides of any of the foregoing elements, or combinations thereof.

[0179] Some embodiments are based on optimized pyrolysis of biomass to produce a carbon substrate, mechanical size reduction of the carbon substrate, and optionally the use of a binder to agglomerate the carbon substrate to form bio-carbon pellets with a manageable Hardgrove Grindability Index (HGI). The moisture level of the bio-carbon pellets can be optimized to vary the density within the pellets. The ability to tailor the HGI of the bio-carbon pellets is highly beneficial as downstream applications (e.g., use in blast furnaces) have different HGI requirements. The bio-carbon pellets can be negative carbon and negative water consumption bio-carbon pellets.

[0180] Particle size reduction is necessary in the context of a wide variety of biorefinery processes for converting biomass (e.g., wood chips) into products. The size reduction step is essential but very energy intensive due to the presence of strong bonds in the naturally occurring cellulose, hemicellulose, and lignin polymers. This problem is particularly acute when small particles are encountered. For example, the energy consumption of hammer mill grinding of biomass increases exponentially as a function of screen mesh size reduction.

[0181] Raw biomass is inferior to pyrolyzed forms of biomass (many of which are described in this patent application) for a wide variety of commercial applications. Once biomass is pyrolyzed into bioreagents, its mechanical properties often do not lend themselves to downstream applications such as blast furnaces or pulverized coal boilers. Therefore, it may be preferable to pelletize the bioreagents into biocarbon pellets. However, once pelletized, the problematic grinding energies discussed above for raw biomass also make it difficult, and often even worse, to convert the pellets into industrial powders. This could potentially be overcome by creating loose agglomerates that are inherently weak pellets, but these agglomerates can defeat the purpose of pelleting when durability of the pellets is required during transportation and plant processing, and sometimes within the reactor itself (e.g., to support a metal bed). This problem is difficult to solve because, on the one hand, pellet durability is desired, but, on the other hand, pellet grindability is desired. However, the present disclosure overcomes this problem by providing biocarbon pellets and processes for making them that have good grindability and adequate durability.

[0182] Furthermore, since there are numerous downstream uses of bio-carbon pellets, each with its own unique requirements, being able to adjust the grindability of the pellets is highly advantageous. The inventors have designed a process and composition that is well suited for controllably grindable bio-carbon pellets.

[0183] Some embodiments are bio-carbon pellets, which may be carbon negative, negative water consumption bio-carbon pellets; (a) about 35% to about 99% by weight of a bioreagent, the bioreagent comprising at least about 60% by weight of carbon on a dry basis; (b) about 0% to about 35% by weight of water; (c) about 1% by weight to about 30% by weight of a binder; The bio-carbon pellets are characterized by a Hardgrove Crushability Index of at least 30.

[0184] In some embodiments, the bio-reagent comprises at least about 70%, at least about 80%, or at least about 90% carbon by weight on a dry basis. In various embodiments, the bio-reagent comprises about or at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% carbon by weight on a dry basis. These percentages refer to the concentration of total carbon (fixed carbon and volatile carbon) relative to the entire bio-reagent.

[0185] In some embodiments, the bioreagent comprises at least about 50% by weight fixed carbon, at least about 75% by weight fixed carbon, or at least about 90% by weight fixed carbon. In various embodiments, the bioreagent comprises about or at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight fixed carbon. These percentages refer to the concentration of fixed carbon relative to the entire bioreagent, not to total carbon. Fixed carbon is total carbon minus volatile carbon.

[0186] In some biocarbon pellets, the carbon is 14 C / 12 At least 50% is reproducible, as determined by measurements of the C isotope ratio. 14 C / 12 It may be at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or at least 99.9% renewable, as determined from C isotope ratio measurements. In certain embodiments, the carbon is 14 C / 12 It is completely renewable, as determined by measuring the C isotope ratio. 14 C / 12 The C isotope ratio can be measured using ASTM D6866.

[0187] In certain embodiments, the biological reagent comprises, on a dry basis, about 75% to about 94% carbon by weight, about 3% to about 15% oxygen by weight, and about 1% to about 10% hydrogen by weight.

[0188] The moisture present in the biocarbon pellets may be water that is chemically bound to the carbon or binder, water that is physically bound (absorbed or adsorbed) to the carbon or binder, free water present in the water phase that is not chemically or physically bound to the carbon or binder, or a combination thereof. When moisture is desired during the binding process, it is preferred that such moisture be chemically or physically bound to the carbon or binder rather than being free water.

[0189] Various moisture levels may be present in the pellet product. For example, the biocarbon pellets may contain about 1% to about 30% (e.g., 32%) by weight, such as about 5% to about 15% moisture, about 2% to about 10% moisture, or about 0.1% to about 1% moisture. In some embodiments, the biocarbon pellets contain about 4-8% moisture. In various embodiments, the biocarbon pellets contain about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% moisture, including all intervening ranges.

[0190] Although water is present in the process of making biocarbon pellets, these pellets are then optionally dried, meaning that the final biocarbon pellets do not necessarily contain moisture. In some market applications, such as agriculture, higher moisture levels are desirable for dust control or other reasons. In other market applications, lower moisture levels may be desirable (e.g., 1% moisture by weight, or even lower). In some metallurgical applications, low moisture is desirable, while in others some moisture is tolerable or even desirable to aid in the overall chemical reaction.

[0191] In some biocarbon pellets, the biocarbon pellets include about 2% to about 25% binder by weight, about 5% to about 20% binder by weight, or about 1% to about 5% binder by weight. In various embodiments, the biocarbon pellets include about, at least about, or up to about 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, or 30% binder by weight, including all intervening ranges. In some embodiments, there is an inverse relationship between moisture content and binder concentration.

[0192] The binder may be pore-filled within the bio-reagent of the bio-carbon pellet. Alternatively or additionally, the binder may be disposed on the surface of the bio-carbon pellet.

[0193] The binder may be an organic binder or an inorganic binder. In some embodiments, the binder is or comprises a renewable material. In some embodiments, the binder is or comprises a biodegradable material. In some embodiments, the binder may be partially oxidized or combusted.

[0194] In various embodiments, the binder is selected from starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing shingles, recycled tires, derivatives thereof, or combinations thereof. The binder may be or may include a grindable plasticizer.

[0195] In certain embodiments, the binder is selected from starch, thermoplastic starch, crosslinked starch, starch-based polymers (e.g., polymers based on amylose and amylopectin), derivatives thereof, or combinations thereof. The starch can be a nonionic starch, anionic starch, cationic starch, or zwitterionic starch.

[0196] Starch is one of the most abundant biopolymers. It is completely biodegradable, inexpensive, renewable, and can be easily chemically modified. The ring structure of starch molecules, together with the strong hydrogen bonds, give starch a rigid structure, resulting in highly ordered crystalline and granular regions. Starch in its granular state is generally not suitable for thermoplastic processing. To obtain thermoplastic starch, semicrystalline starch granules can be decomposed by thermal and mechanical forces. Since the melting point of pure starch is significantly higher than its decomposition temperature, plasticizers such as water or glycols can be added. The native crystallinity can then be destroyed by vigorous mixing (shear) at high temperatures resulting in thermoplastic starch. Starch can be plasticized (destroyed) by relatively low levels of molecules that can hydrogen bond with starch hydroxyl groups, such as water, glycerol, or sorbitol.

[0197] Thermoplastic starch can be chemically modified or blended with other biopolymers to produce stronger, more ductile and resilient bioplastics. For example, starch can be blended with natural and synthetic (biodegradable) polyesters such as polylactic acid, polycaprolactone, or polyhydroxybutyrate. To improve the compatibility of starch / polyester blends, suitable compatibilizers such as poly(ethylene-co-vinyl alcohol) or polyvinyl alcohol can be added. The hydrophilic hydroxyl groups (-OH) of starch can be replaced with hydrophobic reactive groups, such as by esterification or etherification.

[0198] In some embodiments, the starch-containing binder is or comprises crosslinked starch. Various methods for crosslinking starch are known in the art. Starch materials can be crosslinked, for example, under acidic or alkaline conditions after dissolving or dispersing in an aqueous medium. Aldehydes (e.g., glutaraldehyde or formaldehyde) can be used to crosslink starch.

[0199] An example of a crosslinked starch is the reaction product of starch with glycerol or another polyol, such as (but not limited to) ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. The reaction product can be formed from a crosslinking reaction catalyzed by an acid, such as (but not limited to) formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, or combinations thereof. Inorganic acids, such as sulfuric acid, can also be utilized to catalyze the crosslinking reaction. In some embodiments, the thermoplasticized or crosslinked reaction product can instead be formed from a crosslinking reaction catalyzed by a base, such as (but not limited to) ammonia or sodium borate.

[0200] In some embodiments, the binder is designed to be a water-resistant binder. For example, in starch, hydrophilic groups can be replaced by hydrophobic groups that better resist water.

[0201] In some embodiments, the binder serves other purposes such as (but not limited to) moisture retention within the biocarbon pellets and as a food source for microorganisms.

[0202] In some embodiments, the binder reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the binder, which can refer to thermal or chemical reactivity (or both).

[0203] In the case of thermal reactivity, the biocarbon pellets may have a low self-heating tendency compared to otherwise comparable biocarbon pellets without the binder. "Self-heating" refers to biocarbon pellets that undergo a spontaneous exothermic reaction in the absence of any external ignition, at relatively low temperatures and in an oxidizing atmosphere, to increase the internal temperature of the biocarbon pellets. In some embodiments, the biocarbon pellets are characterized as non-self-heating when subjected to a self-heating test according to Manual of Tests and Criteria, Seventh revised edition 2019, United Nations, Page 375, 33.4.6 Test N.4: "Test method for self-heating substances".

[0204] The chemical reactivity can be with oxygen, water, hydrogen, carbon monoxide, metals (e.g., iron), or combinations thereof. Chemical reactivity can be, for example, with CO, CO 2 , H 2 O, pyrolysis oils, and reactions to heat.

[0205] Optionally, the carbon-containing pellets include one or more additives (not necessarily binders), such as inorganic bentonite clay, limestone, starch, cellulose, lignin, or acrylamide. When lignin is used as a binder or other additive, the lignin can be obtained from the same biomass feedstock used in the pyrolysis process. For example, the starting biomass feedstock can be subjected to a lignin extraction step to remove some amount of lignin for use as a binder or additive.

[0206] Other possible additives include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime. In some embodiments, the additives are selected from acids, bases, or salts thereof. In some embodiments, at least one additive is selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. For example, the additives can be selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, or combinations thereof. The additives can be added before, during, or after any one or more steps of the process, including adding to the feedstock itself at any time before or after the feedstock is harvested.

[0207] The Hardgrove Grindability Index of the biocarbon pellets can be at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. In some embodiments, the Hardgrove Grindability Index is from about 30 to about 50 or from about 50 to about 70. ASTM-Standard D409 / D409M for "Standard Test Method for Grindability of Coal by the Hardgrove-Machine Method" is incorporated herein by reference in its entirety. Unless otherwise indicated, all references to Hardgrove Grindability Index or HGI in this disclosure refer to ASTM-Standard D409 / D409M.

[0208] In various embodiments, the Hard Glove Crushability Index is about, at least about, or up to about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 13 , 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0209] Bio-carbon pellets (e.g., carbon negative and negative water consumption bio-carbon pellets) can be characterized by a pellet durability index of at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%. Bio-carbon pellets can be characterized by a pellet durability index of less than 99%, less than 95%, less than 90%, less than 85%, or less than 80%. Unless otherwise indicated, all references to pellet durability index in this disclosure refer to ISO 17831-1:2015 "Solid biofuels - Determination of mechanical durability of pellets and briquettes - Part 1: Pellets", which is incorporated herein by reference in its entirety.

[0210] The size and geometry of biocarbon pellets can vary. As used herein, "pellets" refers to aggregated bodies rather than loose powders. The geometry of pellets is not limited to spherical or nearly spherical. Also, in this disclosure, "pellets" is synonymous with "briquettes." The geometry of pellets can be spherical (round or ball shaped), cubic (square), octagonal, hexagonal, honeycomb / honeycomb shaped, elliptical, ovoid, cylindrical, rod shaped, pillow shaped, random, or combinations thereof. For convenience of disclosure, the term "pellets" is used generally for any body comprising powders aggregated using a binder.

[0211] Biocarbon pellets can be characterized by an average pellet diameter, which is the true diameter in the case of a sphere, or an equivalent diameter in the case of any other 3D geometric shape. The equivalent diameter of a non-spherical pellet is the diameter of a sphere of equivalent volume to the actual pellet. In some embodiments, the average pellet diameter is about or at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, or 25 millimeters, including all intervening ranges. In some embodiments, the average pellet diameter is about or at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, or 6500 microns, including all intervening ranges.

[0212] In some embodiments, there are a plurality of bio-carbon pellets that are relatively uniform in size, such as a standard deviation of less than ±100%, less than ±50%, less than ±25%, less than ±10%, or less than ±5% of the average pellet diameter. In other embodiments, there are a wide range of sizes of bio-carbon pellets, as this may be advantageous in some applications.

[0213] In this specification, (a) about 35% to about 99% by weight of a bioreagent, the bioreagent comprising at least about 60% by weight of carbon on a dry basis; (b) about 0% to about 35% by weight of water; (c) about 1% by weight to about 30% by weight of a reactivity moderator; Bio-carbon pellet compositions are provided, which may be negative water units and carbon negative pellets, in which the reactivity mitigating agent reduces the reactivity of the bio-carbon pellets compared to otherwise identical bio-carbon pellets without the reactivity mitigating agent.

[0214] In some embodiments, the bio-reagent comprises at least 70% carbon by weight on a dry basis. The bio-reagent may comprise at least about 50% fixed carbon by weight.

[0215] The bioreagent may contain, on a dry basis, about 75% to about 94% by weight carbon, about 3% to about 15% by weight oxygen, and about 1% to about 10% by weight hydrogen.

[0216] In some embodiments, the biocarbon pellets contain between about 1% and about 30% moisture by weight.

[0217] In some embodiments, the carbon is 14 C / 12 In certain embodiments, the carbon is at least 50% renewable as determined by C isotope ratio measurements. 14 C / 12 It is determined from measurements of C isotope ratios and is fully reproducible.

[0218] In some bio-carbon pellets, the bio-carbon pellets include from about 2% to about 25% by weight of the reactive mitigating agent. The bio-carbon pellets can include, for example, from about 5% to about 20% by weight, or from about 1% to about 5% by weight of the reactive mitigating agent.

[0219] The reactive mitigating agent may be organic or inorganic. The reactive mitigating agent may be a renewable material.

[0220] In some embodiments, the reactive moderator may be partially oxidized or combusted.

[0221] The reactive modifier may be selected from starch, thermoplastic starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations thereof.

[0222] In some embodiments, the reactive modifier is selected from starch, thermoplastic starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof.

[0223] In certain embodiments, the reactive modifier is an optionally crosslinked thermoplastic starch. For example, the thermoplastic starch can be a reaction product of starch and a polyol. The polyol can be selected from ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, erythritol, xylitol, sorbitol, or combinations thereof. The reaction product can be formed from a reaction catalyzed by an acid, such as formic acid, acetic acid, lactic acid, citric acid, oxalic acid, uronic acid, glucuronic acid, and combinations thereof, or by a base.

[0224] In some biocarbon pellets, where the reactivity mitigating agent reduces the reactivity of the biocarbon pellets, the reactivity is thermal reactivity, e.g., the biocarbon pellets can be characterized by lower self-heating compared to otherwise equivalent biocarbon pellets without the reactivity mitigating agent.

[0225] Reactivity mitigating agents reduce the reactivity of bio-carbon pellets. For some bio-carbon pellets, the reactivity is chemical reactivity with oxygen, water, hydrogen, carbon monoxide, metals (such as iron), or combinations thereof.

[0226] In some biocarbon pellets, the reactivity mitigating agent is loaded into pores within the bioreagent of the biocarbon pellet. In other biocarbon pellets, the reactivity mitigating agent is disposed on the surface of the biocarbon pellet. In still other biocarbon pellets, the reactivity mitigating agent is loaded into pores within the bioreagent of the biocarbon pellet and disposed on the surface thereof.

[0227] The reactive mitigating agent can function as a binder to adjustably control the Hard Grove Grindability Index of the bio-carbon pellets. In some embodiments, the bio-carbon pellets are characterized by a Hard Grove Grindability Index of at least 30, such as from about 30 to about 50 or from about 50 to about 70. Other HGI ranges are disclosed elsewhere herein and are equally applicable to embodiments in which a reactive mitigating agent is used and functions as a binder.

[0228] For example, a binder can be selected that controllably adjusts the HGI while also functioning as a reactive mitigation agent. In such embodiments, it may be desirable to ensure that the binder is not only located on the surface of the biocarbon pellet, but is also dispersed throughout the biocarbon (filling the pores of the biocarbon pellet). The concentration of the binder may be different on the surface compared to the bulk (interior) of the pellet. In some embodiments, a higher concentration of binder is present in the pellet bulk relative to the surface, while in other embodiments (e.g., certain embodiments for reduced self-heating pellets), a higher binder concentration at the surface is desired. It is also possible to have two different binders (chemical species), one in the bulk of the pellet and one on the surface. In such embodiments, the bulk binder may be referred to as the binder and the pellet surface agent may be referred to as the pellet reactive mitigation agent. Even in such embodiments, if the binder is added during the pellet manufacturing process, it will be understood that some amount of the binder will be present on the pellet surface. Similarly, if the reactive mitigation agent is coated onto the pellet after it is formed, some amount of the reactive mitigation agent may be expected to diffuse into the pellet pores.

[0229] Another variation is a process for producing bio-carbon pellets, the pellets may be water negative and carbon negative pellets, the process comprising: (a) drying a biomass feedstock; (b) pyrolyzing the biomass feedstock to produce a bio-reagent, the bio-reagent comprising at least about 50% by weight carbon and at least about 5% by weight moisture; (c) mechanically treating the biological reagent to generate a plurality of carbon-containing particles; (d) combining the carbon-containing particles with a binder to form a carbon-binder mixture; (e) subsequent to or simultaneously with step (d), pelletizing the carbon-binder mixture to produce bio-carbon pellets; (f) optionally, at least partially drying the bio-carbon pellets; (g) condensing at least a portion of the first vapor collected in step (a) to produce a first condensed liquid having a first pH of about 1 to about 7; (h) condensing at least a portion of the second vapor collected in step (b) or step (f) to produce a second condensed liquid having a second pH of about 1 to about 7; (i) forming an acidic water containing at least a portion of the first condensed liquid, at least a portion of the second condensed liquid, or a mixture containing at least a portion of the first condensed liquid and at least a portion of the second condensed liquid; (j) washing and cooling the hot solids with at least a portion of the acidic water to produce washed cooled solids; (k) collecting the bio-carbon pellets, the bio-carbon pellets comprising at least about 50% by weight carbon.

[0230] In some process embodiments, the bioreagent comprises, on a dry basis, at least about 70%, at least about 80%, or at least about 90% carbon by weight.

[0231] In some process embodiments, the bioreagent comprises at least about 50% by weight fixed carbon, at least about 75% by weight fixed carbon, or at least about 90% by weight fixed carbon.

[0232] Carbon is carbon 14 C / 12 As determined from C isotope ratio measurements, the carbon may be at least 50%, at least 90%, at least 95%, or completely renewable. 14 C / 12 The C isotope ratio is measured according to ASTM D6866.

[0233] In one particular process, the bioreagent comprises, on a dry basis, about 75% to about 94% carbon by weight, about 3% to about 15% oxygen by weight, and about 1% to about 10% hydrogen by weight.

[0234] In some processes, the bioreagent comprises at least about 10%, 15%, 20%, 25%, 30%, 35%, or 40% moisture by weight in step (b). If the moisture content is more than 40% by weight, biocarbon pellets can still be produced, but the pellet density is expected to be low (too low for many applications). In some embodiments, step (c), step (d), or step (e) is performed at a moisture content lower than that of step (b). For example, when performing step (f), drying may result in a moisture content lower than that in step (b), and optionally a moisture content lower than that in step (c), step (d), or step (e).

[0235] In some embodiments, step (f) occurs after step (e). In these or other embodiments, step (f) is integrated with step (e). For example, the pelletizing unit can allow water to escape from the pellets as they are being formed. That is, the pelletizing unit can also act as a dryer. In certain embodiments, some amount of drying occurs during pelletizing, and additional drying occurs after pelletizing, for example, in a drying unit or under ambient conditions.

[0236] In some embodiments, the biological reagents are not dried during step (c). In these or other embodiments, the biological reagents are not dried during step (d). In these or other embodiments, the biological reagents are not dried during step (e).

[0237] The biocarbon pellets may contain about 1% to about 30% moisture by weight, for example, about 5% to about 15% moisture by weight, about 2% to about 10% moisture by weight, or about 0.1% to about 1% moisture by weight.

[0238] In some processes, step (b) is carried out at a pyrolysis temperature selected from about 250° C. to about 1250° C., for example, from about 300° C. to about 700° C. In some processes, step (b) is carried out for a pyrolysis time selected from about 10 seconds to about 24 hours. Other possible pyrolysis conditions are described later in this specification.

[0239] Step (c) may utilize mechanical processing equipment selected from a hammer mill, an extruder, an attrition mill, a disc mill, a pin mill, a ball mill, a cone crusher, a jaw crusher, or combinations thereof.

[0240] In some processes, steps (c) and (d) are integrated. For example, the binder can be fed directly into a hammer mill or extruder, or other mechanical processing device.

[0241] The biocarbon pellets may include about 2% to about 25% by weight of binder, such as about 5% to about 20% by weight of binder, or about 1% to about 5% by weight of binder. The binder may be organic or inorganic.

[0242] The binder may be selected from starch, crosslinked starch, starch polymers, cellulose, cellulose ethers, carboxymethylcellulose, cellulose esters, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana flour, wheat flour, wheat starch, soy flour, corn flour, wood flour, coal tar, coal fines, metcoke, asphalt, coal tar pitch, petroleum pitch, bitumen, pyrolysis tar, Gilsonite, bentonite clay, borax, limestone, lime, wax, vegetable wax, baking soda, baking powder, sodium hydroxide, potassium hydroxide, iron ore concentrate, silica fume, gypsum, Portland cement, guar gum, polyvidone, polyacrylamide, polylactide, phenol-formaldehyde resin, vegetable resin, recycled roofing boards, recycled tires, derivatives thereof, or combinations thereof. In certain processes, the binder is selected from starch, crosslinked starch, starch polymers, derivatives thereof, or combinations thereof.

[0243] Step (e) may utilize a pelletizing device selected from an extruder, a ring die pellet mill, a flat die pellet mill, a roll compactor, a roll briquetter, a wet agglomerate mill, a dry agglomerate mill, or a combination thereof.

[0244] In some processes, steps (d) and (e) are integrated. For example, the binder can be introduced directly into a pelletizing unit. When steps (d) and (e) are performed separately, the binder is mixed with the carbon-containing particles to form a carbon-binder mixture before introducing such mixture into a unit configured to pelletize the carbon-binder mixture.

[0245] In some embodiments, biocarbon pellets are utilized as starting materials for making smaller objects, and "pellets" may also be referred to as biocarbon pellets, since "pellets" does not limit the geometric shape. For example, initial biocarbon pellets with an average pellet diameter of 10 mm can be made. These initial biocarbon pellets can then be crushed using various mechanical means (e.g., using a hammer mill). The crushed pellets can be separated according to size, such as by screening. In this manner, smaller biocarbon pellets can be produced, for example, having an average pellet diameter of about, at least about, or up to about 50, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, or 5000 microns. The average pellet diameter of the smaller biocarbon pellets may be greater than the average particle diameter of the initial carbon-containing particles used to make the pellets with the binder.

[0246] When the bio-carbon pellets are crushed to produce smaller bio-carbon pellets, the crushing (and optionally screening) step can be integrated with step (e), can occur after step (e), can occur after step (f), or can occur after step (f), potentially including at an industrial site. The optional step to produce smaller bio-carbon pellets can utilize a crushing device selected from a hammer mill, attrition mill, disc mill, pin mill, ball mill, cone crusher, jaw crusher, rock crusher, or combinations thereof.

[0247] In various process embodiments, the Hardgrove Crushability Index is at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 100. For example, the Hardgrove Crushability Index can be from about 30 to about 50, or from about 50 to about 70.

[0248] In various processes, the process conditions may range from about, at least about, or up to about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1081, 1092, 1094, 1096, 1098, 1098, 1099, 1000, 1001, 1002, 10 8, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100.

[0249] In some processes, the biocarbon pellets are characterized by a pellet durability index of at least 80%, at least 90%, or at least 95%.

[0250] In some embodiments, the process includes preselecting a hardgrove grindability index, adjusting process conditions based on the preselected hardgrove grindability index, and achieving within ±20% of the preselected hardgrove grindability index for the biocarbon pellets, where the adjusted process conditions include adjusting one or more of pyrolysis temperature, pyrolysis time, mechanical treatment conditions, pelletizing conditions, binder type, binder concentration, binding conditions, and drying. The process of certain embodiments can achieve within ±10%, or within ±5%, of the preselected hardgrove grindability index for the biocarbon pellets.

[0251] The biocarbon pellets disclosed herein have a wide variety of downstream applications. They can be stored, sold, distributed, and converted into other products. They can be pulverized, crushed, or milled to feed furnaces, such as blast furnaces in metal production. They can be fed directly to furnaces, such as Tecnored furnaces in metal production. They can be pulverized for use in boilers to burn carbon and generate electrical energy or heat. They can be pulverized, crushed, or milled to feed gasifiers for the purpose of making syngas from the biocarbon pellets.

[0252] In some embodiments, the biocarbon pellets are water negative and carbon negative metallurgical carbon pellets that are fed directly or after a step of pulverizing, crushing, grinding, or otherwise reducing the particle size into a furnace. The furnace can be a blast furnace, a top gas recirculating blast furnace, a shaft furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a silencer furnace, a retort furnace, a flash furnace, a Tecnored furnace, an Ausmelt furnace, an ISASMELT furnace, a puddle furnace, a bogie hearth furnace, a continuous chain furnace, a pusher furnace, a rotary hearth furnace, a walking beam furnace, an electric arc furnace, an induction furnace, a basic oxygen furnace, a puddle furnace, a Bessemer furnace, a direct reduction metal furnace, or a combination or derivative thereof.

[0253] It should be noted that despite the Hardgrove Crushability Index of biocarbon pellets, they do not necessarily undergo a subsequent grinding process. For example, biocarbon pellets can be used directly in agricultural applications. As another example, biocarbon pellets can be directly incorporated into engineered structures, such as landscape walls. Then, at the end of the life of the structure containing the biocarbon pellets, the pellets can be crushed, combusted, gasified, or otherwise reused or recycled.

[0254] Pyrolysis Processes and Systems Suitable processes and systems for pyrolyzing biomass feedstocks to produce carbon-containing bio-reagents will now be described in further detail.

[0255] "Pyrolysis" and "pyrolyzing" generally refer to the thermal decomposition of carbonaceous materials. Pyrolysis requires the use of oxygen (O 2 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% (on a molar basis). In some embodiments, pyrolysis is carried out in the absence of oxygen.

[0256] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the temperature within the feedstock; (ii) the initiation of primary pyrolysis reactions at this higher temperature liberates volatiles and forms char; (iii) the flow of hot volatiles toward the cooler solids results in heat transfer between the hot volatiles and the cooler non-pyrolyzed feedstock; (iv) some of the volatiles in the cooler portions of the feedstock may condense and subsequently undergo secondary reactions to produce tars; (v) autocatalytic secondary pyrolysis reactions proceed while competing primary pyrolysis reactions occur simultaneously; and (vi) further pyrolysis, reforming, water-gas shift reactions, free-radical recombination, or dehydration may also occur, which are a function of residence time, temperature, and pressure profiles.

[0257] Pyrolysis can at least partially dewater the starting material (e.g., lignocellulosic biomass). In various embodiments, pyrolysis removes about 50%, 75%, 90%, 95%, 99% or more of the water from the starting material.

[0258] In some embodiments, the starting biomass feedstock is softwood chips, hardwood chips, timber harvest residues, tree branches, tree stumps, leaves, bark, sawdust, corn, corn stover, wheat, wheat straw, rice, rice straw, sugarcane, sugarcane bagasse, sugarcane straw, energy sugarcane, sugar beet, sugar beet pulp, sunflower, sorghum, canola, algae, miscanthus, alfalfa, switchgrass, fruit, fruit husks. , 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 shavings, food packaging, construction or demolition waste, railroad ties, lignin, animal manure, municipal solid waste, municipal sewage, or combinations thereof. It is noted that the biomass feedstock comprises carbon, hydrogen, and oxygen.

[0259] The bioreagent may contain at least about 50%, at least about 75%, or at least about 90% carbon by weight (total carbon). In various embodiments, the bioreagent contains about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% carbon by weight. Total carbon is the sum of fixed carbon and non-fixed carbon present in the volatile materials. In some embodiments, the weight percentages of the components are on an absolute basis, which is assumed unless otherwise stated. In other embodiments, the component weight percentages are on a dry and ash-free basis.

[0260] The bioreagent may comprise at least about 50%, at least about 75%, or at least about 90% by weight fixed carbon. In various embodiments, the bioreagent comprises about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% by weight fixed carbon.

[0261] The carbon (within the bioreagent) can be, for example, at least about 50%, at least about 75%, or at least about 90% by weight fixed carbon, with the remainder of the carbon being volatile carbon. In various embodiments, the carbon comprises about, at least about, or up to about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100% by weight fixed carbon.

[0262] Pyrolysis conditions can vary widely depending on the desired composition of the bioreagents and pyrolysis exhaust gas, the starting materials, the reactor configuration, and other factors.

[0263] 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.

[0264] In some non-limiting embodiments, the temperature and residence time can be selected to achieve a relatively slow pyrolysis chemical reaction. An advantage can be substantial preservation of the cell walls contained in the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, equipment that does not mechanically break down the cell walls or otherwise convert the biomass particles into small fines may be utilized. Certain suitable reactor configurations are discussed in accordance with the process description below.

[0265] 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.

[0266] 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.

[0267] In some embodiments, the second zone of the pyrolysis reactor is configured as a primary reaction zone, where the preheated biomass undergoes pyrolysis chemical reactions to release gases and condensable vapors, leaving behind a significant amount of solid material that is a high-carbon reaction intermediate. Biomass components (mainly cellulose, hemicellulose, and lignin) decompose to create vapors that escape by penetrating pores or creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0268] In some embodiments, the third zone of the pyrolysis reactor is configured to receive the high carbon reaction intermediates and to cool the solids to some extent. Typically, the third zone is at a lower temperature than the second zone. In the third zone, the chemical reactions and mass transfer can be surprisingly complex. Without being limited by a particular theory or proposed mechanism, it is believed that secondary reactions can occur in the third zone. Essentially, carbon-containing components in the gas phase can decompose to form additional fixed carbon or become adsorbed onto carbon. Thus, in some embodiments, the final carbonaceous material is not simply the solid degassed residue of the processing step, but includes additional carbon deposited from the gas phase, such as by decomposition of organic vapors (e.g., tars) that can form carbon.

[0269] Certain embodiments extend the concept of additional carbon formation by including a separate unit in which the cooled carbon is subjected to an environment containing carbon-containing species to enhance the carbon content of the product. If the temperature of this unit is below the pyrolysis temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0270] There are numerous options with regard to intermediate input and output (purge or probe) streams of one or more phases present in any particular zone, various mass and energy recycle schemes, various additives that can be introduced anywhere in the process, adjustability of process conditions, including both reaction and separation conditions to tailor product distribution, etc. Zone-specific input and output streams allow for better process monitoring and control, such as by FTIR sampling and dynamic process adjustments.

[0271] Some embodiments do not use fast pyrolysis, and some embodiments do not use slow pyrolysis.Surprisingly, high quality carbon materials, including compositions having a very high percentage of fixed carbon, can be obtained from the disclosed processes and systems.

[0272] 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 raw material to remove at least a portion of the moisture contained in the raw material; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in the presence of a substantially inert gas phase at at least one temperature selected from about 250° C. to about 700° C. for at least 10 minutes to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the high temperature pyrolysis solid to produce a cooled pyrolysis solid; (g) recovering a carbon-rich biological reagent comprising at least a portion of the cooled pyrolysis solids.

[0273] "Biomass" for the purposes of this disclosure should be construed as any living material or mixture of living and non-living materials. Essentially, biomass contains at least carbon, hydrogen, and oxygen. The technology can be adapted to a wide range of materials of different types, sizes, and moisture contents.

[0274] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal waste, poultry waste, and municipal solid waste. In various embodiments utilizing biomass, the biomass feedstock may include one or more materials selected from 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 fabrics. One skilled in the art will readily appreciate that the options for feedstock are virtually limitless.

[0275] This technology can also be used with mixtures of biomass and fossil fuels (e.g., biomass / coal blends), recognizing that the carbon intensity of the final product, while not as low as a pure biomass feedstock, is lower than when a pure fossil fuel feedstock is used. In some embodiments, the feedstock includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Feedstocks can include waste tires, recycled plastics, recycled paper, construction waste, demolition waste, and other waste or recycled materials.

[0276] The selection of the particular feedstock or feedstocks 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 be (in some embodiments) screening to remove undesirable materials. The feedstock may be optionally dried before processing. The carbon-containing feedstock may be transportable by any known means, such as trucks, trains, ships, barges, tractor trailers, or any other vehicle or conveyance.

[0277] The raw materials used can be provided or processed into a wide variety of particle sizes or shapes. For example, the feed material can be a fine powder, or a mixture of fine and coarse particles. The feed material can be in the form of larger pieces of material, such as wood chips or other forms of wood (e.g., round, cylindrical, square, etc.). In some embodiments, the feed material comprises pellets or other agglomerated forms of particles that are pressed together or otherwise bound, such as with a binder.

[0278] It should be noted that size reduction is a costly and energy intensive process. Pyrolyzed material can be sized with significantly less energy input, i.e., it may be preferable to reduce the particle size of the product rather than the feedstock. This is an option since the process does not require fine starting material and there is not necessarily any significant particle size reduction during processing. The ability to process very large feedstock pieces is an important economic advantage. In particular, some market applications of high carbon products actually require large sizes (e.g., on the order of centimeters), so in some embodiments, large pieces are supplied, manufactured and sold.

[0279] 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. 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.

[0280] 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.

[0281] The starting feedstock may be provided with a range of moisture levels, as will be appreciated. In some embodiments, the feedstock may already be sufficiently dry that further drying prior to pyrolysis is not required. Typically, it is desirable to utilize commercial sources of biomass that are normally moist, and to feed the biomass through a drying step prior to introduction into the pyrolysis reactor. However, in some embodiments, dry feedstock may be utilized.

[0282] In the pyrolysis reactor, about or up to about 10 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, 0.1 mol%, 0.05 mol%, 0.02 mol%, or 0.01 mol% O is present in the gas phase. 2 It is desirable to provide a relatively low oxygen environment, such as CO. First, uncontrolled combustion should be avoided in the pyrolysis reactor for safety reasons. 2 Some amount of total carbon oxidation to solids may occur, and the heat released from the exothermic oxidation may support the endothermic decomposition chemical reactions. Large amounts of carbon oxidation, including partial oxidation to syngas, will reduce the carbon yield to solids.

[0283] In practice, it can be difficult to achieve a strictly oxygen-free environment in the reactor. This limit can be approached, and in some embodiments, the reactor is substantially free of molecular oxygen in the gas phase. To ensure that there is little or no oxygen in the pyrolysis reactor, it may be desirable to remove air from the feed before it is introduced into the reactor. There are various methods to remove or reduce air in the feed.

[0284] In some embodiments, before or after drying, a degassing unit is utilized in which the feedstock is conveyed in the presence of another gas that can remove adsorbed oxygen and permeate the feedstock pores to remove oxygen from the pores. Essentially, less than 21% by volume O 2 Any gas having a nitrogen content may be used with varying effectiveness. In some embodiments, nitrogen is used. In some embodiments, CO or CO 2 can be used. Mixtures such as a mixture of nitrogen and small amounts of oxygen can be used. Water vapor may be present in the degassed gas, but adding significant moisture back to the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or to an emissions treatment unit) or recycled.

[0285] 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.

[0286] Various types of degassing units can be used. If drying is performed, it may be inefficient to clean soluble oxygen from the moisture present, so drying and then degassing may be preferred. In certain embodiments, the drying and degassing steps are combined in a single unit, or some amount of degassing is achieved during drying, etc.

[0287] The optionally dried and optionally degassed feedstock is introduced into the pyrolysis reactor or multiple reactors in series or parallel. The feedstock can be introduced using any known means including, for example, a screw feeder or a lock hopper. In some embodiments, the feed system incorporates an air knife.

[0288] When a single reactor is used, there can be multiple zones, such as two, three, four or more zones, which can allow separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, or pressure to adjust the overall process performance.

[0289] 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, the boundaries of zones may relate to structures such as the presence of flights within the reactor or separate heating elements to provide heat to separate zones. Alternatively or additionally, the boundaries of zones in continuous reactors may relate to functions such as, for example, separate temperatures, fluid flow patterns, solids flow patterns, extent of reaction, etc. In single batch reactors, a "zone" is an operating regime in time rather than space. Multiple batch reactors may also be used.

[0290] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary, some amount of pyrolysis may occur in a portion of the preheat zone, and some amount of "preheat" may continue to occur in the pyrolysis zone. The temperature profile within the reactor is typically continuous, including at the zone boundaries within the reactor.

[0291] 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., for example, from about 300° C. to about 400° C. The temperature of the first zone is not so high as to bombard the biomass material and rupture the cell walls and initiate rapid decomposition of the solid phase into steam and gas.

[0292] All references to zone temperatures herein should be interpreted without limitation to include temperatures that may be applied to the bulk solids present, or the gas phase, or the reactor walls (process side). It will be understood that temperature gradients exist in each zone, both axially and radially, and over time (i.e., after start-up or due to transients). Thus, references to zone temperatures may be references to average temperatures or other effective temperatures that may affect actual kinetics. Temperatures may be measured directly by thermocouples or other temperature probes, or may be measured or estimated indirectly by other means.

[0293] The second zone, or generally the primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone can be selected from about 250°C to about 700°C, for example, about, or at least about, or up to about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemical reactions releasing gases and condensable vapors, leaving behind a significant amount of solid material as a high carbon reaction intermediate. Biomass components (mainly cellulose, hemicellulose, and lignin) decompose to create steam, which escapes by penetrating pores or by creating new pores. The preferred temperature depends on at least the residence time of the second zone, as well as the nature of the feedstock and the desired product properties.

[0294] The third zone, or cooling zone, is operated to cool the high carbon reaction intermediates to various degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone can be selected from about 100°C to about 550°C, for example, from about 150°C to about 350°C.

[0295] Chemical reactions can continue to occur in the cooling zone. Without being limited to a particular theory, it is believed that a secondary pyrolysis reaction can be initiated in the third zone. Carbon-containing components that are in the gas phase can condense (due to the reduction in temperature in the third zone). However, the temperature remains high enough to promote reactions that can form additional fixed carbon from the condensed liquid (secondary pyrolysis), or at least reactions that can form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that can occur is the Boudouard reaction to convert carbon monoxide to carbon dioxide and fixed carbon.

[0296] 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.

[0297] It should be recognized that in a multiphase reactor, there are multiple residence times. In the present context, there are residence times (and residence time distributions) for both solid and vapor phases in each zone. For a given apparatus using multiple zones, at a given throughput, the residence times across the zones are generally combined on the solid side, but if multiple inlet and outlet ports are utilized in the individual zones, the residence times may not be combined on the vapor side. The residence times of the solids and vapor are not combined.

[0298] 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 not be desirable unless some amount of mild pyrolysis is intended in the preheat zone, as it contributes to higher capital costs.

[0299] The solids residence time in the pyrolysis zone can be selected from about 10 minutes to about 120 minutes, for example, about 20, 30, 40, 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in this zone, there should be enough time for the necessary heat transfer to occur followed by the chemical reaction of carbonization. For times less than about 10 minutes, the temperature needs to be very high, such as above 700° C., to remove a large amount of non-carbon elements. This temperature promotes fast pyrolysis and its production of steam and gases derived from the carbon itself, but should be avoided if the intended product is solid carbon.

[0300] In a static system, there will be an equilibrium conversion that can be substantially reached at a certain time. When steam is continuously flowing over the solids with continuous devolatilization, as in certain embodiments, the equilibrium constraint can be removed to allow pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times do not tend to substantially change the remaining refractory solids.

[0301] The solids residence time in the cooling zone can be selected from about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40, or 50 minutes. Depending on the cooling temperature in this zone, there should be enough time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature dictate the minimum residence time required to allow the carbon to cool. In some embodiments, additional time is not desired unless some amount of secondary pyrolysis is desired.

[0302] As discussed above, the residence times of the vapor phases can be selected and controlled separately. The vapor residence time of the preheat zone can be selected from about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. The vapor residence time of the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 minutes. The vapor residence time of the cooling zone can be selected from about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes. A short vapor residence time promotes rapid clearing of volatiles from the system, while a longer vapor residence time promotes reaction of components in the vapor phase with the solid phase.

[0303] The mode of operation of the reactor, and the overall system, can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the reactor is a continuous countercurrent reactor, with solids and vapor flowing in substantially opposite directions. The reactor can also be operated in batch, but with simulated countercurrent flow of vapor, for example, by periodically introducing and removing the gas phase from the batch vessel.

[0304] A variety of flow patterns may be desired or observed. In chemical reactions and simultaneous separations involving multiple phases in multiple reactor zones, the fluid dynamics can become very complex. Typically, the flow of solids can approach plug flow (well mixed in the radial dimension), while the flow of vapor can approach perfectly mixed flow (high velocity transport in both radial and axial dimensions). Multiple inlet and outlet ports for the vapor can contribute to the overall mixing.

[0305] The pressure in each zone can be separately selected and controlled. The pressure in each zone can be independently selected from about 1 kPa to about 3000 kPa, for example, about 101.3 kPa (standard atmospheric pressure). Independent zone control of pressure is possible when multiple gas inlets and outlets are used, including vacuum ports for withdrawing gas when subatmospheric zone pressures are desired.

[0306] The process may be conveniently operated at atmospheric pressure in some embodiments. Operation at atmospheric pressure has many advantages ranging from mechanical simplicity to improved safety. In certain embodiments, the pyrolysis zone is operated at a pressure of about 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute).

[0307] Vacuum operation (e.g., 10-100 kPa) promotes rapid clearing of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) may be useful when feeding exhaust gas to high pressure operation. Higher pressures may also be useful to promote heat transfer, chemical reactions, or separations.

[0308] 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.

[0309] The sweep gas is, for example, N 2 , Ar, CO, CO 2 , H 2 , H 2 O, C.H. 4 , other light hydrocarbons, or combinations thereof. The sweep gas may be first preheated before introduction, or may be cooled if obtained from a heated source.

[0310] The sweep gas removes volatile components more completely by removing them from the system before they can condense or further react. The sweep gas allows volatiles to be removed at a higher rate than would be possible from simply volatilization at a given process temperature. Alternatively, the use of a sweep gas allows a more gentle temperature to be used to remove a particular amount of volatiles. The reason the sweep gas improves volatile removal is because the mechanism of separation is not simply relative volatility, but rather liquid / vapor phase separation assisted by the sweep gas. The sweep gas can reduce the mass transfer limitations of volatilization as well as the thermodynamic limitations by continuously depleting a given volatile species to allow more volatile species to evaporate and achieve thermodynamic equilibrium.

[0311] Some embodiments remove gases full of volatile organic carbon from subsequent processing steps to produce products with high fixed carbon. Otherwise, the volatile carbon may be adsorbed or absorbed onto the pyrolyzed solids, thereby requiring additional energy (cost) to achieve a purer form of carbon that may be desired. It is also speculated that the rapid removal of steam can increase porosity in the pyrolyzed solids. Higher porosity is desirable for some products.

[0312] 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.

[0313] In some embodiments, the sweep gas flows countercurrent to the feed flow direction. In other embodiments, the sweep gas flows cocurrent to the feed flow direction. In some embodiments, the flow patterns of the solids approach plug flow, while the flow patterns of the sweep gas and vapor phase generally approach perfectly mixed flow in one or more zones.

[0314] The sweep may be performed in any one or more of the reactor zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted (along with generated volatiles) from the cooling 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 may be introduced into each of the preheating zone, pyrolysis zone, and cooling zone, and may also be extracted from each of the zones.

[0315] In some embodiments, the zone or zones in which the separation is carried out are units physically separated from the reactor. Separation units or zones can be located between reactor zones, if desired. For example, a separation unit can be installed between a pyrolysis unit and a cooling unit.

[0316] The sweep gas can be introduced continuously, especially if the solids flow is continuous. If the pyrolysis reaction is operated as a batch process, the sweep gas can be introduced after a certain amount of time or periodically to remove volatiles. Even if the pyrolysis reaction is operated continuously, the sweep gas can be introduced semi-continuously or periodically, if desired, with suitable valves and controls.

[0317] The volatiles-containing sweep gas can exit one or more reactor zones or can be combined if obtained from multiple zones. The resulting gas stream containing various vapors can then be fed to a thermal oxidizer for controlled air emissions. Any known thermal oxidation unit can be used. In some embodiments, natural gas and air are fed to the thermal oxidizer to reach a temperature sufficient to substantially destroy the volatiles contained therein.

[0318] The effluent of the thermal oxidizer is a hot gas stream containing water, carbon dioxide, and nitrogen. This effluent stream can be purged directly to an air exhaust if desired. The energy content of the thermal oxidizer effluent can be recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (such as a sweep gas). The energy content can be utilized by directly or indirectly heating or assisting in heating units elsewhere in the process, such as a dryer or reactor. In some embodiments, essentially all of the thermal oxidizer effluent is used to indirectly heat (utility side) the dryer. The thermal oxidizer can use fuels other than natural gas.

[0319] The yield of carbonaceous materials may vary depending on the factors mentioned above, including the type of feedstock and process conditions. In some embodiments, the net yield of solids as a percentage of the starting material on a dry basis is at least 25%, 30%, 35%, 40%, 45%, 50% or more. The remainder is split between condensable vapors, such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and non-condensable gases, such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amount of condensable vapors compared to non-condensable gases also depends on the process conditions, including the water present.

[0320] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 65%, 70%, 75%, 80% or more. For example, in some embodiments, the carbonaceous material comprises from about 40% to about 70% of the carbon contained in the starting feedstock. The remaining carbon forms methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, tars, terpenes, alcohols, acids, aldehydes, or ketones to varying degrees.

[0321] 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 resulting gas stream from the reactor, including various vapors, can be at least partially condensed and then passed over cooled pyrolysis solids originating from a cooling zone or a separate cooling unit. These embodiments are described in more detail below.

[0322] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids may be introduced into a separate cooling unit. In some embodiments, the solids are collected and simply cooled at a slow rate. If the carbonaceous solids are reactive or unstable in air, it may be desirable to maintain an inert atmosphere or to rapidly cool the solids, e.g., to a temperature below 40° C., such as ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. "Cooling unit" should be interpreted broadly to include vessels, tanks, pipes, or portions thereof.

[0323] In some embodiments, the process further comprises operating a cooling unit to cool the warm pyrolyzed solids with steam, thereby producing low temperature pyrolyzed solids and superheated steam, and drying is performed at least in part with the superheated steam obtained from the external cooler. Optionally, the cooling unit can be operated to first cool the warm pyrolyzed solids with steam to reach a first cooling unit temperature and then with air to reach a second cooling unit temperature, the second cooling unit temperature being lower than the first cooling unit temperature and associated with a reduced risk of combustion of the warm pyrolyzed solids in the presence of air.

[0324] 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.

[0325] Some other means for screening or separation based on particle size may be included. Grinding, if present, may be upstream or downstream of grinding. A portion of the screened material (e.g., large chunks) may be returned to the grinding unit. Small and large particles may be recovered for separate downstream uses. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as a finely divided carbon or activated carbon product.

[0326] Various additives can be introduced throughout the process before, during, or after any of the steps disclosed herein. Additives can be broadly categorized as process additives selected to improve process performance, such as carbon yield or pyrolysis time / temperature to achieve a desired carbon purity, and 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) properties.

[0327] The additives can be added before, during, or after any one or more steps of the process, including adding to the feedstock itself at any time before or after the feedstock is harvested. The additive treatment can be incorporated before, during, or after sizing, drying, or other preparation of the feedstock. The additives can be incorporated into or on the feedstock supply facility, transport truck, landing equipment, storage bin, conveyor (including open or closed conveyor), dryer, process heater, or any other unit. The additives can be added anywhere in the pyrolysis process itself, using a suitable means for introducing the additives. If desired, the additives can be added after carbonization, or even after pulverization.

[0328] In some embodiments, the additive is selected from a metal, a metal oxide, a metal hydroxide, or a combination thereof. For example, the additive can be selected from, but is in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorspar, fluorospar, bentonite, calcium oxide, lime, and combinations thereof.

[0329] 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.

[0330] In some embodiments, the additive is selected from metal halides. Metal halides are compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form many compounds with metals. Metal halides are generally obtained by direct combination of basic metal salts with hydrohalic acids, or more commonly by neutralization. In some embodiments, the additive is ferric chloride (FeCl 2 or FeCl3 ), iron bromide (FeBr 2 or FeBr 3 ), their hydrates, or any combination thereof.

[0331] The additives can result in a final product with a higher energy content (energy density). The increase in energy content can result from an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content can result from the removal of non-combustible materials or materials with a lower energy density than carbon. In some embodiments, the additives reduce the extent of liquid formation in favor of the formation of solids and gases, or in favor of the formation of solids.

[0332] Without being limited to any particular hypothesis, the additives can chemically modify the starting biomass, or the treated biomass prior to pyrolysis, to reduce cell wall fracture for greater strength / integrity. In some embodiments, the additives can increase the fixed carbon content of the biomass feedstock prior to pyrolysis.

[0333] The additives may result in the bioreagent having improved mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. The additives may improve mechanical properties by simply being present (e.g., the additive itself imparts strength to the mixture) or by some transformation that occurs within the additive phase or the resulting mixture. For example, a reaction such as vitrification may occur within a portion of the bioreagent that contains the additive, thereby improving the final strength.

[0334] Chemical additives can be applied to wet or dry biomass feedstock. The additives can be applied as a solid powder, spray, mist, liquid, or vapor. In some embodiments, the additives can be introduced by spraying of a liquid solution (such as in an aqueous solution or solvent) or by immersion in a tank, bin, bag, or other container.

[0335] 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.

[0336] In some embodiments, the 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, the additives applied to the feedstock can provide desirable functionality for the intended use of the carbonaceous product.

[0337] Throughput or process capacity can vary widely from small laboratory scale units to full operations, including any pilot, demonstration, or semi-commercial scale. In various embodiments, the process capacity (of feedstock, product, or both) is at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tons are metric tons), 10 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day, or more.

[0338] In some embodiments, a portion of the solids produced may be recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the reactor. By returning to the front end and passing through the process again, the treated solids may be higher in fixed carbon. The solids, liquids, and gas streams produced or present in the process may be independently recycled, passed to a subsequent step, or removed / purged from the process at any point.

[0339] 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, a secondary process is carried out using heated inert gas (heated N 2This can be done in a simple vessel such as a steel drum through which a secondary sweep gas (such as hexane, hexanediamine, hexanediaminetetraacetate ...

[0340] Some variations include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; and (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solid-state cooler disposed in operative communication with the multi-zone reactor; and (e) a high carbon biological reagent production system comprising a high carbon biological reagent recovery unit disposed in operative communication with the solid-state cooler.

[0341] Some variations include: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; and (c) an optional preheater disposed in operative communication with the dryer and configured to heat or gently pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operative communication with the preheater and configured to pyrolyze the feedstock; (e) a cooler disposed in operative communication with the pyrolysis reactor and configured to cool the pyrolysis solids; (f) a high carbonation biological reagent recovery unit disposed in operative communication with the cooler, The system utilizes a high carbon bio-reagent production system configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0342] The feed system can be physically integrated with the multi-zone reactor, such as through the use of a screw feeder or auger mechanism to introduce the feed solids into the first reaction zone.

[0343] In some embodiments, the system further comprises a pre-heating zone disposed in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and pre-heating zone (if present) may be located in a single unit or may be located in separate units.

[0344] 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).

[0345] 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.

[0346] 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.

[0347] 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.

[0348] The gas inlets and outlets not only allow for the introduction and removal of vapors, but the gas outlets (probes) in particular allow for accurate process monitoring and control over various stages of the process, up to and potentially including all stages of the process. Accurate process monitoring is expected to result in improved yields and efficiency, both dynamically and over time, when operating history can be utilized to adjust process conditions.

[0349] In some embodiments, a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful to extract gases and analyze them to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as by adjusting the feed rate, the rate of inert gas sweep, temperature (in one or more zones), pressure (in one or more zones), additives, etc.

[0350] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more samplings via the reactive gas probe, and, optionally, making process or equipment adjustments based on the measurements, if deemed necessary or desirable, using well-known principles of process control (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0351] The reaction gas probe can be configured to extract a gas sample in many ways. For example, the sampling line can have a pressure lower than the pyrolysis reactor pressure, so that when the sampling line is opened, a quantity of gas can be easily extracted from the pyrolysis zone. The sampling line can be under vacuum, such as when the pyrolysis zone is at near atmospheric pressure. Typically, the reaction gas probe is associated with one gas output or a portion thereof (e.g., a line branched off from the gas output line).

[0352] In some embodiments, both the gas input and gas output are utilized as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with a process sample ("sample sweep"). Such configurations can be used in zones that do not have a gas inlet / outlet for a substantially inert gas for processing, or the reactive gas probe can be associated with a separate gas inlet / outlet in addition to the process inlet and outlet. The sampling inert gas that is periodically introduced and withdrawn for sampling (in embodiments utilizing a sample sweep) may be different from the process inert gas, if desired, either for reasons of analytical accuracy or to introduce an analytical tracer.

[0353] For example, the concentration of acetic acid 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.). 2 The concentration can be measured and used, for example, as an indicator of pyrolysis selectivity towards gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity towards liquids.

[0354] In some embodiments, the system further comprises at least one additional gas probe disposed in operative communication with the cooling zone, or the drying zone (if present) or the pre-heating zone (if present).

[0355] A gas probe for the cooling zone may be useful, for example, to determine the extent of any additional chemical reactions occurring in the cooling zone. A gas probe in the cooling zone may also be useful as an independent measurement of temperature (e.g., in addition to a thermocouple located in the cooling zone). This independent measurement may be a correlation between cooling temperature and a measured amount of a particular species. The correlation may be developed separately or may be established after a period of process operation.

[0356] A gas probe for the drying zone can be useful to determine the degree of drying, for example by measuring the moisture content. A gas probe in the preheat zone can be useful, for example, to determine the extent of any mild pyrolysis that occurs.

[0357] In certain embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase to the solid phase. Alternatively or additionally, the preheating zone (if present) can be configured with a gas outlet to generate a substantially countercurrent flow of the gas phase to the solid phase. Alternatively or additionally, the drying zone can be configured with a gas outlet to generate a substantially countercurrent flow.

[0358] The pyrolysis reactor or reactors can be selected from any suitable reactor configuration capable of carrying out a pyrolysis process. Exemplary reactor configurations include, but are not limited to, fixed bed reactors, fluidized bed reactors, entrained bed reactors, augers, ablation reactors, rotating cones, rotating drum kilns, calciners, roasters, moving bed reactors, transport bed reactors, ablation reactors, rotating cones, or microwave-assisted pyrolysis reactors.

[0359] 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.

[0360] In some embodiments where an ablation process is used, the feedstock is moved at high velocity relative to the hot metal surface. Ablation of any char formed on the surface can maintain a high heat transfer rate. Such an arrangement can prevent dilution of the product. Alternatively, the feedstock particles can be suspended in a carrier gas and introduced at high velocity through a cyclone with heated walls.

[0361] In some embodiments where a fluidized bed reactor is used, the feedstock may be introduced into a bed of hot sand fluidized by a gas, typically a recycled product gas. References herein to "sand" also include similar substantially inert materials such as glass particles, recovered ash particles, etc. The high rate of heat transfer from the fluidized sand may result in rapid heating of the feedstock. There may be some ablation due to friction with the sand particles. Heat is typically provided by heat exchanger tubes through which the hot combustion gases flow.

[0362] A circulating fluidized bed reactor can be used where gas, sand, and feedstock move together. Exemplary transport gases include recycled product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the feedstock, and ablation is expected to be stronger than in a conventional fluidized bed. A separator can be used to separate the product gas from the sand and char particles. The sand particles can be reheated in a fluidized burner vessel and recycled to the reactor.

[0363] In some embodiments, a multi-zone reactor is a continuous reactor comprising a feed inlet, a plurality of spatially separated reaction zones configured to separately control temperature and mixing within each of the reaction zones, and a carbonaceous solids outlet, one of the reaction zones configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the reaction zones configured with a first gas outlet.

[0364] In various embodiments, the reactor comprises at least two, three, four, or more reaction zones, each of which is disposed in communication with a separately adjustable heating means independently selected from electrical heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat transfer, or combinations thereof. In some embodiments, at least one reactor zone is heated with an effluent stream from a thermal oxidizer, if present.

[0365] 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.

[0366] 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.

[0367] In some embodiments, the feedstock inlet comprises a screw or auger feed mechanism. In some embodiments, the carbonaceous solids outlet comprises a screw or auger output mechanism.

[0368] Certain embodiments utilize a rotary calciner with a screw feeder. In these embodiments, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotational speed affects the solids flow patterns, as well as heat and mass transport. Each of the reaction zones can be configured with flights disposed on the interior walls to provide agitation of the solids. The flights can be separately adjustable in each of the reaction zones.

[0369] Other means of agitating the solids can be used, such as an auger, screw, or paddle conveyor. In some embodiments, the reactor includes a single continuous auger positioned throughout each of the reaction zones. In other embodiments, the reactor includes twin screws positioned throughout each of the reaction zones.

[0370] Some systems are specifically designed with the ability to maintain the approximate size of the feedstock throughout the process, i.e., to process the biomass feedstock without destroying or significantly damaging its structure, hi some embodiments, the pyrolysis zone does not include augers, screws, or rakes, which would tend to significantly reduce the size of the feedstock being pyrolyzed.

[0371] In some embodiments, the system further includes a thermal oxidizer disposed in operative communication with the outlet through which the condensable vapors and non-condensable gases are removed. 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 some of the condensable vapors. 4 It also oxidizes certain non-condensable gases such as CO 2 It can be.

[0372] 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 contribute significantly to the overall energy efficiency of the process.

[0373] In some embodiments, the system further comprises a carbon enrichment unit disposed in operative communication with the solids cooler and configured to combine the condensable vapors in at least partially condensed form with the solids, The carbon enrichment unit can increase the carbon content of the high carbon biological reagent obtained from the recovery unit.

[0374] 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.

[0375] 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.

[0376] Several variations regarding carbon enrichment of solids are now further described. In some embodiments, the process for producing high carbon bio-reagents includes: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the raw material to remove at least a portion of the moisture contained in the raw material; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes and at a pyrolysis temperature selected from about 250° C. to about 700° C. to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) optionally cooling the warm pyrolysis solids to produce cooler pyrolysis solids; (h) thereafter, passing at least a portion of the condensable vapors or at least a portion of the non-condensable gases from step (e) through a warm or cold pyrolytic solid to form an enhanced pyrolytic solid having an increased carbon content; (i) recovering a high carbon biological reagent comprising at least a portion of the enhanced pyrolysis solids.

[0377] In some embodiments, step (h) comprises passing at least a portion of the condensable vapors from step (e), in vapor or condensed form, through the warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gases from step (e) through the warm pyrolytic solids to produce enhanced pyrolytic solids having an increased carbon content.

[0378] Alternatively or additionally, the steam or gas may be contacted with the low temperature pyrolytic solid. In some embodiments, step (h) comprises passing at least a portion of the condensable steam from step (e), in steam or condensed form, through the low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content. In some embodiments, step (h) comprises passing at least a portion of the non-condensable gas from step (e) through the low temperature pyrolytic solid to produce an enhanced pyrolytic solid having an increased carbon content.

[0379] 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.

[0380] The process may include various methods of treating or separating the steam or gas prior to using the steam or gas for carbon enrichment. For example, the intermediate feed stream comprising at least 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 a first and a second output stream. In certain embodiments, the intermediate feed stream comprises all of the condensable steam, all of the non-condensable gas, or both.

[0381] Separation techniques may include or use distillation columns, flash vessels, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separation may be primarily based on, for example, distillation, absorption, adsorption, or diffusion and may exploit differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to a stationary phase, and any combination thereof.

[0382] 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.

[0383] Thus, in some embodiments, the first output stream includes condensable vapors and the second output stream includes non-condensable gases. The condensable vapors may include at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapors from pyrolysis may include aromatic compounds such as benzene, toluene, ethylbenzene, and xylenes. Heavier aromatic compounds such as refractory tars may be present in the vapors. The non-condensable gases may include at least one carbon-containing molecule selected from carbon monoxide, carbon dioxide, or methane.

[0384] 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.

[0385] 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.

[0386] Step (h) can increase the total carbon content of the high carbon bio-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.

[0387] In some embodiments, step (h) increases the fixed carbon content of the high carbon bio-reagent. In these or other embodiments, step (h) increases the volatile carbon content of the high carbon bio-reagent. The volatile carbon content is carbon that is attributable to volatile materials in the reagent. The 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.

[0388] Depending on the conditions associated with step (h), it is possible for some amount of the volatile carbon to become fixed carbon (e.g., via Boudouard carbon formation from CO). Typically, the volatiles enter the micropores of the fixed carbon and exist as condensed / adsorbed species, but remain relatively volatile. This residual volatility may be more advantageous for fuel applications compared to product applications requiring high surface area and porosity.

[0389] 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.

[0390] 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.

[0391] As another example, separation of acetic acid can be performed followed by reduction of the acetic acid to ethanol, which can be accomplished, at least in part, using hydrogen derived from the produced non-condensable gases.

[0392] The condensable vapors can be used either for energy in processes (such as by thermal oxidation) or for carbon enrichment to increase the carbon content of the high carbon bioreagent. 4 Certain non-condensable gases such as may be utilized for energy in the process or as part of the substantially inert gas for the pyrolysis step, as well as any combination of the foregoing.

[0393] A potential advantage of including step (h) is that the gas stream is scrubbed and the resulting gas stream is free of CO and CO. 2 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, the separation of non-condensable gases from condensable vapors allows for a CO / CO ratio. 2 The stream is prepared for use, for example, as an inert gas in a reactor system or a cooling system.

[0394] 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.

[0395] In some embodiments, a batch or continuous process for producing a high carbon bio-reagent comprises: (a) providing a solids stream comprising a carbon-containing material; (b) providing a gas stream comprising a condensable carbon-containing vapor, a non-condensable carbon-containing gas, or a mixture of a condensable carbon-containing vapor and a non-condensable carbon-containing gas; (c) passing the gas stream through the solids stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material.

[0396] In some embodiments, the starting carbon-containing material is a pyrolyzed or torrefied biomass. The gas stream can be obtained during an integrated process to provide the carbon-containing material. Or, the gas stream can be obtained from a separate processing of the carbon-containing material. The gas stream or a portion thereof can be obtained from an external source (e.g., a sawmill oven). Mixtures of gas streams from various sources are possible, as well as mixtures of carbon-containing materials.

[0397] 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.

[0398] In some embodiments, the process further includes introducing the gas stream into a separation unit configured to produce at least first and second output streams, the gas streams including a mixture of condensable carbon-containing vapors and non-condensable carbon-containing gases. The first and second output streams can be separated based on relative volatility, relative polarity, or any other characteristic. The gas streams can be obtained from separate processing of carbon-containing materials.

[0399] 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.

[0400] The carbon-containing product can have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, relative to the starting carbon-containing material.

[0401] In a related variation, the high carbon bio-reagent production system includes: (a) a feeder configured to introduce a carbon-containing feedstock; (b) an optional dryer disposed in operative communication with the feeding apparatus and configured to remove moisture contained in the carbon-containing feedstock; and (c) a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a solid-state cooler disposed in operative communication with the multi-zone reactor; and (e) a material enrichment unit disposed in operative communication with the solids cooler and configured to pass 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 operative communication with the material concentrating unit.

[0402] The system may further comprise a preheat zone disposed in operative communication with the pyrolysis zone. In some embodiments, the dryer is configured as a drying zone within the multi-zone reactor. Each of the zones may be located within a single unit or in separate units. A solids cooler may also be disposed within the multi-zone reactor.

[0403] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet, thereby producing a substantially countercurrent flow of the gas phase to the solid phase. In these or other embodiments, the preheating zone or drying zone (or dryer) is configured with a gas outlet, thereby producing a substantially countercurrent flow of the gas phase to the solid phase.

[0404] In certain embodiments, the system incorporates an ingredient enrichment unit, the ingredient enrichment unit comprising: (i) a housing having an upper portion and a lower portion; (ii) an inlet at a bottom of the lower portion of the housing configured to carry condensable vapors and non-condensable gases; (iii) an outlet at the top of the upper portion of the housing configured to carry a concentrated gas stream derived from the condensable vapors and non-condensable gases; (iv) a passageway defined between the upper and lower portions of the housing; and (v) a transport system following the pathway, the transport system configured to transport the solid, the housing being shaped such that the solid adsorbs at least a portion of the condensable vapor or at least a portion of the non-condensable gas.

[0405] This technique can produce a variety of compositions useful as high carbon bio-reagents, and products incorporating such reagents. In some variations, the high carbon bio-reagents can be prepared using any of the processes disclosed herein, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the raw material to remove at least a portion of the moisture contained in the raw material; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained in the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes and at a pyrolysis temperature selected from about 250° C. to about 700° C. to produce high temperature pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high temperature pyrolysis solids; (f) cooling the hot pyrolysis solid in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and at a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid; (g) cooling the warm pyrolysis solid to produce a cooler pyrolysis solid; (h) recovering a high carbon bio-reagent comprising at least a portion of the cold pyrolysis solids.

[0406] In some embodiments, the reagent comprises about at least 70%, at least 80%, at least 90%, or at least 95% total carbon by weight on a dry basis. Total carbon includes at least fixed carbon and may further include carbon from volatile matter. In some embodiments, carbon from volatile matter is about at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the high carbon biological reagent. For example, fixed carbon can be measured using ASTM D3172 and volatile carbon can be measured using ASTM D3175.

[0407] The high carbon bio-reagent may contain about 10% or less, e.g., about 5% or less, hydrogen by weight on a dry basis. The bio-reagent may contain about 1% or less, e.g., about 0.5% or less, nitrogen by weight on a dry basis. The bio-reagent may contain about 0.5% or less, e.g., about 0.2% or less, phosphorus by weight on a dry basis. The bio-reagent may contain about 0.2% or less, e.g., about 0.1% or less, sulfur by weight on a dry basis.

[0408] 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.

[0409] Certain embodiments provide reagents that contain little or essentially no hydrogen (except for any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture present. Thus, some embodiments provide bioreagents that have 100% or less carbon on a dry / ash-free (DAF) basis.

[0410] Generally speaking, feedstocks such as biomass contain non-volatile species, including silica and various metals, that are not readily released during pyrolysis. Ashless feedstocks can be utilized, in which case there should be no substantial amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0411] Varying amounts of non-combustible materials, such as ash, may be present. The high carbon bio-reagent may contain about 10% or less, e.g., about 5%, about 2%, about 1% or less, by weight of non-combustible materials on a dry basis. In certain embodiments, the reagent contains little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon, including 100% carbon on a dry basis.

[0412] Various amounts of moisture may be present. On a total mass basis, 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 at least on the local environment, such as relative humidity. Moisture may also vary during shipping, preparation for use, and other logistics. Moisture may be measured, for example, using ASTM D3173.

[0413] High carbon bioreagents can have a variety of energy contents, which for the present purposes means an energy density based on the higher calorific value associated with the total combustion of the bone dry reagent. For example, high carbon bioreagents can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In certain embodiments, the energy content is about 14,000-15,000 Btu / lb. Energy content can be measured, for example, using ASTM D5865.

[0414] The high carbon bio-reagent can be formed into a powder, such as a coarse or fine powder. For example, the reagent can, in embodiments, be formed into a powder having an average mesh size of about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, about 6 mesh, about 4 mesh, or about 2 mesh.

[0415] In some embodiments, the high carbon bio-reagents are formed into structures comprising compressed, bonded, or aggregated particles. The starting material for forming these bodies may be a powder form of the reagent, such as an intermediate obtained by particle size reduction. The bodies may be formed by mechanical pressing or other forces, optionally with binders or other means of agglomerating the particles together.

[0416] In some embodiments, the high carbon bio-reagent is produced in the form of a structure whose structure is substantially derived from the feedstock. For example, a feedstock chip can produce a product chip of high carbon bio-reagent. Or, a feedstock 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.

[0417] The high carbon bio-reagent may be produced or formed into an object having a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or more. In various embodiments, the minimum or maximum dimension may be a length, width, or diameter.

[0418] Other variations 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.

[0419] 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% by weight or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof.

[0420] 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.

[0421] 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% by weight or less of phosphorus; 0.2% by weight or less of sulfur; and an additive selected from an acid, a base, or a salt thereof.

[0422] 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.

[0423] In certain embodiments, the high carbon bio-reagent comprises, on a dry basis: 70% by weight or more of total carbon; 5% by weight or less of hydrogen; 1% by weight or less of nitrogen; 0.5% by weight or less of phosphorus; 0.2% by weight or less of sulfur; 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.

[0424] 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.

[0425] Some high carbon bioreagents consist essentially of, on a dry basis, 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.

[0426] Certain high carbon biological reagents consist essentially of, on a dry basis, 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.

[0427] The amount of additive (or total additives) can vary widely, such as from about 0.01% to about 25% by weight, including about 0.1%, about 1%, about 5%, about 10%, or about 20% by weight. It will be appreciated, therefore, that when relatively large amounts of additives, such as greater than about 1% by weight, are incorporated, the energy content calculated based on the total reagent weight (including additives) will be reduced. Further, in various embodiments, the high carbon bioreagent with additives can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0428] The above discussion regarding product form also applies to embodiments incorporating additives, and indeed certain embodiments incorporate additives as binders, fluxing agents, or other modifiers to enhance final properties for particular applications.

[0429] In some embodiments, the majority of the carbon contained in the high carbon bio-reagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. There may be certain market mechanisms (e.g., renewable identification numbers, tax credits, etc.) whereby value is attributed to the renewable carbon content in the high carbon bio-reagent.

[0430] 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.

[0431] The high carbon bioreagents produced as described herein are useful for a wide variety of carbonaceous products. The high carbon bioreagents 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.

[0432] In variations, the product may be obtained by the disclosed processes or may comprise any of the high carbon biological reagents described in the compositions set forth herein, or any portion, combination, or derivative thereof.

[0433] Generally speaking, the high carbon bioreagents may be combusted to produce energy (including electricity and heat); partially oxidized, gasified, or steam reformed to produce syngas; utilized for their adsorption or absorption properties; utilized for their reactive properties in metal refining (such as reduction of metal oxides) or other industrial processes; or utilized for their material properties in carbon steels and various other metal alloys. Essentially, the high carbon bioreagents may be utilized in any market application of carbon-based commodities or advanced materials, including specialized uses to be developed.

[0434] Prior to suitability or actual use in any product application, the disclosed high carbon bio-reagents can be analyzed, measured, and optionally modified (such as by additives) in a variety of ways. Some potentially important properties beyond chemical composition and energy content include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, and basicity, to name a few.

[0435] Products or materials into which these high carbon bio-reagents may 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.

[0436] Use of the disclosed high carbon bio-reagents in metal production can reduce slag, increase overall efficiency, and reduce life cycle environmental impacts. Thus, some embodiments are particularly well suited for metal processing and manufacturing.

[0437] Some variations utilize high carbon bioreagents as carbonaceous blast furnace additive 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 whose 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 the oxygen from the ore, leaving behind the elemental metal.

[0438] The reducing agent may include 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 with oxygen enrichment) is blown into the bottom of the chamber so that chemical reactions occur throughout the furnace as the material moves downward. The end products are usually molten metal and slag phases removed from the bottom, and flue gases exiting the top of the furnace. The downward flow of the ore in contact with the upward flow of hot carbon monoxide-rich gas is a countercurrent process.

[0439] The quality of carbon in a blast furnace is measured by its resistance to degradation. The role of carbon as a permeable medium is important in economical blast furnace operation. The degradation of carbon varies with position in the blast furnace and is influenced by CO 2 , H 2 O or O 2 Degraded carbon particles can cause clogging and reduced performance.

[0440] 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.

[0441] In some embodiments, the high carbon bio-reagent provides a carbon product with properties suitable for direct introduction into a blast furnace.

[0442] 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 with a CSR of at least about 50%, 60%, or 70%. The combination product can also provide a final coke product with a suitable reactivity 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 replacement for metcoal, metcoke, coke breeze, foundry coke, or injectable coal.

[0443] Some embodiments employ 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.

[0444] 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. Furthermore, additives such as those selected from alkaline earth metals, or their oxides or carbonates, can result in lower emissions (e.g., SO 2 ) can be obtained.

[0445] In some embodiments, the blast furnace replacement product is a high carbon bioreagent comprising at least about 55% carbon, about 0.5% or less sulfur, about 8% or less non-combustible materials, and a calorific value of at least about 11,000 Btu / lb. In some embodiments, the blast furnace replacement product further comprises about 0.035% or less phosphorus, about 0.5% to about 50% volatile materials, and optionally one or more additives. In some embodiments, the blast furnace replacement product comprises about 2% to about 15% dolomite, about 2% to about 15% dolomitic lime, about 2% to about 15% bentonite, or about 2% to about 15% calcium oxide by weight. In some embodiments, the blast furnace replacement product has a dimension substantially in the range of about 1 cm to about 10 cm.

[0446] In some embodiments, the high carbon bioreagent 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, no more than about 1.5% by weight volatile matter, no more than about 13% by weight ash, no more than about 8% by weight moisture, no 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.

[0447] Some variations utilize high carbon bioreagents as carbon-based taconite pellet additive products. The ores used in making iron and steel are iron oxides. The main iron oxide ores include hematite, limonite (also called brown ore), taconite, and magnetite, a black ore. Taconite is a low-grade but important ore that contains both magnetite and hematite. The iron content of taconite is generally 25% to 30% by weight. Blast furnaces typically require at least 50% iron-containing ore by weight for efficient operation. Iron ore can undergo beneficiation, including crushing, screening, tumbling, flotation, and magnetic separation. The refined ore is often concentrated to over 60% iron and formed into pellets before delivery.

[0448] For example, taconite can be ground into a fine powder and combined with a binder such as bentonite clay and limestone. For example, pellets about one centimeter in diameter containing about 65% iron by weight can be formed. The pellets are calcined to oxidize the magnetite to hematite. The pellets are durable and ensure that the blast furnace charge remains porous enough to allow heated gases to pass through and react with the pelletized ore.

[0449] The taconite pellets can be fed into a blast furnace to produce iron, as described above with respect to blast furnace additive products. In some embodiments, a high carbon bio-reagent is introduced into the blast furnace. In these or other embodiments, the high carbon bio-reagent is incorporated into the taconite pellets themselves. For example, beneficiated taconite ore powder can be mixed with high carbon bio-reagent and a binder, rolled into small bodies, and then fired until hard. In such an embodiment, taconite-carbon pellets having the appropriate composition can be conveniently introduced into a blast furnace without the need for a separate carbon source.

[0450] Some variations utilize high carbon bioagents as ladle-added carbon-based products. Ladles are containers used to transport and pour out molten metal. Casting ladles are used to pour molten metal into molds to produce castings. Transfer ladles are used to transfer large volumes of molten metal from one process to another. Processing ladles are used for processes that occur in the ladle to change some aspect of the molten metal, such as the conversion of cast iron to ductile iron by the addition of various elements to the ladle.

[0451] The high carbon bio-reagent can be introduced into any type of ladle, but typically the carbon is added to the treatment ladle in a suitable amount based on the target carbon content. The carbon injected into the ladle can be in the form of a fine powder for good mass transfer of the carbon to the final composition. In some embodiments, the high carbon bio-reagent has a minimum dimension of about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or more, when used as a ladle-added product.

[0452] In some embodiments, the high carbon bio-reagent is useful as a ladle added carbon additive, 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).

[0453] 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.

[0454] Direct reduced iron (DRI), also called sponge iron, is produced from the direct reduction of iron ore (in lump, pellet, or fine form) with reducing gases traditionally produced from natural gas or coal. The reducing gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide, which act as reducing agents. The 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.

[0455] Iron nuggets are a high quality steelmaking and iron casting feed material. Iron nuggets are essentially all iron and carbon with little gangue (slag) and low levels of metallic residuals. They are a premium grade pig iron product with excellent shipping and handling characteristics. The carbon contained in the iron nuggets or any portion thereof can be 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.

[0456] Some variations utilize high carbon bioreagents as metallurgical coke carbon-based products. Metallurgical coke, also known as "meth" coke, is a carbonaceous material typically produced by destructive distillation of various blends of bituminous coals. The final solid is unmelted carbon, called metallurgical coke. As a result of the loss of volatile gases and partial melting, metcoke has an open-porous morphology. Metcoke has a very low volatile content. However, ash components that were part of the original bituminous coal feedstock remain encapsulated in the resulting coke. Metcoke feedstock is available in a wide range of sizes, from fine powder to basketball-sized chunks. Typical purity ranges from 86-92% fixed carbon by weight.

[0457] Metallurgical coke is used wherever high quality, tough, resilient wear carbon is required. Applications include, but are not limited to, conductive flooring, friction materials (e.g., carbon linings), foundry coatings, foundry carbon risers, corrosion materials, drilling applications, reducing agents, heat treating agents, ceramic packing media, electrolytic processes, and oxygen scavenging.

[0458] Metcoke can be characterized as having a heating value of about 10,000-14,000 Btu / lb and an ash content of about 10% or more by weight. Thus, in some embodiments, the metcoke replacement product comprises a high carbon bioreagent comprising at least about 80%, 85%, or 90% by weight carbon, about 0.8% or less by weight sulfur, about 3% or less by weight volatiles, about 15% or less by weight ash, about 13% or less by weight moisture, and about 0.035% or less by weight phosphorus. The high carbon bioreagent, when used as a metcoke replacement product, can have a size range of, for example, about 2 cm to about 15 cm.

[0459] In some embodiments, the metcoke replacement product further comprises additives such as chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorospar, calcium oxide, lime, dolomitic lime, bentonite, and combinations thereof.

[0460] Some variations utilize high-carbon bio-reagent as a coal replacement product. Any process or system that uses coal can in principle be adapted to use high-carbon bio-reagent.

[0461] In some embodiments, the high-carbon bio-reagent 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 has lower emissions when combusted than the pure coal-based product.

[0462] For example, low rank coal, such as sub-bituminous coal, can be used in applications that would normally require a high rank coal product, such as bituminous coal, by combining a selected amount of high carbon bio-reagent with the low rank coal product. In other embodiments, the rank of a mixed coal product (e.g., a combination of multiple coals of different ranks) can be improved by combining the mixed coal with an amount of high carbon bio-reagent. The amount of high carbon bio-reagent mixed 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, heating value, etc.), and the desired rank of the final combined product.

[0463] For example, anthracite coal is generally characterized as having at least about 80% carbon by weight, about 0.6% sulfur by weight, about 5% volatile matter by weight, up to about 15% ash by weight, up to about 10% moisture by weight, and a heating value of about 12,494 Btu / lb. In some embodiments, the anthracite coal replacement product is a high carbon bioreagent that includes at least about 80% carbon by weight, up to about 0.6% sulfur by weight, up to about 15% ash by weight, and a heating value of at least about 12,000 Btu / lb.

[0464] In some embodiments, the high carbon bioreagent is useful as a thermal coal replacement product. Thermal coal products are generally characterized as having 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 that includes about 0.5% or less by weight sulfur, about 4% or less by weight ash, and a heating value of at least about 12,000 Btu / lb.

[0465] Some variations utilize high carbon bio-reagent as a carbon-based coking product. Any coking process or system can be adapted to use high carbon bio-reagent to produce coke or use it as a coke feedstock.

[0466] 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 comprises a high carbon bioreagent comprising at least about 50% by weight carbon, about 8% by weight or less ash, about 0.5% by weight or less sulfur, and a heating value of at least about 11,000 Btu / lb. In other embodiments, the thermal coke substitute product further comprises about 0.5% by weight to about 50% by weight volatile matter. The thermal coal or coke substitute product may comprise about 0.4% by weight to about 15% by weight moisture.

[0467] In some embodiments, the high carbon bio-reagent is useful as a petroleum (pet) coke or calcined pet coke replacement product. Calcined pet coke is generally characterized as having at least about 66% carbon by weight, up to about 4.6% sulfur by weight, up to about 5.5% volatiles by weight, up to about 19.5% ash by weight, and up to about 2% moisture by weight, and is typically about 3 mesh or less in size. In some embodiments, the calcined pet coke replacement product is a high carbon bio-reagent that includes at least about 66% carbon by weight, up to about 4.6% sulfur by weight, up to about 19.5% ash by weight, and up to about 2% moisture by weight, and is about 3 mesh or less in size.

[0468] In some embodiments, the high carbon bio-reagent is useful as a coking carbon replacement carbon (e.g., co-calcined with metallurgical coal in a coking furnace). In one embodiment, the coking carbon replacement product is a high carbon bio-reagent that includes 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 replacement product includes about 0.5% to about 50% by weight volatile materials or one or more additives.

[0469] Some variations utilize the high carbon bio-reagent as a carbon breeze product, which typically has a very fine particle size, such as 6 mm, 3 mm, 2 mm, 1 mm, or less. In some embodiments, the high carbon bio-reagent 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 bio-reagent that includes 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.

[0470] In some embodiments, the high carbon bio-reagent is useful as a carbon breeze replacement product, for example, during taconite pellet production or in the steelmaking process.

[0471] Some variations utilize the high carbon bioreagents as feedstock for various fluidized beds or as a fluidized bed carbon-based feedstock replacement product. The carbon can be used in the fluidized bed for total combustion, partial oxidation, gasification, steam reforming, etc. The carbon can be primarily converted to synthesis gas for various downstream uses including the production of energy (e.g., combined heat and power) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel fuel).

[0472] In some embodiments, the high carbon bio-reagent is useful, for example, as a fluidized bed coal replacement product in fluidized bed furnaces where coal is used (eg, for process heat or energy generation).

[0473] 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, which contribute to the degradation of metal products and cause air pollution. In some embodiments, the 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.

[0474] In some embodiments, the high carbon bio-reagent is useful as a furnace-added carbon additive wherever furnace-added carbon is used, for example, in basic oxygen furnaces or electric arc furnace facilities. For example, furnace-added carbon can be added to scrap steel during steel production in electric arc furnace facilities. In electric arc furnace applications, high purity carbon is desirable so that impurities are not returned to the process after early removal.

[0475] In some embodiments, the furnace-added carbon additive is a high-carbon bioreagent comprising at least about 80% by weight carbon, no more than about 0.5% by weight sulfur, no 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 comprises 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.

[0476] Some variations utilize the high carbon bio-reagent as a stoker furnace carbon-based product. In some embodiments, the high carbon bio-reagent 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).

[0477] Some variations utilize high carbon bio-reagent as an injectable (e.g., fine) 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 as having at least about 66% carbon by weight, about 0.55 to about 3% sulfur by weight, up to about 5.5% volatiles by weight, up to about 10% ash by weight, up to about 2% moisture by weight, and is about 6 mesh or less in size. In some embodiments, the calcined pet coke replacement product is a high carbon bio-reagent that includes at least about 66% carbon by weight, up to about 3% sulfur by weight, up to about 10% ash by weight, up to about 2% moisture by weight, and is about 6 mesh or less in size.

[0478] 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 the slag or ladle during steel production), for example, in basic oxygen furnace or electric arc furnace facilities.

[0479] In some embodiments, the high carbon bio-reagent is useful, for example, as a fine carbon replacement product wherever pulverized coal is used (e.g., for process heat or energy generation). In some embodiments, the fine pulverized coal replacement product includes up to about 10 percent calcium oxide.

[0480] Some variations utilize high carbon bioreagent as a carbon addition product for metal production. In some embodiments, the high carbon bioreagent 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, as well as high mercury levels that reduce metal quality and contribute to air pollution. In some embodiments, 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.

[0481] Some variations utilize high carbon bio-reagents in 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.

[0482] Other applications of high carbon bio-reagents in carbon electrodes include applications in 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 can be very important.

[0483] Some variations 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.

[0484] Some variations utilize the high carbon bio-reagent 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. In various embodiments, the high carbon bio-reagent provided herein can provide a superior activated carbon product due to (i) a larger surface area than fossil fuel-based activated carbon; (ii) carbon renewability; (iii) the vascularity of the biomass feedstock in combination with additives allows better penetration / distribution of additives to enhance pollutant control; and (iv) less inert material (ash) resulting in greater reactivity.

[0485] In the above description of market applications for high carbon bio-reagents, it should be recognized that the applications described are not exclusive or exhaustive. Thus, a high carbon bio-reagent described as suitable for one type of carbon product may, in various embodiments, be suitable for any other application described. These applications are exemplary only, and there are other applications for high carbon bio-reagents.

[0486] Additionally, in some embodiments, the same physical material may be used in multiple market processes, either in an integrated manner or sequence. Thus, for example, a high carbon bio-reagent 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.

[0487] Some embodiments may use the bio-reagent for its reactive or adsorptive properties, as well as for use as a fuel. For example, a bio-reagent injected into the exhaust stream may be suitable for removing contaminants and subsequently combusting the bio-reagent particles and possibly the contaminants to generate energy and thermally destroy or chemically oxidize the contaminants.

[0488] Compared to traditional fossil fuel-based products, high carbon bio-reagents can be associated with significant environmental and product use advantages: not only can high carbon bio-reagents be environmentally superior, but also functionally superior from a processing standpoint, for example, due to higher purity.

[0489] For some embodiments of metals production, production of bioreagents by the disclosed process reduces CO, CO2, CO2 emissions, and CO2 emissions compared to the coking of coal-based products required to prepare them for use in metals production. 2 , NO x , S.O. 2 , and emissions of hazardous air pollutants can be significantly lower.

[0490] The use of high carbon bioagents instead of coal or coke also reduced the SO 2 , harmful air pollutants, and mercury emissions into the environment are significantly reduced.

[0491] 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.

[0492] In some embodiments, the bio-reagent functions as activated carbon. In certain embodiments, a portion of the bio-reagent is recovered as an activated carbon product, and another portion of the bio-reagent (e.g., the remaining portion) is pelletized using a binder to produce bio-carbon pellets. In other embodiments, the bio-reagent is pelletized using a binder to produce bio-carbon pellets, and these bio-carbon pellets are delivered for later conversion to activated carbon products. Later conversion can include pulverization back to a powder, and can also include chemical treatment, for example, with steam, acid, or base. In these embodiments, the bio-carbon pellets can be considered activated carbon precursor pellets.

[0493] In certain embodiments, the fixed carbon in the bio-reagent can be used primarily to make activated carbon and the volatile carbon in the bio-reagent can be used primarily to make reducing gas. For example, at least 50% by weight, at least 90% by weight, or essentially all of the fixed carbon in the bio-reagent produced in step (b) can be recovered as activated carbon in step (f), while, for example, at least 50% by weight, at least 90% by weight, or essentially all of the volatile carbon in the bio-reagent produced in step (b) can be directed to reducing gas (e.g., via a steam reforming reaction of the volatile carbon to CO).

[0494] The activated carbon, as produced, can be characterized, for example, by an iodine value 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. In some embodiments, 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 is characterized as a (fully) renewable activated carbon, as determined from C isotope ratio measurements.

[0495] In some embodiments, the pyrolysis reactor is configured to optimize the production of different types of activated carbon. For example, reaction conditions (e.g., time, temperature, and water vapor concentration) can be selected for an activated carbon product with a particular attribute, such as iodine value. Different reaction conditions can be selected for a different activated carbon product, such as one with a higher iodine value. The pyrolysis reactor can be operated in a campaign mode to produce one product and then switched to another mode for another product. The first product may be removed continuously or periodically during the first campaign, or may be removed before switching the reaction conditions of the pyrolysis reactor.

[0496] The activated carbon can be characterized, for example, by an iodine value of at least about 500, 750, 1000, 1500, or 2000. The activated carbon is preferably 14 C / 12 The activated carbon may be characterized by a renewable carbon content of at least 90% as determined from C isotope ratio measurements. 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 is characterized as a (fully) renewable activated carbon, as determined from C isotope ratio measurements.

[0497] The activated carbon produced by the processes disclosed herein can be used in a number of ways.

[0498] In some embodiments, activated carbon 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 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 is utilized as a soil amendment to aid in the generation of new biomass, which may be the same type of biomass utilized on-site as the local feedstock.

[0499] Activated carbon prepared according to the processes disclosed herein may have the same or better properties as conventional fossil-based activated carbon. In some embodiments, the activated carbon has a surface area comparable to, equal to, or greater than that associated with fossil-based activated carbon. In some embodiments, the activated carbon can control contaminants as well as or better than conventional activated carbon products. In some embodiments, the activated carbon has an inert material (e.g., ash) level comparable to, equal to, or less than that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle size or particle size distribution comparable to, equal to, greater than, or less than that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle shape comparable to, substantially similar to, or the same as that associated with conventional activated carbon products. In some embodiments, the activated carbon has a particle shape substantially different from that associated with conventional activated carbon products. In some embodiments, the activated carbon has a pore volume comparable to, equal to, or greater than that associated with a conventional activated carbon product. In some embodiments, the activated carbon has a pore size comparable to, substantially similar to, or the same as that associated with a conventional activated carbon product. In some embodiments, the activated carbon has a particle abrasion resistance value comparable to, substantially similar to, or the same as that associated with a conventional activated carbon product. In some embodiments, the activated carbon has a hardness value comparable to, substantially similar to, or the same as that associated with a conventional activated carbon product. In some embodiments, the activated carbon has a bulk density value comparable to, substantially similar to, or the same as that associated with a conventional activated carbon product. In some embodiments, the activated carbon product has an adsorption capacity comparable to, substantially similar to, or the same as that associated with a conventional activated carbon product.

[0500] Prior to suitability or actual use in any product application, the disclosed activated carbons can be analyzed, measured, and optionally modified (such as by additives) in a variety of ways. Some properties of potential importance include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, reactivity, desulfurization activity, basicity, hardness, and iodine number.

[0501] 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.

[0502] The bulk density for bioactivated carbon can be, for example, from about 50 g / liter to about 650 g / liter.

[0503] The surface area of ​​the bioactivated carbon can vary widely. An exemplary surface area (e.g., BET surface area) is about 400 m 2 / g~about 2000m 2 / g or more, e.g., about 500m 2 / g, 600m 2 / g, 800m 2 / g, 1000m 2 / g, 1200m 2 / g, 1400m 2 / g, 1600m 2 / g, or 1800m 2 / g. Surface area generally correlates with adsorption capacity.

[0504] The pore size distribution can be important in determining the ultimate performance of the activated carbon. Pore size measurements can include micropore content, mesopore content, and macropore content.

[0505] Iodine number is a parameter used to characterize activated carbon performance. Iodine number measures the degree of activation of the carbon and is a measure of the micropore (e.g., 0-20 Å) content. It is an important measurement for liquid phase applications. Exemplary iodine numbers for activated carbon products produced by embodiments of the present disclosure include about 500, 600, 750, 900, 1000, 1100, 1200, 1300, 1500, 1600, 1750, 1900, 2000, 2100, and 2200, including all intervening ranges. The units of iodine number are milligrams of iodine per gram of carbon.

[0506] Another pore-related measurement is the Methylene Blue Number, which measures mesopore content (e.g., from 20 to 500 Å). Exemplary Methylene Blue Numbers for activated carbon products produced by embodiments of the present disclosure include about 100, 150, 200, 250, 300, 350, 400, 450, and 500, including all intervening ranges. The units of Methylene Blue Number are milligrams of methylene blue (methylthioninium chloride) per gram of carbon.

[0507] Another pore-related measurement is the Molasses Number, which measures macropore content (e.g., >500 Å). Exemplary Molasses Numbers for activated carbon products produced by embodiments of the present disclosure include 100, 150, 200, 250, 300, 350, and 400, including all intervening ranges. The units of Molasses Number are milligrams of molasses per gram of carbon.

[0508] In some embodiments, the activated carbon is at least about 0.5 cm 3 / g, e.g., at least about 1 cm 3 / g.

[0509] Activated carbon can be characterized by its water retention capacity. In various embodiments, activated carbon products produced according to embodiments of the present disclosure have a water retention capacity at 25° C. of about 10% to about 300% (weight of water divided by weight of dry activated carbon), e.g., about 50% to about 100%, e.g., about 60-80%.

[0510] Hardness or wear number is a measure of the wear resistance of activated carbon. It is an indication of the physical integrity of activated carbon to withstand frictional forces and mechanical stresses during handling or use. While some hardness is desirable, too much hardness can cause excessive equipment wear. Exemplary wear numbers measured according to ASTM D3802 range from about 1% to greater than about 99%, for example, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, or at least greater than about 99%.

[0511] In some embodiments, the activated carbon can achieve an optimum range of hardness that is moderately abrasive but does not cause wear and tear on the capital equipment that processes the activated carbon. This optimum is possible in some embodiments of the present disclosure through the selection of feedstocks and processing conditions. In some embodiments where downstream uses can handle high hardness, the processes of the present disclosure can be operated to increase or maximize hardness to produce a bioactivated carbon product having 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%.

[0512] The biogenic activated carbon provided by the present disclosure has a wide range of commercial uses. For example, but not limited to, the biogenic activated carbon can be utilized in emission control, water purification, ground water treatment, wastewater treatment, air stripper applications, PCB removal applications, odor removal applications, soil vapor extraction, manufactured gas plants, industrial water filtration, industrial fumigation, tanks and process vents, pumps, blowers, filters, pre-filters, mist filters, piping, piping modules, adsorber, absorbers, and columns.

[0513] In one embodiment, a method of using activated carbon to reduce emissions includes: (a) providing activated carbon particles comprising a bioactivated carbon composition recovered from a second reactor as disclosed herein; (b) providing a gas phase exhaust stream containing at least one selected contaminant; (c) providing an additive selected to assist in the removal of selected contaminants from the gas phase effluent stream; (d) introducing the activated carbon particles and the additive into the gas-phase exhaust stream, thereby adsorbing at least a portion of the selected contaminants onto the activated carbon particles, thereby producing contaminant-adsorbed carbon particles in the gas-phase exhaust stream; (e) separating 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.

[0514] The additive for the bioactivated carbon composition may be provided as part of the activated carbon particles. Alternatively or additionally, the additive may be introduced directly into the gas phase exhaust stream, fuel bed, or combustion zone. As will be appreciated by those skilled in the art, other methods of directly or indirectly introducing the additive into the gas phase exhaust stream for removal of selected pollutants are also possible.

[0515] The contaminant (in the gas phase exhaust stream) may be a metal, such as a metal selected from mercury, boron, selenium, arsenic, and any compound, salt, or combination 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 greater amount than a comparable amount of a 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.

[0516] A hazardous air pollutant is a pollutant that causes 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 as a possible selected pollutant in this context.

[0517] Volatile organic compounds (some of which are also hazardous air pollutants) are organic chemicals that have high vapor pressures at normal room temperature conditions. Examples include short-chain alkanes, olefins, alcohols, ketones, and aldehydes. Many volatile organic compounds are hazardous to human health or harmful to the environment. The EPA regulates volatile organic compounds in air, water, and land. The EPA definition of volatile organic compounds is found in 40 CFR section 51.100, which is incorporated herein by reference in its entirety.

[0518] A non-condensable gas is a gas that does not condense under normal room temperature conditions and may include, but is not limited to, oxides of nitrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, sulfur dioxide, sulfur trioxide, methane, ethane, ethylene, ozone, ammonia, or combinations thereof.

[0519] Multiple contaminants can be removed by the disclosed activated carbon particles. In some embodiments, the contaminant-adsorbed carbon particles include at least two contaminants, at least three contaminants, or more. Activated carbon as disclosed herein can allow for the control of multiple contaminants as well as the control of specific target contaminants (e.g., selenium).

[0520] 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.

[0521] 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, fluorspar, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, an organic acid (e.g., citric acid), or a combination thereof.

[0522] In some embodiments, the gas phase exhaust stream is derived from metal processing, such as the processing of high sulfur content metal ores.

[0523] As an exemplary embodiment for mercury control, activated carbon can be injected (such as into piping) upstream of a particulate control device such as an electrostatic precipitator or fabric filter. In some embodiments, a flue gas desulfurization (dry or wet) system can be located downstream of the activated carbon injection point. The activated carbon can be pneumatically injected as a powder. The injection location can be determined by the existing plant configuration (unless this is a new site) and whether additional downstream particulate control equipment is being modified.

[0524] For boilers currently equipped with particulate control devices, implementing bioactivated carbon injection for mercury control may involve (i) injecting powdered activated carbon upstream of the existing particulate control device (electrostatic precipitator or woven fabric filter), (ii) injecting powdered activated carbon downstream of the existing electrostatic precipitator and upstream of a retrofit woven fabric filter, or (iii) injecting powdered activated carbon between the fields of the electrostatic precipitator. The inclusion of iron or iron-containing compounds can dramatically improve the performance of electrostatic precipitators for mercury control. Additionally, the inclusion of iron or iron-containing compounds can separate spent activated carbon solids from other ash, potentially dramatically changing end-of-life options.

[0525] In some embodiments, the powdered activated carbon injection approach uses existing SO 2 Activated carbon may be used in conjunction with a control device to reduce the amount of SO2 trapped in the adsorbent, subject to the availability of a means to collect the activated carbon adsorbent downstream of the injection point. 2 Before or after the control device 2 It can be injected after the control device.

[0526] In some embodiments, the same physical material can be used in multiple processes, either in an integrated manner or sequence, so for example, activated carbon can be introduced at the end of its useful life as a performance material, into a combustion process for its energy value, or into a metal fabrication process that requires carbon but does not require the properties of activated carbon, etc.

[0527] The bioactivated carbon and principles of the present disclosure can be applied to liquid phase applications including, for example, the treatment of water, aqueous streams of various purities, solvents, liquid fuels, polymers, molten salts, and molten metals. As intended herein, "liquid phase" includes slurries, suspensions, emulsions, multi-phase systems, or any other material that has (or can be adjusted to have) at least some amount of a liquid state present.

[0528] In one embodiment, the present disclosure, in some variations, provides a method of using activated carbon to purify a liquid, comprising: (a) providing activated carbon particles recovered from a second reactor; (b) providing a liquid containing at least one selected contaminant; (c) providing an additive selected to assist in the removal of the selected contaminant from the liquid; (d) contacting the liquid with the activated carbon particles and the additive to adsorb at least a portion of the selected contaminants onto the activated carbon particles, thereby producing contaminant-adsorbing carbon particles and a contaminant-reducing liquid.

[0529] The additive may be provided as part of the activated carbon particles. Alternatively, the additive may be introduced directly into the liquid. In some embodiments, the additive (which may be the same or different) is introduced both as part of the activated carbon particles and directly into the liquid.

[0530] 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, fluorspar, fluorospar, bentonite, calcium oxide, lime, sodium hydroxide, potassium hydroxide, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, an organic acid (e.g., citric acid), or a combination thereof.

[0531] In some embodiments, the selected contaminant (in the liquid to be treated) is a metal, such as a metal selected from arsenic, boron, selenium, mercury, and any compound, salt, or combination 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-adsorbed carbon particles may include two, three, or more contaminants. In some embodiments, the activated carbon product adsorbs, absorbs, or chemisorbs the selected contaminant in greater amounts than a comparable amount of a 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 includes mercury. In some embodiments, the selected contaminant includes one or more VOCs. In some embodiments, the biogenic activated carbon includes at least about 1% hydrogen by weight or at least about 10% oxygen by weight.

[0532] The liquid to be treated may typically be aqueous, but this is not required by the principles of the present disclosure. In some embodiments, the liquid is treated with activated carbon particles in a fixed bed. In other embodiments, the liquid is treated with activated carbon particles in solution or in a moving bed.

[0533] In one embodiment, the present disclosure provides a method for removing at least a portion of a sulfur-containing contaminant from a liquid using a biogenic activated carbon composition, comprising: (a) providing activated carbon particles recovered from a second reactor as disclosed herein; (b) providing a liquid containing sulfur-containing contaminants; (c) providing an additive selected to assist in the removal of sulfur-containing contaminants from the liquid; and (d) contacting the liquid with the activated carbon particles and the additive to adsorb or absorb at least a portion of the sulfur-containing contaminants onto or within the activated carbon particles.

[0534] In some embodiments, the sulfur-containing contaminant is selected from elemental sulfur, sulfuric acid, sulfurous acid, 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, and combinations, salts, or derivatives thereof. For example, the sulfur-containing contaminant can be sulfate in an anionic or salt form.

[0535] The liquid may 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 may also be (or a portion of) a natural body of water, such as a lake, river, or stream.

[0536] In one embodiment, the present disclosure provides a process for reducing a concentration of sulfate in water, the process comprising: (a) providing activated carbon particles recovered from a second reactor as disclosed herein; (b) providing a volume or flow of water containing sulfate; (c) providing an additive selected to assist in the removal of sulfates from the water; and (d) contacting the water with the activated carbon particles and the additive to adsorb or absorb at least a portion of the sulfate onto or into the activated carbon particles.

[0537] 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 anion. Depending on the pH, sulfate can also be present in the form of sulfate.

[0538] The water may be derived from some or all of a wastewater stream. Exemplary wastewater streams may be associated with metal mining, acid mine drainage, mineral processing, municipal sewage treatment, pulp and paper, ethanol, or any other industrial process that may discharge sulfur-containing contaminants into the wastewater. The water may be a natural body of water, such as a lake, river, or stream. In some embodiments, the process is performed continuously. In other embodiments, the process is performed in batches.

[0539] When treating water with activated carbon, there may be water filtration, water permeation, or direct addition of activated carbon particles to the water (with sedimentation, clarification, etc.). When using permeation, activated carbon can be used in several ways within or to assist the permeation device. In some embodiments, activated carbon particles and additives are introduced directly into the water prior to permeation. Activated carbon particles and additives are optionally used in pre-filtration prior to permeation. In certain embodiments, activated carbon particles and additives are incorporated into the membrane for permeation.

[0540] The present disclosure also provides a method of using a biogenic activated carbon composition for removing sulfur-containing contaminants from a gas phase, comprising: (a) providing activated carbon particles recovered from a second reactor as disclosed herein; (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 exhaust stream; and (d) introducing activated carbon 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 particles from the gas-phase exhaust stream.

[0541] In some embodiments, the sulfur-containing contaminant is selected from elemental sulfur, sulfuric acid, sulfurous acid, 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 combinations, salts, or derivatives thereof.

[0542] Generally speaking, the disclosed activated carbon can be used in any application where conventional activated carbon may be used. In some embodiments, the activated carbon is used as a total (i.e., 100%) replacement for conventional activated carbon. In some embodiments, the activated carbon comprises essentially all or substantially all of the activated carbon used in a particular application. In some embodiments, the activated carbon comprises about 1% to about 100% bioactivated carbon.

[0543] For example, but not by way of limitation, activated carbon can be used in filters, either alone or in combination with conventional activated carbon products. In some embodiments, a packed bed or packed column contains the disclosed activated carbon. In such embodiments, the biogenic activated carbon has size characteristics suitable for a particular packed bed or packed column. Injection of biogenic activated carbon into gas streams can be useful for controlling pollutant emissions in gas or liquid streams from coal-fired power plants, biomass-fired power plants, metal processing plants, crude oil refineries, chemical plants, polymer plants, pulp and paper plants, cement plants, waste incinerators, food processing plants, gasification plants, and syngas plants.

[0544] Use of biocarbon in metal oxide reduction There are various embodiments in which carbon negative biocarbon, such as in pellet form or in its pulverized form, is fed to a metal ore furnace or a chemical reduction furnace. See, for example, Figures 2 and 3.

[0545] The metal ore furnace or chemical reduction furnace may be a blast furnace, a top gas recirculating blast furnace, a shaft furnace, a reverberatory furnace (also known as an air furnace), a crucible furnace, a silencer furnace, a retort furnace, a flash furnace, a Tecnored furnace, an Ausmelt furnace, an ISASMELT furnace, a puddle furnace, a bogie hearth furnace, a continuous chain furnace, a pusher furnace, a rotary hearth furnace, a walking beam furnace, an electric arc furnace, an induction furnace, a basic oxygen furnace, a puddle furnace, a Bessemer furnace, a direct reduction metal furnace, or a combination or derivative thereof.

[0546] Metal ore furnaces or chemical reduction furnaces can be arranged horizontally, vertically, or inclined. The flow of solids and fluids (liquid or gas) can be co-current or counter-current. The solids in the furnace can be in a fixed bed or a fluidized bed. Metal ore furnaces or chemical reduction furnaces can be operated at a variety of process conditions of temperature, pressure, and residence time.

[0547] Some variations relate specifically to blast furnaces. A blast furnace is a type of metallurgical furnace used in smelting to produce industrial metals such as iron or copper. Blast furnaces are utilized in smelting iron ore to produce pig iron, an intermediate material used in commercial iron and steel production. Blast furnaces are also used in conjunction with sintering plants, for example, in base metal smelting.

[0548] The term "blast" refers to the forced or fed combustion air above atmospheric pressure. In a blast furnace, metal ore, carbon (e.g., in this disclosure, bioagents or their derivatives), and usually flux (e.g., limestone) are continuously fed through the top of the furnace, while a hot blast of air (optionally with oxygen enrichment) is blown into the lower part of the furnace through a series of pipes called tuyere. Chemical reduction reactions occur throughout the furnace as the material falls downward. The end products are usually molten metal and slag phases removed from the bottom, and waste gases (reduced off-gas) exiting the top of the furnace. The downward flow of metal ore along with the flux in countercurrent contact with the upward flow of hot CO rich gas allows for efficient chemical reactions that reduce the metal ore to metal.

[0549] Air furnaces (such as reverberatory furnaces) are usually naturally aspirated by convection of hot gases in the chimney flue. According to this broad definition, bloomery furnaces for iron, blowing houses for tin, and smelting plants for lead are classified as blast furnaces.

[0550] Blast furnaces remain an important part of modern iron production. Modern furnaces are highly efficient and include cowper stoves that preheat the incoming blast air with waste heat from the flue gases, and recovery systems that extract heat from the hot gases leaving the furnace. Blast furnaces are typically built in the form of tall structures lined with refractory bricks and contoured to expand as the feed material heats on its descent, then reduce in size as melting begins to occur.

[0551] In some embodiments for iron production, bio-carbon pellets, iron ore (iron oxide), and limestone flux are charged to the top of a blast furnace. The iron ore or limestone flux can be incorporated into the bio-carbon pellets. Optionally, the bio-carbon pellets are reduced in size before being fed to the blast furnace. For example, the bio-carbon pellets can be pulverized into a powder that is fed to the blast furnace.

[0552] A blast furnace may be configured to allow hot, dirty gases with high carbon monoxide content to exit the furnace throat, while a bleeder valve may protect the top of the furnace from sudden gas pressure surges. Coarse particles in the exhaust gases may settle and be disposed of, while the gases may flow through a venturi scrubber or electrostatic precipitator or gas cooler to reduce the temperature of the cleaned gases. A casting chamber at the bottom of the furnace includes equipment for casting liquid iron and slag. A tap hole may be drilled into the refractory plug so that the liquid iron and slag flow down the launder through the opening, separating the iron and slag. Once the pig iron and slag have been tapped, the tap hole may be plugged with fireclay. A nozzle called a tuyere is used to supply hot air to increase the efficiency of the blast furnace. The hot air is directed into the furnace through a cooled tuyere near the base. The hot air temperature may be, for example, about 900°C to 1300°C (air temperature). The temperature in the blast furnace can be at least about 2000° C. or higher. Other carbonaceous materials or oxygen can also be injected into the furnace at the tuyere level to combine with the carbon (from the bio-carbon pellets) to release additional energy and increase the percentage of reducing gas present, which increases productivity.

[0553] Blast furnaces operate on the principle of chemical reduction, where carbon monoxide, which has a stronger affinity for oxygen in metal ores (e.g., iron ore) than the corresponding metals, reduces the metals to their elemental forms. Blast furnaces differ from bloomery and reverberatory furnaces in that in a blast furnace, the flue gases come into direct contact with the ore and metal, diffusing the carbon monoxide into the ore and reducing the metal oxides to elemental metal mixed with carbon. Blast furnaces usually operate as a continuous countercurrent exchange process.

[0554] Silica is usually removed from the pig iron. It reacts with calcium oxide to form silicates, which float to the surface of the molten pig iron as slag. The downward moving column of metal ores, fluxes, carbon, and reaction products must be porous enough to allow the flue gases to pass through. This requires that the bioreagent carbon be particles large enough (e.g., biocarbon pellets or smaller objects derived from pellets) to be permeable. Thus, the pellets or crushed pellets must be strong enough not to be crushed by the weight of the material above them. In addition to the physical strength of the carbon, it can also be low in sulfur, phosphorus, and ash.

[0555] Many chemical reactions take place in a blast furnace. The chemical reactions start with hematite (Fe 2 O 3 This form of iron oxide is common in iron ore processing, either in the initial feedstock or as produced in the blast furnace. Other forms of iron ore (e.g., taconite) contain varying concentrations of different iron oxides (Fe 3 O 4 , Fe 2 O 3 , FeO, etc.

[0556] The main overall chemical reactions producing molten iron in a blast furnace are as follows: Fe 2 O 3 +3CO → 2Fe+3CO 2 This is an endothermic reaction. The entire reaction occurs in many steps, the first of which is that the preheated blast air blown into the furnace reacts with carbon (e.g., from the biocarbon pellets) to produce carbon monoxide and heat: 2C+O 2 →2CO Hot carbon monoxide is a reducing agent for the iron ore and reacts with the iron oxide to produce molten iron and carbon dioxide. Depending on the temperature in different parts of the furnace (typically highest at the bottom), the iron is reduced in several steps. At the top, where temperatures usually range from 200 to 700 °C, the iron oxide is reduced to ferric oxide (II, III) Fe 3 O 4 is partially reduced to: 3Fe 2 O 3 +CO→2Fe 3 O 4 +CO 2 Further down the furnace, at a temperature of about 850° C., the iron (II,III) is further reduced to iron (II) oxide, FeO: Fe 3 O 4 +CO→3FeO+CO 2 Hot carbon dioxide, unreacted carbon monoxide, and nitrogen from the air pass upwardly through the furnace as fresh feed material moves downward into the reaction zone. As the material moves downward, countercurrent gas preheats the feed charge and decomposes limestone (if used) into calcium oxide and carbon dioxide: CaCO 3 →CaO+CO 2 The calcium oxide formed by decomposition reacts with various acidic impurities in the iron (especially silica) to form mainly calcium silicate, CaSiO 3 Form a slug that is: SiO 2 +CaO → CaSiO 3 As the FeO moves into the higher temperature region, up to the 1200°C range, the FeO is further reduced to iron metal, again using carbon monoxide as a reactant: FeO+CO→Fe+CO 2 The carbon dioxide formed in this process can be converted back to carbon monoxide by reacting it with carbon via the reverse Boudouard reaction: C+CO 2 →2CO

[0557] It is important to note that in the chemical reactions shown above, the reducing gas can alternatively or additionally be introduced directly into the blast furnace rather than being an in situ product in the furnace. Typically, in these embodiments, the reducing gas includes both hydrogen and carbon monoxide, both of which function to chemically reduce metal oxides. Optionally, the reducing gas can be produced separately from the bio-carbon pellets by reforming, gasification, or partial oxidation.

[0558] In a conventional blast furnace, there is no hydrogen available to cause the reduction of metal oxides. In the present disclosure, hydrogen can be directly injected into the blast furnace. Alternatively or additionally, hydrogen may be available within the bio-carbon pellets fed to the blast furnace if the bio-carbon pellets contain volatile carbon (e.g., heavy tar components) associated with hydrogen. Alternatively or additionally, hydrogen may be available within the bio-carbon pellets fed to the blast furnace if the bio-carbon pellets contain volatile carbon (e.g., heavy tar components) associated with hydrogen. 2 O and CO react to produce H 2 and CO 2 Hydrogen can be available as a result of the water gas shift to produce CO or from the steam reforming reaction of carbon. Either of these reactions (water gas shift or steam reforming) can be assisted by moisture coming in with the biocarbon (e.g., carbon negative biocarbon pellets). Hydrogen can be obtained by the same process as above but converting CO to H 2 Additional reduction reactions can be induced by replacing: 3Fe 2 O 3 +H 2 →2Fe 3 O 4 +H 2 O Fe 3 O 4 +4H 2 →3Fe+4H2 O These reactions occur in parallel with reduction reactions with CO. Hydrogen can also react with carbon dioxide in a reverse water gas shift reaction to produce more CO. In one particular embodiment, a reducing gas consisting essentially of hydrogen is fed to the blast furnace.

[0559] "Pig iron" produced by blast furnaces typically has a relatively high carbon content, around 3-6% by weight. Pig iron can be used to make cast iron. The pig iron produced by blast furnaces usually undergoes further processing to reduce the carbon and sulfur content and to produce the various grades of steel used commercially. In a further process step called basic oxygen steelmaking, the carbon is oxidized by blowing oxygen into the liquid pig iron to form crude steel.

[0560] Desulfurization is conventionally performed during transportation of liquid iron to the steel mill by adding calcium oxide, which reacts with the iron sulfides contained in the pig iron to form calcium sulfide. In some embodiments, desulfurization can also occur in the furnace or downstream of the furnace by reacting the metal sulfides with CO (in the reducing gas) to form metal and carbonyl sulfide, CSO. In these or other embodiments, desulfurization can also occur in the furnace by reacting the metal sulfides with H (in the reducing gas) to form calcium sulfide. 2 reacting with metals and hydrogen sulfide H 2 The formation of S can occur in the furnace or downstream of the furnace.

[0561] Other types of furnaces can use other chemical reactions. It will be understood that in chemical conversion of metal oxides to metals using carbon or reducing gas in the conversion, the carbon can be renewable carbon. The present disclosure provides renewable carbon in bioreagents produced via pyrolysis of biomass. In certain embodiments, some carbon utilized in the furnace is not renewable carbon. In various embodiments, the percentage of renewable carbon of the total carbon consumed in the metal ore furnace can be at least about 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%.

[0562] In some variations, a Tecnored furnace, or a variation thereof, is utilized. The Tecnored process was originally developed by Tecnored Desenvolvimento Tecnologico SA in Brazil and is based on a low-pressure moving bed reduction furnace that reduces cold-bonded, carbon-containing, autogenous, and self-reducing pellets. Reduction is carried out in a low-profile shaft furnace at typical reduction temperatures. The process produces hot metal (typically liquid iron) with high efficiency.

[0563] The Tecnored technology was developed to be a cokeless steelmaking process, thus avoiding the investment and operation of environmentally harmful coke ovens, in addition to significantly reducing greenhouse gas emissions in the production of hot metal. The Tecnored process uses a combination of hot and cold blasting and does not require additional oxygen. It eliminates the need for coke plants, sinter plants, and tonnage oxygen plants. The process therefore has much lower operating and investment costs than those of the traditional steelmaking route.

[0564] In this disclosure, the Tecnored process can be adapted for use with bio-reagents in a variety of ways. Some embodiments provide self-reducing aggregates (e.g., bio-carbon pellets) produced from iron ore fines or iron-bearing residues plus a bio-reagent. These materials, mixed with fluxing and binders, are agglomerated and thermally hardened to produce bio-carbon pellets with sufficient strength for the physical and metallurgical demands of the Tecnored process. The produced aggregates are then smelted in a Tecnored furnace. The fuel for the Tecnored furnace can also be the bio-carbon pellets themselves.

[0565] By combining fine particles of iron oxide with the reducing agent within the briquette, the surface area of ​​the oxide in contact with the reducing agent and therefore the reaction rate is dramatically increased. The autoreduced briquette can be designed to contain sufficient reducing agent to fully reduce the iron-bearing raw material contained therein, and optionally, a desired flux can be used to provide slag chemistry. The autoreduced briquette is hardened at low temperature before being fed into the furnace. The heat required to drive the reaction within the autoreduced briquette is provided by a bed of solid fuel, which can also be in the form of briquettes, onto which the autoreduced briquette is fed into the furnace.

[0566] The Tecnored furnace has three zones: (i) the upper shaft zone, (ii) the melting zone, and (iii) the lower shaft zone. The upper shaft zone is where the bioreagent, a solid fuel, is charged. In this zone, the Boudouard reaction (C+CO 2 →2CO) is prevented, thereby saving energy. Post-combustion in this zone of the furnace burns the CO, which provides the energy for pre-heating and reduction of the charge. Inside the pellets the following reactions take place at a very fast rate: Fe x O y +yCO →xFe+yCO 2 yCO 2 +yC=2yCO In the formula, x is 1 to typically 5, and y is 1 to typically 7.

[0567] In the melting zone, reoxidation is prevented by the reducing atmosphere in the charge. Melting of the charge occurs under a reducing atmosphere. In the lower shaft zone, solid fuel is charged. The solid fuel may include, or in some embodiments consists essentially of, biocarbon pellets. In this zone, further reduction of residual iron oxide and slagging reactions of gangue material and fuel ash occur in the liquid state. Also, superheating of metal and slag droplets occurs. These superheated metal and slag droplets sink by gravity to the hearth of the furnace and accumulate there.

[0568] This modified Tecnored process uses two different inputs of carbon units: a reductant and a solid fuel. The reductant is traditionally coal fines, but in this disclosure, the reductant may include finely ground bio-carbon pellets. The self-reducing aggregates may be bio-carbon pellets as disclosed herein. The amount of carbon fines required is established by the C / F (carbon to ore fines) ratio, which can be selected to achieve complete reduction of the metal oxides.

[0569] The solid fuel does not have to be in the form of a fine powder. For example, the solid fuel can be in the form of chunks, such as about 40-80 mm in size, to address the physical and thermal needs required from the solid fuel in the Tecnored process. These chunks can be made by breaking down (e.g., crushing) biocarbon pellets, but not completely pulverizing them. The solid fuel is loaded through a side feeder (to avoid the endothermic Boudoir reaction in the upper shaft) and provides the majority of the energy required by the process. This energy is generated in the primary blast (C+O 2 →CO 2 ) and the upstream CO formed by the secondary blast and produced by gasification of solid fuel in the hearth is burned (2CO+O 2 →2CO 2 ).

[0570] In one particular exemplary embodiment, the modified Tecnored process involves pelletizing iron ore fines having a size less than 140 mesh, bio-reactant fines having a size less than 200 mesh, and flux such as hydrated lime having a size less than 140 mesh using cement as a binder. The pellets are hardened and dried at 200°C before being fed to the top of the Tecnored furnace. The total residence time of the charge in the furnace is about 30-40 minutes. Bio-reagents in the form of solid fuels in the size range of 40mm-80mm are fed into the furnace below the hot pellet area using a side feeder. Hot blast air at about 1150°C blows through tuyeres located on the sides of the furnace to provide combustion air for the bio-carbon. A small amount of furnace gas is flowed through the side feeder for use in drying and pre-heating the solid fuel. Low temperature blast air blows at a higher point to promote post-combustion of CO in the upper shaft. The produced molten iron is tapped into a ladle on a ladle cart, which can tilt the ladle for slag removal. The liquid iron is optionally desulfurized in the ladle, and the slag is scraped into a slag pot. The molten iron typically contains about 3-5% carbon by weight.

[0571] Conventionally, external CO or H 2 does not play a significant role in the autoreduction process using the Tecnored furnace. However, in the context of this disclosure, external H 2 or CO (from the reducing gas) reacts with Fe x O y +yCO →xFe+yCO 2 ) or in reaction with hydrogen as a reactant (Fe x O y +yH 2 →xFe+yH 2O) can aid in the overall chemical reaction by increasing the rate or conversion of iron oxide. The reduction chemical reaction can be aided at least at the surface of the pellets or briquettes and possibly within the bulk phase of the pellets or briquettes due to the fast mass transfer of the hot reducing gas. Some embodiments of the present disclosure combine aspects of the blast furnace with aspects of the Tecnored furnace, whereby self-reducing pellets or briquettes are utilized in addition to the use of reducing gas in the furnace.

[0572] As mentioned, there are many possible furnace configurations for metal ore processing, and while this specification does not detail the various conditions and chemical reactions that may occur in every possible furnace, it will be understood by those skilled in the art that the principles of the present technology may be applied to essentially any furnace or process that uses carbon somewhere in the process of making metals from metal ores.

[0573] It will also be observed that some processes utilize bio-carbon pellets, some utilize reducing gas, and some utilize both bio-carbon pellets and reducing gas. The processes provided herein can produce both solid bio-carbon pellets and reducing gas. In some embodiments, only solid bio-carbon pellets are used in the metal ore conversion process. In other embodiments, only reducing gas is used in the metal ore conversion process. In still other embodiments, both bio-carbon pellets and reducing gas are used in the metal ore conversion process. In those embodiments using both sources of renewable carbon, the percentage of total carbon usage in the metal ore conversion from reducing gas can be about, at least about, or up to about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 100%. The other carbon usage can be from bio-carbon pellets. Alternatively, some or all of the other carbon usage can be from traditional carbon inputs such as coal fines.

[0574] Conversion of biocarbon into reducing gases Some variations use carbon-negative bio-carbon (e.g., bio-carbon pellets) to produce a carbon-negative reducing gas (e.g., carbon-negative syngas or carbon-negative hydrogen) that can be utilized on-site in a process (e.g., a metals manufacturing process) or can be captured and sold.

[0575] The optional generation of a reducing gas (also referred to herein as a "bio-reductant gas") will now be further described with reference to carbon-negative bio-carbon in the form of bio-carbon pellets, it being understood that these are non-limiting embodiments and that the carbon-negative bio-carbon can be in powder form, slurry form, or another form.

[0576] The conversion of the biocarbon pellets to a reducing gas takes place in a reactor that can be referred to as a bioreductant formation unit. A reactant is used to react with the biocarbon to produce a reducing gas. The reactant can be selected from oxygen, water vapor, or a combination thereof. In some embodiments, oxygen is mixed with water vapor and the resulting mixture is added to a second reactor. Oxygen or oxygen-enriched air is added to cause an exothermic reaction such as partial or total oxidation of carbon with oxygen; or H, which is more preferred in the reducing gas. 2 (iii) increase the yield of reducing gas; or (iv) achieve a desired ratio of CO 2 The purity of the reducing gas can be increased by reducing the amount of pyrolysis products, tars, aromatics, or other undesirable products.

[0577] In some embodiments, water vapor is the preferred reactant. Water vapor (i.e., H in the vapor phase) 2 O) can be introduced into the reactor in one or more input streams. The water vapor can include water vapor generated by moisture contained in the biocarbon pellets, as well as water vapor generated by any chemical reaction that produces water.

[0578] All references herein to "ratios" of chemical species are references to molar ratios unless otherwise indicated. For example, H 2 The / CO ratio means one mole of hydrogen per mole of carbon dioxide.

[0579] Steam reforming, partial oxidation, water gas shift (WGS), or combustion reactions can occur when oxygen or steam is added. Exemplary reactions can be seen, for example, in the reaction of cellulose repeat units (C 6 H 10 O 5 ) is shown below. Similar reactions can occur with any carbon-containing feedstock, including biocarbon pellets. [Table 1]

[0580] The bioreductant formation unit is any reactor capable of causing at least one chemical reaction that produces a reducing gas. Conventional steam reformers known in the art can be used with or without a catalyst. Other possibi...

Claims

**Claim 1** A negative water source unit method for manufacturing a biocarbon product, the method comprising: providing a raw material comprising biomass and at least 0 wt% to a maximum of 75 wt% water; drying the raw material, thereby producing a dried raw material and a first vapor, wherein the dried raw material comprises at least 0 wt% to a maximum of 50 wt% water, said drying; pyrolyzing the dried raw material, thereby producing a high-temperature solid and a second vapor; producing acidic water, condensing at least a portion of the first vapor, thereby producing a first condensed liquid, wherein the first condensed liquid has a first pH of at least 1 to a maximum of 7, said condensing, and condensing at least a portion of the second vapor, thereby producing a second condensed liquid, wherein the second condensed liquid has a second pH of at least 1 to a maximum of 7, said condensing, wherein producing the acidic water comprises the acidic water comprising at least a portion of the first condensed liquid, at least a portion of the second condensed liquid, or a mixture thereof; washing and cooling the high-temperature solid, achieved using the acidic water, thereby producing a washed and cooled solid, said washing and cooling, and recovering the washed and cooled solid as a biocarbon product, wherein the biocarbon product comprises at least 50 wt% carbon, said recovering, wherein the method, wherein the biocarbon product has a water source unit defined as the number of kilograms of external water utilized divided by the metric ton of the biocarbon product. **Claim 2** The negative water source unit method according to claim 1, wherein the dried raw material comprises at least 0 wt% to a maximum of 25 wt% water, or the dried raw material comprises a maximum of 10 wt% water. **Claim 3** The negative water source unit method according to claim 1, wherein the first pH is at least 2 to a maximum of 7, at least 3 to a maximum of 6.5, or at least 4 to a maximum of 6.

5. **Claim 4** The negative water source unit method according to claim 1, wherein the second pH is at least 2 to a maximum of 7, at least 3 to a maximum of 6.5, or at least 4 to a maximum of 6.

5. **Claim 5** The method for producing negative hydrogen water unit according to claim 1, wherein the first pH is at most 7 and the second pH is at most 7, the first pH is at most 7 and the second pH is 7, or the second pH is at most 7 and the first pH is 7.

6. The acidic water contains the first condensed liquid and does not contain the second condensed liquid. It contains the second condensed liquid and does not contain the first condensed liquid. It contains the first condensed liquid and the second condensed liquid. It contains the whole of the first condensed liquid produced. It contains the whole of the second condensed liquid produced, or The method for producing negative hydrogen water unit according to claim 1, which contains the whole of the first condensed liquid produced and the whole of the second condensed liquid produced.

7. The step of producing the acidic water includes producing at least 1 to a maximum of 500 gallons of acidic water per dry metric ton of the raw material 1, or producing at least 50 to a maximum of 100 gallons of acidic water per dry metric ton of the raw material 1. The method for producing negative hydrogen water unit according to claim 1.

8. The method according to claim 1 further includes recovering a part of the acidic water as a water co-product.

9. The washing and cooling are achieved using a water supply source that consists essentially of the acidic water. The method for producing negative hydrogen water unit according to claim 1.

10. The high-temperature solid is characterized by a substrate temperature of at least 300°C to a maximum of 800°C, and the washed and cooled solid is characterized by a cooling substrate temperature lower than the substrate temperature. Optionally, the cooling substrate temperature is at most 300°C, at most 200°C, at most 100°C, or at most 50°C. The method for producing negative hydrogen water unit according to claim 1.

11. The washing and cooling include removing ash from the high-temperature solid. Optionally, the washed and cooled solid contains a total ash of at most 5 wt%, at most 1 wt%, or at most 0.2 wt% after the removal. The method for producing negative hydrogen water unit according to claim 1.

12. The washing and cooling includes removing impurities selected from aluminum, aluminum oxide, antimony, arsenic, barium, beryllium, boron, boron oxide, bromine, cadmium, calcium, chlorine, chromium, cobalt, copper, fluorine, gold, iron, iron oxide, lead, lithium, magnesium, manganese, mercury, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silicon oxide, silver, sodium, strontium, sulfur, tellurium, thallium, tin, titanium, titanium oxide, tungsten, vanadium, zinc, zirconium, or combinations thereof, and optionally, after the removal, the washed and cooled solid contains at most 1000 ppm of the impurity, at most 100 ppm of the impurity, or at most 50 ppm of the impurity. The negative water source unit method according to claim 1.

13. The washed and cooled solid has a calorific value of at least 22 MJ / kg on a dry basis, or at least 33 MJ / kg on a dry basis. The negative water source unit method according to claim 1.

14. The method does not utilize external water. The negative water source unit method according to claim 1.

15. The maximum water source unit is -10 kgH per metric ton of the bio-carbon product ２ O, the maximum -100 kgH per metric ton of the bio-carbon product ２ O, the maximum -200 kgH per metric ton of the bio-carbon product ２ O, the maximum -500 kgH per metric ton of the bio-carbon product ２ O, or the maximum -1000 kgH per metric ton of the bio-carbon product ２ O, The negative water source unit method according to any one of claims 1 to 14.

16. The bio-carbon product has a maximum of 0 kg CO per metric ton of the bio-carbon product ２ e, a maximum of -100 kg CO per metric ton of the bio-carbon product ２ e, a maximum of -200 kg CO per metric ton of the bio-carbon product ２ e, a maximum of -300 kg CO per metric ton of the bio-carbon product ２ e, a maximum of -400 kg CO per metric ton of the bio-carbon product ２ e, or a maximum of -500 kg CO per metric ton of the bio-carbon product ２ e in terms of carbon units, the negative water unit method according to any one of claims 1 to 14.

17. The bio-carbon product contains total carbon, and the total carbon is determined from the measurement of the C / １４ C / １２ C isotope ratio, with at least 90% being bio-carbon, or the total carbon is determined from the measurement of the C / １４ C / １２ C isotope ratio and is 100% bio-carbon. The method of negative water source unit according to any one of claims 1 to 14.

18. A biocarbon product manufactured by the negative water source unit method according to any one of claims 1 to 14, optionally comprising total carbon, wherein the total carbon is determined from the measurement of the １４ C / １２ C isotope ratio and at least 90% is biogenic carbon, said biocarbon product.

19. The bio-carbon product contains total carbon, and the total carbon is determined from the measurement of the C / １２ C isotope ratio, and at least 90% is biogenic carbon, the bio-carbon product according to claim 18. １４ C / １２ C isotope ratio, and at least 90% is biogenic carbon, the bio-carbon product according to claim 18.

20. A low water source unit method for producing a biocarbon product, the method comprising providing a raw material containing biomass and at least 0 wt% to a maximum of 75 wt% of water, optionally drying the raw material, thereby producing a dried raw material and a first vapor, wherein the dried raw material contains at least 0 wt% to a maximum of 50 wt% of water, the drying, pyrolyzing the raw material or the dried raw material, thereby producing a high-temperature solid and a second vapor, producing acidic water, optionally condensing at least a portion of the first vapor, thereby producing a first condensed liquid, wherein the first condensed liquid has a first pH of at least 1 to a maximum of 7, the condensing, or Condensing at least a portion of the second vapor, thereby producing a second condensed liquid, wherein the second condensed liquid has a second pH of at least 1 to a maximum of 7, said condensing, and producing the acidic water, wherein the acidic water comprises at least a portion of the second condensed liquid, at least a portion of the first condensed liquid, or a mixture thereof. Washing and cooling the high-temperature solid, achieved using the acidic water, thereby producing a washed and cooled solid, said washing and cooling, and Recovering the washed and cooled solid as a biochar product, wherein the biochar product contains at least 50 wt% carbon, said recovering, including The low water source unit method, wherein the biochar product has a water source unit defined as the number of kilograms of external water utilized divided by the metric ton of the biochar product.

21. Performing drying of the raw material, wherein the dried raw material contains at least 0 wt% to a maximum of 25 wt% water, preferably, the dried raw material contains at least 0 wt% to a maximum of 10 wt% water, the low water source unit method according to claim 20.

22. The first pH is at least 2 to a maximum of 7, or at least 3 to a maximum of 6.5, The second pH is at least 2 to a maximum of 7, or at least 3 to a maximum of 6.5, or The first pH is at most 7 and the second pH is at most 7, the low water source unit method according to claim 20.

23. The acidic water Contains the first condensed liquid and does not contain the second condensed liquid, Contains the second condensed liquid and does not contain the first condensed liquid, Contains the first condensed liquid and the second condensed liquid, Contains the entire first condensed liquid, Contains the entire second condensed liquid, or Contains the entire first condensed liquid and the entire second condensed liquid, the low water source unit method according to claim 20.

24. The step of producing the acidic water includes producing at least 1 to a maximum of 500 gallons of acidic water per dry metric ton of the raw material 1, the low water source unit method according to claim 20.

25. The method further includes recovering a portion of the acidic water as a water co-product, the low water source unit method according to claim 20. Claim 26 The method of low water source unit according to claim 20, wherein the washing and cooling are achieved using a water supply source, and the water supply source consists essentially of the acidic water. Claim 27 The method of low water source unit according to claim 20, wherein the high-temperature solid is characterized by a substrate temperature of at least 300 °C to a maximum of 800 °C, and the washed and cooled solid is characterized by a cooled substrate temperature below the substrate temperature, and optionally, the cooled substrate temperature is a maximum of 100 °C, or a maximum of 50 °C. Claim 28 The method of low water source unit according to claim 20, wherein the washing and cooling include removing ash from the high-temperature solid, and optionally, the washed and cooled solid contains a maximum of 1 wt% total ash, or a maximum of 0.2 wt% total ash after the removal. Claim 29 The method of low water source unit according to claim 20, wherein the washing and cooling include removing impurities selected from aluminum, aluminum oxide, antimony, arsenic, barium, beryllium, boron, boron oxide, bromine, cadmium, calcium, chlorine, chromium, cobalt, copper, fluorine, gold, iron, iron oxide, lead, lithium, magnesium, manganese, mercury, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silicon oxide, silver, sodium, strontium, sulfur, tellurium, thallium, tin, titanium, titanium oxide, tungsten, vanadium, zinc, zirconium, or combinations thereof, and optionally, the washed and cooled solid contains a maximum of 1000 ppm of the impurities, or a maximum of 100 ppm of the impurities after the removal. Claim 30 The low water footprint method according to claim 20, further comprising pelletizing the washed and cooled solid, thereby producing biochar pellets, optionally wherein the pelletizing does not include introducing an external binder to the washed and cooled solid, or the pelletizing includes introducing a binder to the washed and cooled solid, and optionally, when the pelletizing includes introducing a binder to the washed and cooled solid, the binder is selected from starch, thermoplastic starch, cross-linked starch, starch polymer, cellulose, cellulose ether, hemicellulose, methylcellulose, chitosan, lignin, lactose, sucrose, dextrose, maltodextrin, banana powder, wheat flour, wheat starch, 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, sodium bicarbonate, 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 roof board, recycled tire, derivatives thereof, or combinations of the foregoing, said low water footprint method.

31. The low water footprint method according to claim 20, wherein the method does not utilize external water.

32. The water source unit is at most 1000 kgH per metric ton of the biocarbon product ２ O, at most 100 kgH per metric ton of the biocarbon product ２ O, at most 0 kgH per metric ton of the biocarbon product ２ O, or at most -100 kgH per metric ton of the biocarbon product ２ O. The low water source unit method according to any one of claims 20 to 31.

33. The bio-carbon product contains a maximum of 0 kg CO ２ e carbon units per metric ton of the bio-carbon product, and the method for producing a low carbon unit product according to any one of claims 20 to 31.

34. The bio-carbon product contains total carbon, and the total carbon is determined from the measurement of the C / １４ C / １２ C isotope ratio, and at least 90% is bio-carbon, or the total carbon is determined from the measurement of the C / １４ C / １２ C isotope ratio, and 100% is bio-carbon. The low water source unit method according to any one of claims 20 to 31.

35. A biochar product manufactured by the low water footprint method according to any one of claims 20 to 31.

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