Bio-reduction of metal ores integrated with biomass pyrolysis

Abstract

To provide a method for reducing a metal ore.SOLUTION: There is provided a process for reducing a metal ore, the process comprising: providing a biomass feedstock; pyrolyzing the biomass feedstock, thereby generating a biogenic reagent and a pyrolysis off-gas, wherein the biogenic reagent comprises carbon, wherein the pyrolysis off-gas comprises hydrogen or carbon monoxide; obtaining a metal ore, wherein the metal ore comprises a metal oxide and the metal ore is in particulate form; combining the carbon with the metal ore, thereby generating a carbon-metal ore particulate; and chemically reducing the metal oxide, wherein the chemically reducing is achieved using the pyrolysis off-gas.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a continuation of U.S. Provisional Patent Application No. 63 / 083,222, filed September 25, 2020. No. 6,293,523, filed on Oct. 1, 2007, which claims the benefit of U.S. Pat. No. 6,293,523, filed on Oct. 1, 2007, the entire contents of which are incorporated herein by reference.

[0002] Incorporation by Reference All publications, patents, and patent applications mentioned herein are hereby incorporated by reference in their entirety. or patent application(s) to the same extent as if the application(s) were specifically and individually indicated to be incorporated by reference. , which is incorporated herein by reference.

[0003] The present disclosure provides a process for treating metal ores and producing metals using carbon-containing reagents. , systems, and devices. [Background technology]

[0004] Biomass is a term used to describe biologically produced material. The chemical energy contained in biomass is generated from solar energy using the natural process of photosynthesis. This is because plants take in carbon dioxide and water from their surroundings and energy from sunlight. It uses energy to break them down into sugars, starch, cellulose, hemicellulose, and lignin. Of all renewable energy sources, biomass is the It is unique in that it is effectively stored solar energy. is the only renewable carbon source.

[0005] Carbonaceous materials for industrial use are generally derived from chemical sources such as natural gas, petroleum, coal, and lignite. It is supplied from petroleum resources, but also from lignocellulosic biomass and various carbon-rich waste materials. There is growing interest in renewable resources.

[0006] Various conversion technologies exist for converting biomass feedstocks into carbonaceous materials. The increased use of carbonaceous materials is due to technological challenges arising from raw material variability, operational difficulties, and capital intensity. This raises technical and economic challenges.

[0007] Improved pyrolysis process to optimize yield and quality of solids, especially as a high-carbon reagent Historically, the slow pyrolysis of wood has Traditionally, large piles have been run as simple batch processes without emissions controls. Conventional charcoal production techniques are not only energy inefficient but also highly polluting. Continuous commercial-scale production of high-quality carbon while managing energy balance and controlling emissions Scaling up such processes for do.

[0008] Metal processing is a very important industry worldwide. For example, with regard to steel (iron alloys), Steel Market Size, Share & Trends Analysis 2018-2025,Grand View Research,I (2017) predicts it will reach US$1 trillion by 2025. Contractors' growing trend toward sustainable, low-cost, and durable building materials is driving demand for steel in industrial infrastructure and residential projects In pre-engineered metal buildings with high structural integrity, steel provides stability, design It serves an important function in flexibility and aesthetic appeal. Green and energy efficient building Strict regulations driving construction also contribute to the demand for steel, especially in industrial structures.

[0009] Approximately 70% of all steel is produced in an oxygen furnace using coke or coal before being reduced in a basic oxygen furnace. It is made from pig iron produced by reducing iron oxides. The use of coke derived from coal not only depletes fossil fuel resources but also produces non-renewable carbon dioxide. is released into the atmosphere.

[0010] Oxygenated iron ore is mined worldwide. Typically, iron ore is beneficiated through a mineral processing process. The iron fraction is crushed and concentrated, then rolled into pellets (with a binder). The pellets are then heated in a hardening furnace, which burns coal for heat, to solidify them into pellets and transport them to the blast furnace. The oxygenated ore is then reduced to metallic iron using coke. The process creates large amounts of CO2 and other pollutants.

[0011] Generally speaking, metal processing causes significant net global CO2 emissions each year. For example: One of the biggest drawbacks of conventional blast furnaces is that iron is reduced from iron oxide by carbon. Steelmaking is one of the largest producers of CO2 in the world today. It is one of the biggest industrial contributors to making metal fabrication processes more environmentally friendly. is strongly desired.

[0012] In view of the foregoing needs, an improved process and system for converting metallic ores into metals is provided. stems are commercially desirable. Summary of the Invention

[0013] Carbon-based reagents can, in theory, be made from virtually any material that contains carbon. As the economic, environmental, and social costs associated with fossil fuels rise, Preferably, renewable biomass is utilized to produce the carbon-based reagents.

[0014] Pyrolysis occurs in the complete absence of oxidizing agents (air or oxygen) or in the presence of any appreciable amount of oxidation. It is a process for the thermal conversion of solid materials in limited supply that does not occur in the future. Depending on the process conditions and additives, biomass pyrolysis can be regulated to produce widely varying amounts of gas, Liquids and solids can be produced at lower process temperatures and longer vapor residence times. High temperatures and longer residence times favor the production of solids. To increase conversion, moderate temperatures and short vapor residence times are generally used to produce liquids. It is ideal for converting biomass into high-quality syngas or liquids as precursors to liquid fuels. Technological advances in pyrolysis and related processes for achieving this are needed.

[0015] The present disclosure addresses deficiencies in the art and provides a method for producing metals using carbon-containing reagents. This application relates to processes, systems and equipment for the processing of metal ores for the production of metals.

[0016] Disclosed herein is a process for reducing metal ores. The process is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide. To achieve Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Chemical reduction of metal oxides, achieved using pyrolysis off-gas; and reducing.

[0017] In some embodiments, the process comprises pelletizing the carbon metal ore particles, In some embodiments, the metal oxide is used to produce carbon-metal ore pellets. The material is contained within carbon metal ore pellets.

[0018] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal sewerage, or a combination thereof.

[0019] In some embodiments, the biological reagent comprises at least about 50% by weight, at least about 75% by weight % by weight, or at least about 90% by weight total carbon. is at most about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or It can contain 99% by weight of total carbon. Total carbon is the sum of the fixed carbon present in the volatile matter and the It is the sum of the fixed carbon and the non-fixed carbon.

[0020] In some embodiments, the biological reagent comprises at least about 50% by weight, at least about 75% by weight In some embodiments, the biosample contains about 90% or at least about 90% fixed carbon by weight. The drug may be administered in an amount of about, at least about, or at most about 50, 55, 60, 65, 70, 75, 80, Contains 85, 90, 95, 96, 97, 98, 99, or 100% by weight fixed carbon.

[0021] The carbon (in the bioreagent) may be, for example, at least about 50% by weight, at least about 75%, or It may be at least about 90% by weight fixed carbon, with the remainder of the carbon being volatile carbon. In embodiments, the carbon is about, at least about, or at most about 50, 55, 60, 65, 70 , 75, 80, 85, 90, 95, 96, 97, 98, 99, or 100% by weight of solids Contains constant carbon.

[0022] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The minerals are tungsten ore, molybdenum ore, or a combination thereof. In embodiments, the metal ore is iron ore. In some embodiments, the iron ore is hematite. Some of the compounds are tungsten, magnetite, limonite, taconite, or combinations thereof. In some embodiments, the metal ore is a beneficiated metal ore. The metal ore is in particulate form, which is in powder form. In some embodiments, the carbon metal ore particles are carbon metal ore fines. The carbon metal ore particles are carbon metal ore chunks.

[0023] In some embodiments, the carbon metal ore particles comprise at least about 0.1 wt.% to more than about 0.1 wt.% of the carbon metal ore particles. In some embodiments, the carbon metal ore particles contain at least about 50% carbon by weight. It contains at least about 1% by weight and at most about 10% by weight of carbon. In some embodiments, such as those described herein, the carbon metal ore particles are at least about three times as thick as the % to at most about 6% by weight of carbon.

[0024] In some embodiments, the carbon metal ore pellets include an additive. In some embodiments, the additive comprises a binder. Exemplary binders include inorganic bentonite clay, stone, These include ash, starch, cellulose, lignin, and acrylamide.

[0025] In some embodiments, the additive is selected from an acid, a base, or a salt or derivative thereof. In some embodiments, the additive is selected from the group consisting of metals, metal oxides, metal hydroxides, metal For example, the additive may be a hydroxyl group, ... Sodium chloride, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate Sodium, potassium permanganate, magnesium, manganese, aluminum, nickel, chromium Aluminum, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, halogen Iron fluoride, iron chloride, iron bromide, dolomite, dolomitic lime, fluorite, fluorite, bentonite, acid The compound may be selected from calcium chloride, lime, or combinations or derivatives thereof. .

[0026] Additives may be added before, during, or after any one or more steps in the process. This includes adding it to the raw material itself at any time.

[0027] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0028] In some embodiments, the chemical reducing utilizes the pyrolysis off-gas directly. In some embodiments, the chemical reduction step involves first partially oxidizing the pyrolysis off-gas. The reducing gas is then utilized to convert the carbon metal ore particles into a granular form. Indirectly utilizes pyrolysis off-gas by chemically reducing metal oxides within the In some embodiments, the chemical reduction may first be carried out by partially reducing the pyrolysis off-gas. The carbon metal ore pellets are then oxidized to produce a reducing gas. Indirectly utilizes pyrolysis off-gas by chemically reducing metal oxides in the reactor. .

[0029] In some embodiments, the chemical reduction can include gasification of the bioreagent or a portion thereof; The reducing gas obtained from partial oxidation or steam reforming is simultaneously utilized.

[0030] In some embodiments, the process further comprises obtaining heavy hydrocarbons during pyrolysis. In some embodiments, the biological reagent comprises a heavy hydrocarbon, which is converted into a reducing gas. It will be exchanged.

[0031] In some embodiments, the chemical reduction can be achieved by gasification, partial oxidation of light hydrocarbons. Alternatively, reducing gas obtained from steam reforming is simultaneously utilized.

[0032] In some embodiments, the pyrolysis off-gas comprises light hydrocarbons. In some embodiments, the pyrolysis off-gas contains at least 1 mol % hydrogen. In some embodiments, the pyrolysis off-gas contains at least 10 mole percent hydrogen. The cracked off-gas contains at least 1 mole percent carbon monoxide. The cracked off-gas contains at least 10 mole percent carbon monoxide.

[0033] In some embodiments, the chemically reducing is carried out in a metal ore furnace. In some embodiments, the chemical reduction occurs upstream of the metal ore furnace. In an embodiment, chemically reducing is performed using a compound produced by combustion or partial oxidation of carbon. In some embodiments, the chemical reduction is achieved by burning or partially reducing carbon. It utilizes external heat that is produced separately by partial oxidation.

[0034] In some embodiments, the process is co-located at a metal ore mine. In embodiments, the process is co-located with a metal ore processing plant. In this case, the thermal decomposition and chemical reduction take place in the same place.

[0035] Disclosed herein is a process for reducing metal ores. Such a process is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrocarbons. and, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; partially oxidizing the pyrolysis off-gas, thereby producing reducing gas and heat; Chemical reduction of metal oxides and partial oxidation of pyrolysis off-gas and reducing the reactant gas by heating the reactant gas to a temperature of 100° C., Pyrolysis is accomplished using heat generated from the partial oxidation of pyrolysis off-gas. can be.

[0036] In some embodiments, the process comprises pelletizing the carbon metal ore particles, In some embodiments, the metal ore pellets are formed by the addition of carbon ore to the metal ore pellets. The oxide is contained within the carbon metal ore pellets.

[0037] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal sewerage, or a combination thereof.

[0038] In some embodiments, the biological reagent comprises at least 50% carbon by weight. In some embodiments, the bio-reagent comprises at least 75% carbon by weight. In some embodiments, the bioreagent comprises at least 90% carbon by weight. The reagent comprises at least 50% by weight of fixed carbon. In some embodiments, the biological reagent is In some embodiments, the biological reagent comprises at least 75% by weight of fixed carbon. It contains at least 90% by weight of fixed carbon.

[0039] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The minerals are tungsten ore, molybdenum ore, or a combination thereof. In embodiments, the metal ore is iron ore. In some embodiments, the iron ore is hematite. Some of the compounds are tungsten, magnetite, limonite, taconite, or combinations thereof. In an embodiment, the metal ore is a beneficiated metal ore.

[0040] In some embodiments, the metal ore in granular form is metal ore in powder form. In some embodiments, the carbon metal ore particles are carbon metal ore fines. In form, the carbon metal ore particles are carbon metal ore chunks.

[0041] In some embodiments, the carbon metal ore particles comprise at least about 0.1 wt.% to more than about 0.1 wt.% of the carbon metal ore particles. In some embodiments, the carbon metal ore particles contain at least about 50% carbon by weight. It contains at least about 1% by weight and at most about 10% by weight of carbon.

[0042] In some embodiments, the carbon metal ore pellets include an additive. In one embodiment, the additive comprises a binder.

[0043] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0044] In some embodiments, the process further comprises obtaining heavy hydrocarbons during pyrolysis; The biological reagent includes a heavy hydrocarbon.

[0045] In some embodiments, the chemical reduction can be achieved by gasification, partial oxidation of light hydrocarbons. Alternatively, reducing gas obtained from steam reforming is simultaneously utilized.

[0046] In some embodiments, the process further comprises obtaining light hydrocarbons during pyrolysis. In some embodiments, the pyrolysis off-gas comprises light hydrocarbons. In some embodiments, the pyrolysis off-gas contains at least 1 mol % hydrogen. In some embodiments, the pyrolysis off-gas contains at least 10 mol % hydrogen. In some embodiments, the pyrolysis off-gas contains at least 1 mol % carbon monoxide. Also contains 10 mol % carbon monoxide.

[0047] In some embodiments, the chemically reducing occurs in a metal ore furnace. In some embodiments, the chemical reduction occurs upstream of the metal ore furnace.

[0048] In some embodiments, the chemical reduction is by combustion or partial oxidation of carbon. In some embodiments, the chemical reduction utilizes the internal heat produced by the carbon The external heat is produced separately by combustion or partial oxidation of the

[0049] In some embodiments, the process is co-located at a metal ore mine. In embodiments, the process is co-located with a metal ore processing plant. In this case, the thermal decomposition and chemical reduction take place in the same place.

[0050] Further processes for reducing metal ores are disclosed herein. Process is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; generating a reducing gas from gasification, partial oxidation, or steam reforming of a biological reagent; and chemically reducing the metal oxide using a reducing gas.

[0051] In some embodiments, the process comprises pelletizing the carbon metal ore particles, In some embodiments, the metal ore pellets are formed by the addition of carbon ore to the metal ore pellets. The oxide is contained within the carbon metal ore pellets.

[0052] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal sewerage, or a combination thereof.

[0053] In some embodiments, the biological reagent comprises at least 50% carbon by weight. In some embodiments, the bio-reagent comprises at least 75% carbon by weight. In some embodiments, the bioreagent comprises at least 90% carbon by weight. The reagent comprises at least 50% by weight of fixed carbon. In some embodiments, the biological reagent is In some embodiments, the biological reagent comprises at least 75% by weight of fixed carbon. It contains at least 90% by weight of fixed carbon.

[0054] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The minerals are tungsten ore, molybdenum ore, or a combination thereof. In embodiments, the metal ore is iron ore. In some embodiments, the iron ore is hematite. Some of the compounds are tungsten, magnetite, limonite, taconite, or combinations thereof. In some embodiments, the metal ore is a beneficiated metal ore. Metal ore in powder form is metal ore in powder form.

[0055] In some embodiments, the carbon metal ore particulates are carbon metal ore fines. In some embodiments, the carbon-metal ore particles are carbon-metal ore chunks.

[0056] In some embodiments, the carbon metal ore particles comprise at least about 0.1 wt.% to more than about 0.1 wt.% of the carbon metal ore particles. In some embodiments, the carbon metal ore particles contain at least about 50% carbon by weight. It contains at least about 1% by weight and at most about 10% by weight of carbon.

[0057] In some embodiments, the carbon metal ore pellets include an additive. In one embodiment, the additive comprises a binder.

[0058] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0059] In some embodiments, the bio-reagent comprises heavy hydrocarbons obtained during pyrolysis. In some embodiments, the chemical reduction is performed by gasification, partial oxidation, or In some embodiments, a second reducing gas obtained from steam reforming is co-utilized. Hydrocarbons are obtained during pyrolysis.

[0060] In some embodiments, the reducing gas comprises at least 20 mole percent hydrogen. In some embodiments, the reducing gas comprises at least 40 mole percent hydrogen. In some embodiments, the reducing gas comprises at least 20 mole percent carbon monoxide. The reducing gas contains at least 40 mole percent carbon monoxide.

[0061] In some embodiments, the chemically reducing occurs in a metal ore furnace. In some embodiments, the chemical reduction occurs upstream of the metal ore furnace.

[0062] In some embodiments, the chemical reduction is by combustion or partial oxidation of carbon. In some embodiments, the chemical reduction utilizes the internal heat produced by the carbon The external heat is produced separately by combustion or partial oxidation of the

[0063] In some embodiments, the process is co-located at a metal ore mine. In embodiments, the process is co-located with a metal ore processing plant. In this case, the thermal decomposition and chemical reduction take place in the same place.

[0064] Disclosed herein are processes for processing metal ores. These processes include , Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide. To achieve Obtaining metal ore, wherein the metal ore is in particulate form and contains metal oxides, metal sulfides, metal hydrides, metal nitrides, metal carbides, metal borides, metal phosphides, or the like and obtaining, combining carbon and metal ore, thereby producing carbon-metal ore particles; Metal oxides, metal sulfides, metal hydrides, metal nitrides, metal carbides, metal borides, gold Chemically producing elemental metals from metal phosphides, or combinations thereof, comprising: and producing the product, which is achieved using cracking off-gas.

[0065] In some embodiments, the process comprises pelletizing the carbon metal ore particles, and forming carbon metal ore pellets therefrom.

[0066] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal sewerage, or a combination thereof.

[0067] In some embodiments, the biological reagent comprises at least 50% carbon by weight. In some embodiments, the bio-reagent comprises at least 75% carbon by weight. In some embodiments, the bioreagent comprises at least 90% carbon by weight. The reagent comprises at least 50% by weight of fixed carbon. In some embodiments, the biological reagent is In some embodiments, the biological reagent comprises at least 75% by weight of fixed carbon. It contains at least 90% by weight of fixed carbon.

[0068] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The minerals are tungsten ore, molybdenum ore, or a combination thereof. In embodiments, the metal ore is iron ore. In some embodiments, the iron ore is hematite. Some of the compounds are tungsten, magnetite, limonite, taconite, or combinations thereof. In an embodiment, the metal ore is a beneficiated metal ore.

[0069] In some embodiments, the metal ore in particulate form is metal ore in powder form. In some embodiments, the carbon metal ore particulates are carbon metal ore fines. In an embodiment, the carbon metal ore particles are carbon metal ore chunks.

[0070] In some embodiments, the carbon metal ore particles comprise at least about 0.1 wt.% to more than about 0.1 wt.% of the carbon metal ore particles. In some embodiments, the carbon metal ore particles contain at least about 50% carbon by weight. It contains at least about 1% by weight and at most about 10% by weight of carbon.

[0071] In some embodiments, the carbon metal ore pellets include an additive. In one embodiment, the additive comprises a binder.

[0072] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0073] In some embodiments, the chemical manufacturing utilizes pyrolysis off-gas directly. In some embodiments, the chemical production may involve first partially oxidizing pyrolysis off-gas. The reducing gas is then utilized to produce metal oxides, metal sulfides, and the like. metal hydrides, metal nitrides, metal carbides, metal borides, metal phosphides, or any of these Indirectly converting pyrolysis off-gas into elemental metals by chemically producing them from a combination of Use it.

[0074] In some embodiments, chemically producing may involve gasification, partial oxidation, or the like of a biological reagent. simultaneously utilizes the reducing gas obtained from steam reforming.

[0075] In some embodiments, the bioreagent comprises heavy hydrocarbons obtained during pyrolysis, The hydrocarbons are converted at least in part into a reducing gas.

[0076] In some embodiments, the chemically producing may be performed by gasification, partial oxidation of light hydrocarbons. Alternatively, reducing gas obtained from steam reforming is simultaneously utilized.

[0077] In some embodiments, light hydrocarbons are obtained during pyrolysis as part of the pyrolysis off-gas. can be done.

[0078] In some embodiments, the pyrolysis off-gas contains at least 1 mole percent hydrogen. In some embodiments, the pyrolysis off-gas contains at least 10 mole percent hydrogen. In some embodiments, the pyrolysis off-gas contains at least 1 mole percent carbon monoxide. In this embodiment, the pyrolysis off-gas comprises at least 10 mole % carbon monoxide.

[0079] In some embodiments, the chemically producing occurs in a metal ore furnace. In some embodiments, the chemical producing occurs upstream of a metal ore furnace.

[0080] In some embodiments, chemically producing includes producing by combustion or partial oxidation of carbon. In some embodiments, the chemical production utilizes the internal heat generated by the carbon The external heat is produced separately by combustion or partial oxidation of the

[0081] In some embodiments, the process is co-located at a metal ore mine. In embodiments, the process is co-located with a metal ore processing plant. In this case, pyrolysis and chemical production take place in the same location.

[0082] Disclosed herein are methods for optimizing the reduction of metal oxides. These methods include: pyrolyzing the biomass, thereby producing carbon and pyrolysis off-gas; The pyrolysis off-gas is oxidized with oxygen that is intentionally less than the combustion stoichiometric amount of oxygen, thereby generating heat and carbon monoxide; Reducing metal oxides, which is accomplished using heat and carbon monoxide. This can include:

[0083] In some embodiments, oxidation of the pyrolysis off-gas produces hydrogen, which is then reacted with a metal oxide. In some embodiments, carbon is used to reduce metal oxides. In some embodiments, the carbon is directly utilized to generate additional carbon monoxide. and subsequently reacting additional carbon monoxide with the metal oxide to form the metal oxide It is used indirectly to reduce

[0084] Further methods for optimizing the reduction of metal oxides are disclosed herein. The law is pyrolyzing the biomass, thereby producing carbon and pyrolysis off-gas; The pyrolysis off-gas is oxidized with oxygen that is intentionally less than the combustion stoichiometric amount of oxygen, thereby generating heat and hydrogen; Reducing metal oxides, which is accomplished using heat and hydrogen. and

[0085] In some embodiments, oxidation of the pyrolysis off-gas produces carbon monoxide, In some embodiments, carbon is also utilized to reduce metal oxides. In some embodiments, the carbon is used directly to reduce metal oxides. by converting the additional carbon monoxide to the metal oxide and subsequently reacting the additional carbon monoxide with the metal oxide. and indirectly used to reduce metal oxides.

[0086] Disclosed herein is a process for producing carbon metal ore pellets. The process disclosed in the book is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets and the biological reagent contains at least 50% by weight of fixed carbon; The carbon metal ore particulates have at least about 0.1 wt. % to at most about 50 wt. % total carbon. Includes:

[0087] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal wastewater, or a combination thereof.

[0088] In some embodiments, the bio-reagent comprises at least 60% total carbon by weight. In some embodiments, the bio-reagent comprises at least 75% total carbon by weight. In some embodiments, the bio-reagent comprises at least 90% total carbon by weight. In some embodiments, the bioreagent comprises at least 55% by weight of fixed carbon. The reagent comprises at least 75% by weight of fixed carbon. In some embodiments, the biological reagent , containing at least 90% by weight of fixed carbon.

[0089] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The ore is selected from the group consisting of tungsten ore, molybdenum ore, and combinations thereof. In some embodiments, the metal ore is iron ore. In some embodiments, the iron ore is Choose from hematite, magnetite, limonite, taconite, or a combination thereof will be done.

[0090] In some embodiments, the metal ore is a beneficiated metal ore.

[0091] In some embodiments, the metal ore in particulate form is metal ore in powder form.

[0092] In some embodiments, the carbon metal ore particulates are carbon metal ore fines.

[0093] In some embodiments, the carbon metal ore particles are carbon metal ore chunks.

[0094] In some embodiments, the carbon metal ore particles comprise at least about 0.5% by weight to more than In some embodiments, the carbon metal ore particles comprise: It contains at least about 1% to at most about 10% by weight of total carbon.

[0095] In some embodiments, the carbon metal ore pellets include an additive.

[0096] In some embodiments, the additive comprises a binder.

[0097] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0098] Disclosed herein is a process for manufacturing metal nuggets. The process is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide. To achieve Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets And, Chemically reducing metal oxides to thereby produce metal nuggets, wherein the chemical reduction is achieved using pyrolysis off-gas; Retrieving a metal nugget, the metal nugget comprising a metal, the metal being a metal oxide. and recovering the reduced form of the compound.

[0099] In some embodiments, the metal nugget consists essentially of metal and carbon.

[0100] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal wastewater, or a combination thereof.

[0101] In some embodiments, the biological reagent comprises at least 50% carbon by weight. In some embodiments, the bio-reagent comprises at least 75% carbon by weight. In some embodiments, the bioreagent comprises at least 90% carbon by weight. The reagent comprises at least 50% by weight of fixed carbon. In some embodiments, the biological reagent is In some embodiments, the biological reagent comprises at least 75% by weight of fixed carbon. It contains at least 90% by weight of fixed carbon.

[0102] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The ore is selected from the group consisting of tungsten ore, molybdenum ore, and combinations thereof. In some embodiments, the metal ore is iron ore. In some embodiments, the iron ore is Choose from hematite, magnetite, limonite, taconite, or a combination thereof In some embodiments, the metal ore is a beneficiated metal ore.

[0103] In some embodiments, the metal ore in particulate form is metal ore in powder form. In some embodiments, the carbon metal ore particulates are carbon metal ore fines.

[0104] In some embodiments, the carbon metal ore particles are carbon metal ore chunks.

[0105] In some embodiments, the carbon metal ore particles comprise at least about 0.1 wt.% to more than about 0.1 wt.% of the carbon metal ore particles. In some embodiments, the carbon metal ore particles contain at least about 50% carbon by weight. It contains at least about 1% by weight and at most about 10% by weight of carbon.

[0106] In some embodiments, the carbon metal ore pellets include an additive. In one embodiment, the additive comprises a binder.

[0107] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0108] In some embodiments, the chemical reducing utilizes the pyrolysis off-gas directly. In some embodiments, the chemical reduction step involves first partially oxidizing the pyrolysis off-gas. and then using the reducing gas to form a carbon metal ore or a carbon Pyrolysis off-gas is generated by chemically reducing the metal oxides in the base metal ore pellets. In some embodiments, the chemical reduction is indirectly utilized. The reduction gas obtained from oxidation, partial oxidation, or steam reforming is simultaneously utilized. In this state, chemical reduction is achieved by using a reducing gas, and bioreagents are obtained during pyrolysis. In some embodiments, the heavy hydrocarbons are converted to reducing gases. Chemical reduction is achieved by gasification, partial oxidation, or steam reforming of light hydrocarbons. In some embodiments, the light hydrocarbons are subjected to thermal cracking. It is obtained during pyrolysis as part of the gas.

[0109] In some embodiments, the pyrolysis off-gas contains at least 1 mole percent hydrogen. In some embodiments, the pyrolysis off-gas contains at least 10 mole percent hydrogen. In some embodiments, the pyrolysis off-gas contains at least 1 mole percent carbon monoxide. In this embodiment, the pyrolysis off-gas comprises at least 10 mole % carbon monoxide.

[0110] In some embodiments, the chemically reducing occurs in a metal ore furnace. In some embodiments, the chemical reduction occurs upstream of the metal ore furnace.

[0111] In some embodiments, the chemical reduction is by combustion or partial oxidation of carbon. In some embodiments, the chemical reduction utilizes the internal heat produced by the carbon The external heat is produced separately by combustion or partial oxidation of the

[0112] In some embodiments, the process is co-located at a metal ore mine. In embodiments, the process is co-located with a metal ore processing plant. In this case, the thermal decomposition and chemical reduction take place in the same place.

[0113] Disclosed herein is a process for producing metals from metal ores. The disclosed process is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets And, introducing carbon metal ore pellets into a chemical reduction furnace; Air or oxygen is introduced into the chemical reduction furnace, thereby containing the carbon metal ore particles. oxidizing carbon, thereby producing heat and carbon monoxide; Chemically reducing metal oxides within carbon metal ore pellets, thereby producing metals wherein the chemical reduction is accomplished using carbon monoxide in a chemical reduction reactor. To generate, and recovering the metal.

[0114] In some embodiments, the bioreagent is co-fed directly into the chemical reduction reactor.

[0115] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal wastewater, or a combination thereof.

[0116] In some embodiments, the biological reagent comprises at least 50% carbon by weight. In some embodiments, the bio-reagent comprises at least 75% carbon by weight. In some embodiments, the bioreagent comprises at least 90% carbon by weight. The reagent comprises at least 50% by weight of fixed carbon. In some embodiments, the biological reagent is In some embodiments, the biological reagent comprises at least 75% by weight of fixed carbon. It contains at least 90% by weight of fixed carbon.

[0117] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The ore is selected from the group consisting of tungsten ore, molybdenum ore, and combinations thereof. In some embodiments, the metal ore is iron ore. In some embodiments, the iron ore is Choose from hematite, magnetite, limonite, taconite, or a combination thereof In some embodiments, the metal ore is a beneficiated metal ore.

[0118] In some embodiments, the metal ore in particulate form is metal ore in powder form. In some embodiments, the carbon metal ore particulates are carbon metal ore fines.

[0119] In some embodiments, the carbon metal ore particles are carbon metal ore chunks.

[0120] In some embodiments, the carbon metal ore particles comprise at least about 0.1 wt.% to more than about 0.1 wt.% of the carbon metal ore particles. In some embodiments, the carbon metal ore particles contain at least about 50% carbon by weight. It contains at least about 1% by weight and at most about 10% by weight of carbon.

[0121] In some embodiments, the carbon metal ore pellets include an additive. In one embodiment, the additive comprises a binder.

[0122] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0123] In some embodiments, the metal is iron, copper, nickel, magnesium, manganese, aluminum, or the like. aluminum, tin, zinc, cobalt, chromium, tungsten, molybdenum, or combinations thereof is selected from a combination.

[0124] Disclosed herein are compositions for reducing metal ores. The composition may include carbon metal ore particulates, the carbon metal ore particulates being anhydrous and Contains at least about 0.1% by weight to at most about 50% by weight of fixed carbon on an ash-free basis, The element is carbon 14 C / 12At least about 50% renewable as determined from C isotope ratio measurements It is a carbon that can be used.

[0125] In some embodiments, the fixed carbon 14 C / 12 The measurement of C isotope ratio is performed according to ASTM D Use 6866.

[0126] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The ore is selected from the group consisting of tungsten ore, molybdenum ore, and combinations thereof. In some embodiments, the metal ore is iron ore. , a combination of copper ore and nickel ore.

[0127] In some embodiments, the composition may be in the form of a powder, chunks, pellets, nuggets, or a combination thereof. The object is in the form of an object selected from a combination of:

[0128] In some embodiments, the carbon metal ore particles have, on a dry and ash-free basis, at least about It contains from 0.5% to at most about 25% by weight of fixed carbon. In some embodiments, the carbon The metal ore particulates are at least about 1% by weight and at most about 15% by weight on a dry and ash-free basis. In some embodiments, the carbon metal ore particles comprise an anhydrous and ashless base. In some embodiments, the composition contains at least about 2% to at most about 10% fixed carbon by weight. In this state, the carbon metal ore particles comprise at least about 3% by weight on a dry and ash-free basis and at most about It contains about 6% fixed carbon by weight.

[0129] In some embodiments, the fixed carbon is 14 C / 12 Determined from C isotope ratio measurements In some embodiments, the carbon content is at least about 90% renewable carbon. is the carbon 14 C / 12 At least about 99% renewable as determined from C isotope ratio measurements In some embodiments, the fixed carbon is 14 C / 12 C isotope ratio It is approximately 100% renewable carbon as determined from measurements.

[0130] In some embodiments, the carbon metal ore pellets include an additive. In some embodiments, the composition includes a binder.

[0131] In some embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore. do.

[0132] In some embodiments, the fixed carbon is at least 400 m 2 The BET surface area in g / g is In some embodiments, the fixed carbon is at least 800 m 2 / g BET table It is characterized by area.

[0133] In some embodiments, the fixed carbon is at least 0.5 cm 3 / g mesopore volume In some embodiments, the fixed carbon is at least 1 cm 3 / g mesopores Characterized by volume. [Brief explanation of the drawings]

[0134] [Figure 1] FIG. 1 is a simplified block flow diagram of a process for converting metal ores into metal products utilizing high-carbon bio-reagents, according to some embodiments.

[0135] [Figure 2] FIG. 1 is a simplified block flow diagram of a process for converting metal ores into metal products utilizing high-carbon bio-reagents, according to some embodiments.

[0136] [Figure 3] FIG. 1 is a simplified block flow diagram of a process for converting metal ores into metal products utilizing high-carbon bio-reagents, according to some embodiments.

[0137] [Figure 4] FIG. 1 is a simplified block flow diagram of a process for producing carbon metal ore pellets utilizing a high-carbon bio-reagent, according to some embodiments.

[0138] [Figure 5] FIG. 1 is a simplified block flow diagram of a process for producing metal nuggets utilizing a high-carbon bio-reagent, according to some embodiments.

[0139] [Figure 6] FIG. 1 is a simplified block flow diagram of a process for converting metal ores into metal products utilizing high-carbon bio-reagents, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0140] This description will enable any person skilled in the art to make and use the disclosed disclosure and will be provided as a guide to the present disclosure. Several embodiments, adaptations, variations, alternatives, and uses are described. These and other embodiments of the present disclosure are Embodiments, features, and advantages of the present invention will become more apparent from the following detailed description of the present disclosure taken in conjunction with the accompanying drawings. , will become more apparent to those skilled in the art.

[0141] For the purpose of enabling technical disclosure, various explanations, hypotheses, theories, conjectures, assumptions, etc. are disclosed. This disclosure does not rely on any of these being actually true. Any explanations, hypotheses, theories, speculations, or assumptions contained herein shall not be construed as limiting the scope of this disclosure in any way. should not be interpreted.

[0142] The headings provided herein are for convenience only and do not limit the scope of the claimed embodiments. or interpretation of the meaning.

[0143] definition As used herein, the singular forms "a," "an," and "the" are used interchangeably. "(the)" includes plural referents unless the context clearly indicates otherwise. For example, at any location where a product is manufactured, the process may include the production of "carbon metal ore particulates." When produced, two or more carbon metal ore particles may be produced so as to produce "multiple carbon metal ore particles." This can also be controlled to produce the above product. For example, if the composition includes carbon metal ore particulates, the composition may include a plurality of The carbon metal ore particles may include

[0144] As used herein, the term "about" means the extent to which the range indicated is exceeded, unless otherwise indicated. ±20% of the range, value, or structure.

[0145] As used herein, any concentration range, percentage range, ratio range, or integer range is Unless otherwise indicated, any integer value within the range listed, and fractions thereof, where appropriate It should be understood that this includes integers (such as tenths and hundredths). Any numerical range recited in the subclause includes any number within the recited range unless otherwise indicated. It should be understood to include integers.

[0146] As used herein, a "living organism" refers to a living organism that is living on a time scale of months, years, or decades. Materials (either raw materials, products, or intermediates) that contain renewable elements such as carbon Non-biological materials may be non-renewable or may not last for centuries, thousands, millions, or even years. It may be renewable on time scales on the order of geological time scales or even longer. For example, coal and traditional fuel sources of petroleum are non-renewable and non-biological.

[0147] The three naturally occurring isotopes of carbon, 12 C. 13 C, and 14 C exists. 12 C and 13 C is stable and exists in a natural ratio of about 93:1. 14 C from cosmic rays in the upper atmosphere produced by thermal neutrons from the atmosphere, transported to Earth and absorbed by living biological material Isotopically, 14 C constitutes a negligible portion. However, this is It is radioactive with a half-life of 1000 and is therefore radiometrically detectable. 14 Suck C Because it doesn't converge, 14 The amount of C is one of the methods used to measure radioactivity in biological materials. be.

[0148] Plants fix atmospheric carbon through photosynthesis 14 C is then incorporated. Animals, when consuming plants or other animals that consume plants, 14 C Therefore, living plants and animals absorb CO2 in the same amount as atmospheric CO2. 1 4 C vs. 12When an organism dies, it stops exchanging carbon with the atmosphere and therefore And there's nothing newer 14 C is not incorporated. Radioactive decay then occurs in living organisms. 14 C gradually This effect is the basis of radiocarbon dating.

[0149] Fossil fuels such as coal are primarily made from plant material deposited millions of years ago. The period is 14 This is equivalent to thousands of half-lives of C, so essentially all of the carbon in fossil fuels 14 C is Also, fossil fuels are not natural because they were originally formed from living organisms. , relative to the atmosphere 13 C is depleted. Therefore, carbon from fossil fuels is being used to replace biogenic carbon. In comparison, 13 C and 14 It is depleted in both C.

[0150] Carbon isotopes of recently depleted organic matter, such as from renewable sources, and carbon isotopes of chemical matter, such as coal. This difference between carbon isotopes of fossil fuels allows the determination of the source of carbon in the composition. whether the carbon in the composition comes from renewable sources or from fossil fuels In other words, whether renewable resources or fossil fuels were used in the production of the composition; is.

[0151] As used herein, "combustion stoichiometric amount of oxygen" refers to air, pure oxygen, or oxygen-enriched Regardless of whether present in the atmosphere, carbon-containing or hydrogen-containing gases are not in stoichiometric excess. It is the amount of oxygen required to completely oxidize the components to CO2 or H2O, respectively. If oxygen is intentionally oxidized in less than the stoichiometric amount for combustion, the percentage of the stoichiometric amount of oxygen for combustion The oxygen utilized as a percentage is at least about 10% to at most about 99%, and at least about 25%. % to at most about 90%, or at least about 40% to at most about 80%. In embodiments, this percentage is about, at least about, or at most about 15%, 20%, 25%, %, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75 %, 80%, 85%, 90%, or 95%. These percentages indicate the percentage of oxygen in the O2 form. is the molar basis.

[0152] As used herein, "including," "containing," or "comprising," which is synonymous with "characterized by," It is open-ended or open-ended and does not exclude additional unrecited elements or method steps. "Comprising" is used in claim language to indicate that a specified claim element is essential. Although it is a technical term used in the literature, other claim elements can be added and still be used in the present invention. Compositions within the scope of the disclosure can be formed.

[0153] As used herein, "consisting of" means any element, step, or elements not specified. or components. When a phrase appears in a section of the text, it limits only the elements listed in that section; other elements are , are not excluded from the claim as a whole. The phrase "" extends the claim to include all elements or method steps specified in the claim in addition to the specified elements or method steps. The scope of the invention is limited to those that do not substantially affect the basis of the subject matter being examined.

[0154] As used herein, a "derivative" is a substance derived from another substance by chemical reaction. It is a compound, molecule, or ion. The substance from which the derivative is derived is an additive. Derivatives are also It is an additive.

[0155] As used herein, "high carbon," as in "high carbon biological reagent," refers to the The drug has a high carbon content relative to the raw materials used to manufacture the high-carbon bioreagent. A high-carbon biological reagent should contain at least about half of its weight as carbon. For example, high carbon biological reagents can be at least 55, 60, 65, 70, 75, 80, 8 5, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% by weight of carbon It can include.

[0156] As used herein, "high carbon biological reagent" refers to the disclosed processes and systems This describes a material that can be produced by: No limitation is implied from the term itself, but rather by reference to a particular embodiment. For example, if a feedstock containing a low carbon content is used in a disclosed process, When subjected to a high carbon yield, the product is highly enriched in carbon relative to the starting material. ), but nevertheless, it is relatively low in carbon (low purity) containing less than 50% by weight of carbon. (carbon) high-carbon biological reagent.

[0157] As used herein, the terms "include," "have," and " The terms "comprise" and "include" are used interchangeably and these terms and variations thereof are intended to be non-exclusive. It is intended to be construed as being.

[0158] As used herein, a "metal ore" refers to a mineral in which the desired metal is not in a pure elemental form, but is present in a Rather, metal oxides, metal sulfides, metal nitrides, metal carbides, metal borides, and metal phosphides , or metal-containing materials that exist as metals in another form.

[0159] The use of the word "or" in relation to a list of two or more items means that all of the following interpretations of that word are true: Contains: any of the items in the list, all of the items in the list, and all of the items in the list Furthermore, "at least one of A, B, and C, etc." The phrase is intended in the sense that one of ordinary skill in the art would understand the practice (e.g., " A "system having at least one of A, B, and C" includes, but is not limited to, A only. , B only, C only, A and B together, A and C together, B and C together, or A and (This would include systems with A, B, or C together, etc.) If a convention similar to "at least one of these" is used, then generally, such a construction It is intended to mean that the trader will understand the terms (e.g., "A, B, or C" The "system having at least one of these" includes, but is not limited to, A only, B only, C only, A and B together, A and C together, B and C together, or A, B and C together, (This would include systems with

[0160] As used herein, "pellets" is synonymous with "briquettes" and refers to pellets. , briquettes, pellets / briquettes, or similar terms, all of which It refers to an agglomerated mass rather than a loose powder. For convenience, the term "pellet" is used interchangeably. The pellet shape is not limited to a spherical or nearly spherical shape. are spherical (round or ball shaped), cubic (square), octagonal, hexagonal, honeycomb / bee Nest-shaped, oval, egg-shaped, cylindrical, rod-shaped, bread-shaped, pillow-shaped, random, or any of these It can be a combination of:

[0161] As used herein, "pyrolysis" is the thermal decomposition of a carbonaceous material. 10%, 5%, 1%, 0.5%, and 0.1% of the oxygen (O2 mole basis) required for complete combustion %, or less than 0.01% oxygen is present than is required for complete combustion of the material. In some embodiments, the pyrolysis is carried out in the absence of oxygen.

[0162] As used herein, a "reagent" is a material in its broadest sense. For example, The reagent may be a fuel, a chemical, a material, a compound, an additive, a blend component, or a solvent. A reagent does not necessarily have to be a chemical reagent that causes or participates in a chemical reaction. However, a reagent can be a chemical reactant that can be consumed in a reaction. , a chemical catalyst for a particular reaction. A reagent is a mechanical, May cause or contribute to modulating physical or hydrodynamic properties. For example, reagents can be introduced into metals to give them particular strength properties. of sufficient purity (typically carbon-pure in the current situation) for use in chemical analysis or physical testing It can be a substance of high purity.

[0163] As used herein, "total carbon" refers to the fixed and unfixed carbon present in the volatile matter. In some embodiments, the weight percentages of the components are absolute and are the sum of the weight percentages of the components and the carbon. This is assumed unless otherwise stated. In other embodiments, the ingredient weight percentages may be either anhydrous or non-anhydrous. It is based on gray.

[0164] As used herein, a "zone" means a single physical unit, a physically separate A continuous reactor is a region of space within a continuous reactor, a unit, or any combination thereof. The boundaries of the zones may be determined by the presence of flights within the reactor or by separate reactors for providing heat to the separate zones. Alternatively or additionally, the heating element may be associated with a structure such as a heating element. The boundaries may be discrete temperatures, fluid flow patterns, solid flow patterns, or degrees of reaction. In a single batch reactor, a "zone" refers to an operating level in time rather than space. There is not necessarily a sharp transition from one zone to another. The boundary between the thermal zone and the pyrolysis zone can be somewhat arbitrary. Solution may occur in part in the preheat zone, and some amount of "preheat" may be added to the pyrolysis zone. The temperature profile in the reactor may continue to occur at various points, including the zone boundaries within the reactor. , typically continuous.

[0165] process The principles of the present disclosure are particularly suited to the co-location of pyrolysis processes in metal mining or ore processing facilities. The technology herein eliminates the need for fossil fuels in curing and coking, and Reduces the need for intermediate transportation of pellets to the blast furnace. Economics relative to current processes used to convert iron ore into iron, including cornitic processing It has economic and environmental benefits.

[0166] The process disclosed herein is an environmentally friendly technology with a reduced carbon footprint. If the starting material is living or renewable carbon-containing biomass, The carbon produced is biodegradable. This means that carbon of 14 C / 12 This can be shown by measuring the C isotope ratio.

[0167] In some embodiments, all of the carbon processed is renewable. Since the starting metal oxide can contain carbon, less than all of the carbon is recyclable. For example, taconite contains iron-bearing carbonates that contain non-biogenic carbon. When used, beneficiation can remove non-biogenic carbon from metal ores.

[0168] Any biogenic carbon that is oxidized to carbon dioxide creates biogenic CO2. This also produces of carbon in the CO2 14 C / 12 This can also be shown by measuring the C isotope ratio. This biogenic CO2 derived from biomass is reabsorbed by the growing biomass via photosynthesis. This significantly reduces net CO2 emissions. Additionally, the hydrogen content of the starting biomass substantially reduces the net CO2 emissions of the process. This is because the hydrogen in the biomass becomes H2 or its partially oxidized form in the pyrolysis off-gas. H2 induces chemical reduction of metal oxides in much the same way as that caused by CO. However, H2 oxidation does not produce CO2, but H2O, It is not considered a problematic greenhouse gas.

[0169] Another reason the disclosed process is environmentally superior to conventional techniques is that it The reduction of metal oxides is essentially endothermic since the overall chemical reaction is endothermic. Decomposition of metal oxides into metal and oxygen, thereby Even known approaches to electrochemical conversion that avoid direct CO2 production require large amounts of electricity. However, this is usually made from non-renewable sources. Traditional metal ore processing involves the use of large amounts of coal. to generate the necessary heat (from coal combustion) and carbon for the reduction chemical reaction. In contrast, some embodiments provide a method for producing carbon and water in an energy efficient manner. In an integrated bioreduction process using hydrogen, the required heat is provided from pyrolysis off-gas. This avoids the pollution caused by burning coal.

[0170] Integrated bioreduction of metal ores is environmentally friendly compared to the traditional use of fossil fuels such as coal. The traditional approach generates This is related to the "carbon intensity" of a given product, which is the amount of net carbon dioxide emitted. Carbon intensity is the net carbon dioxide equivalent produced per tonne of ore processed. "Carbon dioxide equivalent" or "CO2e" is the equivalent global warming As an example, in the case of metal mining processing, the average is 11.9kJ g CO2 / ton (Tost et al., "Metal Mining's Environmental Pressures:A Review and Update ated Estimates on CO2Emissions,Water Us e,and Land Requirements”,Sustainability 2018,10,2881, which is incorporated by reference. In various embodiments, The process disclosed herein reduces the production time by approximately 50%, 60%, 70%, 80%, or even 100% compared to the prior art. %, 90%, 95%, or 99% reduction in carbon intensity or CO2 equivalent carbon intensity In various embodiments, the processes disclosed herein can be carried out in about 10, 9, 8 , 7, 6, 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1 kg C It can be characterized by a carbon intensity of less than 02 / ton or CO2 equivalent. In the processes and methods disclosed herein, most or all of the CO2 produced is biodioxide. As a result, the effective carbon intensity is very low, even zero, or as low as carbon steel. It may even be negative if there is a net carbon sequestration in the final product.

[0171] The present inventors have surprisingly found that intentionally limiting oxygen in the combustion of pyrolysis off-gas can can be produced, thereby producing more CO2 (as opposed to CO2 as in complete combustion). This CO can then be used as a reducing agent. The production of CO from partial oxidation provides some heat, but the CO2 This provides less heat compared to conventional complete oxidation. Various embodiments provide a method for reducing the heat generated by oxidation. Taking advantage of the finding that it may be sufficient to carry out the endothermic reduction of metal oxides, the reduction is carried out by partial oxidation. The CO produced from the oxidation is used chemically.

[0172] Based on the above, some variations include a method for optimizing the reduction of metal oxides, pyrolysis of biomass to obtain carbon and pyrolysis off-gas; and combustion stoichiometry of oxygen. The pyrolysis off-gas is intentionally oxidized with less oxygen, thereby reducing heat, carbon monoxide, and carbon dioxide, and reducing metal oxides using heat and carbon monoxide. and (b) oxidizing the pyrolysis off-gas to produce hydrogen and water. Hydrogen can also be used to reduce metal oxides.

[0173] In some embodiments, carbon can be used directly to reduce metal oxides, e.g., For example, a metal oxide may be reacted with carbon to produce the metal (or a less reduced form of the metal) and carbon monoxide. Alternatively or additionally, carbon dioxide can be produced by the addition of additional monoxide. carbon by converting it to carbon and then reacting additional carbon monoxide with the metal oxide. It can be used indirectly to reduce metal oxides.

[0174] Some embodiments involve pyrolyzing wood into biocarbon, followed by beneficiation into pellets and then reducing Biocarbon as a starting material is mixed with powdered iron ore (or other metal ores) and hydrogen and CO based on a process that uses off-gas from pyrolysis, which is rich in iron, to reduce pellets to elemental iron. High temperature and medium residence time for pyrolysis of biomass (as described herein) The time results in a high fixed carbon product suitable for blending with pellets, and a large amount of CO and Some embodiments provide a gas stream having H2 and H2 to create heat for pyrolysis. Diverting gases from the burner provides more methane and other hydrocarbons for the reduction reaction. It is converted into a gas containing CO and H2.

[0175] Some embodiments involve the production of pellets / briquettes comprising metal oxides and biogenic carbon. These pellets / briquettes are then processed in or upstream of the metal ore furnace. The metal oxides can be treated in the pyrolysis off-gas to remove oxygen.

[0176] Disclosed herein is a process for reducing metal ores. An exemplary diagram of the process is provided. Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide. To achieve Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Chemical reduction of metal oxides, achieved using pyrolysis off-gas; and reducing.

[0177] FIG. 1 illustrates a process 100 for reducing a metal ore 108 utilizing a biological reagent 104. The biomass feedstock 101 is fed into a pyrolysis reactor 103. 1 is pyrolyzed in the presence of heat 102 under conditions further detailed herein below. The pyrolysis of the biomass feedstock 101 produces bioreagents 104 and pyrolysis off-gas 106. The carbon-containing biological reagent 104 and the metal ore 108 are mixed in the carbon-metal ore mixing unit 10 7 to produce carbon-metal ore particles 112. The bio-reagent 104 and the metal ore 108 can be combined in a mixing unit 107. If pellets are used, the product of the carbon-metal ore blending unit 107 is The carbon metal ore pellets can be introduced into a carbon metal ore pelletizing unit 110, thereby Additives 111 are added to the carbon metal ore pelletizing unit 110 to produce pellets. It can be in the form of pellets and incorporated into carbon metal ore pellets. Carbon metal ore particles produced using the carbon metal ore pelletizing unit 110. The resulting mixture 112 and pyrolysis off-gas 106 from the pyrolysis reactor 103 are then passed through the chemical reduction reactor 104. In the chemical reduction reactor 113, the metal ore of the carbon-metal ore particles 112 is introduced into the The metal oxides present in 108 are reduced. The bioreagent 104 is injected into the carbon 105. O2 or air 114 can also be introduced into the chemical reduction reactor 113. The chemical reduction reaction in the chemical reduction reactor 113 can be introduced into the metal production A product 116 and a reduced off-gas 115 are produced.

[0178] Disclosed herein is a further process for reducing metal ores. provides an exemplary diagram of such a process. Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrocarbons. and, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; partially oxidizing the pyrolysis off-gas, thereby producing reducing gas and heat; Chemical reduction of metal oxides and partial oxidation of pyrolysis off-gas and reducing the reactant gas by heating the reactant gas to a temperature of 1000° C., Pyrolysis is accomplished using heat generated from the partial oxidation of pyrolysis off-gas. can be.

[0179] FIG. 2 illustrates a process 200 for reducing a metal ore 208 utilizing a biological reagent 204. The biomass feedstock 201 is fed into a pyrolysis reactor 203. 1 is pyrolyzed in the presence of heat 202 under conditions further detailed herein below. Pyrolysis of biomass feedstock 201 produces bioreagents 204 and pyrolysis off-gas 206. The carbon-containing biological reagent 204 and the metal ore 208 are mixed in the carbon-metal ore mixing unit 20 7 to produce carbon-metal ore particles 212. Additives 209 are added to the carbon-metal ore. A mixing unit 207 can be added to combine the biological reagent 204 and the metal ore 208. If pellets are utilized, the output of the carbon-metal ore blending unit 207 is The metal ore pelletization unit 210 can then be introduced into the chemical reduction reactor. The carbon-metal ore particles 212 introduced into the 213 are in the form of pellets. The additive 211 is added to the carbon metal pelletizing unit 210 to produce carbon ore pellets. and incorporated into carbon metal ore pellets. The pyrolysis off-gas 206 from the pyrolysis reactor 203 is introduced into the chemical reduction reactor 213. , undergoes partial oxidation 217, during which O2 or air 218 is introduced. The heat 220 from the off-gas section is introduced for pyrolysis in the pyrolysis reactor 203. The product reduction gas 219 from the partial oxidation 217 is introduced into the chemical reduction reactor 213. Alternatively, air 214 may also be introduced into the chemical reduction reactor 213. The biological reagent 204 may be Bypass the carbon-metal mixing unit 207 and inject carbon 205 into the chemical reduction reactor 213 O2 or air 214 can also be introduced into the chemical reduction reactor 213. The chemical reduction in the chemical reduction reactor 213 produces a metal product 216 and reduced off-gas. Manufactures the 215.

[0180] Chemical reduction is the reduction obtained from gasification, steam reforming, or partial oxidation217 of light hydrocarbons. The raw gas can be simultaneously used. Chemical reduction occurs in the chemical reduction reactor 213, and the blast furnace The process can be carried out in a metal ore furnace, such as a direct reduction metal furnace, an open hearth furnace, or another type of furnace. Alternatively or additionally, chemical reduction can be carried out upstream of the metal ore furnace. In an embodiment, the chemical reduction is produced by combustion or partial oxidation 217 of injected carbon 205. In such an embodiment, the chemical reduction utilizes the internal heat generated by the injected carbon 20 5. The external heat is produced separately by combustion or partial oxidation 217 of the catalyst.

[0181] The process may be carried out at a metal ore mine, a metal ore processing plant, or itself a metal ore processing plant. The company may co-locate metal mines that are co-located in the same company.

[0182] Disclosed herein is a further process for reducing metal ores. provides an exemplary diagram of such a process. Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; generating a reducing gas from gasification, partial oxidation, or steam reforming of a biological reagent; Chemical reduction of metal oxides, which is achieved using a reducing gas. This can include:

[0183] FIG. 3 illustrates a process 300 for reducing a metal ore 308 utilizing a bioreagent 304. A biomass feedstock 301 is introduced into a pyrolysis reactor 303, and pyrolysis is With optional external heat 302, pyrolysis off-gas 306 and bio-reagents 304 are produced. The carbon-containing biological reagent 304 and the metal ore 308 are mixed in the carbon-metal ore mixing unit 307. The additive 309 is added to the carbon metal ore mixture to produce carbon metal ore particles 312. It can be added to the unit 307 and combined with the biological reagent 304 and metal ore 308. If pellets are utilized, the carbon metal ore particles introduced into the chemical reduction reactor 313 The product of the carbon metal ore mixing unit 307 is carbon 312 in the form of pellets. The additive 311 can be introduced into the metal ore pelletizing unit 310. It can also be introduced into a rock pelletizing unit and incorporated into the pellet product. The alumina particles 312 and reducing gas 319 are fed to a chemical reduction reactor 313 from which gold is extracted. Metal products 316 and reduced off-gas 315 are produced. O2 or air 314 is also produced by chemical reduction. The reaction mixture can be introduced into the reactor 313.

[0184] Chemical reduction in chemical reduction reactor 313 occurs during pyrolysis in pyrolysis reactor 303. Gasification of light hydrocarbons, such as light hydrocarbons, present in the resulting bioreagent 304, A second reducing gas obtained from reforming or partial oxidation 317 can be simultaneously utilized. The bioreagent 304 from the decomposition reactor 303 is decomposed into carbon partial acids with the introduction of O2 or air 318. The reducing gas 319 is introduced into the chemical reduction reactor 313. 304 bypasses the carbon-metal ore mixing unit 307 and is used for chemical reduction as injection carbon 305. It can be introduced into the primary reactor 313.

[0185] The chemical reduction occurs in a chemical reduction reactor 213, which may be a blast furnace, a direct reduction metal furnace, an open hearth furnace, or another Alternatively or additionally, chemical reduction may be performed in a metal ore furnace, such as a furnace of the 2000 type. The decomposition can be carried out upstream of the metal ore furnace.

[0186] The process may be carried out at a metal ore mine, a metal ore processing plant, or itself a metal ore processing plant. The company may co-locate metal mines that are co-located in the same company.

[0187] Disclosed herein is a process for processing metal ores, the process comprising: Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide. To do, Obtaining metal ore, wherein the metal ore is in particulate form and the metal ore is treated with a metal acid. Metal hydrides, metal sulfides, metal hydrides, metal nitrides, metal carbides, metal borides, metal phosphides obtaining, including, combining carbon with a metal ore, thereby producing carbon-metal ore particles; Metal oxides, metal sulfides, metal hydrides, metal nitrides, metal carbides, metal borides, gold Chemically producing elemental metals from metal phosphides, or combinations thereof, comprising: and producing the product, which is achieved using cracking off-gas.

[0188] The process involves pelletizing the carbon metal ore particulates, thereby forming the carbon metal ore pellets. The method may further include generating a report.

[0189] Chemical reduction can directly utilize pyrolysis off-gas. The off-gas is partially oxidized, thereby generating a reducing gas, and then the reducing gas is utilized to Metal oxides, metal sulfides, metal hydrides, metal nitrides, metal carbides, metal borides, metals Chemical production of elemental metals from their phosphides, or combinations thereof, The solution off-gas can be used indirectly.

[0190] When metal-containing species other than metal oxides are converted to metals or other metal-containing species, the temperature, pressure, The process conditions, reaction time, and reactant composition, are designed to achieve the desired chemical reaction. For example, in the case of metal hydrides, carbon dioxide, water, and the like must be added to the corresponding metal. Typically, any metal ore contains at least Both have metal oxides, and the process conditions aimed at reducing the metal oxides are also aimed at reducing other forms of metals. Alternatively or additionally, metal ores may be useful in converting other forms of metals in significant quantities. When the compound contains a metal in a crystalline form (e.g., a metal sulfide), an additional reaction step can be used. Those skilled in the art will be able to use routine experimentation to deduce reaction conditions using the teachings of the present disclosure. It will be possible.

[0191] In some embodiments, the chemical reduction may involve gasification, partial oxidation, or For example, heavy coal obtained during pyrolysis is used in the simultaneous use of reducing gas obtained from steam reforming. The hydrogen chloride can be converted at least in part into a reducing gas.

[0192] Chemical reduction is the process of reducing light hydrocarbons, such as light hydrocarbons, obtained during pyrolysis as part of the pyrolysis off-gas. Simultaneous use of reducing gas obtained from gasification, partial oxidation, or steam reforming of hydrocarbons can be done.

[0193] Chemical reduction is carried out in a metal ore furnace, such as a blast furnace, direct reduction metal furnace, open hearth furnace, or another type of furnace. Alternatively or additionally, chemical reduction can be carried out upstream of the metal ore furnace. can.

[0194] The process may be carried out at a metal ore mine, a metal ore processing plant, or itself a metal ore processing plant. The company may co-locate metal mines that are co-located in the same company.

[0195] Disclosed herein is a process for producing carbon metal ore pellets. , provides an exemplary illustration of such a process. Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets This can include:

[0196] FIG. 4 illustrates a process for producing carbon metal ore pellets 420 utilizing bioreagent 404. A description of the process 400 is provided. Biomass feedstock 401 is introduced into a pyrolysis reactor 403. Pyrolysis by external heat 402 produces pyrolysis off-gas 406 and bio-reagents 404 . The carbon-containing biological reagent 404 and the metal ore 408 are fed to a carbon-metal ore mixing unit 407. The additive 409 is fed to the carbon-metal ore mixing unit to produce carbon-metal ore particles. 407 and can be incorporated with bioreagents 404 and metal ores 408. The carbon-metallic ore particles produced by the metal ore blending unit 407 are From the carbon metal ore pelletizing unit 410, the carbon metal ore is introduced into the pelletizing unit 410. The carbon metal ore pellets 420 are produced. The carbon metal ore pellets 420 may also be incorporated into the pellets.

[0197] Disclosed herein is a further process for producing carbon metal ore pellets. The process is Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets and the biological reagent comprises at least about 50% by weight of fixed carbon; The carbon metal ore particulates have at least about 0.1 wt. % to at most about 50 wt. % total carbon. Includes:

[0198] Disclosed herein is a process for producing metal nuggets. provides an exemplary diagram of such a process. Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide. To achieve Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets And, Chemically reducing metal oxides to thereby produce metal nuggets, wherein the chemical reduction is achieved using pyrolysis off-gas; recovering metal nuggets, wherein the metal nuggets are in reduced form of metal oxides. and recovering the metal nugget, wherein the metal nugget consists essentially of metal and carbon. It is possible.

[0199] FIG. 5 illustrates a process 50 for fabricating a metal nugget 521 utilizing a bioreagent 504. 0. Biomass feedstock 501 is fed to pyrolysis reactor 503. Biomass feedstock 501 is pyrolyzed in the presence of heat 502 under conditions further detailed herein below. The pyrolysis of the biomass feedstock 501 produces bioreagents 504 and pyrolysis off-gas 506. The carbon-containing biological reagent 504 and the metal ore 508 are mixed in a carbon-metal ore mixing unit. 507 to produce carbon-metal ore particles. Additive 509 is added to the carbon-metal ore mixture. The bioreagent 504 can be added to the combining unit 507 to combine the bioreagent 504 with the metal ore 508. The carbon metal ore particles produced by the carbon metal ore mixing unit 507 are The metal ore pellets 510 are introduced into the metal ore pelletizing unit 510, thereby forming carbon metal ore pellets 51 2 is produced. Additive 511 is added to the carbon metal ore pelletizing unit 510 to produce The carbon-metal ore pellets 512 can be incorporated into the carbon-metal ore pellets 512. Metal ore pellets 512 and pyrolysis off-gas 506 are introduced into a chemical reduction reactor 513. In the chemical reduction reactor 513, the carbon-metal ore pellets 512 are depleted of the metal ore 508. The biological reagent 504 is introduced into the chemical reduction reactor 504 as an injection carbon 505. O2 or air 514 can also be introduced into the chemical reduction reactor 513. The chemical reduction reaction in the chemical reduction reactor 513 can be carried out by mixing the metal nuggets 521 and A reduced off-gas 515 is produced.

[0200] Disclosed herein is a process for producing metals from metal ores. provides an exemplary diagram of such a process. Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing a bio-reagent, containing carbon, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; Pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets And, introducing carbon metal ore pellets into a chemical reduction furnace; Oxidizing the carbon contained within the carbon metal ore particles, thereby generating heat and carbon monoxide The oxidation is achieved by introducing air or oxygen into the chemical reduction reactor. To be generated and In the chemical reduction furnace, the metal oxides contained in the carbon metal ore pellets are chemically reduced, and The chemical reduction of the metal by the use of carbon monoxide is and and recovering the metal.

[0201] FIG. 6 shows a process for producing metal 625 from metal ore 608 utilizing bioreagent 604. The pyrolysis reactor 603 is a biomass feedstock 601. The omas feedstock 601 is heated in the presence of heat 602 under conditions further detailed herein below. The pyrolysis of the biomass feedstock 501 produces bioreagents 604 and pyrolysis offgas. The carbon-containing biological reagent 604 and the metal ore 608 form a carbon-metal ore mixture. The additive 609 is fed to a combining unit 607 to produce carbon metal ore particles. Add to metal ore mixing unit 607 to combine bio-reagent 604 with metal ore 608 The carbon-metal ore granules produced by the carbon-metal ore mixing unit 607 can be The material is introduced into a carbon metal ore briquetting unit 622, thereby forming a carbon metal ore The additive 623 is added to the carbon metal ore briquetting unit 62 to produce briquettes 624. 2 and incorporated into carbon metal ore briquettes 624. The rickets 624 are introduced into the chemical reduction reactor 613. The solution off-gas 606 can be introduced into the chemical reduction reactor 613. 13, the metal oxide present in the metal ore 608 of the carbon metal ore briquette 624 The biological reagent 604 is introduced into the chemical reduction reactor 613 as an injection carbon 605. O2 or air 614 can also be introduced into the chemical reduction reactor 613. The chemical reduction reaction in the chemical reduction reactor 613 generates a metal 625, a slag 626, and a reducing agent. Produces offgas 615.

[0202] In some embodiments, a portion of the bioreagent is co-fed directly into the chemical reduction reactor.

[0203] In some embodiments, the pyrolysis off-gas is added to or produced in addition to the carbon metal ore particulates. In addition to the reagent, it can be introduced into the chemical reduction furnace. For example, it can be introduced into the chemical reduction furnace together with the pellets. This is an embodiment that is supplied simultaneously.

[0204] Further processes for producing metals from metal ores are disclosed herein. Seth said, Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises carbon monoxide or hydrogen. To do, Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; introducing carbon metal ore particulates into a chemical reduction furnace; Oxidizing carbon, thereby producing heat and carbon monoxide or carbon dioxide. The oxidation is achieved by introducing air or oxygen into the chemical reduction reactor. and, In the chemical reduction furnace, the metal oxides contained in the carbon metal ore pellets are chemically reduced, and The chemical reduction of the metal by the use of carbon monoxide is and and recovering the metal.

[0205] In some embodiments, after producing the carbon metal ore particles, the process further comprises: and further pelletizing the ore particulates, thereby producing carbon metal ore pellets. In such an embodiment, the carbon metal ore pellets are introduced into a chemical reduction furnace.

[0206] In some embodiments, the process includes introducing the biological reagent or a portion thereof into a chemical reduction reactor. It further includes:

[0207] The carbon that is oxidized in the chemical reduction reactor may be contained within the carbon metal-ore particles or may be present in the oxide. The carbon that is oxidized in the chemical reduction furnace may be contained in the bioreagent.

[0208] In some embodiments, the process includes introducing the pyrolysis off-gas, or a portion thereof, into a chemical reduction furnace. The method further includes inserting the

[0209] Carbon monoxide, used to achieve the chemical reduction of metal oxides, is a major contributor to the oxidation of biological reagents. It may be a product of oxidation of carbon contained within carbon-metallic ore particles. , or may be contained in the pyrolysis off-gas.

[0210] Further processes for producing metals from metal ores are disclosed herein. Seth said, Providing a biomass feedstock; Pyrolyzing a biomass feedstock, thereby producing bioreagents and pyrolysis off-gas. wherein the biological reagent comprises carbon and the pyrolysis off-gas comprises hydrogen; Obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in the form of a particulate material. In form, to obtain and combining carbon with a metal ore, thereby producing carbon-metal ore particles; introducing carbon metal ore pellets into a chemical reduction furnace; Oxidizing carbon, thereby producing heat and carbon monoxide or carbon dioxide. The oxidation is achieved by introducing air or oxygen into the chemical reduction reactor. and, In the chemical reduction furnace, the metal oxides contained in the carbon metal ore pellets are chemically reduced, and The chemical reduction of the metal by the use of carbon monoxide is and producing, which is achieved by using hydrogen or and recovering the metal.

[0211] In some embodiments, after producing the carbon metal ore particles, the process further comprises: and further pelletizing the ore particulates, thereby producing carbon metal ore pellets. In such an embodiment, the carbon metal ore pellets can be introduced into a chemical reduction furnace. Cut.

[0212] In some embodiments, the process includes introducing the biological reagent or a portion thereof into a chemical reduction reactor. It further includes:

[0213] The carbon that is oxidized in the chemical reduction reactor may be contained within the carbon metal-ore particles or may be present in the oxide. The carbon that is oxidized in the chemical reduction furnace may be contained in the bioreagent.

[0214] In some embodiments, the process includes introducing the pyrolysis off-gas, or a portion thereof, into a chemical reduction furnace. The method further includes inserting the

[0215] Carbon monoxide, which can be used to achieve chemical reduction of metal oxides, is a bioreagent or may be a product of oxidation of carbon contained within the carbon metal ore particles. Hydrogen that can be used to achieve chemical reduction of metal oxides can be a thermal The solution may be contained in the off-gas.

[0216] Process Parameters The process parameters provided in this section are intended to be used in the processes described herein, e.g. Process for reducing metal ores, process for treating metal ores, carbon metal ores Process for producing pellets, process for producing metal nuggets, and metal Applied to the process of producing metals from ores.

[0217] In some embodiments, the chemical reduction can include gasification of the bioreagent or a portion thereof; The reducing gas obtained from partial oxidation or steam reforming is simultaneously used. The reducing gas is a mixture of CO and H2, and typically both CO and H2. Includes synthesis gas. Other components such as CH4, CO2, and H2O may also be present in the reducing gas. good.

[0218] In some embodiments, the chemical reduction can be achieved by gasification, partial oxidation of light hydrocarbons. Alternatively, reducing gas obtained from steam reforming is simultaneously utilized.

[0219] Chemical reduction is achieved by using a furnace such as a blast furnace, direct reduction furnace, open hearth furnace, or another type of furnace. Alternatively or additionally, chemical reduction can be carried out in a metal ore furnace. This can be done upstream of the ore furnace.

[0220] In some embodiments, the chemical reduction is by combustion or partial oxidation of carbon. In these or other embodiments, the chemical reduction utilizes the internal heat produced by: External heat can be utilized, produced separately by combustion or partial oxidation of carbon.

[0221] The process may be carried out at a metal ore mine, a metal ore processing plant, or itself a metal ore processing plant. The company may co-locate metal mines that are co-located in the same company.

[0222] In some embodiments, the process comprises pelletizing the carbon metal ore particles, In some embodiments, the metal oxide is used to produce carbon-metal ore pellets. The material is contained within carbon metal ore pellets.

[0223] In some embodiments, the biomass feedstock is softwood chips, hardwood chips, timber harvest residues, or , 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, cabbage Nora, algae, miscanthus, alfalfa, switchgrass, fruit, fruit shells, fruit stems, Fruit peels, fruit seeds, vegetables, vegetable shells, vegetable stems, vegetable peels, vegetable seeds, grape juice Rice dregs, 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 trimming food packaging, construction or demolition waste, lignin, animal manure, municipal solid waste, municipal sewerage, or a combination thereof.

[0224] The bioreagents produced by the pyrolysis step herein contain at least about 50% by weight: It may contain at least about 75% by weight, or at least about 90% by weight, total carbon. In various embodiments, the biological reagent is about, at least about, or at most about 50, 55, 60, Contains 65, 70, 75, 80, 85, 90, 95, or 99% by weight of total carbon. The carbon content is the sum of the fixed and non-fixed carbon present in the volatile material. In this document, weight percentages of ingredients are absolute and are assumed unless otherwise stated. In this embodiment, the component weight percentages are on a dry and ash-free basis.

[0225] The bioreagent produced by the pyrolysis step comprises at least about 50% by weight of at least It may contain about 75% by weight, or at least about 90% by weight, total carbon. In this state, the biological reagent is about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 99% by weight total carbon, with intermediate ranges (e.g., from about 70 to about 99% by weight total carbon). Includes:

[0226] The bioreagent produced in the pyrolysis is at least about 50% by weight, at least about 75% by weight In various embodiments, the composition may comprise at least about 90% by weight of fixed carbon. , the biological reagent is about, at least about, or at most about 50, 55, 60, 65, 70, 75 , 80, 85, 90, 95, or 99 wt. % fixed carbon, including intermediate ranges ( For example, it contains about 70 to about 99% by weight of fixed carbon.

[0227] The carbon contained in the bioreagent may be, for example, at least about 50% by weight, at least about 75% by weight, %, or at least about 90% by weight, of fixed carbon, with the remainder of the carbon being volatile carbon. In various embodiments, the carbon is about, at least about, or at most about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100% by weight of fixed carbon It contains an intermediate range (eg, about 70 to about 99 wt. % fixed carbon).

[0228] The pyrolysis conditions depend on the desired composition of the bioreagent and pyrolysis off-gas, the starting materials, and the metal oxides. The pyrolysis temperature may vary depending on the type, reactor configuration, and other factors described herein. The temperature is an important parameter and should be controlled. Generally speaking, the higher the temperature, the Decomposition temperatures, for example, about 600°C to about 850°C, produce more hydrogen in the pyrolysis off-gas. This is due to the reduction of metal oxides (in other words, the oxidation of the metal). This may be advantageous in embodiments that utilize hydrogen in the off-gas for oxygen removal. Pyrolysis temperatures, for example, about 400°C to about 600°C, leave more hydrogen in the bioreagent, Therefore, there is less hydrogen in the off-gas, which is due to the reduction of metal oxides. Special features such as the use of hydrogen in the reagent, self-reducing pellets or the injection of biogenic carbon into a metal reduction furnace In either scenario, hydrogen is used to reduce the metal oxide. This avoids direct CO2 production and therefore This is desirable as it improves the environmental footprint by reducing carbon intensity.

[0229] In some embodiments, the metal ore is iron ore, copper ore, nickel ore, magnesium ore, ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore The minerals are tungsten ore, molybdenum ore, or a combination thereof. In an embodiment, the metal ore is iron ore, for example, hematite, magnetite, limonite, tantalum, or the like. iron ore selected from the group consisting of iron ore, iron ore, iron ore of chromium ...

[0230] Metal ores are classified as beneficiated metal ores, i.e., those that have been processed in one or more beneficiation units. It may be a metal ore.

[0231] In some embodiments, the particulate form is a powdered form of metal ore.

[0232] The carbon metal ore particulates may be carbon metal ore fines (e.g., powder), carbon metal ore chunks, or If pellets are produced, a wide variety of pellet shapes may be used. The shape of the pellets is not limited to a spherical or nearly spherical shape. The shapes are spherical (circular or ball-shaped), cubic (square), octagonal, hexagonal, honeycomb / Honeycomb, oval, egg, cylinder, rod, bread, pillow, random, or It can be a combination of these.

[0233] The carbon metal ore particulates are at least about 0.1% by weight and at most about 50% by weight carbon; For example, it may contain at least about 1% by weight and at most about 10% by weight of carbon. In certain embodiments, such as those used in connection with blast furnaces, the carbon metal ore particulates include: It contains at least about 3% to at most about 6% carbon by weight.

[0234] In certain embodiments, the carbon-metal ore pellets consist essentially of carbon and metal ore.

[0235] The carbon metal ore pellets may contain additives such as binders. The binders may be inorganic bases. Contains tonite clay, limestone, starch, cellulose, lignin, or acrylamide When lignin is used as a binder (or as a general additive), Lignin can be obtained from the same biomass feedstocks used in the pyrolysis process. For example, the starting biomass feedstock can be subjected to a lignin extraction step to extract lignin for use as a binder. A certain amount of lignin can be removed for further use. The remaining solids can then be recycled to the pyrolysis process. The resulting mixture can be supplied to the process.

[0236] Additives may include fluxing agents such as inorganic chlorides, inorganic fluorides, or lime.

[0237] In some embodiments, the additive is an acid, a base, or a salt or derivative thereof. In some embodiments, the additive is a metal, a metal oxide, a metal hydroxide, a metal halide The additives are sodium hydroxide, water, Potassium oxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium silicate, permanganate potassium phosphate, magnesium, manganese, aluminum, nickel, chromium, silicon, boron Iron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide, iron chloride, Iron bromide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide The inorganic filler may be sodium, lime, or a combination or derivative thereof.

[0238] Additives may be added before, during, or after any one or more steps in the process. This includes adding it to the feedstock itself at any time before or after it is harvested. When in the process the additive is incorporated depends on the desired product. For example, derivatives , the product of pyrolysis of the additive and the raw material, in which case the additive is In such an embodiment, the derivative is an additive. In some embodiments, the catalyst does not substantially react with the raw materials.

[0239] In chemical reduction, pyrolysis off-gas is used to chemically reduce metal oxides. "Utilizing" CO, H, or both CO and H is a metal oxide (e.g., Fe3O4) to the corresponding metal (e.g., Fe) or to a less reduced metal oxide (e.g., For example, FeO is reduced to Fe2O3 (less reduced than Fe2O3) in a chemical reaction. It shows that the metal oxides react chemically with the pyrolysis off-gas. The reduction of the sensible heat contained in the pyrolysis off-gas is carried out by utilizing at least a portion of the sensible heat contained in the pyrolysis off-gas. To cause or enable an endothermic reaction, whether mechanically, kinetically, or both Pyrolysis off-gas is useful for endothermic reactions that require heat. Without being bound by the present invention, the hot off-gas may be separated into a separate stream before being injected into the furnace or reactor. Heat can be exchanged, in this case CO or H2 is chemically utilized, but the heat of reaction is It can be obtained from a source different from the cracking off-gas. The off-gas, even though hot, is at a lower temperature than the reaction zone of the furnace into which it is injected. In such an embodiment, the off-gas does not provide heat but actually The furnace itself can be considered to be heated, and the contents of the furnace are relatively Cooling gas is used so that endothermic chemical reactions are still favored with low overall energy usage. It does not cool as much as occurs with gas injection.

[0240] In some embodiments, chemically reducing comprises reducing at least a portion of the pyrolysis off-gas. Alternatively or additionally, chemical reduction can be performed by first using pyrolysis off-gassing. The carbon dioxide is partially oxidized to generate a reducing gas, which is then utilized to Chemically reducing metal oxides that may be contained within metal ore particles or carbon metal ore pellets. By doing so, the pyrolysis off-gas can be indirectly utilized.

[0241] In some embodiments, heat is generated from partial oxidation rather than complete oxidation (combustion) of the pyrolysis off-gas. is produced, thereby producing CO or H rather than combustion gases containing primarily CO and H0. A reducing gas containing 2 is produced. Heat is used to increase the temperature of pyrolysis or to generate other protons. It can be used for process applications. Partial oxidation requires less heat than complete oxidation. However, more reducing gas is produced, which is useful for chemical reduction. do.

[0242] In some embodiments, the chemical reduction can include gasification of the bioreagent or a portion thereof; The reducing gas obtained from partial oxidation or steam reforming is simultaneously used. The reducing gas is a mixture of CO and H2, and typically both CO and H2. Includes synthesis gas. Other components such as CH4, CO2, and H2O may also be present in the reducing gas. good.

[0243] In some embodiments, the bioreagent or a portion thereof is a heavy hydrocarbon obtained during pyrolysis. wherein the heavy hydrocarbons are converted at least in part into a reducing gas. It may come from decomposition off-gas or from volatile carbon remaining in the biological reagents. hydrocarbons with at least 5 carbon atoms (e.g., n-hexane or toluene) This can be done.

[0244] In some embodiments, the chemical reduction can be achieved by gasification, partial oxidation of light hydrocarbons. The light hydrocarbons are produced by the thermal cracking off-gas. Alternatively or additionally, it may be derived from the gas, in other words, obtained during pyrolysis. Heavy hydrocarbons can be diverted from the feed to the combustion chamber that heats the pyrolysis reactor. Heavy hydrocarbons are hydrocarbons with 1 to 4 carbon atoms (e.g., methane or n-butane). may include:

[0245] The pyrolysis off-gas contains at least 1 mol % hydrogen, for example at least 10 mol % hydrogen. The pyrolysis off-gas may contain at least 1 mole % carbon monoxide, e.g., at least Both may contain 10 mole percent carbon monoxide.

[0246] The reducing gas may be at least 10 mol% hydrogen, for example at least 15 mol%, 20 mol% , 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, or 50 mol% water The reducing gas may contain at least 10 mole percent carbon monoxide, e.g., at least All of the above are 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, and 45 % or 50 mole % carbon monoxide.

[0247] Chemical reduction is achieved by using a furnace such as a blast furnace, direct reduction furnace, open hearth furnace, or another type of furnace. Alternatively or additionally, chemical reduction can be carried out in a metal ore furnace. This can be done upstream of the ore furnace.

[0248] In some embodiments, the chemical reduction is by combustion or partial oxidation of carbon. In these or other embodiments, the chemical reduction utilizes the internal heat produced by: External heat can be utilized, produced separately by combustion or partial oxidation of carbon.

[0249] The process may be carried out at a metal ore mine, a metal ore processing plant, or itself a metal ore processing plant. The company may co-locate metal mines that are co-located in the same company.

[0250] In some embodiments, the pyrolysis and chemical reduction occur in situ. In other embodiments, the pyrolysis and chemical reduction occur at different locations.

[0251] Embodiments utilizing metal ore furnaces or chemical reduction furnaces Metal ore furnaces or chemical reduction furnaces include blast furnaces, top gas recirculation blast furnaces, shaft furnaces, reverberatory furnaces ( Also known as air furnaces, crucible furnaces, silencer furnaces, retort furnaces, flash furnaces, Tecnore d furnace, Ausmelt furnace, ISASMELT furnace, puddling furnace, bogie hearth furnace, continuous chain furnace, pusher furnace, rotary hearth furnace, walking beam furnace, electric arc furnace, induction furnace, base The furnace may be a reactive oxygen furnace, a puddling furnace, a Bessemer furnace, a direct reduction furnace, or a combination thereof. do.

[0252] The metal ore furnace or chemical reduction furnace may be positioned horizontally, vertically or at an angle. The flow of solids or fluids (or liquids or gases) can be co-current or counter-current. The metal ore furnace or chemical reduction furnace can be a fixed bed or a fluidized bed. It is possible to operate at various process conditions for a period of time.

[0253] Some embodiments utilize a blast furnace. A blast furnace is a furnace used to produce industrial metals such as iron or copper. A blast furnace is a type of metallurgical furnace used to smelt iron ore to produce commercial iron. Blast furnaces are also used to produce pig iron, an intermediate material used in the production of iron and steel. For example, they are used in base metal smelting in conjunction with sinter plants.

[0254] The term "blast" in "blast furnace" refers to the combustion air being forced or supplied above atmospheric pressure. In a blast furnace, metal ores, carbon (e.g., bioreagents), and usually Coal (e.g., limestone) is continuously fed through the top of the furnace while hot air ( The steam (which may be oxygen-enriched) is blown into the bottom of the furnace through a series of pipes called tuyere. Chemical reduction reactions occur throughout the furnace as the material falls downward. The final product is usually The molten metal and slag phases are taken out from the bottom, and the waste gas (reducing oil) leaves the top of the furnace. The metal along the flux is in countercurrent contact with the upward flow of hot CO2-rich gas. The downward flow of the ore allows for efficient chemical reactions that reduce the metallic ore to metal.

[0255] Air furnaces (such as reverberatory furnaces) are usually naturally aspirated by the 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.

[0256] Blast furnaces remain an important part of modern iron production. Modern furnaces are highly efficient and a cowper stove to preheat the incoming blast air with waste heat from the flue gases; and It includes a recovery system that extracts heat from the hot gases that exit the furnace. Blast furnaces are typically constructed with refractory bricks. It is constructed in the form of a tall structure lined with mould, and the feed material is heated as it descends. It is contoured to expand as it melts and then shrink in size as melting begins to occur. do.

[0257] In some embodiments related to iron production, renewable carbon, iron ore (iron oxide), and A bioreagent containing a ash flux is charged into the top of the blast furnace. The furnace may be configured to allow hot, dirty gases with high temperature to exit the furnace throat, while The leader valve can protect the top of the furnace from sudden gas pressure surges. The coarse particles settle and can be disposed of, while the gas is scrubbed or It can flow through an electrostatic precipitator or gas cooler to reduce the temperature of the purified gas The casting chamber at the bottom of the furnace houses the equipment for casting liquid iron and slag. and the taphole is refractory so that the slag flows down the launder through the opening and separates the iron and slag. Once the pig iron and slag are tapped, the taphole is filled with a refractory clay plug. Nozzles called tuyere are used to supply hot air to increase the efficiency of the blast furnace. Hot air is directed into the furnace through cooled tuyere holes near the base. The hot air temperature is, for example, at least about 900°C to at most about 1300°C (air temperature). The temperature in the blast furnace may be at least about 2000°C. is injected into the furnace at the tuyere level to combine with carbon (from the bioreagent) to produce additional energy. It is also possible to release and increase the percentage of reducing gas present, which increases productivity. .

[0258] Blast furnaces have a stronger affinity for oxygen in metal ores (e.g., iron ore) than the corresponding metals. It operates on the principle of chemical reduction, where carbon monoxide reduces metals to their elemental form. 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. contact, diffusing carbon monoxide into the ore and reducing the metal oxides to elemental metals mixed with carbon Blast furnaces typically operate as continuous countercurrent exchange processes.

[0259] Silica is usually removed from pig iron by reacting with calcium oxide to form silicates. This forms a slag that floats on the surface of the molten pig iron. The column of reaction products must be porous enough to allow the flue gas to pass through. This requires that the particles be large enough to be permeable to the bioreagent carbon. Therefore, the bioreagent (which may contain additives) must be The carbon must be strong enough to resist being crushed by the sulfur, phosphorus, and ash. In addition to being less bulky, they are physically strong.

[0260] Chemical Reactions in a Blast Furnace Many chemical reactions occur in the blast furnace. The chemical reactions involve the use of hematite (F This form of iron oxide can be understood with reference to the initial raw material: It is common in iron ore processing, either as produced in the blast furnace or as it is produced in the blast furnace. Iron ores in the form of iron (e.g., taconite) contain various concentrations of different iron oxides (Fe3O4, F e2O3, FeO, etc.

[0261] The general chemical reaction for producing molten iron in a blast furnace is the following endothermic reaction: Fe2O3+3CO→2Fe+3CO2

[0262] This reaction occurs in many steps, the first of which is the preheating of the furnace. The blast air reacts with carbon (e.g., from biological reagents) to produce carbon monoxide and heat. To do this. 2C+O2→2CO Hot carbon monoxide is a reducing agent for iron ore and reacts with 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 At the top, where temperatures are typically in the range of 200-700°C, oxidation takes place. The iron is partially reduced to iron (II, III) oxide, Fe3O4. 3Fe2O3+CO → 2Fe3O4+CO2 Further down the furnace, at a temperature of about 850°C, iron (II, III) is converted to iron (II) oxide, FeO. : is further reduced to Fe3O4+CO→3FeO+CO2 Hot carbon dioxide, unreacted carbon monoxide, and nitrogen from the air react with the fresh feed. As the material moves downward into the reaction zone, it passes upward through the furnace. The countercurrent gas preheats the feed charge and converts limestone (if used) into calcium oxide. It decomposes into sodium and carbon dioxide. CaCO3 → CaO + CO2 The calcium oxide formed by decomposition interacts with various acidic impurities (especially silica) in the iron. It reacts to form a slag which is mainly calcium silicate, CaSiO3. SiO2 + CaO → CaSiO3 As FeO moves into the higher temperature region up to 1200 °C, It is further reduced to iron metal, again using carbon monoxide as a reactant. FeO+CO→Fe+CO2 The carbon dioxide formed in this process reacts with the biological reagent via the reverse Boudouid reaction. This can convert it back to carbon monoxide. C+CO2→2CO

[0263] In the chemical reaction shown above, carbon monoxide is an in situ product of carbon oxidation. It should be noted that the molten metal may alternatively or additionally be introduced directly into the blast furnace rather than into the blast furnace. According to the present disclosure, the CO may be pyrolysis off-gas introduced into the furnace. It can also contain CO2, which produces more CO via the reverse Boudouid reaction.

[0264] In a conventional blast furnace, there is no hydrogen available to cause the reduction of metal oxides. Alternatively or additionally, the hydrogen-containing pyrolysis off-gas can be injected into the blast furnace. In general, hydrogen is generated when biological reagents contain volatile carbon (e.g., heavy tar components) that are associated with hydrogen. If hydrogen is used in the same way as above, it may be available in the bioreagents fed to the blast furnace. Similar to the reaction described above, an additional reduction reaction can occur, replacing CO with H2. 3Fe2O3+H2→2Fe3O4+H2O Fe3O4+4H2→3Fe+4H2O

[0265] These reactions occur in parallel with the reduction reaction with CO. Hydrogen is also reacted with CO by the reverse water gas shift reaction. It can react with carbon dioxide in a nitrate reaction to produce more CO.

[0266] "Pig iron" produced by blast furnaces typically has a relatively high carbon content of about 3-6% by weight. Pig iron can be used to make cast iron. The treated pig iron typically has reduced carbon and sulfur content and is used commercially in various grades. It undergoes further processing to produce steel. A further process called basic oxygen steelmaking In the oxidizing step, carbon is oxidized by blowing oxygen onto the liquid pig iron to form crude steel. do.

[0267] Desulfurization has traditionally been carried out using calcium oxide, which reacts with iron sulfide contained in pig iron to form calcium sulfide. This is done during the transportation of liquid iron to the steelworks by adding sodium. In an embodiment, desulfurization also involves reacting metal sulfides with CO (from the pyrolysis off-gas) to form metal sulfides. This can occur in or downstream of the furnace by forming metals and carbonyl sulfides (CSO). do.

[0268] Other types of furnaces may use other chemical reactions. In the chemical conversion of metal oxides to metals using organic gases (such as CO), the carbon is renewable. It will be understood that the carbon can be produced by pyrolysis of biomass. Provides renewable carbon in the bioreagents produced. In certain embodiments, the bioreagents utilized in the furnace Some of the carbon consumed in metal ore furnaces is not renewable carbon. The percentage of renewable carbon in the total carbon generated is at least about 20%, 30%, 40%, It can be 50%, 60%, 70%, 80%, 90%, 95%, 99%, or 100%.

[0269] In some embodiments, a Tecnored furnace, or a variation thereof, is utilized. The ored process was originally developed in Brazil by Tecnored Desenvolvimen Developed and cold-bonded by Tecnologico SA, carbon It is based on a low-pressure moving bed reduction furnace that reduces contained, flash-fluxed, and self-reduced pellets. The process is carried out in a low-profile shaft furnace at typical reduction temperatures. Typically, liquid iron is produced.

[0270] The Tecnored technology was developed to be a cokeless steelmaking process, and therefore This not only significantly reduces greenhouse gas emissions in the production of hot metal, but also eliminates environmentally harmful coke. The Tecnored process combines hot and cold blasting to avoid the investment and operation of a gas furnace. It uses a combination of rust and does not require additional oxygen. This process eliminates the need for a sinter plant and a tonnage oxygen plant. The process has much lower operating and investment costs than those of the traditional steelmaking route. .

[0271] In this disclosure, the Tecnored process is intended for use with biological reagents in a variety of ways. Some embodiments may be adapted for iron ore fines or iron-bearing residues. Cold-bonded self-reduced aggregates (e.g., Pellet) prepared from the addition of biological reagents to These materials, mixed with fluxes and binders, are agglomerated. It is thermally hardened and strong enough to withstand the physical and metallurgical demands of the Tecnored process. The resulting agglomerates are then mixed with Tecnor The fuel for the Tecnored furnace is itself a high-carbon bioreactant. It could be.

[0272] By combining the iron oxide particles with the reducing agent in a briquette, the iron oxide particles are brought into contact with the reducing agent. The surface area of ​​the oxides present in the briquettes, and therefore the reaction rate, increases dramatically. The reducing agent may be designed to contain sufficient reducing agent to completely reduce the iron-containing raw material to be treated. In some embodiments, a flux is used to provide the desired slag chemistry. The self-reducing briquettes are hardened at low temperature before being fed into the furnace. The heat required to drive the reaction is provided by a bed of solid fuel, which may also be in the form of briquettes. On top of that, self-reducing briquettes are fed into the furnace.

[0273] The Tecnored furnace has three zones: (i) the upper shaft zone; (ii) the melting zone; (iii) a lower shaft zone. In the upper shaft zone, a solid fuel In this zone, the Boudouid reaction (C + CO2 → 2CO) occurs. Post-combustion in this zone of the furnace burns off CO and saves energy. This provides the energy for preheating and reduction of the charge. The reaction below occurs very rapidly. Fe x O y +yCO → xFe +yCO2 yCO2+yC=2yCO (wherein x is 1 to typically 5, and y is 1 to typically 7).

[0274] In the melting zone, reoxidation is prevented by the reducing atmosphere in the charge. The process takes place in a reducing atmosphere. In the lower shaft zone, solid fuel is charged. can comprise or consist essentially of high carbon biological reagents. Further reduction of residual iron oxide and slagging of gangue materials and fuel ash occur in the liquid state. In addition, superheating of the metal and slag droplets occurs. The droplets sink by gravity to the hearth of the furnace and accumulate there.

[0275] This modified Tecnored process involves two different inputs of carbon units: That is, a reducing agent and a solid fuel are used. Conventionally, the reducing agent is coal fines, but in this disclosure, The reducing agent is or includes a bioreagent in the form of carbon fines. The bioreagent is self-reducing. The raw agglomerates (pellets or briquettes) are added to the mixture to be produced. The amount of carbon fines is established by the C / F (carbon to ore fines) ratio, which is the total mass of the metal oxide. The reaction can be selected to achieve complete reduction.

[0276] The solid fuel (bioreagent) does not have to be in the form of a fine powder. For example, the solid fuel may be in the form of a Tec To meet the physical and thermal demands required from solid fuel in the nored process The solid fuel may be in the form of chunks, about 40-80 mm in size, for example. The feed is through a side feeder (to avoid the endothermic Boudoir reaction in the reactor) and the This energy is supplied by the primary brass The gasification of solid fuel in the hearth is formed by the secondary blast (C + O2 → CO2) and the secondary blast. The upstream CO produced by this is combusted (2CO + O2 → 2CO2).

[0277] In certain exemplary embodiments, the modified Tecnored process is Iron ore fines with a size of less than 100 mesh, biological reactants with a size of less than 200 mesh Fluxes such as fine powder and hydrated lime of size less than 140 mesh are used as binders for cement. The pellets were hardened and dried at 200°C. The charge is then fed into the top of a Tecnored furnace. The total residence time of the charge in the furnace is about 30- 40 minutes. Bioreagents in the form of solid fuels with sizes ranging from 40mm to 80mm are A hot pellet feeder is used to feed the pellets into the furnace below the hot pellet zone. Lastly, air is blown in through tuyeres located on the side of the furnace to provide combustion air for the biocarbon. A small amount of furnace gas is provided through a side feed system for use in drying and preheating the solid fuel. To promote post-combustion of CO in the upper shaft, a cold brush is used. The hot metal produced is tapped into a ladle on a ladle cart, and the hot metal is then poured into the ladle. The ladle cart can tilt the ladle for slag removal. The liquid iron is desulfurized in the ladle. The hot metal can be poured into a slag pot and the slag can be scraped into a slag pot. contains about 3-5% by weight of carbon.

[0278] Traditionally, external CO or H2 is used in the autoreduction process using a Tecnored furnace. However, in the context of this disclosure, external CO or H 2 (e.g., from pyrolysis off-gas) is reacted with Fe x O y +yCO→xFe+yC O2) or in the reaction with hydrogen as a reactant (Fe x O y +yH2→xFe+yH 2O) aids in the overall chemical reaction by increasing the rate or conversion of iron oxide The reduction chemical reaction can occur at least on the surface of the pellet or briquette. In some cases, this can be achieved within the bulk phase of the pellet or briquette, but this is highly This is because the mass transfer of hot carbon monoxide is fast. Completely self-reducing pellets or briquettes are desirable. In some preferred embodiments, there is no introduction of external CO, H2, or syngas. Some embodiments combine aspects of a blast furnace with aspects of a Tecnored furnace, thereby In addition to the use of pyrolysis off-gas in the furnace, self-reducing pellets or briquettes are utilized. .

[0279] As previously mentioned, there are many possible furnace configurations for metal ore processing. The various conditions and chemical reactions that may occur in all possible furnaces will not be described in detail, but will be within the scope of the present disclosure. The theory is that essentially any furnace that uses carbon somewhere in the process of making metal from metal ore. It will be understood by those skilled in the art that the present invention may be applied to any process.

[0280] Some processes utilize solid carbon and some utilize gaseous carbon monoxide. Some processes utilize both solid carbon and gaseous carbon monoxide. As described herein, the pyrolysis processes provided herein may also be observed. The process involves the use of both solid carbon (bioreagent) and pyrolysis off-gas containing at least carbon monoxide. In some embodiments, only the solid bio-reagent is used in the metal ore conversion process. In another embodiment, only pyrolysis off-gas is used in the metal ore conversion process. In yet another embodiment, both the solid bioreagent and the pyrolysis off-gas are used. These processes use both renewable carbon sources. In this embodiment, the percentage of total carbon usage in the metal ore conversion from the solid bio-reagent is about , at least about, or at most about 5%, 10%, 20%, 30%, 40%, 50%, 60 Other carbon usages may be 70%, 80%, 90%, 95%, or 100%. Alternatively, some or all of the other carbon usage may be from coal fines. It can be from a conventional carbon input such as powder.

[0281] Processes, systems, and compositions of methods Also disclosed herein are compositions produced according to the processes disclosed herein. For example, processes for reducing metal ores, processes for treating metal ores, carbon-gold Process for producing metal ore pellets, process for producing metal nuggets, and and processes for producing metals from metal ores.

[0282] Provided herein is a composition for reducing metal ores, the composition comprising carbon-metal ore particles. and at least about 0.1% by weight of carbon metal ore particles on a dry and ash-free basis. ~Contains at most about 50% by weight of fixed carbon, and the fixed carbon is 14 C / 12 C isotope ratio Disclosed is a composition that is at least 50% renewable carbon as determined from a measurement of:

[0283] Provided herein are additional compositions for reducing metal ores, the compositions comprising: a carbon-metal ore particulates, the carbon metal ore particulates being at least about 0.1 on a dry and ash-free basis % to at most about 50% by weight of total carbon, 14 C / 12 C isotope Disclosed are compositions that are at least 50% renewable carbon as determined from a ratio measurement. .

[0284] In some embodiments, the fixed carbon 14 C / 12 The measurement of C isotope ratio is performed according to ASTM D Use 6866.

[0285] Metal ores include iron ore, copper ore, nickel ore, magnesium ore, manganese ore, aluminum ore, and Aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore, tungsten ore, molybdenum ore, For example, the metal ore may be selected from: , iron ores, such as hematite, magnetite, limonite, taconite, or their In certain embodiments, the metal ore may be selected from copper ore and a combination thereof. It is combined with nickel ore.

[0286] The composition may be selected from, for example, a powder, a lump, a pellet, a nugget, or a combination thereof. The object may be in the form of an object.

[0287] In some embodiments, the carbon metal ore particles have, on a dry and ash-free basis, at least about In some embodiments, the carbon The metal ore particulates are at least about 1% by weight and at most about 15% by weight on a dry and ash-free basis. In some embodiments, the carbon metal ore particles comprise an anhydrous and ashless base. In some embodiments, the composition contains at least about 2% to at most about 10% fixed carbon by weight. In this state, the carbon metal ore particles comprise at least about 3% by weight on a dry and ash-free basis and at most about It contains about 6% fixed carbon by weight.

[0288] In some embodiments, the fixed carbon is 14 C / 12 Determined from C isotope ratio measurements At least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or is 100% renewable carbon.

[0289] In some embodiments, the carbon-metal ore pellets are essentially composed of fixed carbon and metal ore. In some embodiments, the carbon metal ore pellets are essentially composed of carbon and metal ore. The carbon includes fixed carbon, and the carbon can also include volatile carbon.

[0290] The carbon metal ore pellets may contain additives such as binders. The binders may be inorganic bases. tonite clay, limestone, starch, lignin, cellulose, acrylamide, or It may include a combination of these.

[0291] In some embodiments, the fixed carbon is at least about 400 m 2 / g, e.g., at least Also about 800m 2 It is characterized by a BET surface area in g / g.

[0292] In some embodiments, the fixed carbon is at least about 0.5 cm 3 / g, e.g., less Both are about 1 cm 3 It is characterized by its mesopore volume in g / g.

[0293] Pyrolysis Processes and Systems A process and system suitable for pyrolyzing biomass feedstock to produce carbon-containing bioreagents is provided. The process and system are described in more detail herein. Although the present disclosure may be co-located at the site of ore processing, it is not intended that the disclosure be limited to such co-location. I can't.

[0294] Exemplary changes that may occur during pyrolysis include: (i) heat transfer from a heat source to the interior of the feedstock; (ii) the onset of the primary pyrolysis reaction at this higher temperature is due to the (iii) the flow of hot volatiles towards the cooler solids (iv) providing heat transfer between the hot volatiles and the cooler unpyrolyzed feedstock; Condensation of some of the volatiles in the cold areas, followed by secondary reactions, can produce tar. (v) The autocatalytic secondary pyrolysis reaction proceeds while the primary pyrolysis reaction occurs simultaneously and in competition. and (vi) further pyrolysis, reforming, water-gas shift reaction, free radical recombination, or dehydration may also occur, which can be affected by residence time, temperature, and is a function of the pressure profile.

[0295] Pyrolysis converts the starting material (e.g., lignocellulosic biomass) at least partially into In various embodiments, pyrolysis removes about 50% of the water from the starting material. Removes 5%, 90%, 95%, 99% or more.

[0296] In some embodiments, multiple reactor zones provide flexibility to feedstock variations and product requirements. to optimize carbon yield and product quality from pyrolysis while maintaining versatility and controllability. It is designed and operated in this way.

[0297] In some non-limiting embodiments, the temperature and residence time are preferably relatively slow thermal The advantage is that the cells contained in the biomass structure There may be substantial preservation of the wall, which means that the final product retains the shape and structure of the starting biomass. This means that some, most, or all of the strength can be retained. To maximize the benefits, do not mechanically disrupt cell walls or break biomass particles into small micro-particles. It is preferred to utilize equipment that does not convert the powder to powder. Consider the explanation.

[0298] Furthermore, if the raw material is a crushed or sized raw material such as wood chips or pellets Careful grinding or sizing of the raw material may be desirable. They tend to preserve the strength and cell wall integrity present in the natural source (e.g., wood). It is also desirable that the final product retain some, most, or all of the shape and strength of the starting biomass. This can be important when necessary.

[0299] In some embodiments, the first zone of the pyrolysis reactor "shocks" the biomass. The impact is configured to deliver biomass (or another carbon-containing feedstock) in a manner that prevents the impact from This first zone ruptures the cell walls and initiates the rapid decomposition of the solid phase into steam and gas. , which can be considered a mild thermal decomposition.

[0300] In some embodiments, the second zone of the pyrolysis reactor is configured as the primary reaction zone. The preheated biomass undergoes a pyrolysis chemical reaction to release gases and condensable vapors. leaving behind a significant amount of solid material that is a high-carbon reaction intermediate. The sugars (sugars, hemicellulose, and lignin) break down to create steam, which then penetrates the pores. The latter effect is called the porous membrane effect. Contributes to the creation of surface area and porosity.

[0301] In some embodiments, the third zone of the pyrolysis reactor receives the high-carbon reaction intermediates. Typically, the third zone is configured to cool the solids to some extent. In the third zone, the chemical reactions and mass transfer are surprisingly complex. Without being limited by any particular theory or proposed mechanism, it is possible that a secondary reaction may occur. Basically, carbon-containing components in the gas phase are decomposed and then added to the gas phase. can form fixed carbon or become adsorbed on carbon. In some embodiments, the final carbonaceous material is the solid devolatilized residue of the processing step. However, the final carbonaceous material may be formed by decomposition of organic vapors (e.g., tar) to form carbon. Other embodiments further include additional carbon deposited from the vapor phase.

[0302] Certain embodiments may further comprise a step of adding a carbon-containing fluoride to the cooled carbon to increase the carbon content of the final product. By including separate units that are subjected to the environment containing species, the concept of additional carbon formation is If the temperature of this unit is below the pyrolysis temperature, the additional carbon will It is expected to be in the form of adsorbed carbonaceous species rather than carbon.

[0303] Intermediate inputs and outputs (purge or blow) of one or more phases present in any particular zone. flow, various mass and energy recirculation schemes, which may be introduced elsewhere in the process. process, including various additives that can be used, and both reaction and separation conditions to tailor product distribution. There are numerous options for adjusting flow conditions, etc. Zone-specific input and output flows provides good process monitoring and control, such as through FTIR sampling and dynamic process adjustment. Allows for control.

[0304] Some embodiments do not use fast pyrolysis, and some embodiments use slow pyrolysis. Surprisingly, high-quality fertilizers containing compositions with a very high percentage of fixed carbon are Carbon materials can be obtained from the disclosed processes and systems.

[0305] In some embodiments, the pyrolysis process for producing high carbon bio-reagents comprises: providing a carbon-containing feedstock comprising biomass; in the presence of a substantially inert gas phase for at least 10 minutes at least about 250°C to The raw material is pyrolyzed at a temperature selected to be about 700°C, thereby producing a high-temperature pyrolysis solid, a condensed solid. generating condensable vapors and non-condensable gases; separating condensable vapors and non-condensable gases from the high temperature pyrolysis solids; cooling the high temperature pyrolysis solid, thereby producing a cooled pyrolysis solid; and recovering a carbon-rich biological reagent comprising at least a portion of the cooled pyrolysis solids. nothing.

[0306] The process involves drying the feedstock prior to pyrolysis, thereby removing any moisture contained within the feedstock. The process may further comprise degassing the feedstock prior to pyrolysis. Therefore, the method may further include removing interstitial oxygen contained in the raw material.

[0307] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, and forestry waste. These include waste from wood, paper, animal waste, poultry waste, and municipal solid waste. In various embodiments utilizing biomass, the biomass feedstock may be timber harvest residues. , softwood chips, hardwood chips, tree branches, tree roots, knots, leaves, bark, sawdust, non-standard paper pulp , cellulose, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, Switchgrass, Miscanthus, animal manure, municipal solid waste, municipal sewage, commercial waste, grape juice Grounds, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets containing one or more materials selected from cot, cardboard, paper, carbohydrate, plastic, or fabric Those skilled in the art will readily appreciate that the raw material options are virtually limitless. Deaf.

[0308] The processes herein can be used to convert carbon-containing feedstocks other than biomass, such as fossil fuels (e.g., coal or petroleum coke), or any mixture of biomass and fossil fuels (e.g., Any of the methods described herein can also be used for biomass / coal blends. The apparatus or system may be used with any carbonaceous feedstock. Although not "biomass," non-biomass or non-living materials may be used in the process. However, the use of non-biomass or non-living materials can also result in desirable bioproducts. The raw materials are waste tires, recycled plastic, recycled paper, construction waste, demolition waste, etc. Carbon-containing feedstocks include trucks, dumps, and other waste or recycled materials. Such as a train, ship, barge, tractor trailer, or any other vehicle or means of transportation. It may be transportable by any known means.

[0309] The selection of specific raw materials can be made in a manner that favors an economical process. Typically, regardless of the source selected, (in some embodiments) undesirable materials There may be screening to remove

[0310] The raw materials used can be provided or processed into a wide variety of particle sizes or shapes. The feed material can be a fine powder or a mixture of fine and coarse particles. Large pieces of material such as wood chips or other shapes of wood (e.g. round, cylindrical, square, etc.) In some embodiments, the feed materials may be in the form of pressed together or It also includes particles in pellet or other agglomerated form that are otherwise bound together by a binder or the like.

[0311] Size reduction can be a costly and energy-intensive process. Materials can be sized with significantly less energy input, i.e., raw materials It may be desirable to reduce the particle size of the product without increasing the particle size of the product. This is because the process may require a fine starting material. This disclosure provides a method for preparing a polymeric nanoparticle that does not require any additives and does not necessarily involve any significant particle size reduction during processing. The ability to process very large pieces of feedstock is a significant economic advantage of this disclosure. Notably, some commercial applications of high-carbon products are limited to large sizes (e.g. For example, on the order of centimeters), so in some embodiments, Pieces are supplied, manufactured and sold.

[0312] It is desirable to produce a final carbonaceous bioreagent that has structural integrity, such as a cylindrical shape. In this case, the material produced from the process is recovered and then further mechanically processed into the desired form. For example, the product can be pressed or pelletized with a binder. Alternatively or additionally, a feedstock generally having a desired size or shape for the final product. Use processing steps that allow the material to be used and do not destroy the basic structure of the feed material In some embodiments, the feed and product may be in the form of a sphere, cylinder, or cube. which have similar geometric shapes.

[0313] The ability to maintain the approximate size of the feed material throughout the process is critical to product strength This is also beneficial when pelletizing high fixed carbon materials due to the difficulty and cost involved. Avoid strikes.

[0314] The starting feedstock may be provided at a range of moisture levels, as will be appreciated. In this embodiment, the feedstock may already be sufficiently dry and may need to be further dried prior to pyrolysis. Drying is not required. Typically, commercial sources of biomass that normally contain moisture are used. It is preferred to use a drying step prior to introducing the biomass into the pyrolysis reactor. However, in some embodiments, dry ingredients may be utilized.

[0315] In the pyrolysis reactor, about, or at most about 10 mol%, 5 mol%, 4 mol%, 3 mol %, 2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%, 0.2 mol%, 0.1 mol%, Low oxygen content, such as 0.05 mol%, 0.02 mol%, or 0.01 mol% O2 in the gas phase First, uncontrolled combustion is a safety concern, as it can lead to pyrolysis. Some amount of total carbon oxidation to CO2 may occur in the reactor, which should be avoided. The heat released from the exothermic oxidation can support endothermic pyrolysis chemical reactions, e.g., to syngas. Oxidation of large amounts of carbon, including partial oxidation, reduces the carbon yield to solids.

[0316] In practice, achieving a strictly oxygen-free environment in the reactor can be difficult. However, this limit can be approached, and in some embodiments, the reactor contains molecules in the gas phase. Substantially free of oxygen. Ensure that there is little or no oxygen in the pyrolysis reactor. To ensure this, interstitial air is removed from the feed before it is introduced into the reactor. There are various methods to remove or reduce air in the feedstock.

[0317] In some embodiments, before or after drying, adsorbed oxygen is removed and the raw material pores are infiltrated. A degassing unit in which the feedstock is conveyed in the presence of another gas capable of removing oxygen from the pores. Essentially any gas with less than 21% O2 by volume can be used with varying degrees of effectiveness. In some embodiments, nitrogen is used. In some cases, CO or CO2 is used. Mixtures such as nitrogen and a small amount of oxygen are used. Water vapor may be present in the degassed gas, but this does not add significant moisture to the feed. The effluent from the degassing unit should be directed to the atmosphere or an exhaust. The effluent may be purged (to a waste treatment unit) or recycled.

[0318] In principle, the effluent from the degassing unit (or a portion of it) contains the oxygen removed from the solids. is highly diluted and can be introduced into the pyrolysis reactor itself. , when the reactor is operated in a countercurrent configuration, the degassed effluent gas is introduced into the last zone of the reactor. It may be advantageous to

[0319] Various types of degassing units can be used. In this case, cleaning the soluble oxygen from the moisture present may be inefficient, so drying is recommended. In certain embodiments, it may be preferable to dry the mixture and then degas it. The degassing steps may be combined into a single unit, or some amount of degassing may be performed during drying. It is achieved, etc.

[0320] The dried and degassed feedstock is introduced into a pyrolysis reactor or multiple reactors in series or parallel. The feed material may be introduced into any known feed system, including, for example, a screw feeder or a lock hopper. In some embodiments, the material supply system may include a , incorporating an air knife.

[0321] When a single reactor is used, there are preferably multiple zones: 2, 3, 4 Multiple zones, such as one or more zones, can be used to adjust overall process performance. In addition, separate restrictions on temperature, solids residence time, gas residence time, gas composition, flow pattern, or pressure may be imposed. This allows for control.

[0322] References to "zone" include a single physical unit, a physically separate unit, or The term "continuous anti-reverse" shall be construed broadly to include regions of space within any combination of these. With respect to reactors, zone boundaries may be defined by the presence of flights within the reactor or by the provision of heat to separate zones. Alternatively or additionally, a continuous reactor may be provided. The boundaries of the zones in the In a single batch reactor, a "zone" can be defined as a function of the temperature, volume, and / or temperature of the reaction. The operating regime is time-dependent rather than time-dependent. Multiple batch reactors can also be used.

[0323] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheating zone and the pyrolysis zone can be somewhat arbitrary. Some amount of pyrolysis may occur in some of the preheat zones, and some amount of "preheating" may occur in the heat The temperature profile in the reactor may continue to occur in the decomposition zone. It is typically continuous, including the boundary.

[0324] Some embodiments include a first zone operated under preheat or mild pyrolysis conditions. The temperature of the first zone is about 150°C to about 500°C, for example, about 300°C to about 400°C. The temperature of the first zone can be selected from 0°C to 100°C. It is preferred that the temperature is not so high as to destroy the cell walls and initiate rapid decomposition of the solid phase into vapors and gases. .

[0325] All references herein to zone temperatures refer to the bulk solid or gas phase or It is to be construed, without limitation, to include temperatures that can be applied to the reactor wall (process side). Both axially and radially, and over time (i.e., after start-up or over It will be appreciated that a temperature gradient exists in each zone (due to the transition phenomenon). Therefore, reference to zone temperatures should not be construed as limiting the average temperature or other factors that may affect the actual kinetics. It may refer to an effective temperature. The temperature may be measured directly by a thermocouple or other temperature probe. The amount of carbon dioxide produced may be determined by the oxidative stress test or may be indirectly measured or estimated by other means.

[0326] The second zone, or generally the first pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the second zone is about 250°C to about 700°C, for example, about, or at least about, Or at most about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C In this zone, the preheated biomass is The gas undergoes a pyrolysis chemical reaction, releasing gases and condensable vapors, and is released as a high-carbon reaction intermediate. leaving a reasonable amount of solid material. Biomass components (mainly cellulose, hemicellulose, and The cellulose (lignin) decomposes to create steam, which either permeates through the pores or creates new The preferred temperature is at least 100°C during the residence time of the second zone. The reaction time will depend on the nature of the feedstock and the desired product properties.

[0327] The third zone, or cooling zone, is operated to cool the high carbon reaction intermediate to various degrees. At a minimum, the temperature of the third zone should be lower than the temperature of the second zone. The temperature of the third zone is about 100°C to about 550°C, for example, about 150°C to about 35°C. You can choose from 0°C.

[0328] Chemical reactions can continue to occur in the cooling zone. Although it is not known, it is believed that secondary pyrolysis reactions may be initiated in the third zone. Some carbon-containing components may condense (due to the reduced temperature in the third zone). The temperature can cause reactions that can form additional fixed carbon from the condensed liquid (secondary pyrolysis) or at least promote a reaction capable of forming a bond between the adsorbed species and the fixed carbon. One example reaction that can occur is the conversion of carbon monoxide to carbon dioxide. and the Boudouid reaction for conversion to fixed carbon.

[0329] The residence time in the reactor zone can vary. For the desired amount of pyrolysis, higher temperatures are preferred. The time and temperature can be adjusted to 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.

[0330] It should be recognized that in a multiphase reactor, there are multiple residence times. In the zone, there are residence times (and residence time distributions) for both the solid and vapor phases. For a given machine using a number of zones, at a given throughput, the residence time across the zones is The zones are generally connected on the solid side, but multiple inlet and outlet ports are utilized for individual zones. If the vapor is mixed, the residence times may not be combined on the vapor side. The residence times for the solids and vapor are Not combined.

[0331] The solids residence time in the preheating zone is about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40 Depending on the temperature, the biomass is preheated to the desired temperature for 50 minutes. The type and size of particles, the physical equipment, and the processing The heat transfer rate, which depends on the thermal parameters, is the minimum required to bring the solid to the desired preheat temperature. A small residence time is defined. The additional time allows some amount of mild pyrolysis to occur in the preheat zone. Unless specifically intended, this is likely to be undesirable as it contributes to higher capital costs. .

[0332] The solids residence time in the pyrolysis zone is about 10 minutes to about 120 minutes, for example, about 20, 30, 40 You can choose from 50, 60, 70, 80, 90, or 100 minutes. Depending on the pyrolysis temperature in the A time of less than about 10 minutes is not sufficient to remove a large amount of non-carbon elements. To do this, temperatures need to be very high, such as above 700°C. This temperature is necessary for fast pyrolysis and carbonization. It promotes the production of vapors and gases from the element itself, which is a problem when the intended product is solid. It should be avoided if the body is carbon monoxide.

[0333] In a static system, there will be an equilibrium transformation that can be reached substantially at a particular time. As in certain embodiments, the vapor is continuously passed over the solid with continuous volatile removal. When the flow is constant, equilibrium constraints force pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times tend to substantially alter the remaining persistent solids. There is no direction.

[0334] The solids residence time in the cooling zone is about 5 minutes to about 60 minutes, for example, about 10, 20, 30, 40 Depending on the cooling temperature in this zone, the carbon solidification time can be selected from 100 minutes to 50 minutes. There should be sufficient time for the body to cool to the desired temperature. The cooling rate and temperature should be It specifies the minimum residence time required to allow the carbon to cool. Some amount of secondary pyrolysis is desired. Unless this is possible, the additional time is likely to be undesirable.

[0335] As mentioned above, the residence time of the vapor phase can be selected and controlled separately. The vapor residence time of the ozone is about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, The vapor residence time in the pyrolysis zone can be selected from 6, 7, 8, 9, or 10 minutes. , 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 retention time is about 0.1 minutes to about 15 minutes, for example, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, A short vapor residence time allows for greater vapor retention and reduces the amount of volatiles in the system. The longer vapor residence time promotes rapid clearing of materials, while the longer vapor residence time promotes the separation of components in the vapor phase from the solid phase. Accelerates the reaction.

[0336] The mode of operation of the reactor and the entire system may be continuous, semi-continuous, batch, or any combination thereof. Any combination or variation may be used. In some embodiments, the reactor is The reactor is a continuous countercurrent reactor in which the steam and the catalyst flow in substantially opposite directions. Alternatively, for example, by periodically introducing and removing a gas phase from a batch vessel. , can be operated with simulated steam countercurrent.

[0337] A variety of flow patterns may be desired or observed. In chemical reactions involving phases and simultaneous separations, the fluid dynamics can become very complex. Typically, The flow of solids can approach plug flow (well mixed in the radial dimension). On the other hand, the steam flow is a perfectly mixed flow (high velocity transport in both radial and axial dimensions). Multiple inlet and outlet ports for steam provide comprehensive mixing. can contribute.

[0338] The pressure in each zone can be selected and controlled separately. The pressure in each zone is about 1 kPa to approximately 3000 kPa, for example, approximately 101.3 kPa (standard atmospheric pressure) can be selected independently Independent zone control of pressure can be achieved when subatmospheric zone pressures are desired. Multiple gas inlets and outlets are sometimes used, including a vacuum port for gas removal. This is possible.

[0339] The process may, in some embodiments, be conveniently operated at atmospheric pressure. Pressure operation has many advantages ranging from mechanical simplicity to improved safety. In the form, the pyrolysis zone is at about 90 kPa, 95 kPa, 100 kPa, 101 kPa, It is operated at a pressure of 102 kPa, 105 kPa, or 110 kPa (absolute).

[0340] Vacuum operation (e.g., 10-100 kPa) allows rapid purge of volatiles from the system. If the off-gas is supplied to a high-pressure operation, a higher pressure (e.g., 100-1 High pressures can also enhance heat transfer, chemical reactions, or separations. It may be useful to

[0341] At least a portion of the condensable vapor and at least a portion of the non-condensable gas are separated from the high temperature pyrolysis solid. The separation step can be achieved 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 zone in the sweep gas and removed from the reactor. It comes out.

[0342] The sweep gas may be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, or other light carbon. The sweep gas may be first preheated before being introduced. or can be cooled if available from a heat source.

[0343] The sweep gas removes the volatile components from the system before they can condense or further react. By removing the sweep gas, the volatile components are more completely removed. This allows the removal of volatiles at a higher rate than would be obtained simply from volatilization. The use of gas allows for milder temperatures to be used to remove a certain amount of volatile material. The reason that sweep gas improves the removal of volatiles is that the separation mechanism is not simply a matter of relative volatility, but rather of sweep gas-assisted liquid / vapor phase separation. The sweep gas continuously depletes a given volatile species, resulting in more volatile species. Reduce mass transfer limitations of volatilization by evaporating reactive species to achieve thermodynamic equilibrium. At the same time, the thermodynamic limitations can be reduced.

[0344] Some embodiments may utilize subsequent processing steps to produce a product with high fixed carbon. Remove gases full of volatile organic carbons from the floor. Otherwise, the volatile carbons will It may be adsorbed or absorbed onto the decomposed solids, thereby providing the desired carbon. Requires additional energy (cost) to achieve purer forms. It is also speculated that the porosity in the pyrolysis solid can be increased by selectively removing the porosity. Higher porosity is desirable for some products.

[0345] In certain embodiments, the sweep gas is at a relatively low process pressure, such as atmospheric pressure. It provides fast vapor removal without requiring large amounts of inert gas.

[0346] In some embodiments, the sweep gas flows countercurrently to the feed flow direction. In some embodiments, the sweep gas flows co-currently with respect to the feedstock flow direction. In this case, the flow pattern of the solids approaches plug flow, but the flow patterns of the sweep gas and gas phase are generally This results in one or more zones approaching perfectly mixed flow.

[0347] The sweep can be performed in any one or more of the reactor zones. In this mode, the sweep gas is introduced into the cooling zone and is then removed from the cooling or pyrolysis zone (where the volatiles produced are removed). In some embodiments, the sweep gas is introduced into the pyrolysis zone. In some embodiments, the sweep gas is introduced into and extracted from the pyrolysis or preheating zone. , introduced into the preheating zone and extracted from the pyrolysis zone. A sweep gas may be introduced into each of the preheating zone, pyrolysis zone, and cooling zone. It can also be extracted from each of the zones.

[0348] In some embodiments, the zone or zones in which separation is performed are physically separated from the reactor. Separation units or zones may be separated into reactor zones, if desired. For example, a separation unit can be placed between the pyrolysis unit and the cooling unit. You can place a nit.

[0349] The sweep gas can be introduced continuously, especially if the solids flow is continuous. If the decomposition reaction is operated as a batch process, a sweep gas is used to remove volatiles. The pyrolysis reaction may be operated continuously. Even in this case, the sweep gas may be semi-continuous or continuous, if desired, using suitable valves and controls. It can be introduced periodically.

[0350] The volatile-containing sweep gas can exit one or more reactor zones and can be used to separate multiple zones. If the mixture is obtained from a variety of vapors, they can be combined. The resulting gas stream can be fed to a thermal oxidizer for air emission control. In some embodiments, the thermal oxidizer may include a natural gas thermal oxidizer. and air to a temperature sufficient to substantially destroy the volatile materials contained therein. Reach the desired degree.

[0351] The effluent of the thermal oxidizer is a hot gas stream containing water, carbon dioxide, and nitrogen. The stream can be purged directly to the air exhaust if desired. The energy content of the effluent is recovered, for example in a waste heat recovery unit. The content can also be recovered by heat exchange with another stream (such as a sweep gas). The ghee content can be measured directly or indirectly in units elsewhere in the process such as dryers or reactors. It can be used by direct or indirect heating or by assisted heating. In some embodiments, essentially all of the thermal oxidizer effluent is used to indirectly heat the dryer (utility Thermal oxidizers can use fuels other than natural gas.

[0352] The yield of carbonaceous materials varies 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 rest is Condensable vapors such as terpenes, tars, alcohols, acids, aldehydes, or ketones, and monoacids The gases are divided between hydrocarbons, hydrogen, carbon dioxide, and non-condensable gases such as methane. The relative amount of condensable vapor compared to reactive gas also depends on process conditions, including water present.

[0353] Regarding carbon balance, in some embodiments, the carbon balance is determined as a percentage of the starting carbon in the feedstock. The net yield of carbon is at least 25%, 30%, 40%, 50%, 60%, 65%, 70% %, 75%, 80% or more. For example, in some embodiments, the carbonaceous material is It contains about 40% to 70% of the carbon contained in the raw material. The remaining carbon is methane, monocarbons, and Carbon dioxide, light hydrocarbons, aromatic compounds, tar, terpenes, alcohols, acids , aldehydes, or ketones to varying degrees.

[0354] In an alternative embodiment, some portion of these compounds contributes to the carbon and energy content of the product. In these embodiments, the ghee is enriched with carbon-rich solids. A part or all of the gas stream obtained from the reactor, containing various vapors, is at least partially and then cooled pyrolysis solids from the cooling zone or a separate cooling unit. These embodiments are described in more detail below.

[0355] Following reaction and cooling in the cooling zone (if present), the carbonaceous solids are transferred to a separate cooling unit. In some embodiments, the solids are collected and simply introduced into the knit. If the carbonaceous solid is reactive or unstable in air, an inert atmosphere should be maintained. Alternatively, it may be desirable to rapidly cool the solid to a temperature below 40°C, e.g., ambient temperature. In some embodiments, a water quench is used for rapid cooling. In some embodiments, a fluidized bed cooler is used. A "cooling unit" is a container, tank, or , pipes, or parts thereof.

[0356] In some embodiments, the process comprises operating a cooling unit to cool the warm pyrolysis solids. with steam, thereby producing a cold pyrolysis solid and superheated steam. Optionally, the drying is carried out at least in part using superheated steam from a cooling unit. Optionally, the cooling unit may be configured to first cool the warm pyrolysis solids with steam to form a first cooling unit. temperature and then cooled with air to reach the second cooling unit temperature. The second cooling unit temperature can be lower than the first cooling unit temperature, and the air associated with a reduced risk of combustion of warm pyrolysis solids in the presence of

[0357] Following cooling to ambient conditions, the carbonaceous solids are recovered, stored, and transported to another field operation. may be disposed of, traded, or sold, transported to another site, or otherwise disposed of, traded, or sold. Solids can be fed into the unit to reduce particle size. Various size reduction units including binders, crushers, jet mills, pin mills, and ball mills Knits are known in the art.

[0358] Some other means for screening or separation based on particle size may be included. If present, grinding may be upstream or downstream of the grinding. A portion (e.g., large chunks) can be returned to the grinding unit. The particles can be collected for separate downstream uses. In some embodiments, the cooled particles The pyrolysis solids are ground into a fine powder, such as a finely divided carbon or activated carbon product.

[0359] Various additives may be added to the process before, during, or after any of the steps disclosed herein. The additives can be introduced throughout the carbon to achieve the desired carbon purity. Process additions selected to improve process performance such as yield or pyrolysis time / temperature and a downstream product incorporating the high-carbon biological reagent or reagents to improve one or more properties of the downstream product. Certain additives can be broadly classified as product additives selected for enhanced The process and product (biological reagent or product containing biological reagent) characteristics can be provided. can.

[0360] Additives may be added before, during, or after any one or more steps in the process. This includes adding it to the feedstock itself at any time before or after harvest. Additive treatments may be incorporated before, during, or after sizing, drying, or other preparation of the raw materials. Additives can be transported through raw material supply facilities, transport trucks, unloading facilities, storage bins, conveyors, etc. (including open or closed conveyors), dryers, process heaters, or any other units The additive may be incorporated into or onto any suitable means for introducing the additive. It can be added anywhere in the pyrolysis process itself using charcoal, if desired. Additives can be added after pulverization or even after milling.

[0361] In some embodiments, the additive is a metal, metal oxide, metal hydroxide, or a combination thereof. For example, the additive may be, but is in no way limited to, magnesium, manganese, , aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, thiamin ungsten, vanadium, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite from lime, fluorite, fluorspar, bentonite, calcium oxide, lime, or combinations thereof You can choose.

[0362] In some embodiments, the additive is an acid, a base, or a salt thereof. Agents include, but are in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, Hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof You can choose from:

[0363] In some embodiments, the additive is a metal halide. The metal halide is Compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine) Halogens can form many compounds with metals. Metal halides are generally These are obtained by direct combination of basic metal salts with hydrohalic acids, or more commonly by neutralization. In some embodiments, the additive is iron chloride (FeCl or FeCl) , iron bromide (FeBr2 or FeBr3), or hydrates thereof, and any of these It's a combination.

[0364] Additives result in a final product with a higher energy content (energy density) The increase in energy content can be determined by the total carbon, fixed carbon, volatile carbon, or even Alternatively or additionally, the increase in energy content may result from an increase in hydrogen. This can result from the removal of materials that have a lower energy density than carbon or iron. In terms of form, the additive may be shaped to favor the formation of a solid and a gas, or to favor the formation of a solid. The degree of liquid formation is reduced so that

[0365] Without being limited to any particular hypothesis, the additive may be added to the starting biomass or pyrolysis. Chemically modifying the previously processed biomass to enhance the cell walls for greater strength / integrity In some embodiments, the additive may be added to biomass prior to pyrolysis. The fixed carbon content of the mass feedstock can be increased.

[0366] The additives may provide improved mechanical properties, such as yield strength, compressive strength, tensile strength, and fatigue strength. , impact strength, elastic modulus, bulk modulus, or shear modulus. The additive may be present merely by its presence (e.g., the additive itself imparts strength to the mixture). or any transformation occurring within the additive phase or the resulting mixture to alter the mechanical properties For example, reactions such as vitrification can improve the quality of some biological reagents containing additives. This can occur within the crack, thereby improving the final strength.

[0367] Chemical additives can be applied to wet or dry biomass feedstock. It can be applied as a powder, spray, mist, liquid, or vapor. In the form, the additive may be added by spraying a liquid solution (such as an aqueous solution or in a solvent) or by adding it to a tank, It can be introduced by immersion in a bottle, bag, or other container.

[0368] In certain embodiments, a soaking pretreatment is used, and the solid feedstock is pretreated in either a batch or continuous manner. The solid feed material is immersed in a bath containing the additive for a time sufficient to allow the additive to penetrate the solid feed material. do.

[0369] In some embodiments, the additive applied to the feedstock reduces the energy requirements for pyrolysis. These and other embodiments may reduce the amount of carbonaceous product or increase the yield of carbonaceous products. In embodiments, the additives applied to the feedstock may be additives that provide desirable functionality for the intended use of the carbonaceous product. It can provide sex.

[0370] Throughput or process capacity can range from small laboratory scale units to any pilot scale. The scale of the process can vary widely from pilot scale, demonstration scale, to full scale operations, including semi-commercial scale. In this case, the process capacity (of the feedstock, product, or both) is at least about 1 kg / day. , 10kg / day, 100kg / day, 1 ton / day (all tons are metric tons), 1 0 tons / day, 100 tons / day, 500 tons / day, 1000 tons / day, 2000 tons / day or more Above.

[0371] In some embodiments, a portion of the solids produced are present at the front end of the process. That is, it can be recycled to a drying or degassing unit or directly to the reactor. By returning the solids to the process and going through it again, the treated solids are enriched with more fixed carbon. Solid, liquid, and gas streams produced or present in the process can be independently recycled. It can be passed on to a subsequent step or removed / purged from the process at any point.

[0372] In some embodiments, the pyrolyzed material is recovered and then recycled for further pyrolysis. The carbon dioxide is then fed into separate units to create a product with higher carbon purity. In some embodiments, the secondary process involves passing a heated inert gas (such as heated N2). This can be done in simple containers such as steel drums that are used for this purpose. Examples include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas containing volatiles can be sent to, for example, a thermal oxidizer, or To cool the final product, it can be initially cooled, e.g., by heating at ambient temperature. A separate stream of inert gas at a temperature is passed through the solid to cool it, and then the inert gas preheat system is It can be returned to the stem.

[0373] Some variations of the present disclosure include: a feeder configured to introduce a carbon-containing feedstock; a multi-zone reactor disposed in operative communication with the dryer, the multi-zone reactor being spatially separated; a pyrolysis zone disposed in operative communication with a cooling zone, a multi-zone reactor configured with an outlet for removing condensable gases from the solids; , a solids cooler disposed in operable communication with the multi-zone reactor; a high-carbon biological reagent recovery unit disposed in operative communication with the solid-state cooler. Utilize a high-carbon bioreagent generation system.

[0374] In some embodiments, the system is disposed in operative communication with a supply device, and The method further includes a dryer configured to remove moisture contained within the raw materials.

[0375] Some variations are: a feeder configured to introduce a carbon-containing feedstock; a supply device disposed in operable communication with the supply device and adapted to remove moisture contained within the carbon-containing feedstock; an optional dryer configured as follows: a dryer disposed in operable communication with the dryer and configured to heat or gently pyrolyze the feedstock; an optional preheater, a pyrolysis reactor disposed in operative communication with the preheater and configured to pyrolyze the feedstock; The vessel and a cooling system disposed in operable communication with the pyrolysis reactor and configured to cool the pyrolyzed solids; a cooler provided with the cooling system; a high-carbon biological reagent recovery unit disposed in operable communication with the cooler. A bioreagent production system comprising: The system includes at least one filter for removing condensable vapors and non-condensable gases from the solids. A high carbon bioreagent generating system is utilized, configured with a gas outlet.

[0376] The feed system may be a screw feed system or an oil feed system for introducing feed solids into the first reaction zone. The reactor may be physically integrated with a multi-zone reactor, such as by use of a gas mechanism.

[0377] In some embodiments, the system is disposed in operative communication with the pyrolysis zone. The pyrolysis zone, the cooling zone, and the preheating zone (if present) are further included. ) can be located within a single unit or can be located in separate units. It is possible.

[0378] Optionally, the dryer can be configured as a drying zone within a multi-zone reactor. Optionally, a solid-state cooler can be placed in the multi-zone reactor (i.e., configured as an additional cooling zone or integrated with the main cooling zone).

[0379] The system may include a purge means for removing oxygen from the system. For example, the purging means may include one or more inlets for introducing a substantially inert gas and a substantially one or more outlets for removing the inert gas and displaced oxygen from the system. In some embodiments, the purging means may be a means for purging the dryer and the multi-zone reactor. a degassing device disposed in operable communication between the

[0380] The multi-zone reactor preferably comprises at least a first gas inlet and a first gas outlet. The first gas inlet and the first gas outlet may be in different zones or in the same zone. They can be arranged in communication.

[0381] In some embodiments, the multi-zone reactor includes a second gas inlet or a second gas outlet. In some embodiments, the multi-zone reactor comprises a third gas inlet or In some embodiments, the multi-zone reactor is configured with a third gas outlet. In some embodiments, the gas supply system may be configured with four gas inlets or four gas outlets. Each zone present in the reactor is configured with a gas inlet and a gas outlet.

[0382] The gas inlet and outlet not only allow the introduction and removal of steam, but also, in particular, the gas outlet (Probe) up to and potentially including all stages of the process This allows for accurate process monitoring and control over the various stages of the process. Process monitoring can also be dynamic, where operational history can be used to adjust process conditions. Over time, this is expected to result in improved yields and efficiency.

[0383] In a preferred embodiment, a reactive gas probe is disposed in operative communication with the pyrolysis zone. Such reactive gas probes can be used to measure the extent of reaction, pyrolysis selectivity, or other process It may be useful to extract gases and analyze them to determine monitoring. Based on the measurements, the process can be adjusted to adjust the feed rate, the rate of inert gas sweep (for one or more zones), ) by adjusting temperature, pressure (in one or more zones), additives, etc. It can be controlled or adjusted in a number of ways.

[0384] As intended herein, "monitoring and controlling" via a reactive gas probe refers to monitoring and controlling the reactive gas. This includes any one or more sample extractions via a probe, as deemed necessary or desirable. When this is done, well-known principles of process control (feedback, feedforward, proportional integral differential) are used. Optionally, make process or equipment adjustments based on the measurements using analytical logic, such as analytical logic. Includes:

[0385] Reactive gas probes can be configured to extract gas samples in a number of ways. For example, the sampling line can have a pressure lower than the pyrolysis reactor pressure. As a result, when the sampling line is opened, a certain amount of gas can be easily removed from the pyrolysis zone. The sampling line can be used when the pressure in the pyrolysis zone is close to atmospheric pressure. Typically, the reactive gas probe has one gas output or a portion thereof ( For example, a line branching off from a gas output line.

[0386] In some embodiments, both the gas input and the gas output are configured to periodically inject an inert gas into the zone. The inert gas is introduced automatically and drawn off from the gas output along with the process sample ("sample"). Such a configuration can be used as a reactive gas probe by It can be used in zones that do not have a gas inlet / outlet for a substantially inert gas. Alternatively, the reaction gas probe may be provided with a separate gas inlet / outlet in addition to the process inlet and outlet. (In embodiments utilizing sample sweeps) Sampling inert gas is periodically introduced and withdrawn for analysis, as required. Process inert, either for accuracy reasons or to introduce analytical tracers It may be different from gas.

[0387] For example, the concentration of acetic acid in the gas phase of the pyrolysis zone was measured using a gas probe to extract the sample. The sample can then be analyzed using a suitable technique, e.g., gas chromatography. , GC, mass spectrometry (MS, GC-MS, or Fourier transform infrared spectroscopy (FTIR), etc.) It is analyzed using the CO or CO2 concentration in the gas phase, e.g. It can be used as an indicator of thermal decomposition selectivity. For example, it can be used as an indicator of thermal cracking selectivity to liquids.

[0388] In some embodiments, the system includes a cooling zone, or a drying zone (if present). or at least one disposed in operable communication with the preheating zone (if present). An additional gas probe is further provided.

[0389] The gas probe for the cooling zone may, for example, detect any additional chemical reactions occurring in the cooling zone. A gas probe in the cooling zone can be useful for determining the degree of It can also be useful as an independent measure of temperature (in addition to thermocouples placed within the zone). An independent measurement of the amount of a particular species can be a correlation between the cooling temperature and the measured amount of that species. It may be developed incrementally or may be established after a period of process operation.

[0390] A gas probe for the drying zone determines the degree of drying, for example by measuring the moisture content. A gas probe in the preheat zone can be useful to determine, for example, any calming that occurs. It may be useful to determine the extent of mild thermal decomposition.

[0391] In certain embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas inlet. and a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Additionally or additionally, the preheating zone (if present) may be configured with a gas outlet to allow the gas to pass through the solid phase. Alternatively or additionally, a drying zone may be provided to produce a substantially countercurrent flow of the gas phase. The nozzle may be configured with a gas outlet to generate a substantially counter-current flow.

[0392] The pyrolysis reactor(s) may be any suitable reactor capable of carrying out a pyrolysis process. Exemplary reactor configurations include a fixed bed reactor, a flow reactor, a Moving bed reactors, entrained bed reactors, auger reactors, ablation reactors, rotating cones, rotating drum reactors Roaster, calciner, roaster, moving bed reactor, transport bed reactor, ablation reactor, rotary These include, but are not limited to, cone, or microwave-assisted pyrolysis reactors.

[0393] In some embodiments where an auger is used, sand or another heat carrier is optionally used. For example, the raw material and sand can be fed at one end of the screw. The screw mixes the sand and raw materials and conveys them through the reactor. It can provide good control of residence time and the pyrolysis products can be transported with a carrier or fluidizing gas. Do not dilute. Sand can be reheated in a separate container.

[0394] In some embodiments where an ablation process is used, the raw material is Any char formed on the surface is ablated by the high heat Such a device can prevent dilution of the product. Alternatively, the feed particles are suspended in a carrier gas and passed through a cyclone with heated walls. This allows for rapid deployment.

[0395] In some embodiments where a fluidized bed reactor is used, the feedstock is typically a recycle product. The gas may be introduced into a bed of hot sand fluidized by a gas. References to "sand" in this document include glass particles, recovered ash particles, and similar substantially inert materials. The high heat transfer rate from the fluidized sand can result in rapid heating of the material. There may be some abrasion due to friction with the particles. Heat is usually generated by hot combustion gases. provided by flowing heat exchanger tubes.

[0396] A circulating fluidized bed reactor can be used in which the gas, sand, and feedstock move together. Suitable transport gases include recycled product gas and combustion gas. High heat transfer coefficient from sand This ensures rapid heating of the material, 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 fuel can be reheated in a fluidized burner vessel and recycled to the reactor.

[0397] In some embodiments, the multi-zone reactor has a feed inlet and a temperature a plurality of spatially separated reaction zones configured to separately control the concentration and mixing; a carbonaceous solids outlet, wherein one of the reaction zones is substantially a first gas inlet for introducing an inert gas into the reactor, One of them is configured with a first gas outlet.

[0398] In various embodiments, the reactor comprises at least two, three, four or more reaction zones. Each reaction zone is equipped with electrical heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, and waste heat heat transfer. or a combination thereof. In some embodiments, at least one reactor zone, if present, is arranged In this case, it is heated by the effluent from the thermal oxidizer.

[0399] The reactor may comprise at least two reaction zones up to all reaction zones present in the reactor. It can be configured to adjust the gas phase composition and gas phase residence time separately.

[0400] The reactor may be equipped with a second gas inlet or a second gas outlet. In an embodiment, the reactor is configured with a gas inlet in each reaction zone. In an embodiment, the reactor is configured with a gas outlet in each reaction zone. may be a countercurrent reactor.

[0401] In some embodiments, the feed inlet comprises a screw or auger feed mechanism. In some embodiments, the carbonaceous solids outlet comprises a screw or auger output mechanism.

[0402] Certain embodiments utilize a rotary calciner equipped with a screw feeder. In this configuration, the reactor is axially rotatable, i.e., the reactor rotates about its central axis. The rotation speed affects the solid flow pattern and the heat and mass transport. Each of the reaction zones is 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.

[0403] Using other means to agitate solids, such as augers, screws, or paddle conveyors In some embodiments, reactors are positioned throughout each of the reaction zones. In another embodiment, the reactor comprises a single continuous auger. The system includes twin screws arranged across the shaft.

[0404] Some systems, in particular, require the approximate size of the feed material throughout the process. Ability to maintain, i.e., to retain, the biomass feedstock without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone is designed with the ability to process pyrolyzed The use of augers, screws, or rakes tends to greatly reduce the size of the feed material being fed. Not accommodated.

[0405] In some embodiments of the present disclosure, the system is configured to remove condensable vapors and non-condensable gases. The thermal oxidizer preferably further comprises a thermal oxidizer disposed in operable communication with the outlet. The method uses separate fuels (e.g., natural gas) and oxidizers (e.g., air) in a gas atmosphere with low levels of fuel and condensable vapors. The CO or Certain non-condensable gases, such as CH4, can also be oxidized to CO2.

[0406] When a thermal oxidizer is used, the system is disposed between the thermal oxidizer and the dryer and The dryer may include a heat exchanger configured to utilize at least a portion of the heat of the roasting. This embodiment can contribute significantly to the overall energy efficiency of the process. .

[0407] In some embodiments, the system is disposed in operative communication with a solid-state cooler, carbon configured to combine condensable vapors in at least partially condensed form with a solid; The carbon enrichment unit further comprises a carbon enrichment unit for enriching the high carbon biomass obtained from the recovery unit. The carbon content of the reagent can be increased.

[0408] The system is adapted to further pyrolyze the high carbon bioreagent to further increase its carbon content. The separate pyrolysis unit may further comprise an adapted separate pyrolysis unit. Relatively simple containers such as bins, barrels, bins, drums, totes, sacks, or roll-offs , unit, or device.

[0409] The entire system may be at a fixed location or may be distributed across several locations. The system is modular and can be easily replicated for practical scale-up. Systems can also be built using conventional methods, as are well known in the process industries. can be constructed using the principles of economies of scale.

[0410] Next, some variations on solid carbon reinforcement will be further described. In one embodiment, the process for producing a high carbon bioreagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the ingredients to remove at least a portion of the moisture contained within the ingredients; To remove (c) Optionally, degas the feedstock to remove as much interstitial oxygen, if any, contained in the feedstock. and removing at least a portion of the (d) in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes; and the raw material is thermally decomposed at a pyrolysis temperature selected from about 250°C to about 700°C to form a high-temperature pyrolyzer. producing a dissolution solid, a condensable vapor, and a non-condensable gas; (e) extracting at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high-temperature pyrolysis solids; and separating the (f) in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and Cooling the hot pyrolysis solid to a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid And, (g) optionally cooling the warm pyrolysis solid to produce a cold pyrolysis solid; , (h) then removing at least a portion of the condensable vapor or non-condensable gas from step (e). At least a portion of the mixture is passed through a warm or cold pyrolysis solid to determine whether the carbon content is forming an increased enhanced pyrolysis solid; (i) recovering a high-carbon bioreagent comprising at least a portion of the enhanced pyrolysis solids; Includes:

[0411] In some embodiments, step (h) comprises removing at least some of the condensable vapor from step (e). At least a portion of the pyrolysis solids is passed, in vapor or condensed form, through the warm pyrolysis solids to increase the carbon content. In some embodiments, step (h) comprises producing a strengthened pyrolytic solid. passing at least a portion of the non-condensable gases from step (e) through the warm pyrolysis solids; , producing an enhanced pyrolysis solid having an increased carbon content.

[0412] Alternatively or additionally, the vapor or gas can be contacted with cold pyrolysis solids. In some embodiments, step (h) comprises removing at least the condensable vapor from step (e). A portion of the slag is passed through a low-temperature pyrolysis solid in vapor or condensed form to increase the carbon content. In some embodiments, step (h) comprises producing a strengthened pyrolysis solid. passing at least a portion of the non-condensable gases from step (e) through a cold pyrolysis solid; producing an enhanced pyrolysis solid having an increased carbon content.

[0413] In certain embodiments, step (h) comprises substantially removing the condensable vapor from step (e). All are passed through a low temperature pyrolysis solid in vapor or condensed form to produce a reinforcement with increased carbon content. In certain embodiments, step (h) comprises producing a pyrolysis solid. e) Passing substantially all of the non-condensable gases from the pyrolysis solid through the cold pyrolysis solid to reduce the carbon content. and producing an enhanced pyrolysis solid with increased

[0414] The process involves treating or dissolving the steam or gas prior to using the steam or gas for carbon enrichment. For example, the condensable vapor obtained from step (e) may be separated by various methods. The intermediate feed stream, which comprises at least a portion of the gas and at least a portion of the non-condensable gas, comprises at least may also be fed to a separation unit configured to produce first and second output streams. In certain embodiments, the intermediate feed stream is all of the condensable vapors, all of the non-condensable gases, or It includes both.

[0415] Separation techniques include distillation columns, flash vessels, centrifuges, cyclones, membranes, and filters. , packed beds, capillary columns, etc. Separation can be primarily performed by: For example, it can be based on distillation, absorption, adsorption, or diffusion, and can be characterized by vapor pressure, activity, molecular weight, density, , viscosity, polarity, chemical functionality, affinity to the stationary phase, and any combination thereof. The difference can be exploited.

[0416] In some embodiments, the first and second output streams are separated into intermediate feed streams based on their relative volatility. For example, the separation unit may be a distillation column, a flash tank, or a condenser. It could be.

[0417] Thus, in some embodiments, the first output stream comprises condensable vapor and the second output stream comprises condensable vapor. The power stream contains non-condensable gases. Condensable vapors include terpenes, alcohols, acids, aldehydes, or ketones. The vapors from the reactor contain aromatic compounds such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic compounds such as refractory tars may be present in the vapor. The non-condensable gas is at least one selected from carbon monoxide, carbon dioxide, and methane. The carbon-containing molecule may include:

[0418] In some embodiments, the first and second output streams are separated based on their relative polarities. For example, the separation unit may be a stripping column, a packed bed, a chromatographic column, or a The substrate may be a lithography column or a membrane.

[0419] Thus, in some embodiments, the first output stream contains polar compounds and the second output stream contains The current contains non-polar compounds. The polar compounds are methanol, furfural, and acetic acid. The non-polar compound may comprise at least one carbon-containing molecule selected from the group consisting of monoxide, nitrite, nitrite, nitrite-containing ... At least one selected from carbon, carbon dioxide, methane, terpene, and terpene derivatives The molecule may include two carbon-containing molecules.

[0420] Step (h) is a high-performance process for the same process except that it does not include step (h). The total carbon content of the carbon bioreagent can be increased. The degree of increase in carbon content varies. In various embodiments, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more. It can be more than that.

[0421] In some embodiments, step (h) increases the fixed carbon content of the high carbon biological reagent. In these or other embodiments, step (h) comprises removing the volatile carbon from the high-carbon biological reagent. Increase the content. The volatile carbon content is the carbon due to volatile substances in the reagent. Volatile substances include aliphatic or aromatic compounds (e.g., terpenes); alcohols, aldehydes or oxygenates, including ketones; and hydrocarbons, including various tars. Volatile carbon typically remains bound or adsorbed to solids at ambient conditions. However, when heated, the fixed carbon is oxidized, gasified, or released as steam. is released to

[0422] Depending on the conditions associated with step (h), some amount of volatile carbon may become fixed carbon. It is possible to evaporate the carbon dioxide (e.g., via Boudoir carbon formation from CO). The volatile species enter the micropores of the fixed carbon and exist as condensed / adsorbed species, but remain relatively volatile. This residual volatility is a significant disadvantage compared to product applications that require high surface area and porosity. It may be more advantageous for fuel applications.

[0423] Step (h) determines the energy content (i.e., energy density) of the high-carbon bioreagent. The increase in energy content can increase total carbon, fixed carbon, and volatile carbon. The degree of increase in energy content can vary depending on the various embodiments. So, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even higher. obtain.

[0424] With further separation, one or more non-condensable components may be separated for use in the process or further processing. Reactive gases or condensable vapors can be recovered, for example, purified carbon monoxide or hydrogen Further processing can be included to produce

[0425] As another example, separation of acetic acid can be performed, followed by reduction of the acetic acid to ethanol. The reduction of acetic acid is carried out, at least in part, using hydrogen derived from the non-condensable gases produced. It can be realized.

[0426] Condensable vapors are used in processes (such as thermal oxidation) to increase the carbon content of high-carbon bioreagents. It can be used for energy either in the form of coal (by coal mining, etc.) or in carbon enrichment. Certain non-condensable gases, such as CO or CH4, are used for energy in the process and can be utilized as part of the substantially inert gas for the pyrolysis step. Any combination of the above is also possible.

[0427] A potential advantage of including step (h) is that the gas stream is scrubbed and the resulting gas stream is C The resulting gas stream can be used for energy recovery. and can be recycled for carbon enrichment of the solids or can be cooled to room temperature in the reactor using an inert gas. Similarly, by separating non-condensable gases from condensable vapors, Thus, the CO / CO stream may be, for example, an inert gas in the reactor system or the cooling system. It is prepared for use as:

[0428] Another variation is that the principle of the carbon enhancement step is to add carbon to any source to which it is desired to add carbon. This is based on the understanding that the fee may be applied.

[0429] In some embodiments, a batch or continuous process for producing a high-carbon biological reagent , (a) providing a solids stream comprising a carbon-containing material; (b) Condensable carbon-containing vapor, non-condensable carbon-containing gas, or condensable carbon-containing vapor and non-condensable carbon-containing gas. providing a gas stream comprising a mixture of a volatile carbon-containing gas and a volatile carbon-containing gas; (c) passing the gas stream through the solid stream under suitable conditions to form an increased carbon content for the carbon-containing material; and forming a carbon-containing product having a carbon content.

[0430] In some embodiments, the starting carbon-containing material is pyrolyzed biomass or torrefied biomass. The gas stream can be obtained during an integrated process to provide a carbon-containing material; or The gas stream may be obtained from a separate process of a carbon-containing material. It can be obtained from external sources (e.g., sawmill ovens). Mixtures of gas streams, as well as mixtures of carbon-containing materials, are possible.

[0431] In some embodiments, the process includes repeating the process to obtain carbon from the carbon-containing product. or further comprising recycling or reusing the gas stream to further increase the energy content. In some embodiments, the process is carried out to obtain a carbon-containing material that is different from the carbon-containing material. Recycling or reusing a gas stream to increase the carbon or energy content of another feedstock Further includes:

[0432] In some embodiments, the process is adapted to produce at least a first and a second output stream. The method further comprises introducing the gas stream into a separation unit configured as follows: The first and second output streams comprise a mixture of carbon-containing vapor and non-condensable carbon-containing gas. The gas stream can be separated based on purity, relative polarity, or any other characteristic. The organic materials can be obtained from separate processing.

[0433] In some embodiments, the process includes repeating the process to obtain carbon from the carbon-containing product. It further includes recycling or reusing the gas stream to further increase the content. In an embodiment, the process comprises: The method further includes recycling or reusing the gas stream.

[0434] The carbon-containing product may have an increased total carbon content, a higher fixation rate, or a higher yield relative to the starting carbon-containing material. carbon content, higher volatile carbon content, higher energy content, or any of these The combination of

[0435] In a related variation, the high carbon bio-reagent production system comprises: (a) a feeder configured to introduce a carbon-containing feedstock; (b) a carbon-containing feedstock material disposed in operable communication with the feeder, the carbon-containing feedstock material being adapted to remove moisture contained within the feedstock material; an optional dryer configured to (c) a multi-zone reactor disposed in operable communication with the dryer, At least one pyrolysis zone disposed in operative communication with a separate cooling zone. and configured to have an outlet for removing condensable vapors and non-condensable gases from the solids. a multi-zone reactor, (d) a solids cooler disposed in operable communication with the multi-zone reactor; (e) a solid-state cooler disposed in operable communication with the solid-state cooler for converting condensable vapors or non-condensable gases into solid a material enrichment unit configured to pass the material through a and (f) a high-carbon biological reagent recovery unit disposed in operable communication with the material concentration unit; And, it is equipped with.

[0436] The system may further comprise a preheating zone disposed in operative communication with the pyrolysis zone. In some embodiments, the dryer can be used as a drying zone in a multi-zone reactor. Each of the zones may be located within a single unit or within separate units. Also, a solid-state cooler can be placed in the multi-zone reactor.

[0437] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is , configured with a gas outlet to create a substantially countercurrent flow of the gas phase relative to the solid phase. In these or other embodiments, the preheating zone or drying zone (or dryer) may include a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase.

[0438] In certain embodiments, the system incorporates a material enrichment unit, , (i) a housing having an upper portion and a lower portion; (ii) at the bottom of the lower portion of the housing; an inlet configured to carry a condensable vapor and a non-condensable gas; (iii) at the top of the upper portion of the housing; an outlet configured to carry a concentrated gas stream derived from the condensable vapor and the non-condensable gas; (iv) a passageway defined between the upper and lower portions of the housing; (v) A route-following transportation system, a transport system configured to transport the solids, the housing configured to transport the solids Shaped to adsorb at least a portion of the condensable vapor or at least a portion of the non-condensable gas It has been done.

[0439] The present disclosure provides various compositions useful as high-carbon biological reagents, as well as methods incorporating such reagents. In some variations, the high carbon biological reagent can be prepared as described herein. Any process disclosed in, e.g., (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the ingredients to remove at least a portion of the moisture contained within the ingredients; and (c) Optionally, degas the feedstock to remove as much interstitial oxygen, if any, contained in the feedstock. removing at least a portion of the (d) in a pyrolysis zone in the presence of a substantially inert gas for at least 10 minutes; and the raw material is thermally decomposed at a pyrolysis temperature selected from about 250°C to about 700°C to form a high-temperature pyrolyzer. producing a dissolved solid, a condensable vapor, and a non-condensable gas; (e) extracting at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the high-temperature pyrolysis solids; and separating the portion. (f) in a cooling zone in the presence of a substantially inert gas for at least 5 minutes and Cooling the hot pyrolysis solid to a cooling temperature below the pyrolysis temperature to produce a warm pyrolysis solid Steps and (g) cooling the warm pyrolysis solid to produce a cold pyrolysis solid; (h) recovering the high-carbon biological reagent comprising at least a portion of the cooled pyrolysis solid; The present invention is manufactured by a process including the steps of:

[0440] In some embodiments, the reagents are at least about 70% by weight on a dry basis, at least 8 0%, at least 90%, or at least 95% by weight of total carbon. , which contains at least fixed carbon and may further contain carbon from volatile materials. In this embodiment, the carbon from the volatiles accounts for at least part of the total carbon present in the high-carbon biological reagent. At least about 5%, at least 10%, at least 25%, or at least 50%. For example, fixed carbon can be measured using ASTM D3172, and volatile carbon can be measured using It can be measured using ASTM D3175.

[0441] The high-carbon biological reagent contains less than about 10% by weight, e.g., less than about 5% by weight, hydrogen on a dry basis. The biological reagent may contain less than about 1% by weight, e.g., less than about 0.5% by weight, nitrogen on a dry basis. The biological reagent may contain less than about 0.5% by weight, for example, about 0.2% by weight, on a dry basis. Bioreagents may contain up to about 0.2% by weight of phosphorus on a dry basis, e.g. For example, it may contain up to about 0.1% by weight of sulfur.

[0442] Carbon, hydrogen, and nitrogen, 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.

[0443] Certain embodiments contain approximately 100% hydrogen (excluding any moisture that may be present), nitrogen, phosphorus, or sulfur. A reagent that is almost or essentially free of carbon plus any ash and moisture present. Thus, some embodiments provide 100% on a dry / ash-free (DAF) basis. A biological reagent having the following carbon is provided:

[0444] Biomass feedstocks contain non-volatile organic compounds, including silica and various metals, that are not readily released during pyrolysis. Of course, it is also possible to use ashless raw materials, in which case the pyrolysis solids There should not be a substantial amount of ash in the mixture. Ash should be measured using, for example, ASTM D3174. and can be measured.

[0445] Varying amounts of non-combustible material such as ash may be present. High carbon bioreagents are approximately 10 times as dense as the dry material. % or less, for example, about 5%, about 2%, or about 1% by weight or less of non-combustible material. In certain embodiments, the reagent contains little ash or is free of ash or other impurities. It contains essentially no flammable materials. Thus, some embodiments contain 1% or less of flammable materials on a dry basis. It provides essentially pure carbon containing 0.00% carbon.

[0446] Varying amounts of water may be present. Based on the total mass, the high carbon bioreagent should contain at least 1% by weight. , 2% by weight, 5% by weight, 10% by weight, 15% by weight, 25% by weight, 35% by weight, 50% by weight As intended herein, "moisture" includes absorbed moisture, adsorbed moisture, and Any form of hydrate present in a biological reagent, including hydrated water molecules, chemical hydrates, and physical hydrates. The equilibrium water content should be interpreted as including water in the volatile state. The moisture content may also vary depending on the local environment. The moisture content may also vary during transportation, preparation for use, and other logistics processes. Moisture content can be measured, for example, using ASTM D3173.

[0447] High carbon biological reagents are used for this purpose based on the higher heat release associated with the total combustion of bone dry reagents. The energy content can vary, meaning the energy density based on the , high carbon bioreagents are about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000Btu / lb, at least 14,000Btu / lb, or an energy content of at least 15,000 Btu / lb. In certain embodiments, the energy content is about 14,000 to 15,000 Btu / lb. Energy content can be measured, for example, using ASTM D5865. This can be done.

[0448] The high carbon bioreagent can be formed into a powder, such as a coarse powder or a fine powder. In embodiments, the drug may be sieved at about 200 mesh, about 100 mesh, about 50 mesh, about 10 mesh, or about 10 mesh. mesh, having an average mesh size of about 6 mesh, about 4 mesh, or about 2 mesh It can be formed into a powder.

[0449] In some embodiments, the high-carbon biological reagent is compressed, bound, or aggregated. The starting material for forming these bodies is a particle-reducing material. The object may be in powder form of a reagent, such as an intermediate obtained by mechanical pressing or other optionally with a binder or other means to clump the particles together. It is possible.

[0450] In some embodiments, the high carbon biological reagent has a structure substantially derived from the source material. For example, raw chips are used to produce high-carbon bioreagent product chips. Alternatively, the source cylinder can be used to produce a high-carbon bioreagent cylinder. This can be somewhat reduced, but otherwise the basic structure and The geometry can be maintained.

[0451] The high carbon biological reagents according to the present disclosure may be at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm Manufactured as objects with minimum dimensions of 6cm, 7cm, 8cm, 9cm, 10cm or more In various embodiments, the minimum dimension or maximum The major dimension can be a length, width, or diameter.

[0452] Other variations of the present disclosure include the incorporation of additives into the process, into the product, or both. In some embodiments, high-carbon biological reagents are incorporated into the process. In these or other embodiments, the reagents include at least one process additive. The reagents contain at least one product additive that is introduced into the reagents after the reaction.

[0453] In some embodiments, the high-carbon biological reagent comprises, on a dry basis: at least about 70% by weight total carbon; at most about 5 wt. % hydrogen; at most about 1% by weight of nitrogen; at most about 0.5 wt. % phosphorus; at most about 0.2 wt. % sulfur; Selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. and an additive selected therefrom.

[0454] Additives include, but are not limited to, magnesium, manganese, aluminum, nickel , chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, Iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar The material may be selected from quartz, bentonite, calcium oxide, lime, or a combination thereof. can.

[0455] In some embodiments, the high-carbon biological reagent comprises, on a dry basis: at least about 70% by weight total carbon; at most about 5 wt. % hydrogen; at most about 1% by weight of nitrogen; at most about 0.5 wt. % phosphorus; at most about 0.2 wt. % sulfur; and an additive selected from an acid, a base, or a salt thereof.

[0456] Additives include, but are not limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, sodium, hydrogen bromide, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof You can choose from a combination.

[0457] In certain embodiments, the high carbon biological reagent comprises, on a dry basis: at most about 70% by weight total carbon; at most about 5 wt. % hydrogen; at most about 1% by weight of nitrogen; at most about 0.5 wt. % phosphorus; at most about 0.2 wt. % sulfur; Selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. a first additive selected from the group consisting of: a second additive selected from an acid, a base, or a salt thereof; The first additive is different from the second additive.

[0458] The first additive is magnesium, manganese, aluminum, nickel, chromium, silicon , boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, Magnesium oxide, dolomite, dolomitic lime, fluorite, fluorospar, bentonite A second additive can be selected from calcium oxide, lime, or a combination thereof. The agents are sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, sodium permanganate, potassium permanganate, or a combination thereof. It is possible.

[0459] Certain high-carbon biological reagents contain, on a dry basis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible materials, and magnesium, manganese, aluminum, nickel, chromium, silicon, boron, and parsley Smoke, molybdenum, phosphorus, tungsten, vanadium, iron chloride, iron bromide, magnesium oxide Dolomite, dolomitic lime, fluorite, fluorospar, bentonite, calcium oxide The composition of the present invention consists essentially of an additive selected from gum, lime, or a combination thereof.

[0460] Certain high-carbon biological reagents contain, on a dry basis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible materials, and sodium hydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide, hydrogen chloride, silica the additive selected from the group consisting of sodium carbonate, sodium phosphate ...

[0461] The amount of additive (or total additives) may be about 0.1 wt%, about 1 wt%, about 5 wt%, about 10 wt%, or %, or may vary widely, such as from about 0.01% to about 25% by weight, including about 20% by weight. Therefore, when relatively large amounts of additives, such as more than about 1 wt.%, are incorporated, the entire test It is understood that the energy content calculated based on the drug weight (including excipients) will be reduced. Further, in various embodiments, the high carbon bio-reagent with additives may comprise at least about 1 1,000Btu / lb, at least 12,000Btu / lb, at least 13,00 0 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb It can have an energy content of tu / lb.

[0462] The above considerations regarding product form also apply to embodiments incorporating additives. Certain embodiments may incorporate binders, fluxes, or other additives to enhance final properties for specific applications. Additives are incorporated as additives or other modifiers.

[0463] In a preferred embodiment, the majority of the carbon contained in the high carbon bio-reagent is renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. Specific markets where value is attributed to the renewable carbon content within high-carbon bioreagents There may be mechanisms (eg, renewable identification numbers, tax credits, etc.).

[0464] In certain embodiments, fixed carbon is classified as non-renewable carbon (e.g., derived from coal). volatile carbon, which can be added separately, has a higher energy content. It can be made of renewable carbon to increase the renewable carbon value as well.

[0465] The high carbon bioreagents produced as described herein can be used to produce a wide variety of carbonaceous products. High carbon bioreagents may themselves be desirable commercial products. The high carbon bioreagents used have lower levels of impurities, reduced protease activity, and reduced oxidative stress compared to state-of-the-art technologies. process emissions and improved sustainability (including higher renewable carbon content) Can be linked.

[0466] In a variant, the product may be obtained by the disclosed process or may be prepared by the process of the present invention. Any of the high-carbon biological reagents described in the compositions set forth in the subsection, or any portion thereof , combinations, or derivatives.

[0467] Generally speaking, high-carbon biological reagents are burned to produce energy (including electricity and heat). It can be partially oxidized, gasified, or steamed to produce synthesis gas. modified and utilized for their adsorption or absorption properties, metal purification (in accordance with the present disclosure) They are utilized for their reactive properties in catalytic processes (such as the reduction of metal oxides) or other industrial processes. , or utilized for their material properties in carbon steel and various other metal alloys. Essentially, high carbon bioreagents are any carbon-based commodity or advanced material, including those for which special applications are being developed. It can be used for any market application.

[0468] Prior to suitability or actual use in any product application, the disclosed high carbon bioreagents must: Can be analyzed, measured, and optionally modified (e.g., by additives) in a variety of ways Other potentially important properties besides chemical composition and energy content include: Some of these properties include density, particle size, surface area, microporosity, absorption, adsorption, binding capacity, and reaction. These include reactivity, desulfurization activity, and basicity.

[0469] Products or materials that can incorporate these high carbon bioreagents include carbon-based blast furnace Addition products, carbon-based taconite pellet addition products, ladle addition carbon-based products, metcoke carbonaceous products, coal substitute products, carbonaceous coking products, carbon breeze products, fluid bed carbonaceous feedstock, carbonaceous furnace additive products, injectable carbonaceous products, finely divided carbonaceous products, stove Examples of suitable electrode materials include, but are by no means limited to, carbon-based products, carbon electrodes, or activated carbon products. I can't.

[0470] The use of the disclosed high carbon bioreagents in metal production reduces slag and increases overall efficiency. Therefore, implementation of the present disclosure can increase the life cycle environmental impact. The form is particularly suitable for metal processing and manufacturing.

[0471] Some variations of the present disclosure utilize high-carbon bioreagents as carbon-based blast furnace addition products. Blast furnaces are used in smelting to produce industrial metals, including (but not limited to) iron. Smelting is a form of extractive metallurgy, the primary use of which is to extract metals from their ores. The production of metals. Smelting uses heat and chemical reducing agents to break down ores. The carbon, or carbon monoxide derived from carbon, removes oxygen from the ore, leaving behind the elemental metal.

[0472] The reducing agent may consist of or include a high carbon bioreagent. The raw material, ore, and typically limestone, can be fed continuously through the top of the furnace. while air (optionally enriched with oxygen) is blown into the bottom of the chamber, resulting in As a result, a chemical reaction occurs throughout the furnace as the material moves downward. The final product is , the molten metal and slag phases, which are usually removed from the bottom, and flue gases, which exit from the top of the furnace. The downward flow of ore in contact with the upward flow of hot carbon monoxide-rich gas is a countercurrent process. is.

[0473] The quality of carbon in a blast furnace is measured by its resistance to degradation. The breakdown of carbon varies with location in the blast furnace. The reaction of carbon particles with CO2, H2O, or O2, with each other and with other components of the input, This is combined with the abrasion of carbon particles. The broken down carbon particles cause clogging and performance degradation. It may cause.

[0474] The coke reactivity test is a highly regarded measure of the performance of carbon in a blast furnace. , which has two components: Coke Reactivity Index (CRI) and Coke Strength after Reaction (CSR). Carbon-based materials with low CRI (high reactivity) and high CSR values ​​are more suitable for high performance. CRI is measured according to any suitable method known in the art. For example, ASTM Method DS341 determines the as-received condition. can.

[0475] In some embodiments, the high carbon bioreagent has properties that make it suitable for direct introduction into a blast furnace. The present invention provides a carbon product.

[0476] The strength of the high carbon bioreagent can be determined by any suitable method known in the art, for example, It can be determined by a drop to crush test or a CSR test. The high carbon bioreagent, optionally blended with another carbon source, is at least about 50% The combined product provides a final carbon product with a CSR of 60% or 70%. It is also possible to provide a final coke product with a reactivity suitable for combustion in a blast furnace. In some embodiments, the product is prepared by treating the high carbon bioreagent with methocol, methocoke, powder, or the like. Suitable for use as an additive or replacement for coke, foundry coke, or injectable coal The CRI is such that

[0477] Some embodiments have insufficient CRI or CSR for use as a blast furnace product. When added to another carbon source (e.g., coke), sufficient carbon is produced for use in a blast furnace. in an amount sufficient to provide a high-carbon biological reagent that provides a conjugated product having RI or CSR. In some embodiments, the one or more additives comprise about 40% Present in sufficient quantity to provide a high-carbon bioreagent with a CRI of 30%, or less than 20% do.

[0478] In some embodiments, an alkaline earth metal or an oxide or carbonate thereof is selected from the group consisting of: One or more additives may be introduced during or after the process of producing the high carbon bioreagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or carbonate Magnesium can be introduced as an additive before, during, or after pyrolysis. The addition of compounds can increase the reactivity of high-carbon biological reagents in the blast furnace. These compounds result in stronger materials, i.e., higher CSR, and therefore In addition, alkaline earth metals or their oxides or Additives such as those selected from carbonates may result in lower emissions (e.g., SO2). It can be done.

[0479] In some embodiments, the high carbon biological reagent is a biological reagent that has a high fixed carbon content, as described above. It also contains a fairly high proportion of volatile carbon. The volatile material is converted to metal oxide at lower temperatures. It is expected that the SiO2 has better mass transport to the oxide, making it desirable for metal oxide reduction. Compared to fossil fuel-based products such as coke, high-carbon bioreagents have sufficient strength and have more fixed volatile carbon, which leads to greater reactivity results.

[0480] In some embodiments, the blast furnace replacement product is at least about 55% by weight carbon, about 0. Not more than 5% by weight of sulfur, not more than about 8% by weight of non-combustible materials, and at least about 11,000 Bt In some embodiments, a high-carbon biological reagent according to the present disclosure includes a calorific value of 1000 u / lb. The blast furnace replacement product contains less than about 0.035 wt.% phosphorus, and between about 0.5 wt.% and about 50 wt.% In some embodiments, the composition further comprises a volatile material of: The blast furnace substitute product is about 2% by weight to about 15% by weight of dolomite, about 2% by weight to about 15% by weight of % of dolomitic lime, about 2% to about 15% by weight of bentonite, or about 2% to about 15% by weight of % by weight of calcium oxide. In some embodiments, the blast furnace replacement product comprises substantially It has dimensions ranging from about 1 cm to about 10 cm.

[0481] In some embodiments, the high carbon bio-reagent according to the present disclosure is a foundry coke replacement product. Foundry coke generally has a carbon content of at least about 85% by weight, Sulfur content of about 0.6% by weight, volatile matter of about 1.5% by weight or less, ash of about 13% by weight or less , about 8% by weight or less moisture, about 0.035% by weight phosphorus, a CRI value of about 30, and a thickness of about 5 cm It is characterized by having dimensions ranging from 25 cm to about 25 cm.

[0482] Some variations of the present disclosure involve the addition of high-carbon bioreagents to carbon-based taconite pellets. Iron oxide is the ore used to make iron and steel. These include hematite, limonite (also called brown ore), taconite, and magenta. Examples of ores include gnetite and black ore. Taconite is a low-grade but important ore. It contains both magnetite and hematite. The iron content of taconite is generally 2 5% to 30% by weight. Blast furnaces typically require at least Iron ore containing 50% iron by weight is required. Iron ore is crushed, screened, tumbled, and The ore can be subjected to beneficiation processes including flotation, flotation, and magnetic separation. Refined ore can have over 60% The iron is concentrated in the coal and is often formed into pellets before transport.

[0483] For example, taconite can be ground into a fine powder and combined with a binder such as bentonite clay and limestone. For example, a pen about 1 centimeter in diameter containing about 65% iron by weight can be used. The pellets can be fired to convert the magnetite to hematite. The pellets are durable and the blast furnace charge passes through the heated gases, This ensures that the molten ore remains porous enough to react with the molten ore.

[0484] Taconite pellets are used to produce iron, as described above for blast furnace adducts. In some embodiments, a high carbon bioreagent can be introduced into the blast furnace. In these or other embodiments, the high carbon biological reagent is incorporated into the taconite pellet itself. For example, beneficiated taconite ore powder is mixed with high-carbon bioreagents and binders. The material may be melted, rolled into small bodies, and then fired until hard. has developed a method for producing taconite-carbon pellets with the appropriate composition, without the need for a separate carbon source, for high-temperature oxidation. It can be conveniently introduced into the furnace.

[0485] Some variations of the present disclosure utilize high-carbon biological reagents as ladle-added carbon-based products. A ladle is a vessel used to transport and pour out molten metal. Used to pour molten metal into molds to produce castings. Used to transfer metal from one process to another. Some aspects of molten metals, such as the conversion of cast iron to ductile iron by the addition of various elements, It is used to change the process that occurs in the ladle.

[0486] The high carbon bioreagent can be introduced into any type of ladle, but typically, is added to the treatment ladle in a suitable amount based on the target carbon content. can be in the form of a fine powder for good mass transfer of carbon into the final composition. In embodiments, the high carbon bioreagent according to the present disclosure, when used as a ladle adduct, having a smallest dimension of about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or greater .

[0487] In some embodiments, a high carbon bioreagent according to the present disclosure may be prepared by, for example, ladle addition of carbon. Used (e.g., added to ladle carbon during steelmaking) in basic oxygen furnaces or electric arc furnaces It is useful as a ladle-added carbon additive in facilities.

[0488] In some embodiments, the ladle-added carbon additive contains up to about 5 wt. % manganese, up to about It further comprises 5% by weight calcium oxide or up to about 5% by weight dolomitic lime.

[0489] Direct reduced iron (DRI), also known as sponge iron, is a type of reduced iron traditionally produced from natural gas or coal. It is produced from the direct reduction of iron ore (in the form of lumps, pellets, or fines) with raw gas. The gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide, which act as reducing agents. The high carbon biological reagents provided herein can be converted into a gas stream containing CO to form a reducing agent. The iron can be directly reduced by acting as a catalyst.

[0490] Iron nuggets are a high quality steelmaking and iron casting feed material. Iron nuggets are essentially all Iron and carbon, almost no gangue (slag), and low levels of metallic residues. These are premium grade pig iron products with excellent transport and handling characteristics. or the carbon contained in any portion thereof may be a high-carbon biological reagent provided herein. Iron nuggets are produced in a rotary hearth using a high-carbon bioreagent as a reducing agent and energy source. It can be produced by reducing iron ore in a furnace.

[0491] Some variations of the present disclosure utilize high-carbon bioreagents as metallurgical coke carbonaceous products. Metallurgical coke, also known as "met" coke, is typically a blend of various blends of bituminous coal. It is a carbon material produced by the decomposition and distillation of coke. The final solid is called metallurgical coke. As a result of the loss of volatile gases and partial melting, metcoke is Metcoke has a very low volatile content. However, The ash components that were part of the original bituminous coal feedstock remain encapsulated in the resulting coke. The coke raw material is available in a wide range of sizes, from fine powder to basketball-sized chunks. Typical purities range from 86 to 92% fixed carbon by weight.

[0492] Metallurgical coke is used where high quality, tough, resilient abrasive carbon is required. Applications include conductive flooring, friction materials (e.g., carbon linings), and foundry coatings. Carbon risers for casting, corrosion materials, drilling applications, reducing agents, heat treatment agents, ceramic filling media These include, but are not limited to, electrolytic processes, and oxygen scavenging.

[0493] Metcoke has a calorific value of about 10,000 to 14,000 Btu / lb and a weight of about 10. % or more of ash. In embodiments, the metcoke replacement product is at least about 80 wt.%, 85 wt.%, or 90 wt.%. 0% by weight carbon, less than about 0.8% by weight sulfur, less than about 3% by weight volatile matter, less than about 15% by weight % or less ash, about 13% or less by weight moisture, and about 0.035% or less by weight phosphorus. The high-carbon bioreagent according to the present disclosure includes a metcoke replacement product. When used as a stencil, it can have a size range of, for example, about 2 cm to about 15 cm. do.

[0494] In some embodiments, the metcoke replacement product is a product containing chromium, nickel, manganese, Magnesium oxide, silicon, aluminum, dolomite, fluorite, calcium oxide, lime, It may further include additives such as dolomitic lime, bentonite, or combinations thereof.

[0495] Some variations of the present disclosure utilize high-carbon bioreagents as coal replacement products. Any process or system that uses charcoal is, in principle, similar to that using high-carbon biological reagents. It can be adapted as follows.

[0496] In some embodiments, the high-carbon biological reagent is combined with one or more coal-based products. and have a higher rank than coal-based products or produce pure coal-based products when combusted. to form a complex product with less emissions than

[0497] For example, low rank coals such as sub-bituminous coals may be less likely to retain selected amounts of high carbon bioreagents according to the present disclosure. By combining it with a high-rank coal product, it is possible to reduce the amount of coal that would normally require a high-rank coal product, such as bituminous coal. In other embodiments, mixed coal products (e.g., different The rank of the coal mixture is determined by adding a certain amount of high-carbon bioreagent to the coal mixture. This can be improved by combining it with high-carbon biomass that is mixed with the coal product. The amount of reagent depends on the rank of the coal product, the properties of the high-carbon bioreagent (e.g., carbon content, heat value, etc.). etc.), and the desired rank of the final combination product.

[0498] For example, anthracite coal generally contains at least about 80% by weight carbon, about 0.6% by weight sulfur, About 5% by weight volatile matter, up to about 15% by weight ash, up to about 10% by weight moisture, and about 12% by weight ,494 Btu / lb. In the present invention, an anthracite substitute product is at least about 80% by weight carbon and not more than about 0.6% by weight sulfur. , about 15% by weight or less ash, and a high calorific value of at least about 12,000 Btu / lb. Carbon bioreagent.

[0499] In some embodiments, the high carbon bioreagents are useful as thermal coal replacement products. Coal products generally have high sulfur levels, high phosphorus levels, high ash content, and up to about 15,000 kJ / kg. In some embodiments, the thermal coal is characterized by having a heating value of 0.00 Btu / lb. The replacement product has less than about 0.5% by weight sulfur, less than about 4% by weight ash, and at least about 12% by weight of It is a high-carbon biological reagent containing a calorific value of 1,000 Btu / lb.

[0500] Some variations of the present disclosure utilize high-carbon bioreagents as carbon-based coking products. Any coking process or system uses a high carbon bioreagent to produce coke. The coke feedstock may be manufactured or adapted for use as a coke feedstock.

[0501] In some embodiments, the high carbon bioreagent is useful as a thermal coal or coke replacement product. For example, a thermal coal or coke replacement product may be at least about 50% by weight carbon, about 8% by weight or less ash, about 0.5% by weight or less sulfur, and at least about 11,000 Btu In another embodiment, a thermal coke substitute may be used. The product further comprises from about 0.5% to about 50% by weight of volatile materials. The alternative product may contain from about 0.4% to about 15% water by weight.

[0502] In some embodiments, the high carbon bio-reagent is petroleum (pet) coke or calcined pet Calcined pet coke is useful as a coke replacement product. 6% by weight carbon, up to 4.6% by weight sulfur, up to about 5.5% by weight volatile matter, up to about 1 It is characterized by having 9.5% ash by weight and a maximum of about 2% moisture by weight, typically about 3 In some embodiments, the calcined pet coke replacement product is a mixture of 100% ethanol and 100% ethanol. at least about 66% by weight carbon, not more than about 4.6% by weight sulfur, not more than about 19.5% by weight Ash, a high-carbon biological reagent containing less than about 2% water by weight, with a size of less than about 3 mesh. be.

[0503] In some embodiments, the high-carbon bio-reagent may be a coking carbon-substituted carbon (e.g., coking carbon). In one embodiment, coke is used as a coke. The carbon-replacement product is at least about 55% by weight carbon, not more than about 0.5% by weight sulfur, and Contains no more than 8% by weight of non-combustible material and a calorific value of at least about 11,000 Btu / lb. In some embodiments, the coking carbon replacement product is a high-carbon bioreagent containing about 0. 0.5% to about 50% by weight of volatile material or one or more additives.

[0504] Some variations of the present disclosure utilize high-carbon biological reagents as carbon breath products, Carbon breeze products are typically very small particles such as 6mm, 3mm, 2mm, and less than 1mm. In some embodiments, the high-carbon bio-reagent according to the present disclosure is a powdered carbon nanotube. Coke breeze is generally a material with a maximum size of about 6 mm or less, a small amount of coke, and a high carbon content. 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 substitute product is at least about 80% by weight of coke. less than about 0.8% by weight of sulfur; less than about 20% by weight of volatile matter; less than about 13% by weight of ash , a high-carbon biological reagent according to the present disclosure comprising about 13% or less water by weight, and a maximum dimension of about 6 mm. is.

[0505] In some embodiments, the high carbon bioreagent is used in, for example, taconite pellet manufacturing or It is useful as a carbon breeze substitute in the steelmaking process.

[0506] Some variations are useful as feedstocks for various fluidized beds or as a fluidized bed carbonaceous feedstock replacement. Uses high carbon bioreagents as the product. Carbon can be produced by total combustion, partial oxidation, gasification, steam reforming, etc. It can be used in fluidized beds for its quality, etc. Carbon is primarily used for energy (e.g., heat and and electricity) or liquid fuels (e.g., methanol or Fischer-Tropsch can be converted into syngas for a variety of downstream uses, including the production of diesel fuel .

[0507] In some embodiments, a high-carbon biological reagent according to the present disclosure can be prepared, for example, by using a method in which coal (e.g., Fluidized bed coal replacement in fluidized bed furnaces used for process heat or energy production It is useful as a composition.

[0508] Some variations utilize high-carbon bioreagents as carbon-based furnace adducts. Carbon furnace adducts generally have high sulfur levels, high phosphorus levels, and high ash content. These contribute to the degradation of metal products and cause air pollution. In some embodiments, the carbon furnace addition surrogate product containing the high carbon bioreagent is about 0.5 wt. % or less of sulfur, about 4% or less of ash by weight, about 0.03% or less of phosphorus by weight, and about 7.5 cm In some embodiments, the carbon furnace additive substitute product comprises about 0.5 wt. It contains about 50% by weight of volatile substances and about 0.4% to about 15% by weight of water.

[0509] In some embodiments, the high carbon bioreagent may be, for example, It is useful as a furnace carbon additive in any basic oxygen furnace or electric arc furnace facility. For example, furnace added carbon is added to scrap steel during steel production in electric arc furnace facilities. In electric arc furnace applications, the impurities are removed early and then returned to the process. High purity carbon is desirable to avoid this.

[0510] In some embodiments, the furnace-added carbon additive is at least about 80% by weight carbon, about 0 0.5% by weight or less of sulfur, about 8% by weight or less of non-combustible materials, and at least about 11,000 B In some embodiments, the furnace-added carbon is a high-carbon bioreagent containing a calorific value of 1000 tu / lb. The additives are up to about 5% by weight of manganese, up to about 5% by weight of fluorite, and about 5% to about 10% by weight of fluorite. % by weight of dolomite, about 5% to about 10% by weight of dolomitic lime, or about 5% to about 1 Further contains 0% by weight calcium oxide.

[0511] Some variations utilize high carbon bioreagents as the stoker furnace carbon-based product. In some embodiments, a high carbon bioreagent according to the present disclosure is used, for example, coal ( stoker furnaces in stoker furnace installations (e.g., for process heat or energy production) It is useful as a coal replacement product.

[0512] Some variations include the use of high-carbon bioreagents as injectable (e.g., finely divided) carbon-based materials. In some embodiments, the high carbon bioreagent is calcined injection grade PET. Injection grade calcined pet coke is generally useful as a pet coke replacement product. At least about 66% by weight of carbon, about 0.55 to about 3% by weight of sulfur, and a maximum of about 5.5% by weight of volatile organic compounds. and a maximum of about 6% by weight of flammable materials, about 10% by weight of ash, and about 2% by weight of moisture. In some embodiments, the calcined pet coke replacement product is a mixture of 100% ethanol and 100% ethanol. is at least about 66% by weight carbon, not more than about 3% by weight sulfur, not more than about 10% by weight ash, It is a high-carbon biological reagent containing less than 2% water by weight and is approximately 6 mesh or smaller in size.

[0513] In some embodiments, the high carbon bioreagent is injectable carbon (e.g., In any application (injected into the slag or ladle during steelmaking), e.g., basic oxygen furnace or is useful as an injectable carbon replacement product in electric arc furnace facilities.

[0514] In some embodiments, the high carbon bioreagent may be, for example, pulverized coal (e.g., process heat). Whenever carbon dioxide is used in the atmosphere (for energy production or for other purposes), it is a valuable alternative to fine carbon. In some embodiments, the finely divided carbon replacement product has up to about 10 percent acid Contains calcium chloride.

[0515] Some variations utilize high-carbon biological reagents as carbon addition products for metal production. In some embodiments, the high carbon biological reagent according to the present disclosure comprises carbon steel or carbon. Useful as a carbon addition product for the production of other metal alloys. Coal-based late stage carbon addition The products generally have high sulfur levels, high phosphorus levels, and high ash content, as well as low metal quality. These are characterized as having high mercury levels that contribute to air pollution. In some embodiments, the carbon addition products contain up to about 0.5 wt. % sulfur, up to about 4 wt. % less than about 0.03% by weight of ash, less than about 0.03% by weight of phosphorus, a minimum size of about 1 to 5 mm, and a minimum size of about 8 to 12 mm Including the largest dimension.

[0516] Some variations utilize high carbon bioreagents within carbon electrodes. In this case, the high carbon bioreagent is suitable for use in, for example, aluminum production, for example, electrodes (e.g. , anode) materials.

[0517] Other applications of high carbon bioreagents on carbon electrodes include batteries, fuel cells, capacitors, and other energy storage or energy delivery devices. In lithium-ion batteries, high-carbon biological reagents are used to intercalate lithium. In these applications, carbon purity and low ash content are very important. can be important.

[0518] Some variations of the present disclosure utilize high-carbon biological reagents as catalyst supports. Mixed acid synthesis from synthesis gas using a carbon-supported cobalt-molybdenum sulfide metal catalyst For alcohol synthesis or Fischer-Tropsch synthesis of higher hydrocarbons from synthesis gas is a known catalyst support in a wide range of catalytic chemical reactions, including carbon-supported iron-based catalysts. .

[0519] Some variations utilize high carbon bioreagents as activated carbon products. A wide variety of fluids, including processing, air purification, solvent vapor recovery, food and beverage processing, and pharmaceuticals For activated carbon, the porosity and surface area of ​​the material are generally The high-carbon biological reagents provided herein, in various embodiments, include: (i) a hydroxylated (ii) Higher surface area than fossil-based activated carbon; (iii) Carbon renewable; (iv) Use with additives The vascularity of biomass feedstocks allows for better penetration / distribution of additives to enhance pollutant control and (iv) less inert material (ash) allows for greater reactivity. As a result, an excellent activated carbon product can be provided.

[0520] In the above description of the market applications of high-carbon biological reagents, the applications described are not exclusive and are not intended to be exhaustive. It should be recognized that the method is not inclusive. Therefore, it is not possible to favor one type of carbon product. The high-carbon biological reagents described as suitable may, in various embodiments, be used in combination with any other described reagents. These uses are exemplary only and there are other uses for high carbon biological reagents.

[0521] Additionally, in some embodiments, the same physical material may be used in any of the following ways: Thus, for example, High carbon bioreagents used as electrodes or activated carbon are expected to have a long useful life as performance materials. Finally, combustion processes for energy value or metal production (e.g., metal ore reduction) It can be introduced into processes, etc.

[0522] Some embodiments utilize bioreagents for their reactive / adsorbent properties and as fuels. For example, bioreagents injected into the exhaust stream can be used to remove contaminants. subsequently combusting the bio-reagent particles and possibly contaminants to produce energy; It may be suitable for thermally destroying or chemically oxidizing contaminants.

[0523] Compared to traditional fossil fuel-based products, high-carbon bioreagents have significant environmental and product use implications. High carbon bioreagents are not only environmentally superior, but also have the potential to be more efficient, e.g. It may also be functionally superior from a processing standpoint due to its higher purity.

[0524] For some embodiments of metal manufacturing, the production of bioreagents by the disclosed process , coking of coal-based products necessary for preparing them for use in metal production Compared to CO, CO2, and NO x , SO2, and significantly lower emissions of harmful air pollutants This can result in:

[0525] The use of high carbon bioreagents instead of coal or coke also reduces SO2, harmful Air pollutants and mercury emissions into the environment are significantly reduced.

[0526] Additionally, due to the purity of these high carbon bioreagents (including low ash content), the disclosed bioreagents has the potential to reduce slag and increase production capacity in batch metal manufacturing processes. do.

[0527] This detailed description provides several embodiments of the present disclosure and how the disclosure can be understood and implemented. Reference is made to non-limiting examples of how this can be accomplished. Other embodiments may be utilized that do not provide all of the features and advantages described herein without the need for a separate, non-transitory, non-transitory, non-commercial, non-transitory, non-proprietary ...commercial, non-proprietary, non-proprietary, non-transitory, non-profit, non-profit organization. The present disclosure is based on routine experimentation and testing of the methods and systems described herein. Such modifications and variations are within the spirit and scope of the present invention as defined by the claims. are considered to be within the range indicated.

[0528] All publications, patents, and patent applications cited herein are the property of their respective owners. Each and every patent application is hereby incorporated by reference in its entirety as if specifically and individually set forth herein. incorporated herein.

[0529] This disclosure is incorporated herein by reference in its entirety. ,440, U.S. Patent Application Publication No. 2019-0169518, U.S. Patent Application Publication No. 20 15-0144831, U.S. Patent Application Publication No. 2015-0126362, U.S. Patent No. Publication No. 2015-0196896, U.S. Patent Application Publication No. 2016-0280554 and U.S. Patent Application Publication No. 2016-0114308, which are incorporated herein by reference. .

[0530] Where the methods and steps described above indicate particular events occurring in a particular order, those skilled in the art will recognize the particular It is recognized that the order of the steps may be changed and that such changes are in accordance with variations of this disclosure. Furthermore, some of the steps will be performed simultaneously in parallel processes if possible. The steps may be performed sequentially or sequentially.

[0531] Therefore, any and all modifications and variations of the present invention that fall within the spirit of this disclosure or that are found in the appended claims are within the spirit of the present disclosure and are not intended to be limiting unless expressly stated. To the extent there are variations of this disclosure that are equivalent to this disclosure, this patent also covers those variations. The present disclosure is intended to be limited only by the claims. do. [Example]

[0532] Example 1: Reduction of iron ore using biomass pyrolysis off-gas. Douglas fir (Pseudotsuga menziesii) in the form of wood chips serves as biomass feedstock The average size of the wood chips is about 25mm long and 25mm wide. It is about 5 millimeters thick.

[0533] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). Taconite is found mainly in the Mesabi Iron Range and the Minnesota Iron Ore District in the United States. It is mined in the Marquette Iron Range in Michigan, USA.

[0534] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 600°C and a pyrolysis residence time of approximately 30 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of N2. The reactor is at atmospheric pressure. There is a solid output and a vapor output from the pyrolysis reactor. The solid output is , a biological reagent containing carbon, is collected in a hopper. The steam output is hydrogen and carbon monoxide. The pyrolysis off-gas is stored at high pressure, such as about 5 to 10 bar. or compressed and fed directly to the reduction reactor. can be done.

[0535] Granular iron ore and bioreagents produce carbon-iron ore particles as a mixture of chunks and fines The mixture of lumps and fines is then continuously mixed in a grinding unit. It is pelletized in a pelletizing unit to produce carbon iron ore pellets.

[0536] The carbon-iron ore pellets are then fed into the continuous reduction reactor using a solids inlet port. The pyrolysis off-gas containing H2 and CO is pumped into the cylindrical vessel using a steam inlet port. The steam flows cocurrently with the solids stream. The reduction reactor is The reduction temperature is about 00°C and the reduction residence time is about 1 hour. The reduction pressure is about 5 bar ( In the reduction reactor, Fe3O4 is reacted with H2 and C O and solid carbon to a mixture of FeO and Fe (FeO is F (It is in a lower oxidation state than e3O4). The steam output from the reduction reactor is the reaction from the chemical reduction. The solid output from the reduction reactor contains water and carbon dioxide as by-products. Fe and possibly some unreacted carbon. The solid output of is recycled and passed through the reduction reactor again to remove additional reducing gas or residual carbon. The content can be used to reduce FeO to Fe.

[0537] Example 2: Reduction of iron ore using biomass pyrolysis reducing gas. Douglas fir (Pseudotsuga menziesii) in the form of wood chips serves as biomass feedstock The average size of the wood chips is about 25mm long and 25mm wide. It is about 5 millimeters thick.

[0538] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). It's a stone.

[0539] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 500°C and a pyrolysis residence time of approximately 40 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of N2. The reactor is at atmospheric pressure. There is a solid output and a vapor output from the pyrolysis reactor. The solid output is The steam output is a bio-reagent containing carbon and is collected in a hopper. The pyrolysis off-gas is directed to a container for storing pyrolysis off-gas. is a light alkane such as methane, a light alcohol such as methanol, a light organic solvent such as acetic acid, Acids and terpenes.

[0540] Granular iron ore and bioreagents produce carbon-iron ore particles as a mixture of chunks and fines The mixture of lumps and fines is then continuously mixed in a grinding unit. It is pelletized in a pelletizing unit to produce carbon iron ore pellets.

[0541] The pyrolysis off-gas is partially oxidized in a continuous partial oxidation reactor to produce a gas containing hydrogen and carbon monoxide. The partial oxidation reactor may utilize a catalyst. is exothermic and releases some heat, which is thermally integrated with the pyrolysis reactor and its adsorption Provides thermal requirements. The reducing gas is stored at high pressure, such as about 5-10 bar. It can be directed into a cylindrical vessel for the reduction reactor or compressed and fed directly to the reduction reactor. can be done.

[0542] The carbon-iron ore pellets are then fed into the continuous reduction reactor using a solids inlet port. The reducing gas containing H2 and CO is introduced from the cylindrical vessel using a vapor inlet port. The steam is metered into the reduction reactor. The steam flows cocurrently with the solids stream. The reduction reactor is The reduction temperature is about 100°C and the reduction residence time is about 1 hour. The reduction pressure is about 5 bar (pressure In the reduction reactor, Fe3O4 is reacted with H2 and CO and solids. The steam from the reduction reactor is reduced to a mixture of FeO and Fe by reaction with carbon. The output contains water and carbon dioxide as reaction by-products from the chemical reduction. The solid product is a mixture of FeO and Fe, and possibly some unreacted carbon. Optionally, this solid output is recycled and passed through the reduction reactor again to add Additional reducing gas or residual carbon content can be used to reduce FeO to Fe.

[0543] Example 3: Reduction of iron ore using biomass pyrolysis reducing gas. Corn (Zea mays) stover from Iowa, USA, is provided as a biomass feedstock. Corn stover includes leaves, stalks, and cobs and has an average grain length of about 25 mm. do.

[0544] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). It's a stone.

[0545] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 500°C and a pyrolysis residence time of approximately 30 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of Ar. The reactor is at atmospheric pressure. There is a solid output and a vapor output from the pyrolysis reactor. The solid output is The carbon-containing biological reagent is collected in a hopper. The steam output is used for energy production. The pyrolysis off-gas is burned for the purpose of

[0546] The first part of the granular iron ore and bioreagent is prepared by mixing the granular iron ore with the fine powder. The lumps and fines are then combined in a continuous grinding unit to produce a The mixture is pelletized in a continuous pelletizing unit to produce carbon iron ore pellets.

[0547] The second portion of the biological reagent is gasified in a gasifier to produce a gas containing hydrogen and carbon monoxide. The gasifier uses air as the oxidizing medium and operates at a temperature of approximately 1200°C. The process is operated continuously at 1000 K.P.M., resulting in the production of residual (unreacted) solids containing reducing gas and ash. The reducing gas is directed into a cylindrical container for storing the reducing gas at high pressure, such as about 5-10 bar. The fuel can be compressed and fed directly to the reduction reactor.

[0548] The carbon-iron ore pellets are then fed into the continuous reduction reactor using a solids inlet port. The reducing gas containing H2 and CO is introduced from the cylindrical vessel using a vapor inlet port. The vapor is metered into the reduction reactor. The vapor flows cocurrently with the solids stream. The reduction reactor is The reduction temperature is 0°C and the reduction residence time is about 1 hour. The reduction pressure is about 10 bar ( In the reduction reactor, Fe3O4 is reacted with H2 and CO and The steam output from the reduction reactor is used to The solid output from the reduction reactor contains water and carbon dioxide as reaction by-products from Contains fully reduced Fe from the starting Fe3O4 in taconite.

[0549] Example 4: Production of carbon iron ore pellets. Douglas fir (Pseudotsuga menziesii) in the form of wood chips serves as biomass feedstock The average size of the wood chips is about 25mm long and 25mm wide. It is about 5 millimeters thick.

[0550] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). It's a stone.

[0551] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 650°C and a pyrolysis residence time of approximately 30 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of N2. The reactor is at atmospheric pressure. There is a solid output and a vapor output from the pyrolysis reactor. The solid output is , a biological reagent containing at least 50% by weight of fixed carbon, is collected in a hopper. The output is pyrolysis off-gas, which can be stored and combusted to generate energy, or can be used elsewhere in the process.

[0552] Granular iron ore and bioreagents are crushed in a continuous grinding unit to produce carbon iron ore fines. The fines are then pelletized in a continuous pelletizing unit to form carbonite. Stone pellets are produced using a binder (e.g., bentonite clay, limestone, or starch). Carbon-iron ore pellets contain about 40% total carbon by weight. Contains.

[0553] Example 5: Production of iron nuggets from iron ore and biomass. Douglas fir (Pseudotsuga menziesii) in the form of wood chips serves as biomass feedstock The average size of the wood chips is about 25mm long and 25mm wide. It is about 5 millimeters thick.

[0554] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). It's a stone.

[0555] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 500°C and a pyrolysis residence time of approximately 1 hour. The pyrolysis pressure is approximately 2 bar under an inert gas consisting essentially of N2. There is a solid output and a steam output from the pyrolysis reactor. The solid output contains carbon. The steam output is a thermal component containing hydrogen and carbon monoxide. Cylinders for storing pyrolysis off-gas at high pressures, such as about 5-10 bar. The refrigerant may be directed into a shaped vessel or may be compressed and fed directly to the reduction reactor.

[0556] Granular iron ore and bioreagents produce carbon-iron ore particles as a mixture of chunks and fines The mixture of lumps and fines is then continuously mixed in a grinding unit. It is pelletized in a pelletizing unit to produce carbon iron ore pellets.

[0557] The carbon-iron ore pellets are then fed into a continuous reduction reactor using a solid inlet port. The pyrolysis off-gas containing H2 and CO is fed into the rotary hearth furnace through the steam inlet port. The vapor flows countercurrently to the solids flow. The reduction reactor is operated at a reduction temperature of about 700°C and a reduction residence time of about 50 minutes. The initial pressure is about 10 bar (via the compressed pyrolysis off-gas). In the reduction reactor: Fe3O4 is reduced to Fe by reaction with H2 and CO. The reduction reaction occurs on solid carbon. The steam output from the reduction reactor is optimized to prevent all of the iron oxides from reacting with the chemical reduction reactor. The original reaction by-products include water and carbon dioxide. The solid product from the reduction reactor is , containing Fe. The solid product is in the form of iron nuggets consisting essentially of iron and carbon. Iron nuggets are a high quality steelmaking and iron casting feed material. Iron nuggets have excellent transport and It is a high-quality pig iron product with excellent handling properties.

[0558] Example 6: Production of iron from iron ore and biomass. Douglas fir (Pseudotsuga menziesii) in the form of wood chips serves as biomass feedstock The average size of the wood chips is about 25mm long and 25mm wide. It is about 5 millimeters thick.

[0559] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). It's a stone.

[0560] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 700°C and a pyrolysis residence time of approximately 20 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of N2. There is a solid output and a steam output from the pyrolysis reactor. The solid output contains carbon. The vapor output is pyrolysis off-gas.

[0561] The granular iron ore and at least a portion of the biological reagent are combined in a continuous grinding unit to form a carbonite. Generates stone blocks.

[0562] A solids inlet port is then used to feed the carbon-iron ore chunks into a continuous chemical reduction furnace. The chemical reduction furnace was operated at a reduction temperature of about 1100°C, a reduction residence time of about 1 hour, and a pressure of about 3 bar. Air is supplied to the chemical reduction furnace to oxidize the carbon contained in the carbonaceous iron ore mass. This produces heat and carbon monoxide. Fe3O4 reacts with the CO and residual C. Optionally, a portion of the bioreagent produced from pyrolysis is reduced to Fe by the reaction. Co-fed directly to the chemical reduction furnace (not as carbon iron ore lump). The output contains Fe, i.e., iron products.

[0563] Example 7: Composition for reducing iron ore. Douglas fir (Pseudotsuga menziesii) in the form of wood chips serves as biomass feedstock The average size of the wood chips is about 25mm long and 25mm wide. It is about 5 millimeters thick.

[0564] Granular iron ore is provided as the metallic ore. The iron ore is in the form of taconite. Magnetite is a low-grade siliceous iron ore containing 20-30% by weight of magnetite (Fe3O4). It's a stone.

[0565] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 650°C and a pyrolysis residence time of approximately 30 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of N2. The reactor is at atmospheric pressure. There is a solid output and a vapor output from the pyrolysis reactor. The solid output is , a biological reagent containing approximately 70% fixed carbon by weight, is collected in a hopper. is pyrolysis off-gas, which can be stored, combusted for energy generation, or processed. It may be used elsewhere in the process.

[0566] Granular iron ore and bioreagents are crushed in a continuous grinding unit to produce carbon iron ore fines. The fines are then pelletized in a continuous pelletizing unit to form carbonite. Stone pellets are produced. Limestone is used to improve binding efficiency. Limestone is used to It contains calcite and aragonite, which are different crystalline forms of calcium CaCO3.

[0567] The final composition comprises carbon-iron ore pellets, the carbon-iron ore pellets being on a dry and ash-free basis. It contains about 30% fixed carbon by weight. 14 C / 12 C isotope ratio measurement Slightly less than 100% renewable carbon as determined by a small percentage of non-renewable carbon. The available carbon comes from the carbon contained in the CaCO3 binder.

[0568] Example 8: Composition for reducing copper-nickel ores. Nordic birch (Betula pendula) in the form of wood chips as a biomass feedstock The average size of the wood chips is about 50 mm long and 50 mm wide. The thickness is about 10 mm.

[0569] A particulate metal ore containing mixed copper ore and nickel ore is provided.

[0570] The biomass raw material was subjected to continuous pyrolysis at a pyrolysis temperature of approximately 650°C and a pyrolysis residence time of approximately 30 minutes. The pyrolysis pressure is approximately 1 bar under an inert gas consisting essentially of N2. The reactor is at atmospheric pressure. There is a solid output and a vapor output from the pyrolysis reactor. The solid output is , a bioreagent containing approximately 75% fixed carbon by weight, is collected in a hopper. is pyrolysis off-gas, which can be stored, combusted for energy generation, or processed. It may be used elsewhere in the process.

[0571] The granulated metal ore and bioreagent are mixed with a continuous metal ore to produce carbon metal ore fines. The fine powder is then pelletized in a continuous pelletizing unit. The cornstarch is used to increase the binding efficiency. The carbon in cornstarch is renewable and biogenic.

[0572] The final composition comprises carbon metal ore pellets, the carbon metal ore pellets being water-free and ash-free. It contains about 35% fixed carbon by weight. 14 C / 12 Measurement of C isotope ratio It is 100% renewable carbon as determined by the

Claims

1. 1. A method for reducing metal ore, the method comprising: providing a biomass feedstock; pyrolyzing the biomass feedstock, thereby producing a bio-reagent and a pyrolysis off-gas, wherein the bio-reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide; obtaining a metal ore, wherein the metal ore comprises a metal oxide and the metal ore is in particulate form; combining the carbon with the metal ore, thereby producing carbon-metal ore particulates; and chemically reducing the metal oxide, wherein the chemical reduction is achieved using the pyrolysis off-gas.

2. 10. The method of claim 1, further comprising pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets.

3. The method of claim 2 wherein the metal oxide is contained within the carbon metal ore pellets.

4. The method of claim 1 , wherein the bioreagent comprises at least 50% carbon by weight.

5. 10. The method of claim 1, wherein the metal ore is iron ore, copper ore, nickel ore, magnesium ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore, tungsten ore, molybdenum ore, or a combination thereof.

6. 10. The method of claim 1, wherein the carbon metal ore particulates comprise at least about 0.1% to at most about 50% carbon by weight.

7. The method of claim 1 , wherein the carbon metal ore pellets include a binder.

8. 10. The method of claim 1, wherein said chemically reducing directly utilizes said pyrolysis off-gas.

9. 2. The method of claim 1, wherein said chemically reducing indirectly utilizes said pyrolysis off-gas by first partially oxidizing said pyrolysis off-gas, thereby producing a reducing gas, and then utilizing said reducing gas to chemically reduce said metal oxides within said carbon-metal ore particles.

10. 10. The method of claim 1, wherein said chemically reducing co-utilizes a reducing gas obtained from gasification, partial oxidation, or steam reforming of said bio-reagent or a portion thereof.

11. 10. The method of claim 1, wherein the pyrolysis off-gas comprises at least 10 mole percent hydrogen.

12. 10. The method of claim 1, wherein the pyrolysis off-gas comprises at least 10 mole percent carbon monoxide.

13. 1. A method for reducing metal ore, comprising: providing a biomass feedstock; pyrolyzing the biomass feedstock, thereby producing a bio-reagent and a pyrolysis off-gas, wherein the bio-reagent comprises carbon and the pyrolysis off-gas comprises hydrocarbons; obtaining a metal ore, wherein the metal ore comprises a metal oxide and the metal ore is in particulate form; combining the carbon with the metal ore, thereby producing carbon-metal ore particulates; partially oxidizing the pyrolysis off-gas, thereby producing a reducing gas and heat; and chemically reducing the metal oxide, wherein the pyrolysis is achieved using the heat produced from partially oxidizing the pyrolysis off-gas.

14. 14. The method of claim 13, comprising pelletizing the carbon metal ore particulates, thereby producing carbon metal ore pellets.

15. 14. The method of claim 13, wherein the bio-reagent comprises at least 50% carbon by weight.

16. 14. The method of claim 13, wherein the metal ore is iron ore, copper ore, nickel ore, magnesium ore, manganese ore, aluminum ore, tin ore, zinc ore, cobalt ore, chromium ore, tungsten ore, molybdenum ore, or a combination thereof.

17. 14. The method of claim 13, wherein the carbon metal ore particulates comprise at least about 0.1% to at most about 50% carbon by weight.

18. The method of claim 13 , wherein the carbon metal ore pellets include a binder.

19. 14. The method of claim 13, wherein the pyrolysis off-gas comprises at least 10 mole percent hydrogen.

20. 14. The method of claim 13, wherein the pyrolysis off-gas comprises at least 10 mole percent carbon monoxide.

21. 1. A method for reducing a metal ore, the method comprising: providing a biomass feedstock; pyrolyzing the biomass feedstock, thereby producing a bio-reagent, the bio-reagent comprising carbon; obtaining a metal ore, the metal ore comprising a metal oxide, the metal ore being in particulate form; combining the carbon with the metal ore, thereby producing carbon-metal ore particulates; generating a reducing gas from gasification, partial oxidation, or steam reforming of the bio-reagent; and chemically reducing the metal oxide using the reducing gas.

22. 1. A method for processing metal ores, the method comprising: providing a biomass feedstock; pyrolyzing the biomass feedstock, thereby producing a bio-reagent and a pyrolysis off-gas, wherein the bio-reagent comprises carbon and the pyrolysis off-gas comprises hydrogen or carbon monoxide; obtaining a metal ore, wherein the metal ore is in particulate form and comprises a metal oxide, a metal sulfide, a metal hydride, a metal nitride, a metal carbide, a metal boride, a metal phosphide, or a combination thereof; combining the carbon and the metal ore, thereby producing carbon-metal ore particulates; and chemically producing elemental metals from the metal oxide, metal sulfide, metal hydride, metal nitride, metal carbide, metal boride, metal phosphide, or a combination thereof, wherein the production is achieved using the pyrolysis off-gas.

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