System and apparatus for generating high-carbon bioreagents

Abstract

Providing a process and system for converting biomass into high-carbon bioreagents suitable for a variety of commercial applications. Some embodiments employ pyrolysis in the presence of an inert gas to produce hot pyrolysis solids, condensable vapors, and non-condensable gases, followed by separation of the vapors and gases and cooling of the hot pyrolysis solids in the presence of an inert gas. Additives may be introduced during the process or combined with the reagent, or both. The bioreagent may contain at least 70 wt%, 80 wt%, 90 wt%, 95 wt%, or more total carbon on an anhydrous basis. The bioreagent may have an energy content of at least 12,000 Btu / lb, 13,000 Btu / lb, 14,000 Btu / lb, or 14,500 Btu / lb on an anhydrous basis. The bioreagent may be formed into a powder or structure.

Description

Technical Field

[0001] The present invention generally relates to processes, systems, and apparatuses for the manufacture of high-carbon bioreagents, as well as related compositions, products, and uses.

Background Art

[0002] Carbon is a platform element in a wide variety of industries and has a vast number of chemical, material, and fuel uses. Carbon is a good fuel for generating energy, including electricity. Carbon has very great chemical value for a variety of commodities and advanced materials, including metals, metal alloys, mixtures, carbon fibers, electrodes, and catalyst supports. In metal production, carbon is useful as a reagent for reducing metal oxides to metals during processing; as a fuel for supplying heat for processing; and also as a component of the final metal alloy. Carbon is a very important element in steel as it enables the steel to be hardened by heat treatment.

[0003] Carbon-based reagents can, in principle, be produced from any material substantially containing carbon. Carbonaceous materials generally include fossil resources such as natural gas, petroleum, coal, and peat; as well as renewable resources such as lignocellulosic biomass and various carbon-rich waste materials.

[0004] Biomass is a term used to describe any biologically produced substance or biogenic material. The chemical energy contained in biomass is derived from solar energy using the natural process of photosynthesis. This is the process by which plants absorb carbon dioxide and water from the environment and use the energy from sunlight to convert them into sugars, starches, cellulose, hemicellulose, and lignin. Among all renewable energy sources, biomass is unique in that it is effectively stored solar energy. Furthermore, biomass is the only renewable resource of carbon.

[0005] By utilizing bio-based carbon as fuel, the carbon is reused to further cultivate biomass, so combustion-related CO2 emissions do not contribute to net life-cycle carbon dioxide emissions. Furthermore, the use of bio-based carbon as fuel will typically reduce sulfur dioxide and mercury emissions compared to the use of coal or other solid fossil fuels for energy production.

[0006] By utilizing bio-based carbon for chemical and material applications where carbon is not immediately combusted, carbon can be effectively sequestered over long periods (for example, when carbon is added to steel for permanent structures). In this way, net carbon dioxide emissions are substantially negative, meaning that CO2 from the atmosphere is used to cultivate the bio-based raw materials, and then carbon is sequestered within the bio-based product.

[0007] However, converting biomass into high-carbon reagents presents both technical and economic challenges, stemming from the diversity of available raw materials, operational difficulties, and capital intensity. Various conversion technologies exist for transforming biomass raw materials into high-carbon materials. Most well-known conversion technologies utilize some form of pyrolysis.

[0008] Pyrolysis is a process for the thermal conversion of solids with an oxidizing agent (air or oxygen) that is either completely absent or limited in supply so that oxidation does not occur to a significant degree. Depending on the process conditions and additives, biomass pyrolysis can be adjusted to produce a wide variety of gases, liquids, and solids. Low processing temperatures and long vapor residence times are favorable for solid production. Higher temperatures and longer residence times increase the conversion of biomass to synthesis gas, but moderate temperatures and short vapor residence times are generally optimal for liquid production. Recently, there has been considerable interest in pyrolysis and related processes for converting biomass into liquids as precursors for high-quality synthesis gas and / or liquid fuels.

[0009] On the other hand, there has been little interest in improving pyrolysis processes, particularly to optimize the yield and quality of solids as high-carbon reagents. Historically, slow pyrolysis of wood has been carried out in large quantities in simple batch processes without emission control. Conventional charcoal production techniques are not only highly polluting but also energy inefficient. Clearly, there are economic and practical challenges to scaling up such processes for the sustainable commercial production of high-quality carbon while managing energy balance and controlling emissions. [Overview of the Initiative] [Means for solving the problem]

[0010] In some modified forms, the present invention provides a process for producing high-carbon bioreagents, the process being (a) To supply carbon-containing raw materials including biomass, (b) Optionally, dry the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degas the feed material or dried feed material in order to remove, if present, at least some of the interstitial oxygen contained in the feed material. (d) In the pyrolysis zone, the feed material is pyrolyzed at a pyrolysis temperature selected from about 250°C to about 700°C for at least about 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) In the cooling zone, cool the hot pyrolysis solids at a cooling zone temperature lower than the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (g) Further cooling of warm pyrolysis solids in an optional cooling device separate from the cooling zone in order to produce cold pyrolysis solids, (h) Recover the high-carbon bioreagent containing at least some of the warm or cold pyrolysis solids. Includes.

[0011] In this specification, the term “reactor” refers to an individual unit within which atmospheric and temperature conditions can be controlled, and where physical and / or chemical reactions can occur. In this context, the term “zone” refers to an area within the reactor where temperature and atmospheric conditions can be controlled, relative to other zones within the reactor.

[0012] In this specification, the term “biomass processing unit” refers to a reactor comprising multiple zones, as will be described in more detail below. In various embodiments, the biomass processing unit ("BPU") includes multiple output passages configured to transfer raw materials, feedstock at different stages of processing, gases, condensate byproducts, and heat from various reactors and zones to other reactors or zones, material supply systems, carbon recovery units, and any other planned components of the systems described herein. In one embodiment, the raw materials are carbonized after passing through each zone of the BPU.

[0013] In this specification, the term “carbonization” means an increase in the carbon content within a given amount of biomass. Carbonization can be achieved, for example, by reducing non-carbon-containing material from biomass and adding carbon atoms to the biomass or both to form a “high-carbon biogenic reagent.”

[0014] As described below, various multi-zone BPU embodiments include a single reactor, and various multi-zone BPU embodiments may also include two or more separate reactors. Other embodiments described below will be understood to include multiple separate reactors, each reactor having at least one zone. For the purposes of this disclosure, the characteristics, principles, alternatives, and embodiments described in relation to all single-reactor multi-zone BPU embodiments apply similarly to all multiple separate reactor embodiments, and vice versa.

[0015] In some embodiments, the process includes drying the feed material to remove at least some of the moisture contained within it. In these or other embodiments, the process includes degassing the feed material to remove at least some of the interlattice oxygen contained within it.

[0016] The process further includes, prior to step (d), preheating the feed material in a preheating zone in the presence of a substantially inert gas for at least about 5 minutes at a preheating temperature selected from about 80°C to about 500°C or from about 300°C to about 400°C.

[0017] In some embodiments, the pyrolysis temperature is selected from about 400°C to about 600°C. In some embodiments, the pyrolysis in step (d) is carried out for at least 20 minutes. The cooling zone temperature may be selected, for example, from about 150°C to about 350°C.

[0018] The thermal decomposition conditions may be selected to maintain structural integrity or mechanical strength of the feedstock for high-carbon bioreagents, if so desired for a particular product application.

[0019] In some embodiments, each zone is located within a single reactor or BPU. In other embodiments, each zone is located within a separate BPU or reactor. Some embodiments will be understood to include one or more BPUs, each including at least one zone.

[0020] The substantially inert gas can be selected from the group consisting of N2, Ar, CO, CO2, H2, CH4, and combinations thereof. Some of the substantially inert gases may include one or more noncondensable gas species (e.g., CO and CO2) reused from step (e). In some embodiments, each of the pyrolysis zone and the cooling zone includes a gas phase containing less than 5 wt% oxygen, such as less than about 1 wt% oxygen.

[0021] The process can be continuous, semi-continuous, or batch. In some continuous or semi-continuous embodiments, the inert gas flow is substantially counterflowing with respect to the direction of the solid flow. In other continuous or semi-continuous embodiments, the inert gas flow is substantially parallel with the direction of the solid flow.

[0022] In some embodiments, the process includes monitoring and controlling the process with at least one reaction gas probe, such as two or more reaction gas probes. Monitoring and controlling the process can improve the energy efficiency of the process. Monitoring and controlling the process can also improve product properties associated with high-carbon bioreagents, such as (but not limited to) carbon content, energy content, structural integrity, or mechanical strength.

[0023] The process further includes thermal oxidation (i.e., combustion) of at least a portion of the condensable and non-condensable vapors with an oxygen-containing gas. The thermal oxidation can be related to the combustion of natural gas. At least a portion of the heat generated from the thermal oxidation can be utilized to dry the feedstock. Additionally, at least a portion of the heat generated from the thermal oxidation can be utilized to heat a substantially inert gas before it enters one of the zones or reactors, such as a pyrolysis zone.

[0024] The process can further include combining at least a portion of the vapor with the cooled pyrolysis solids to increase the carbon content of the high-carbon bioreagent. Alternatively or additionally, the process can further include combining at least a portion of the condensable vapor with the warm pyrolysis solids to increase the carbon content of the high-carbon bioreagent.

[0025] The condensable vapor can then be used either in the process (such as by thermal oxidation) or for energy in carbon enrichment to increase the carbon content of the high-carbon bioreagent. Some non-condensable gas, such as CO or CH4, can be utilized either for energy in the process or as part of the substantially inert gas for the pyrolysis step.

[0026] In some embodiments, the process further includes introducing at least one additive selected from an acid, a base, or a salt thereof. The additive can be selected from (but not limited to) the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

[0027] In some embodiments, the process further includes introducing at least one additive selected from the group consisting of metals, metal oxides, metal hydroxides, metal halides, and combinations thereof. The additive may be selected from (but is not limited to) the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0028] Additives may be added before, during, or after any one or more steps of the process, including adding them to the feedstock itself at any time before or after the feedstock is harvested. Additives may be introduced, for example, before or during step (b), before or during step (d), during step (f), during step (g), between step (f) and step (g), or after step (g). Additives may be introduced into the warm pyrolysis solids. For example, in step (g), the additive may be introduced in the form of an aqueous solution, vapor, or aerosol to assist in the cooling of the warm pyrolysis solids. In these and other embodiments, the additive is introduced into the cold pyrolysis solids to form a high-carbon bioreagent containing the additive.

[0029] In some embodiments, the process further includes introducing at least a portion of the cold pyrolysis solids into a separate unit for further pyrolysis at a pyrolysis temperature selected from about 200°C to about 600°C for at least about 30 minutes in the presence of a substantially inert gas, in order to produce a solid product having a higher carbon content than the cold pyrolysis solids.

[0030] In some embodiments, the process further includes operating a cooling device to cool the warm pyrolysis solids, thereby producing cold pyrolysis solids and superheated steam, with drying being performed at least partially with the superheated steam obtained from an external cooling device. Optionally, the cooling device may be operated to first cool the warm pyrolysis solids with steam to a first cooling device temperature, and then cool them with air to a second cooling device temperature, the second cooling device temperature being lower than the first cooling device temperature, which relates to a reduced risk of combustion for the warm pyrolysis solids in the presence of air.

[0031] In some modified forms, the present invention provides a process for producing high-carbon bioreagents, the process being (a) Provide carbon-containing raw materials including biomass (from which some or all of the water has been removed, at the discretion of the party), (b) In the pyrolysis zone, pyrolysis of the feed material at a pyrolysis temperature selected from about 250°C to about 700°C for at least 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (c) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (d) In the cooling zone, cool the hot pyrolysis solids at a cooling temperature lower than the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (e) Further cooling of warm pyrolysis solids in an optional cooling device separate from the cooling zone in order to produce cold pyrolysis solids, (f) Recovering high-carbon bioreagents that contain at least some of the warm or cold pyrolysis solids. Includes.

[0032] In some modified forms, the present invention provides a process for producing high-carbon bioreagents, the process being (a) To supply carbon-containing raw materials including biomass, (b) Optionally, dry the feed material in order to remove at least some of the moisture contained in the feed material, if any. (c) Optionally, degas the feedstock to remove at least some of the interstitial oxygen contained in the feedstock, if any. (d) Preheat the raw material in the preheating zone for at least about 5 minutes in the presence of a substantially inert gas at a preheating temperature selected from about 80°C to about 500°C. (e) In the pyrolysis zone, pyrolysis of the feed material at a pyrolysis temperature selected from about 250°C to about 700°C for at least about 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (f) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (g) In the cooling zone, cool the hot pyrolysis solids at a cooling zone temperature lower than the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (h) Further cooling of warm pyrolysis solids in an optional cooling device separate from the cooling zone in order to produce cold pyrolysis solids, (i) comprising recovering a high-carbon bioreagent containing at least a portion of warm or cold pyrolysis solids, The process further includes introducing at least one additive somewhere within the process (i.e., at any one or more locations or number of times).

[0033] In some modified forms, the present invention provides a process for producing high-carbon bioreagents, the process being (a) To supply carbon-containing raw materials including biomass, (b) Optionally, drying the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degass the feed material in order to remove, if present, at least some of the interlattice oxygen contained in the feed material or the dried feed material. (d) In the pyrolysis zone, pyrolysis of the feed material at a pyrolysis temperature selected from about 250°C to about 700°C for at least about 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) Further cooling the hot pyrolysis solids in an optional cooling zone at a cooling zone temperature lower than the pyrolysis temperature for at least 5 minutes in the presence of the substantially inert gas in order to generate warm pyrolysis solids. (g) Cooling a warm or cold pyrolysis solid in a cooling device separated from the cooling zone in order to produce a cold pyrolysis solid, (h) To recover the high-carbon bioreagent containing at least a portion of the cold pyrolysis solids, and (i) Forming fine powder from the high-carbon bioreagent, The process optionally includes introducing at least one additive into the process before, during, or after step (i).

[0034] High-carbon bioreagents may contain at least 35% of the carbon contained in the feedstock, such as at least 50% or at least 70% of the carbon contained in the feedstock. In some embodiments, high-carbon bioreagents contain between approximately 40% and 70% of the carbon contained in the feedstock.

[0035] In some embodiments, the additive is introduced into the dried feedstock before or during step (d), but the presence of the additive in this process increases the carbon content of the high-carbon bioreagent compared to a process that is otherwise identical and does not include the additive.

[0036] High-carbon bioreagents may contain at least 55 wt% carbon on an anhydrous basis, for example, at least 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 90 wt%, 95 wt%, or more on an anhydrous basis. The total carbon may include fixed carbon and carbon from volatile substances. In some embodiments, high-carbon bioreagents contain at least 90 wt% or at least 95 wt% fixed carbon on an anhydrous basis.

[0037] High-carbon bioreagents may have an energy content of at least 11,000 Btu / lb on an anhydrous basis, for example, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, at least 14,500 Btu / lb, or at least 14,700 Btu / lb on an anhydrous basis.

[0038] High-carbon bioreagents can be formed into fine powders by micronization. Alternatively, or subsequently, high-carbon bioreagents can be formed into structures by compression, binding, pelletization, or agglomeration. In some embodiments, the high-carbon bioreagent is in the form of a structure whose structure and / or strength are substantially derived from the feedstock. In some embodiments, the high-carbon bioreagent is substantially the same structural form as the feedstock.

[0039] Another variant of the present invention provides a high-carbon bioreagent generation system, the system is (a) A material supply system configured to introduce carbon-containing raw materials, (b) An optional drying device, which is operably connected to the material supply system and configured to remove moisture contained in the carbon-containing feed material. (c) A biomass processing unit, which is operably connected to a material supply system or drying apparatus (if any), wherein the biomass processing unit includes at least one pyrolysis zone operably connected to a spatially separated cooling zone, and the biomass processing unit is configured with an outlet for removing condensable vapors and noncondensable gases from solids, (d) Cooling device, which is operably connected to the biomass processing unit, (e) A high-carbon bioreagent recovery device that is configured to be operationally connected to a cooling device. It is equipped with.

[0040] A drying apparatus, if present, may be configured as a drying zone within the BPU. In some embodiments, the system further includes a purging system for removing oxygen from the system. The purging system may include one or more intake ports for introducing a substantially inert gas, and one or more outlet ports for removing the substantially inert gas and replaced oxygen from the solids. The purging system may be a deaerater located between the material supply system (or, if present, the drying apparatus) and the BPU.

[0041] Optionally, the system may include a preheating zone that is operably connected to the pyrolysis zone.

[0042] Each of at least one pyrolysis zone, cooling zone, and preheating zone (if any) may be located within a single unit or separate units. The material supply system may be physically integrated with the BPU. In some embodiments, the cooling system is located within the BPU.

[0043] The system may further include one or more additive supply devices for introducing additives, such as any of the aforementioned additives, into the system. In some embodiments, the additive supply device is configured to combine the additive with the carbon-containing feedstock. The additive supply device may be inserted between the material supply system (for biomass) and the BPU. The additive supply device may be operably connected to the BPU. The additive supply device may be operably connected to the cooling device. The additive supply device may be inserted between the cooling device and the carbon recovery unit. The additive supply device may be operably connected to the carbon recovery unit, including downstream of the carbon recovery unit.

[0044] The BPU may be configured with a first gas inlet and a first gas outlet. The first gas inlet and first gas outlet may be located in different zones or in communication with the same zone. In various embodiments, the BPU may be configured with any one or more of a second gas inlet, a second gas outlet, a third gas inlet, a third gas outlet, a fourth gas inlet, and a fourth gas outlet. Optionally, each zone present within the BPU may be configured with a gas inlet and a gas outlet. The gas inlets and outlets not only enable the introduction and recovery of steam or gas, but also allow for precise process monitoring and control across various stages of the process, resulting in improved yield and efficiency.

[0045] In some embodiments, a cooling zone is configured with a gas inlet and a pyrolysis zone is configured with a gas outlet to generate a substantially opposing flow of the gas phase to the solid phase (e.g., feed material). In other embodiments, a cooling zone is configured with a gas inlet and a preheating zone is configured with a gas outlet to generate a substantially opposing flow of the gas phase to the solid phase. In these and other embodiments, a cooling zone is configured with a gas inlet and a drying zone is configured with a gas outlet to generate a substantially opposing flow of the gas phase to the solid phase.

[0046] The system may further include a pyrolysis zone and a first reaction gas probe operably connected to a gas monitoring device such as (but not limited to) a GC, MS, GC-MS, or FTIR. In some embodiments, the system may further include a cooling zone and a second reaction gas probe operably connected to a second gas monitoring device, which may be a gas monitoring device or a different type of instrument. The system may further include a drying zone (if present) and / or a preheating zone (if present), as well as additional reaction gas probes operably connected to a gas monitoring device. If reaction gas probes are included, the system may further include at least one computer-programmed controller capable of utilizing the output from the gas monitoring device to adjust system setpoints (such as pyrolysis temperature or inert gas flow rate).

[0047] In some embodiments, the system may further include a process gas heater operably connected to an outlet for removing condensable vapors and non-condensable gases, the process gas heater being configured to introduce a separate fuel and oxidizer into a combustion chamber adapted to the combustion of at least a portion of the fuel and condensable vapors.

[0048] The system may include a heat exchanger positioned between the process gas heater and the dryer, configured to utilize at least a portion of the heat of combustion for the dryer. Alternatively or additionally, the system may include a heat exchanger positioned between the process gas heater and the gas inlet for the BPU, configured to utilize at least a portion of the heat of combustion to preheat a substantially inert gas before introducing it into the BPU.

[0049] In some embodiments, the system may further include a carbon concentration unit, which is operably connected to a cooling device or BPU and configured to combine the vapors with a solid, including non-condensable vapors and / or condensable vapors in a fully or at least partially condensed form, in order to increase the carbon content of high-carbon bioreagents obtained from the carbon recovery unit.

[0050] In various embodiments, the system is configured to extract and reuse gas from the BPU and / or from the carbon recovery unit.

[0051] In some embodiments, the system may further include a separate pyrolysis apparatus adapted to further pyrolyze high-carbon bioreagents in order to further increase their carbon content.

[0052] Other variants provide a high-carbon bioreagent generation system, and this system is (a) A material supply system configured to introduce carbon-containing raw materials, (b) An optional drying device, which is operably connected to the material supply system and configured to remove moisture contained in the carbon-containing feed material. (c) A preheater, which is operably connected to a material supply system or drying apparatus (if any) and configured to heat and / or moderately thermally decompose the feed material, (d) A pyrolysis reactor, configured to be operably connected to a preheater and to pyrolyze the feed material, (e) A cooling device configured to be operably connected to the pyrolysis reactor and to cool the pyrolysis solids, and (f) A high-carbon bioreagent recovery device that is configured to be operationally connected to a cooling device. Includes, The system comprises at least one gas inlet for introducing a substantially inert gas into the reactor, and at least one gas outlet for removing condensable vapors and non-condensable gases from the reactor.

[0053] The system may include a degasser positioned between the material supply system or drying apparatus (if any) and the preheater. The system may optionally be configured with at least two gas inlets and at least two gas outlets.

[0054] In some embodiments, to generate a substantially opposing flow of gas to solid, the pyrolysis reactor and / or cooling apparatus is configured with a gas inlet(s) and / or preheater is configured with a gas outlet(s).

[0055] In some embodiments, the system further includes a process gas heater, operably connected to at least one gas outlet, for removing condensable vapors and non-condensable gases. The process gas heater may be configured to introduce separate fuels and oxidizers into a combustion chamber adapted to the combustion of at least a portion of the fuels and condensable vapors.

[0056] The system may include a heat exchanger located between the process gas heater and the dryer, configured to utilize at least a portion of the heat of combustion for the dryer. The system may also include a heat exchanger located between the process gas heater and the gas inlet for the BPU, configured to utilize at least a portion of the heat of combustion to preheat a substantially inert gas before introducing it into the pyrolysis reactor.

[0057] One variant provides a biomass pyrolysis continuous reactor comprising a feedstock inlet, a plurality of spatially separated reactors configured for separate temperature control and mixing within each reactor, and a carbonaceous solids outlet, wherein one of the reactors is configured with a first gas inlet for introducing a substantially inert gas into the reactor, and another of the reactors is configured with a first gas outlet.

[0058] In some embodiments, the BPU includes at least two, three, or four zones. Each zone may be arranged in communication with independently adjustable indirect heating means, each independently selected from a group consisting of electric heat transfer, steam heat transfer, hot oil heat transfer, waste heat transfer, and combinations thereof.

[0059] A BPU may be configured to independently adjust the gas phase composition and gas phase residence time of at least two zones. In some embodiments, a BPU may be configured to independently adjust the gas phase composition and gas phase residence time of all zones present within the BPU.

[0060] In some embodiments, the BPU is configured with a second gas inlet and / or a second gas outlet. In some embodiments, the BPU is configured with gas inlets and / or gas outlets within each zone. In some embodiments, the BPU is a counterflow reactor.

[0061] The material feeding system consists of a screw, auger, drop chamber, and drum material feed system. The supply mechanism may be selected from a group consisting of a screw, auger, drop chamber, and drum material supply system. The BPU may include a single auger positioned across each zone.

[0062] In some embodiments, each reactor is configured with flights positioned on the inner wall to provide stirring of the solids. The flights may be independently adjustable within each zone. In some embodiments, the BPU is axially rotatable.

[0063] A further variation of the present invention provides a process for producing high-carbon bioreagents, the process being: (a) To supply carbon-containing raw materials including biomass, (b) optionally drying the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degas the feedstock to remove at least some of the interstitial oxygen contained in the feedstock, if any. (d) In the pyrolysis zone, the feed material is pyrolyzed at a pyrolysis temperature selected from about 250°C to about 700°C for at least about 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) In the cooling zone, cool the hot pyrolysis solids at a cooling temperature lower than the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (g) Optionally, cool the warm pyrolysis solids in a separate cooling device to produce cold pyrolysis solids. (h) Thereafter, in order to form concentrated pyrolysis solids with increased carbon content, at least a portion of the condensable vapor and / or at least a portion of the non-condensable gas from step (e) passes through the warm pyrolysis solids and / or the cold pyrolysis solids, (i) The process includes recovering a high-carbon bioreagent containing at least a portion of the concentrated pyrolysis solids.

[0064] In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through the warm pyrolysis solids in vapor and / or condensed form to produce concentrated pyrolysis solids with increased carbon and / or energy content. In these and other embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through the warm pyrolysis solids to produce concentrated pyrolysis solids with increased carbon and / or energy content.

[0065] In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through the cold pyrolysis solids in vapor and / or condensed form to produce concentrated pyrolysis solids with increased carbon and / or energy content. In these and other embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through the cold pyrolysis solids to produce concentrated pyrolysis solids with increased carbon and / or energy content.

[0066] In some embodiments, step (h) includes substantially all of the condensable vapor from step (e) passing through the cold pyrolysis solids in vapor and / or condensed form to produce concentrated pyrolysis solids with increased carbon and / or energy content. In these and other embodiments, step (h) includes substantially all of the non-condensable gas from step (e) passing through the cold pyrolysis solids to produce concentrated pyrolysis solids with increased carbon and / or energy content.

[0067] Energy can be recovered from condensable vapor, non-condensable gas, or both for use in the process. Energy can be recovered through heat exchange with these streams. Optionally, one or both of the condensable vapor and / or non-condensable gas can be combusted, and the heat of combustion can be recovered for process use.

[0068] The process may further include introducing an intermediate feed stream, obtained from step (e), which includes at least a portion of condensable vapor and at least a portion of non-condensable gas, into a separation unit configured to produce at least first and second output streams. In one embodiment, the intermediate feed stream may include all of the condensable vapor and / or all of the non-condensable gas. A portion of the second output stream may be recycled to step (d) for use as a substantially inert gas in the pyrolysis unit, either alone or in combination with another source of inert gas (e.g., N2).

[0069] The first and second output streams may be separated, for example, based on relative volatility. In some embodiments, the first output stream may consist of condensable vapors (e.g., terpenes, alcohols, acids, aldehydes, or ketones), and the second output stream may consist of non-condensable gases (e.g., carbon monoxide, carbon dioxide, and methane).

[0070] The first and second output streams can be separated based on relative polarity. In these embodiments, the first output stream may consist of polar compounds (e.g., methanol, furfural, and acetic acid), and the second output stream may consist of nonpolar compounds (e.g., carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives).

[0071] In some embodiments, step (h) increases the total carbon content, fixed carbon content, and / or energy content of the high-carbon bioreagent compared to an otherwise identical process without step (h). In some embodiments, step (h) increases the fixed carbon content of the high-carbon bioreagent compared to an otherwise identical process without step (h).

[0072] The present invention also provides a continuous or batch process for increasing the carbon and / or energy content of any carbon-containing material. In some variant forms, the process for producing high-carbon bioreagents is (a) To provide a solid stream containing a starting carbon-containing material, (b) To provide a gas stream containing condensable carbon-containing vapor, non-condensable carbon-containing gas, or a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas, and (c) Passing a gas stream through a solid stream under appropriate conditions to form a carbon-containing product in which the carbon and / or energy content is increased compared to the carbon-containing material. Includes.

[0073] In some embodiments, the starting carbon-containing material is pyrolysis biomass or heat-dried biomass. The gas stream may be obtained during the integrated process supplying the carbon-containing material. Alternatively, the gas stream may be obtained from a separate treatment of the carbon-containing material. The gas stream, or a portion thereof, may be obtained from an external source. Mixtures of gas streams, as well as mixtures of carbon-containing material, from various sources are possible.

[0074] In some embodiments, the process further includes recirculating or reusing the gas stream to repeat the process in order to further increase the carbon and / or energy content of the carbon-containing product. In some embodiments, the process further includes recirculating or reusing the gas stream to run the process in order to increase the carbon and / or energy content of a different feedstock than the carbon-containing material.

[0075] The process may include introducing a gas stream into a separation unit configured to produce at least first and second output streams, the gas stream comprising a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas. The first and second output streams may be separated, for example, based on relative volatility or relative polarity.

[0076] In some embodiments, the carbon-containing product has a higher total carbon content and / or fixed carbon content and / or volatile carbon content than the carbon-containing material. In some embodiments, the carbon-containing product has a higher energy content than the carbon-containing material.

[0077] A high-carbon bioreagent generation system is also provided, and this system is (a) A material supply system configured to introduce carbon-containing raw materials, (b) An optional drying device, which is operably connected to the material supply system and configured to remove moisture contained in the carbon-containing feed material. (c) A BPU operably connected to a material supply system or drying apparatus (if any), wherein the BPU includes at least one pyrolysis zone operably connected to a spatially separated cooling zone, and the BPU is configured with outlets for removing condensable vapors and noncondensable gases from solids, (d) A cooling device of any choice, which is positioned in operational communication with the BPU. (e) A material concentration unit, which is operably connected to a BPU or cooling device (if present), and is configured such that condensable vapor and / or noncondensable gases pass through the solid to form a concentrated solid with increased carbon content, as (f) Carbon recovery unit, which is operably connected to the material concentration unit. It is equipped with.

[0078] In some embodiments, the system further includes a preheating zone operably connected to the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) may be located within a single unit or in separate units. A drying apparatus, if present, may be configured as a drying zone within the BPU.

[0079] To generate a substantially opposing flow of the gas phase to the solid phase, the cooling zone may be configured with a gas inlet, and the pyrolysis zone may be configured with a gas outlet. To generate a substantially opposing flow of the gas phase to the solid phase, the cooling zone may be configured with a gas inlet, and the preheating zone and / or drying zone may be configured with a gas outlet.

[0080] In one embodiment, the material concentration unit is (i) Housing having an upper and lower part, (ii) an inlet located at the bottom of the housing, configured to transport condensable vapors and non-condensable gases, (iii) An outlet located on the upper surface of the housing, configured to transport a concentrated gas stream obtained from condensable vapor and noncondensable gas, (iv) A defined path between the upper and lower parts of the housing, and (v) A transport system following a route, wherein the transport system is configured to transport solids, and the housing is molded such that the solids adsorb at least a portion of condensable vapors and / or at least a portion of noncondensable gases. It is equipped with.

[0081] The present invention also provides various products and compositions. In some modified forms, high-carbon bioreagents are (a) To supply carbon-containing raw materials including biomass, (b) optionally drying the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degas the feedstock to remove at least some of the interstitial oxygen contained in the feedstock, if any. (d) In the pyrolysis zone, the feed material is pyrolyzed at a pyrolysis temperature selected from about 250°C to about 700°C for at least about 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) In the cooling zone, cool the hot pyrolysis solids at a cooling zone temperature lower than the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (g) Cooling a warm pyrolysis solid in an optional cooling device separate from the cooling zone in order to produce a cold pyrolysis solid, (h) Recover the high-carbon bioreagent containing at least some of the warm or cold pyrolysis solids. It is generated by a process that includes each step.

[0082] High-carbon bioreagents may further include at least one process additive incorporated during the process. Alternatively, or additionally, high-carbon bioreagents may further include at least one product additive incorporated into the reagent following the process.

[0083] In some embodiments, process additives and / or product additives are selected to increase the carbon content and / or energy content of the high-carbon bioreagent. In some embodiments, process additives and / or product additives are selected to maintain the structural integrity or mechanical strength of the high-carbon bioreagent relative to the feedstock. Additives may be useful in helping to maintain the structural form before use of the bioreagent.

[0084] In some embodiments, the high-carbon bioreagent may contain at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or at least 95 wt% total carbon on an anhydrous basis. The total carbon includes fixed carbon and carbon from volatile substances. In some embodiments, the carbon from volatile substances is at least 5%, at least 20%, or at least 40% of the total carbon.

[0085] In some embodiments, the high-carbon bioreagent contains about 10 wt% or less of hydrogen on an anhydrous basis, for example, about 5 wt% or less. In some embodiments, the reagent contains about 20 wt% or less of oxygen on an anhydrous basis, for example, between about 1 wt% and about 10 wt%. In some embodiments, the high-carbon bioreagent contains about 1 wt% or less of nitrogen on an anhydrous basis, for example, about 0.5 wt% or less. In some embodiments, the reagent contains about 0.5 wt% or less of phosphorus on an anhydrous basis, for example, about 0.2 wt% or less. In some embodiments, the high-carbon bioreagent contains about 0.2 wt% or less of sulfur on an anhydrous basis, for example, about 0.1 wt% or less.

[0086] In some embodiments, the high-carbon bioreagent contains about 10 wt% or less of non-combustible material (e.g., ash) on an anhydrous basis. In some embodiments, the high-carbon bioreagent contains about 5 wt% or less of non-combustible material, or about 1 wt% or less, on an anhydrous basis. The high-carbon bioreagent may further contain water at varying levels.

[0087] High-carbon bioreagents may have an energy content of at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 14,500 Btu / lb on an anhydrous basis. High-carbon bioreagents may have an energy content of at least 14,700 Btu / lb and a fixed carbon content of at least 95 wt% on an anhydrous basis.

[0088] In some embodiments, the high-carbon bioreagent is an anhydrous base. Total carbon content of 55 wt% or more; Hydrogen at a concentration of 5 wt% or less; Less than 1 wt% nitrogen; Phosphorus at 0.5 wt% or less; Sulfur at a concentration of 0.2 wt% or less; and Additives selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. Includes.

[0089] The additives may be selected from a group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0090] In some embodiments, the high-carbon bioreagent is an anhydrous base. Total carbon content of 55 wt% or more; Hydrogen at a concentration of 5 wt% or less; Less than 1 wt% nitrogen; Phosphorus at 0.5 wt% or less; Sulfur at a concentration of 0.2 wt% or less; and Additives selected from acids, bases, or their salts Includes.

[0091] The additives may be selected from a group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

[0092] In one embodiment, the high-carbon bioreagent is an anhydrous base. Total carbon content of 55 wt% or more; Hydrogen at a concentration of 5 wt% or less; Less than 1 wt% nitrogen; Phosphorus at 0.5 wt% or less; Sulfur content of 0.2 wt% or less; A first additive selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof; and A second additive selected from acids, bases, or salts thereof. Includes, The first additive is different from the second additive.

[0093] The first additive may be selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof. The second additive may be independently selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

[0094] High-carbon bioreagents may contain approximately 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or more total carbon on an anhydrous basis (total carbon includes fixed carbon and carbon associated with volatile substances).

[0095] In some embodiments, the reagent includes about 4 wt% or less of non-combustible material on an anhydrous basis, or about 8 wt% or less of non-combustible material on an anhydrous basis.

[0096] High-carbon bioreagents are basically anhydrous in nature and can consist of carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, non-combustible materials, and additives selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof. Water may or may not be present.

[0097] High-carbon bioreagents are basically anhydrous in nature and can consist of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible materials, and additives selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof. Water may or may not be present.

[0098] High-carbon bioreagents may have an energy content of at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 14,500 Btu / lb on an anhydrous basis.

[0099] High-carbon bioreagents may be fine powders or in the form of structures. Structures may arise from the compression, binding, pelletization, or aggregation of particles. In some embodiments, structures have a structure and / or strength substantially derived from the carbon source. In some embodiments, structures have a structural form substantially identical to the carbon source.

[0100] In some embodiments of high-carbon bioreagents, the majority of the carbon is classified as renewable carbon. Substantially all of the carbon contained in high-carbon bioreagents can be classified as renewable carbon. In one embodiment, for example, the following items are provided. (Item 1) A high-carbon bioreagent generation system, wherein the system: (a) A material supply system configured to introduce carbon-containing raw materials, (b) an optional drying device configured to be operably connected to the material supply system and to remove moisture contained in the carbon-containing supply material, (c) A multizone reactor operably connected to the material supply system or the drying apparatus (if present), wherein the multizone reactor includes at least one pyrolysis zone operably connected to a spatially separated cooling zone, and the multizone reactor is configured with outlets for removing condensable vapors and noncondensable gases from solids, (d) A cooling device that is operably connected to the multi-zone reaction device, (e) A carbon recovery unit and a carbon recovery unit that are operably connected to the cooling device. A high-carbon bioreagent generation system equipped with the following features. (Item 2) The system according to item 1, further comprising a preheating zone operably connected to the pyrolysis zone. (Item 3) The system according to item 1 or item 2, wherein each of the at least one pyrolysis zone, the cooling zone, and the preheating zone (if present) is located within a single biomass processing unit. (Item 4) The system according to item 1 or item 2, wherein each of the at least one pyrolysis zone, the cooling zone, and the preheating zone (if present) is located within a separate biomass processing unit. (Item 5) The system according to item 1, wherein the drying apparatus is present and configured as a drying zone within the multi-zone reactor. (Item 6) The system according to item 1, further comprising a purging means for removing oxygen from the system. (Item 7) The system according to item 6, wherein the purging means includes one or more intake ports for introducing a substantially inert gas, and one or more outlet ports for removing the substantially inert gas and replaced oxygen from the system. (Item 8) The system according to item 6, wherein the purging means is a degasser positioned between the material supply system or the drying apparatus (if any) and the multi-zone reactor. (Item 9) The system according to item 1, wherein the material supply system is physically integrated with the multi-zone reactor. (Item 10) The system according to item 1, wherein the cooling device is located within the multi-zone reactor. (Item 11) The system according to any one of items 1 to 10, further comprising an additive supply device for introducing an additive into the system. (Item 12) The system according to item 11, wherein the additive supply device is configured to combine the additive with the carbon-containing supply material. (Item 13) The system according to item 11, wherein the additive supply device is inserted between the material supply system and the multi-zone reactor. (Item 14) The system according to item 11, wherein the additive supply device is arranged to be operably connected to the multi-zone reaction device. (Item 15) The system according to item 11, wherein the additive supply device is arranged to be operably in communication with the cooling device. (Item 16) The system according to item 11, wherein the additive supply device is inserted between the cooling device and the carbon recovery unit. (Item 17) The system according to item 11, wherein the additive supply device is arranged to be operably in communication with the carbon recovery unit. (Item 18) The system according to any one of items 1 to 17, wherein the multi-zone reactor is configured together with a first gas inlet and a first gas outlet. (Item 19) The system according to item 18, wherein the first gas inlet and the first gas outlet are arranged in communication with different zones. (Item 20) The system according to item 18, wherein the first gas inlet and the first gas outlet are located in communication with the same zone. (Item 21) The system according to item 18, wherein the aforementioned multi-zone reactor is configured together with a second gas inlet. (Item 22) The system according to item 18, wherein the aforementioned multi-zone reactor is configured together with a second gas outlet. (Item 23) The system according to item 21, wherein the aforementioned multi-zone reactor is configured together with a third gas inlet. (Item 24) The system according to item 22, wherein the aforementioned multi-zone reactor is configured together with a third gas outlet. (Item 25) The system according to item 23, wherein the aforementioned multi-zone reactor is configured together with a fourth gas inlet. (Item 26) The system according to item 24, wherein the aforementioned multi-zone reactor is configured together with a fourth gas outlet. (Item 27) The system according to item 1, wherein the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet in order to generate a substantially opposing flow of the gas phase to the solid phase. (Item 28) The system according to item 2, wherein the cooling zone is configured with a gas inlet and the preheating zone is configured with a gas outlet in order to generate a substantially opposing flow of the gas phase to the solid phase. (Item 29) The system according to item 5, wherein the cooling zone is configured with a gas inlet and the drying zone is configured with a gas outlet to generate a substantially opposing flow of the gas phase to the solid phase. (Item 30) The system according to any one of items 1 to 29, wherein each zone within the aforementioned multi-zone reactor is configured with a gas inlet and a gas outlet. (Item 31) The system according to any one of items 1 to 30, further comprising the pyrolysis zone and a gas monitoring device, and a first reaction gas probe operably arranged in communication with the system. (Item 32) The system according to item 31, further comprising the cooling zone and a second reaction gas probe operably connected to the gas monitoring device or a second gas monitoring device. (Item 33) The system according to item 31, further comprising the drying zone (if present) and / or the preheating zone (if present), and an additional reaction gas probe operably connected to the gas monitoring device or additional gas monitoring device. (Item 34) The system according to item 31, wherein the gas monitoring device is selected from the group consisting of GC, MS, GC-MS, FTIR, and combinations thereof. (Item 35) The system according to any one of items 31 to 34, further comprising at least one computer-programmed controller capable of utilizing the output from the gas monitoring device to adjust system settings. (Item 36) The system according to any one of items 1 to 35, further comprising a process gas heater operably connected to the outlet, wherein the process gas heater is configured to receive a separate fuel and oxidizer into a combustion chamber suitable for combustion of the fuel and at least a portion of the condensable vapor and / or noncondensable gas. (Item 37) The system according to item 36, further comprising a separation unit inserted between the outlet and the process gas heater. (Item 38) The system according to item 36, further comprising a heat exchanger inserted between the process gas heater and the drying apparatus and configured to utilize at least a portion of the combustion heat for the drying apparatus. (Item 39) The system according to item 36, further comprising a heat exchanger positioned between the process gas heater and the gas inlet for the multi-zone reactor, and configured to utilize at least a portion of the heat of combustion to preheat a substantially inert gas before introducing it into the multi-zone reactor. (Item 40) The system according to any one of items 1 to 39, further comprising a material concentration unit configured to be operably connected to the cooling device and to combine condensable vapor with the solid in at least a partially condensed form in order to increase the carbon content of the high-carbon bioreagent obtained from the carbon recovery unit. (Item 41) The system according to any one of items 1 to 40, further comprising a separate pyrolysis unit adapted to further pyrolyze the high-carbon bioreagent in order to further increase its carbon content. (Item 42) The system according to any one of items 1 to 41, further comprising a sizing unit operably connected to the carbon recovery unit, wherein the sizing unit enables reduction of the particle size of the high-carbon bioreagent and / or the formation of a structure from the high-carbon bioreagent. (Item 43) A high-carbon bioreagent generation system, wherein the system: (a) A material supply system configured to introduce carbon-containing raw materials, (b) an optional drying device configured to be operably connected to the material supply system and to remove moisture contained in the carbon-containing supply material, (c) A preheater, which is operably connected to the material supply system or the drying apparatus (if present), and configured to heat and / or moderately thermally decompose the supply material, (d) A pyrolysis reactor, which is operably connected to the preheater and configured to pyrolyze the feed material, (e) A cooling device configured to be operably connected to the pyrolysis reaction apparatus and configured to cool the pyrolysis solids, (f) A high-carbon bioreagent recovery unit arranged to be operationally connected to the cooling device and Equipped with, A high-carbon bioreagent production system comprising at least one gas inlet for introducing a substantially inert gas into the pyrolysis reactor, and at least one gas outlet for rapidly removing condensable vapors and non-condensable gases from the pyrolysis reactor. (Item 44) The system according to item 43, further comprising a degassing device positioned between the supply device or the drying device (if present) and the preheater. (Item 45) The system according to item 43, wherein the system comprises at least two gas inlets and at least two gas outlets. (Item 46) The system according to item 43, wherein the pyrolysis reactor and / or the cooling device are configured with a gas inlet (or a plurality of gas inlets) to generate a substantially opposing flow of the gas phase to the solid phase, and the drying device (if present) and / or the preheater are configured with a gas outlet (or a plurality of gas outlets). (Item 47) The system according to any one of items 43 to 46, further comprising an additive supply device for introducing additives into the system. (Item 48) The system according to any one of items 43 to 47, further comprising the pyrolysis reactor and a gas monitoring device, and a first reaction gas probe operably arranged in communication with the system. (Item 49) The system according to item 48, further comprising the preheater and / or the cooling device, and an additional reaction gas probe operably connected to the gas monitoring device or additional gas monitoring device. (Item 50) The system according to item 48, wherein the gas monitoring device is selected from the group consisting of GC, MS, GC-MS, FTIR, and combinations thereof. (Item 51) The system according to any one of items 48 to 50, further comprising at least one computer-programmed controller capable of utilizing the output from the gas monitoring device to adjust system settings. (Item 52) The system according to any one of items 43 to 51, further comprising a process gas heater operably connected to the at least one gas outlet for removing condensable vapors and non-condensable gases, wherein the process gas heater is configured to receive a separate fuel and oxidizer into a combustion chamber suitable for combustion of the fuel and at least a portion of the condensable vapors. (Item 53) The system according to item 52, further comprising a heat exchanger positioned between the process gas heater and the drying apparatus, configured to utilize at least a portion of the combustion heat for the drying apparatus. (Item 54) The system according to item 52, further comprising a heat exchanger positioned between the process gas heater and the gas inlet for the multi-zone reactor, and configured to utilize at least a portion of the heat of combustion to preheat a substantially inert gas before introducing it into the pyrolysis reactor. (Item 55) The system according to any one of items 43 to 54, further comprising a material concentration unit configured to be operably connected to the cooling device and to combine condensable vapor with the solid in at least a partially condensed form in order to increase the carbon content of the high-carbon bioreagent obtained from the carbon recovery unit. (Item 56) The system according to any one of items 43 to 55, further comprising at least one additional pyrolysis reactor adapted to further pyrolyze the high-carbon bioreagent in order to further increase its carbon content. (Item 57) The system according to item 52, wherein the system comprises at least one additional pyrolysis reactor adapted to further pyrolyze the high-carbon bioreagent in the presence of a second substantially inert gas in order to further increase its carbon content, and the process gas heater is configured to preheat the second substantially inert gas. (Item 58) The system according to either item 3 or item 4, wherein the system is configured to extract and reuse gas from the biomass pyrolysis unit. (Item 59) The system according to any one of items 1 to 58, wherein the system is configured to extract and reuse gas from the carbon recovery unit. (Item 60) A biomass pyrolysis continuous reactor comprising a material supply system, a plurality of spatially separated zones configured for separate temperature control and mixing within each of the reaction zones, and a carbonaceous solids outlet, wherein one of the zones is configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the zones is configured with a first gas outlet. (Item 61) The reactor according to item 60, wherein the reactor comprises at least two zones. (Item 62) The reactor according to item 57, wherein the reactor comprises at least three zones. (Item 63) The reactor according to item 62, wherein the reactor comprises at least four zones. (Item 64) The reactor according to item 60, wherein each of the zones is arranged in communication with separately adjustable indirect heating means, each independently selected from a group consisting of electric heat transfer, steam heat transfer, hot oil heat transfer, waste heat transfer, and combinations thereof. (Item 65) The reactor according to item 60, wherein the reactor is configured to separately adjust the gas phase composition and gas phase residence time of at least two zones. (Item 66) The reactor according to item 65, wherein the reactor is configured to separately adjust the gas phase composition and gas phase residence time of all zones present within the reactor. (Item 67) The reactor according to item 60, wherein the reactor is configured with a second gas inlet and / or a second gas outlet. (Item 68) The reactor according to item 5608, wherein the reactor is configured with gas inlets in each zone. (Item 69) The reactor according to item 60, wherein the reactor is configured together with gas outlets in each zone. (Item 70) The reactor according to item 60, wherein the reactor is a countercurrent reactor. (Item 71) The reactor according to item 60, wherein the material supply system includes a supply mechanism selected from the group consisting of a screw, an auger, a drop chamber, and a drum feeder. (Item 72) The reactor according to item 60, wherein the carbonaceous solid discharge port includes an output mechanism selected from the group consisting of a screw, an auger, a drop chamber, and a drum feeder. (Item 73) The reaction apparatus according to item 60, wherein each of the aforementioned zones is configured with flights positioned on the inner wall to provide agitation of solids. (Item 74) The reactor according to item 73, wherein the flights are independently adjustable within each of the zones. (Item 75) The reactor according to item 60, wherein the reactor is a reactor that can rotate in the axial direction. (Item 76) The reactor according to item 60, wherein the reactor includes a single auger arranged across each of the zones. (Item 77) The reactor according to item 60, wherein the reactor is configured to extract and reuse gas from the first gas outlet. (Item 78) The reactor according to item 69, wherein the reactor is configured to extract and reuse gas from the gas outlets in each zone. [Effects of the Invention]

[0101] The present invention also provides a wide range of carbonaceous products, including high-carbon bioreagents. Such carbonaceous products include, but are not limited to, blast furnace addition products, taconite pellet process addition products, taconite pellets, coal substitutes, coking carbon products, carbon breeze products, fluidized bed products, furnace addition products, injectable carbon products, ladle addition carbon products, met coke products, pulverized carbon products, stoker carbon products, carbon electrodes, and activated carbon products. These and other embodiments are further detailed below. [Brief explanation of the drawing]

[0102] [Figure 1] This document illustrates an embodiment of the multiple reaction apparatus of the present invention. [Figure 2]Embodiments of the system of the present invention, including a single reactor and multiple zones, are shown. [Figure 3] An embodiment of a continuous oxygen-free supply mechanism suitable for use in relation to the present invention is shown. [Figure 4] Another embodiment of a single reactor and a multi-zone biomass processing unit suitable for use in connection with the present invention is shown. [Figure 5] An embodiment of a carbon recovery unit suitable for use in connection with the present invention is shown. [Figure 6] This document shows one embodiment of the single-reactor biomass processing unit of the present invention, which is equipped with an optional drying device. [Figure 7] An embodiment of the pyrolysis reaction apparatus system of the present invention, equipped with an optional drying device and a gas inlet, is shown. [Figure 8] This document shows one embodiment of the single-reactor biomass processing unit of the present invention, which includes a gas inlet and an optional cooling device. [Figure 9] An embodiment of the single-reactor biomass processing unit system of the present invention, equipped with an optional drying device and degassing device, as well as an inert gas inlet, is shown. [Figure 10] An embodiment of the multiple reaction system of the present invention, comprising an optional drying device and degassing device, as well as an inert gas inlet, is shown. [Figure 11] An embodiment of the multiple reaction system of the present invention, comprising an optional drying and cooling device, and a material concentration unit, is shown. [Figure 12] An embodiment of the multiple reaction system of the present invention, comprising an optional drying device, degassing device, cooling device, and inert gas inlet, is shown. [Figure 13] An embodiment of the multiple reaction system of the present invention, comprising an optional drying device and degassing device, an inert gas inlet, and a cooling device, is shown. [Figure 14] A graph illustrating the effect of residence time on the fixed carbon content of a bioreagent produced according to one embodiment of this disclosure is shown. [Figure 15]A graph illustrating the effect of thermal decomposition temperature on the fixed carbon content of a bioreagent produced according to one embodiment of this disclosure is shown. [Figure 16] A graph illustrating the effect of biomass particle size on the fixed carbon content of a bioreagent produced according to one embodiment of this disclosure is shown. [Modes for carrying out the invention]

[0103] This description enables those skilled in the art to carry out and use the present invention and also describes several embodiments, adaptations, variations, alternatives, and uses of the present invention. These and other embodiments, features, and advantages of the present invention will become even more apparent to those skilled in the art with reference to the following detailed description of the invention together with the accompanying drawings.

[0104] In this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural references unless the content specifically indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains.

[0105] Unless otherwise specified, all figures used in the specification and claims, such as reaction conditions, stoichiometry, and component concentrations, are understood to be modified in all cases by the word "about." Consequently, unless otherwise specified, the numerical parameters expressed in the following specification and appended claims are approximations that may vary depending at least on the specific analytical technique.

[0106] The term "comprising," synonymous with "including," "containing," or "characterized by," is inclusive or unrestricted and does not exclude additional, unmentioned elements or method steps. "Comprising" is a technical term used in claim language meaning that a named claim element is essential, but other claim elements may be added and still form a construct within the claims.

[0107] In this specification, the phrase "consisting of" excludes any element, step, or component not specified in the claim. If the phrase "consisting of" (or a variation thereof) appears within a section of the claim rather than immediately following a prior art portion, it limits only the elements described within that section, and does not exclude other elements from the claim as a whole. In this specification, "consisting essentially of" limits the claim to the specified element or method step, plus any other elements that do not substantially affect the basis and novel characteristics of the claimed subject matter.

[0108] With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” if any of these three terms is used herein, the subject matter now disclosed and claimed may include the use of any of the other two terms. Accordingly, in some embodiments, unless otherwise specified, any instance of “comprising” may be replaced by “consisting of,” or “consisting essentially of.”

[0109] For the purposes of this discussion, "biogenic" is intended to mean materials containing elements such as carbon that are renewable on a timescale of months, years, or decades (whether raw materials, products, or intermediates). Non-biogenic materials may be non-renewable or renewable on a timescale of centuries, millennia, millions of years, or even longer geological timescales. It should be noted that biogenic materials may include mixtures of bio-sources and non-biogenic sources.

[0110] For the purposes of this discussion, "reagent" is intended to mean a material in its broadest sense, and a reagent can be a fuel, chemical, material, compound, additive, mixture, solvent, etc. A reagent is not necessarily a chemical reagent that causes or participates in a chemical reaction. A reagent may or may not be a chemical reagent, and may or may not be consumed in a reaction. A reagent may be a chemical catalyst for a particular reaction. A reagent may cause or participate in the modification of the mechanical, physical, or hydrodynamic properties to which the reagent may be added. For example, a reagent may be introduced into a metal to impart a certain strength property to that metal. A reagent may be a substance of sufficient purity (which, in the current context, is usually carbon purity) for use in chemical analysis or physical testing.

[0111] In this application, the term "high-carbon" used to describe a bioreagent simply means that the bioreagent has a relatively high carbon content compared to the initial raw materials used to produce the high-carbon bioreagent. Generally, a high-carbon bioreagent will contain at least about half of its weight as carbon. More generally, a high-carbon bioreagent will contain at least 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 90 wt%, or more carbon.

[0112] Notwithstanding the foregoing, the term “high-carbon bioreagent” is used herein for practical purposes to consistently describe the materials that may be produced by the processes and systems of the present invention in various embodiments. Any limitations on carbon content, or any other concentration, arise not from the term itself, but rather from references to specific embodiments and their equivalents. For example, it will be understood that starting materials with a very low carbon content, following the disclosed process, may produce high-carbon bioreagents with a high concentration of carbon (high yield carbon) compared to the starting materials, but nevertheless with relatively low carbon content (low purity carbon), including less than 50 wt% carbon.

[0113] "Pyrolysis" and "pyrolyze" generally refer to the thermal decomposition of carbonaceous materials. In pyrolysis, there is less oxygen present than is necessary for the complete combustion of the material, such as 10%, 5%, 1%, 0.5%, 0.1%, or less than 0.01% of the oxygen required for complete combustion. In some embodiments, pyrolysis is carried out in an oxygen-free environment.

[0114] Exemplary changes that may occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the temperature inside the feedstock; (ii) the initiation of the primary pyrolysis reaction at this high temperature releases volatile substances and forms char; (iii) the flow of hot volatile substances to cold solids results in heat transfer between the hot volatile substances and the cold, unpyrolytic feedstock; (iv) condensation of some of the volatile substances in the cold portion of the feedstock, which may subsequently be followed by a second reaction, can form char; (v) an autocatalytic second pyrolysis reaction proceeds while the first pyrolysis reaction occurs simultaneously in competition with it; (vi) further pyrolysis, reforming, water-gas conversion, free radical recombination, and / or dehydration may also occur, but these are functions of residence time, temperature, and pressure profile.

[0115] Pyrolysis dehydrates at least a portion of the feedstock. In various embodiments, pyrolysis removes about 50%, 75%, 90%, 95%, 99%, or more of the moisture from the feedstock.

[0116] As described above, some variations of the present invention are at least in part based on the finding that multiple reactors or multiple zones within a single reactor can be designed and operated in a manner that optimizes carbon yield from pyrolysis and product quality, while maintaining flexibility and adaptability to fluctuations in feedstock and product requirements.

[0117] Generally speaking, temperature and residence time are selected to achieve a relatively slow pyrolysis chemistry. The benefit is potentially the substantial preservation of the cell walls contained within the biomass structure, meaning that the final product can retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, apparatus can be used that does not mechanically break down the cell walls or converts the biomass particles into a fine powder. Various reactor configurations are described following the process description below.

[0118] In addition, if the feedstock is a crushed or uniformly sized feedstock such as wood chips or pellets, it may be desirable that the feedstock be carefully crushed or uniformly sized. Careful initial processing will make it easier to maintain the strength and cell wall integrity present in the inherent feedstock source (e.g., wood). This may also be important if the final product should retain some, most, or all of the shape and strength of the starting biomass.

[0119] In various embodiments, means are taken to maintain the vascular structure of the woody feedstock in order to create further strength in the bioreagent. For example, and without limitation, in various embodiments, the feedstock is prepared by drying it over a long period of time, such as over 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 5 hours or more, 6 hours or more, 7 hours or more, 8 hours or more, 9 hours or more, 10 hours or more, 11 hours or more, 11 hours or more, 11 hours or more, 11 hours or more, 11 hours or more, 11 hours or more, 11 hours or more, 11 hours or more, 20 hours or more, 21 hours or more, 22 hours or more, 23 hours or more, 24 hours or more, etc., so that moisture and gases can be released from the biomass without destroying the vascular structure of the feedstock. In various embodiments, a slow progressive heat rate is used during pyrolysis over several minutes or hours (in contrast to, for example, rapid pyrolysis) so that moisture and gases can be released from the biomass without destroying the vascular bundle structure of the feedstock. For example, and without limitation, the rate of temperature increase during the pyrolysis step may be in the range of about 1°C to about 40°C per minute, e.g., about 1°C, about 2°C, about 4°C, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, or about 40°C per minute. In some embodiments, the temperature increase occurs in a preheating zone to produce a preheated feedstock. In some embodiments, the temperature increase occurs mainly or entirely in a preheating zone to produce a preheated feedstock. In some embodiments, the temperature of the preheated feedstock is increased in a pre-pyrolysis zone. In some embodiments, the temperature rise occurs at least partially in the carbonization zone or the pyrolysis zone. In some embodiments, the temperature rise occurs mainly or entirely in the carbonization zone or the pyrolysis zone. In some embodiments, the preheating zone, pre-pyrolysis zone, carbonization zone, or pyrolysis zone is configured to have a gradual temperature increase during pyrolysis, from an initial low temperature to a final high temperature. In some embodiments, the temperature rise is linear or substantially linear over time.In some embodiments, the rate of temperature rise is gradually increased or decreased such that the temperature during preheating, pre-thermal decomposition and / or carbonization or thermal decomposition is at least partially nonlinear, for example, logarithmically or substantially logarithmically with respect to at least a portion of the preheating, pre-thermal decomposition and / or carbonization or thermal decomposition steps. In various embodiments, additives are used before drying or thermal decomposition to reduce gas generation that may damage the vascular structure of the feedstock during thermal decomposition. In various embodiments, before thermal decomposition, the dried feedstock is cut to a certain size using a saw or other cutting device designed not to damage the vascular structure of the wood more than other sizing methods such as chipping or shearing of wet wood, which crush the wood and reduce its strength. In such embodiments, the bioreagent has a higher strength index (e.g., CSR value) than an equivalent bioreagent not prepared in such a manner.

[0120] In some embodiments, the feedstock is prepared by grinding biomass to form a plurality of biomass pieces that are substantially uniform in size and shape. For example, and without limitation, biomass can be processed to produce sawdust with substantially uniform particle size (e.g., mesh size). Alternatively, biomass can be processed to produce chips having substantially uniform dimensions (e.g., pieces of about 1 inch × about 1 / 2 inch × about 1 / 8 inch). In other embodiments, the feedstock can be prepared by grinding biomass to form a length of material (e.g., wooden sticks, boards, or dowels) with substantially uniform width and depth dimensions or diameter. In related embodiments, the length of material having substantially uniform width and depth or diameter can be further ground to produce feedstock pieces of substantially uniform length, resulting in feedstock material having substantially uniform size and shape. For example, wooden dowels with a uniform diameter (e.g., 1 to 1 / 8 inch) can be cut into pieces of substantially uniform length (e.g., about 1.5 inches). The resulting feed material pieces have a substantially uniform shape (cylindrical) and substantially uniform size (approximately 1 to 1 / 8 inches in diameter × approximately 1.5 inches in length). In some embodiments, bioreagents prepared from feed material pieces consisting of substantially uniformly shaped and sized pieces are produced in a higher mass yield than equivalent bioreagents prepared from feed material pieces with substantially non-uniform shapes and / or sizes.

[0121] Referring broadly to Figures 1 to 13, block flowcharts of several exemplary multiple reactor embodiments of the present disclosure are shown. Each figure is described below in turn. It will be understood that Figures 1 to 13 represent several examples of embodiments, not all anticipated embodiments of the present disclosure. Various additional unexecuted embodiments and combinations of several components and features described herein are also anticipated, as will be described below. As will be understood in the following description, any of the multiple reactors described herein may be independent reactors, or a single reactor may contain multiple zones of BPU, or a combination thereof. Although each figure illustrates a different alternative embodiment, it will be understood that all other descriptions within the present disclosure apply to each of the exemplary and unexecuted embodiments.

[0122] Referring roughly to Figure 1, a block flowchart of a multiple reactor embodiment of the present disclosure is shown. This embodiment can utilize two or more different reactors. Three reactors are shown in the exemplary embodiment, but any different number of reactors can be employed. In one embodiment, each reactor is connected to at least one other reactor via a material transport unit 304 (shown in Figure 3). In one embodiment, the material transport unit 304 controls atmospheric and temperature conditions.

[0123] In the illustrated embodiment, a raw material 109, such as biomass, is optionally dried and reduced to a certain size outside the system and optionally introduced into a first reactor 112 in a low-oxygen atmosphere through the use of a material supply system 108. As further detailed below and shown in Figure 3, the material supply system 108 reduces the oxygen level of the ambient air within the system to approximately 3% or less. The raw material 109 enters the first reactor 112 after the oxygen level has been reduced within the first reactor, through an enclosed material transport unit 304. In one embodiment, the material transport unit would include an encapsulated jacket or sleeve through which streams and off-gases from the reactor are fed and used to directly preheat the biomass or to send it to a process gas heater, which is then used to preheat or pyrolyze the biomass.

[0124] In the illustrated embodiment, the raw material 109 is first moved from the material supply system 108 on the material transport unit 304 to the first reactor 112 of the BPU.

[0125] As will be described in more detail below, in one embodiment, the first reactor 112 is configured to be connected to any other reactor in the system in order to recover waste heat 132 and save the energy through a suitable waste heat recovery system. In one embodiment, the waste heat released in the first reactor 112 is used to operate a steaming bin or another suitable heating mechanism configured to dry the raw materials 109 inside or outside the system. In various embodiments, other by-products of the waste heat, such as substantially heated inert gas or the like, can be used somewhere in the system at any point between processes to further concentrate the material.

[0126] In the illustrated embodiment, biomass 109 enters the first reactor 112, where the temperature rises in a range from approximately ambient temperature ~ about 150°C to about 100°C ~ about 200°C. In one embodiment, the temperature does not exceed 200°C in the first reactor. As will be described in more detail below, the first reactor 112 may include an output mechanism to capture and discharge off-gas 120 from the biomass 123 while the biomass 123 is being heated. In one embodiment, the off-gas 120 is extracted for use after optional subsequent use. In various embodiments, the heating source used for various zones within the BPU 102 is electricity or gas. In one embodiment, the heating source used for various reactors in the BPU 102 is exhaust gas from other reactors in unit 102 or from an external supply source. In various embodiments, heating is indirect.

[0127] Following preheating in the first reactor 112, the material transport unit 304 transfers the preheated material 123 to an optional second reactor 114. In one embodiment, reactor 114 is identical to reactor 112. In one embodiment where reactor 114 differs from reactor 112, the material transport unit 304 penetrates the second reactor 114 through a high-temperature vapor sealing system (e.g., an airlock), which allows the material transport unit 304 to penetrate the second reactor while preventing gas leakage. In one embodiment, the interior of the second reactor 114 is heated to a temperature of about 100°C to about 600°C or about 200°C to about 600°C. In another embodiment, the second reactor 114 includes an output port similar to that of the first reactor 112 to capture and discharge gas 122 released from the preheated material 123 while the preheated material 123 is being carbonized. In one embodiment, gas 122 is extracted for use after optional removal. In one exemplary embodiment, off-gas 120 from the first reactor 112 and off-gas 122 from the second reactor 114 are mixed into a single gas stream 124. Once carbonized, the carbonized biomass 125 exits the second reactor 114 and enters the third reactor 116 for cooling. In this case as well, the third reactor may be the same reactor as 112 or 114, or it may be different.

[0128] In one embodiment, once the bioreagent 125 enters the third reactor 115, the carbonized biomass 125 is cooled (actively or passively) to a specific temperature range, as described above, to form carbonized biomass 126. In one embodiment, the temperature of the carbonized biomass 125 is reduced within the third reactor under substantially inert atmospheric conditions. In another embodiment, the third reactor cools the carbonized biomass 125 with an additional water cooling mechanism. It will be understood that the carbonized biomass 126 can be cooled within the third reactor 116 to a point where it will not spontaneously combust when exposed to oxygen-containing air. In one such embodiment, the third reactor 116 lowers the temperature of the carbonized biomass to below 200°C. In one embodiment, the third reactor includes a mixer (not shown) for stirring and uniformly cooling the carbonized biomass. Cooling can occur directly or indirectly with water or other liquids; it will be understood that cooling can also occur directly or indirectly with air or other cooled gases, or in any combination thereof.

[0129] In some embodiments (not shown), it will be understood that one or more additional cooling devices or cooling mechanisms are employed to further lower the temperature of the carbonized biomass. In various such embodiments, the cooling device is separated from the other reactors 112, 114, and 116 along the material transport system. In some embodiments, the cooling device comes after the reactors. In some embodiments, the cooling device may be identical to reactors 112, 114, and 116. In other embodiments, the cooling device may cool, for example, a screw, auger, conveyor (specifically a belt conveyor in one embodiment), drum, screen, pan, or counterflow bed, either directly or indirectly with water or other liquids, or directly or indirectly with other gases. These include a bed, a vertical tower, a jacketed paddle, a cooled screw, or a combination thereof, or a combination of the aforementioned. In various embodiments, the cooling device may include a water spray, a cooled inert gas stream, liquid nitrogen, or ambient air, provided it is below the ignition temperature. It will be understood that heat can be recovered from this step by capturing the flash steam produced by the water spray, or the superheated steam produced when saturated steam is introduced and heated by the carbonized biomass.

[0130] As shown in Figures 1 and 5, the gas phase separator unit 200 includes at least one input and multiple outputs. At least one input is connected to the exhaust ports on the first reactor 112 and the second reactor 114 of the BPU 102. One of the outputs is connected to the carbon recovery unit 104, and another output is connected to an acid hydrogenation unit 106 or a collection or further processing equipment such as a distillation column. In various embodiments, the gas phase separator processes off-gases 120, 122 from the first reactor 112 and the second reactor 114 to produce condensates 128 and concentrated gases 204. In various embodiments, the condensables may be used for energy recovery (134) (e.g., in a dryer, reactor or process gas heater) or for other carbon concentration. In various embodiments, non-condensable materials (e.g., CO) may be used for energy recovery (134) (e.g., in a dryer, reactor, or process gas heater), as an inert gas in a process (e.g., in a degassing unit, reactor, BPU, or cooling unit, which will be described in more detail below), or for carbon enrichment.

[0131] In various embodiments, the condensate 128 contains polar compounds such as acetic acid, methanol, and furfural. In another embodiment, the concentrated gas 204 produced by the gas phase separator 200 contains at least non-polar compounds such as carbon monoxide, terpenes, methane, and carbon dioxide. In one embodiment, the gas phase separator includes a fractionation column. In one embodiment, acetic acid is sent through pipeline 128 to an optional oxyhydrogenation unit. In another embodiment, methanol and / or furfural are sent through optional additional pipelines 136 to a distillation / processing unit 138.

[0132] In various embodiments, the carbon recovery unit itself has equipment for concentrating the material, as will be described in more detail below. In various other embodiments, the material is concentrated in a separate material concentration unit from the carbon recovery unit. In some such embodiments, it will be understood that the carbon recovery unit is a container for storing the carbonized material, and the separate material concentration unit is a unit into which gas is introduced to concentrate the material.

[0133] In the illustrated embodiment, the carbon recovery unit 500 also concentrates the carbonized biomass 126. The carbonized biomass 126 exits the third reactor along the material transport unit 304 and enters the carbon recovery unit 500. In various embodiments, as shown in more detail in Figure 5 and as previously described, the carbon recovery unit 500 also includes an input 524 connected to the gas phase separator 200. In one embodiment, the concentrated gas 204 is directed to the carbon recovery unit and combined with the bioreagent 126 to produce a high-carbon bioreagent 136. In another embodiment, carbon concentrated gas from an external source can also be directed to the carbon recovery unit and combined with the carbonized biomass 126 to add further carbon to the resulting ultimate high-carbon bioreagent. In various embodiments, the carbonized biomass 126 is carbonized biomass that has been cooled. As an example, the system 100 can be located in the same location near a woodworking facility, and carbon concentrated gas from the woodworking facility can be used as the gas from an external source.

[0134] Referring roughly to Figure 2, block flowcharts of single-reactor, multi-zone embodiments of the present disclosure are shown. In the illustrated embodiments, a raw material 109, such as biomass, is optionally introduced into the reactor 200 in a low-oxygen atmosphere through the use of a material supply system 108, which has already been described. As will be further detailed below, the material supply system 108 reduces the oxygen level of the ambient air within the system to about 3% or less. After the oxygen level is reduced, the raw material 209 enters a BPU 202 in an enclosed material transport unit 304. In one embodiment, the material transport unit would include an encapsulated jacket or sleeve through which streams and off-gases from the reactor 200 are fed and used to heat the biomass.

[0135] In the illustrated embodiment, the raw material is first transported from the material supply system 108 on the material transport unit 304 through an optional drying zone 210 in the BPU 202. In one embodiment, the optional drying zone 210 heats the raw material to remove water and other moisture before it is passed to the preheating zone 212. In one embodiment, the interior of the optional drying zone 210 is heated to about ambient temperature ~ about 150°C. The water 238 or other moisture removed from the raw material 209 can be discharged, for example, from the optional drying zone 210. In another embodiment, the optional drying zone is adapted to allow for the extraction of vapor and steam. In another embodiment, the vapor and steam from the optional drying zone are extracted for optional subsequent use. As described below, the vapor and steam extracted from the optional drying zone can be used in a suitable waste heat recovery system equipped with a material supply system. In one embodiment, steam and water vapor used within the material supply system preheat the material while the oxygen level is purged within the material supply system. In another embodiment, the biomass is dried outside the reactor, and the reactor does not include a drying zone.

[0136] As will be described in more detail below, in one embodiment, an optional drying zone 210 is configured to be connected to a cooling zone 216 in order to recover waste heat 232 and save energy through a suitable waste heat recovery system. In one embodiment, the waste heat released in the cooling zone 216 is used to operate a heating mechanism configured to dry the raw material 209 in the optional drying zone 210. After drying for a desired period, the dried biomass 221 leaves the optional drying zone 210 and enters the preheating zone 212.

[0137] In the illustrated embodiment, the dried biomass 221 enters a first (preheating) zone where the temperature rises from approximately ambient temperature ~ about 150°C to a temperature range of about 100°C ~ about 200°C. In one embodiment, the temperature does not exceed 200°C within the first / preheating zone 212. It will be understood that if the preheating zone 212 is too hot or not hot enough, the dried biomass 221 may be mistreated before entering the second zone 214. As will be described in more detail below, the preheating zone 212 may include an output mechanism to capture and discharge off-gas 220 from the dried biomass 221 while the dried biomass 221 is being preheated. In another embodiment, the off-gas 220 is extracted for use after optional later use. In various embodiments, the heating source used for the various zones within the BPU 202 is electricity or gas. In one embodiment, the heating source used for various zones of the BPU 202 is exhaust gas from other zones of the unit 202 or from an external supply source. In various embodiments, heating is indirect.

[0138] Following the preheating zone 212, the material transport unit 304 passes the preheated material 223 to a second (pyrolysis) zone 214. In one embodiment, the material transport unit 304 passes through the second (pyrolysis) zone 214 through a high-temperature steam sealing system (such as an airlock, not shown), which allows the material transport unit 304 to pass through the high-temperature pyrolysis zone while preventing (or minimizing) gas leakage. In one embodiment, the interior of the pyrolysis zone 214 is heated to a temperature of about 100°C to about 600°C or about 200°C to about 500°C. In another embodiment, the pyrolysis zone 214 includes an output port similar to that of the preheating zone 212 to capture and discharge gas 222 released from the preheated biomass 223 while the preheated biomass 223 is being carbonized. In one embodiment, gas 222 is extracted for optional subsequent use. In one exemplary embodiment, off-gas 220 from the preheating zone 212 and off-gas 222 from the pyrolysis zone 214 are mixed into a single gas stream 224. Once carbonized, the carbonized biomass 225 exits the second / pyrolysis zone 214 and enters the third / temperature reduction or cooling zone 216.

[0139] In one embodiment, when the carbonized biomass 225 enters the cooling zone 216, the carbonized biomass 225 is cooled to a specified temperature range of approximately 20°C to 25°C (approximately room temperature), as described above, becoming the reduced-temperature carbonized biomass 226. In various embodiments, the BPU 202 includes multiple cooling zones. In one embodiment, the cooling zone 216 cools the carbonized biomass to below 200°C. In one embodiment, the cooling zone includes a mixer for stirring the material and cooling it uniformly. In various embodiments, one or more of the multiple cooling zones are outside the BPU 202.

[0140] As shown in Figures 2 and 5, the gas phase separator unit 200 includes at least one input and multiple outputs. In this exemplary embodiment, at least one input is connected to the exhaust ports on the first / preheating zone 212 and the second / pyrolysis zone 214 of the BPU 202. One of the outputs is connected to a carbon recovery unit 500 (configured to concentrate the material), and another output is connected to a collection device or further processing device such as an oxyhydrogenation unit 206 or a distillation column. In various embodiments, the gas phase separator processes off-gases 220, 222 from the first / preheating zone 212 and the second / pyrolysis zone 214 to produce condensate 228 and concentrated gas 204. In one embodiment, the condensate 228 includes polar compounds such as acetic acid, methanol, and furfural. In one embodiment, the concentrated gas 204 produced by the gas phase separator 200 includes at least non-polar gases. In one embodiment, the gas phase separator includes a fractional distillation column. In one embodiment, acetic acid is sent through conduit 228 to an optional oxyhydrogenation unit 206. In another embodiment, methanol and / or furfural is sent through an optional additional conduit(s) 236 to a distillation / processing unit 238.

[0141] In the illustrated embodiment, the carbonized biomass exits the cooling reactor / zone along the material transport unit 304 and enters the carbon recovery unit 500. In various embodiments, as shown in more detail in Figure 5 and as previously described, the carbon recovery unit 500 also includes an input 524 connected to the gas phase separator 200. In one embodiment, the concentrated gas 204 is directed to the carbon recovery unit 500 and combined with the bioreagent 226 to produce a high-carbon bioreagent 136. In another embodiment, a carbon concentrated gas from an external source can also be directed to the carbon recovery unit 500 and combined with the bioreagent 226 to add further carbon to the bioreagent. In various embodiments, the gas extracted from the carbon recovery unit 500 by reference no. 234 is optionally used in an energy recovery system and / or a system for further carbon enrichment. Similarly, in various embodiments, the gas extracted from one or more zones of the BPU 202 is optionally used in an energy recovery system and / or a system for further carbon enrichment. For example, System 200 can be located in the same location near a woodworking facility, and carbon-concentrated gas from the woodworking facility can be used as gas from an external source.

[0142] Referring roughly to Figure 3, an embodiment of one material feeding system of the present disclosure is shown. As previously noted, high oxygen levels in the ambient air surrounding the raw material during processing can result in undesirable combustion or oxidation of the raw material, which reduces the quantity and quality of the final product. In one embodiment, the material feeding system is a closed system and includes one or more manifolds configured to purge oxygen from the air surrounding the raw material. In one embodiment, an oxygen level of about 0.5% to about 1.0% is used for preheating, pyrolysis / carbonization, and cooling. It will be understood that the primary objective of the closed material feeding system is to reduce the oxygen level to about 3% or less, about 2% or less, about 1% or less, or about 0.5% or less. After the oxygen level has been reduced, the biomass is moved to the BPU along the material feeding system. In various embodiments, it will be understood that preheating an inert gas through recovered process energy, and subsequently introducing the preheated inert gas into the BPU, reactor, or trimming reactor, makes the system even more efficient.

[0143] In some embodiments, a trimming reactor is included in the system. In one trimming reactor embodiment, the pyrolyzed material from the BPU is transported to a separate additional reactor for further pyrolysis, where heated inert gas is introduced to produce a product with an even higher carbon level. In various embodiments, the secondary process may be carried out in a container such as a drum, tank, barrel, bin, tote, pipe, sack, press, or roll-off container. In various embodiments, the final container may also be used for transporting the carbonized biomass. In some embodiments, the inert gas is heated through a heat exchanger that extracts heat from the gas extracted from the BPU and burned in a process gas heater.

[0144] As shown in Figure 3, the closed material supply system 108 includes a raw material supply hopper 300, a material transport unit 304, and an oxygen purge manifold 302.

[0145] In one embodiment, the raw material supply hopper 300 is any suitable open-air or closed-air container configured to receive raw or sized / dried biomass 109 / 209. The raw material supply hopper 300 is operably coupled to a material transport unit 304, which in one embodiment is a screw or auger system operably rotated by a drive source. In one embodiment, the raw material 109 / 209 is poured into the material transport unit 304 by a gravity-feed system. It will be understood that the material transport unit 304 in Figure 3 is adapted so that the screw or auger 305 is enclosed in a suitable enclosure 307. In one embodiment, the enclosure 307 is substantially cylindrical in shape. In various embodiments, the material supply system includes a screw, auger, conveyor, drum, screen, inclined platform, drop chamber, and pneumatic conveying device, including a rotary airlock or a double or triple flap airlock.

[0146] When the raw material 109 / 209 is supplied from the raw material supply hopper 300 to the material transport unit 304, the auger or screw 305 is rotated to move the raw material 109 / 209 toward the oxygen purge manifold 302. When the raw material 109 / 209 reaches the oxygen purge manifold 302, it will be understood that the ambient air between the raw material 109 / 209 in the material transport unit 304 contains approximately 20.9% oxygen. In various embodiments, the oxygen purge manifold 302 is located adjacent to or near the material transport unit 304. Within the oxygen purge manifold of one embodiment, the enclosure 307 of the material transport unit 304 includes a plurality of gas intake ports 310a, 310b, 310c and a plurality of gas exhaust ports 308a, 308b, 308c.

[0147] The oxygen purge manifold 302 includes at least one gas intake line 312 and at least one gas exhaust line 314. In various embodiments, at least one gas intake line 312 of the oxygen purge manifold 302 is operably connected to each of the plurality of gas intake ports 310a, 310b, and 310c. Similarly, in various embodiments, at least one gas exhaust line 314 of the oxygen purge manifold 302 is operably connected to each of the plurality of gas exhaust ports 308a, 308b, and 308c. In one embodiment, it will be understood that the gas intake line 312 is configured to introduce an inert gas into the gas intake ports 310a, 310b, and 310c. In one such embodiment, the inert gas is substantially oxygen-free nitrogen. In one embodiment, the inert gas will flow opposite the biomass.

[0148] Naturally, the introduction of inert gas 312 into the enclosed material transport unit 304 forces the ambient air out of the enclosed system. During operation, when inert gas 312 is introduced into the first gas intake port 310a in one embodiment, a large amount of oxygen-rich ambient air is forced out through the exhaust port 308a. At this point, it will be understood that the desired levels of oxygen, such as less than 2%, less than 1%, less than 0.5%, or less than 0.2%, cannot be reached. Therefore, in various embodiments, additional injection of inert gas 312 is required to purge the necessary amount of oxygen from the ambient air surrounding the raw material 109 in the enclosed system. In one embodiment, following the injection at the first gas intake port 310a, a second gas intake port 310b introduces inert gas 312 into the enclosed system, thereby purging much of the remaining oxygen from the enclosed system. It will be understood that after one or two injections of inert gas 312 to purge oxygen 314, a desired level of less oxygen can be reached. In one embodiment, if the desired oxygen level is still not achieved after two injections of inert gas, a third injection of inert gas 312 at the gas intake port 310c will purge any remaining undesirable amount of oxygen 314 from the enclosed system at the gas exhaust port 308c. Additional intake / exhaust ports may also be incorporated if desired. In various embodiments, the oxygen level is monitored throughout the material supply system to allow calibration of the amount and location of inert gas injection.

[0149] In one alternative embodiment, heat, steam, and gases recovered from the reactor are directed to a supply system, where they are enclosed within a jacket and separated from direct contact with the raw materials, but indirectly heat the supply materials before being introduced into the reactor.

[0150] In one alternative embodiment, heat, steam, and gases recovered from the dry zone of the reactor are directed to a supply system, where they are enclosed within a jacket and separated from direct contact with the raw materials, but indirectly heat the supply materials before being introduced into the reactor.

[0151] It will be understood that in one embodiment, the gas intake ports 310a, 310b, 310c and the corresponding gas exhaust ports 308a, 308b, 308c are each slightly offset from one another with respect to a vertical bisecting plane passing through the material transport unit 304. For example, in one embodiment, the intake port 310a and the corresponding exhaust port 308a are offset on the material transport unit 304 by an amount approximately corresponding to the pitch of the auger 305 within the material transport unit 304. In various embodiments, after the surrounding atmosphere of the raw material 109 / 209 has been satisfactorily deoxygenated, it is supplied from the material supply system 108 to the BPU 102. In various embodiments, the oxygen level is monitored throughout the material supply system to allow calibration of the amount and location of inert gas injection.

[0152] In one embodiment, it will be understood that the raw materials 109 / 209, and the subsequent dried biomass 221, preheated biomass 123 / 223, carbonized biomass 125 / 225, and carbonized biomass 126 / 226, are moved along a continuous material transport unit 304 to the reactor 102 (or multiple reactors). In another embodiment, the material transport units that carry the material differ at different stages in the process. In one embodiment, the process of moving the material through a reactor, zone, or multiple reactors is continuous. In one such embodiment, the speed of the material transport unit 304 is appropriately calibrated and calculated by the associated controller and processor so that the operation of the material transport unit 304 does not require interruption as the material moves through the reactor or multiple reactors.

[0153] In another embodiment, a controller associated with reactor 102 or reactors (112 / 114 / 116) is configured to adjust the speed of material transport unit 304 based on one or more feedback sensors, detected gas (e.g., from an optional FTIR), measured parameters, thermometers, or other appropriate variables in the reactor process. In various embodiments, it will be understood that any appropriate humidity sensor, temperature sensor, or gas sensor, operably communicating with the controller and processor, may be incorporated within or between each zone / reactor, or at an appropriate location along the material transport unit 304. In one embodiment, the controller and processor use information from the sensors or instruments to optimize the speed and efficiency of the BPU 100 / 200. In one embodiment, a controller associated with reactor 102 or reactors (112 / 114 / 116) is configured to operate the material transport unit 304. In one embodiment, a controller associated with the reactor 102 or reactors (112 / 114 / 116) is configured to monitor the gas concentration, temperature, and humidity inside the material transport unit 304 or any reactor. In one embodiment, the controller is configured to adjust the speed of the material transport unit 304, the gas injection into the material transport unit, and the heat applied to the material inside the material transport unit based on one or more measurements obtained by various sensors.

[0154] Referring here to Figures 2 and 4, one embodiment of the BPU 102 is shown. The graphical representation of the BPU 202 in Figure 4 will be understood to substantially correspond to the BPU 202 in Figure 2. In various embodiments, the BPU 202 will also be understood to be surrounded by a kiln shell to control and manipulate the large amount of heat required for the reactor process. As seen in Figure 4, in one embodiment, the kiln shell of the BPU 202 includes several insulating chambers (416, 418) surrounding four zones 210, 212, 214, and 216. In one embodiment, the kiln includes four separate zones. In various embodiments, each of the four zones 210, 212, 214, and 216 of the BPU 202 includes at least one inlet flight and at least one outlet flight. As will be explained in more detail below, within each zone of one such embodiment, the inlet and outlet flights are configured to be adjustable to control the flow of supply material, gas, and heat into and out of the zone. A supply of inert gas can be introduced into the inlet flight, and purged air can be extracted from the corresponding outlet flight. In various embodiments, one or more outlet flights of a zone within the BPU 202 are connected to one or more other inlet or outlet flights within the BPU 202.

[0155] In one embodiment, after the raw material 209 is deoxygenated in the material supply system 108, BPU Specifically, 202 is introduced into the first of four zones, an optional drying zone 210. As seen in Figure 4, the drying zone includes an inlet flight 422b and an outlet flight 420a. In one embodiment, the drying zone is heated to a temperature of about 80°C to about 150°C to remove water or other moisture from the raw material 209. The biomass is then moved to a second or preheating zone 212, where the biomass is preheated as described above.

[0156] In another embodiment, optionally dried and preheated material is moved to a third or carbonization zone. In one embodiment, carbonization is carried out at temperatures of about 200°C to about 700°C, for example, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, about 400°C, about 410°C, about 420°C, about 4 This occurs at 30°C, approximately 440°C, approximately 450°C, approximately 460°C, approximately 470°C, approximately 480°C, approximately 490°C, approximately 500°C, approximately 510°C, approximately 520°C, approximately 530°C, approximately 540°C, approximately 550°C, approximately 560°C, approximately 570°C, approximately 580°C, approximately 590°C, approximately 600°C, approximately 610°C, approximately 620°C, approximately 630°C, approximately 640°C, approximately 650°C, approximately 660°C, approximately 670°C, approximately 680°C, approximately 690°C, or approximately 700°C. In another embodiment, the carbonization zone of the reactor 421 is adapted to allow extraction of the gas produced during carbonization. In another embodiment, the gas produced during carbonization is extracted for optional subsequent use. In one embodiment, the carbonization temperature is selected to minimize or remove methane (CH4) production and maximize the carbon content of the carbonized biomass.

[0157] In another embodiment, the carbonized biomass is passively cooled or actively cooled by being moved to a temperature reduction zone or a cooling zone (third zone). In one embodiment, the carbonized biomass solid is cooled to a temperature of ±10°C, 20°C, 30°C, or 40°C above room temperature.

[0158] In various embodiments, the BPU includes multiple gas introduction probes and gas extraction probes. In the embodiment of the BPU shown in Figure 4, the BPU further includes multiple gas introduction probes: 408, 410, 412, and 414, and multiple gas extraction probes: 400, 402, 404, and 406. In various embodiments, it will be understood that one of each gas introduction probe and one of each gas extraction probe corresponds to one of multiple zones 210, 212, 214, and 216. In various alternative embodiments, it will also be understood that the BPU 202 includes any appropriate number of gas introduction probes and gas extraction probes, including two or more gas introduction probes and two or more gas extraction probes for each of the multiple zones.

[0159] In the illustrated embodiment, the drying zone 210 is associated with a gas introduction probe 412 and a gas extraction probe 402. In one embodiment, the gas introduction probe 412 introduces nitrogen into the drying zone 210, and the gas extraction probe 402 extracts gas from the drying zone 210. In various embodiments, it will be understood that the gas introduction probe 412 is configured to introduce a mixture of gases into the drying zone 210. In one embodiment, the gas to be extracted is oxygen. In various embodiments, it will be understood that the gas extraction probe 402 extracts gas from the drying zone 210 so that it can be reused in a heat or energy recovery system, as detailed above.

[0160] In the illustrated embodiment, the preheating zone 212 is associated with a gas introduction probe 414 and a gas extraction probe 400. In one embodiment, the gas introduction probe 414 introduces nitrogen into the preheating zone 212, and the gas extraction probe 400 extracts gas from the preheating zone 212. In various embodiments, it will be understood that the gas introduction probe 414 is configured to introduce a mixture of gases into the preheating zone 212. In various embodiments, the gas extracted in the gas extraction probe 400 includes a carbon-concentrated off-gas. In one embodiment, as described above, it will be understood that the gases extracted from the preheating zone 212 and the pyrolysis zone 214 are reintroduced into the material at a later stage in the process, for example, in a carbon recovery unit. In various embodiments, the gas extracted from either zone of the reactor is used for energy recovery in a drying unit or process gas heater, or for further pyrolysis in a trimming reactor or carbon concentration unit.

[0161] In the illustrated embodiment, the pyrolysis zone 214 is associated with a gas introduction probe 410 and a gas extraction probe 404. In one embodiment, the gas introduction probe 410 introduces nitrogen into the pyrolysis zone 214, and the gas extraction probe 404 extracts gas from the pyrolysis zone 214. In various embodiments, it will be understood that the gas introduction probe 410 is configured to introduce a mixture of gases into the pyrolysis zone 214. In various embodiments, the gas extracted in the gas extraction probe 404 includes a carbon-concentrated off-gas. In one embodiment, as described above, it will be understood that the carbon-concentrated gas extracted from the pyrolysis zone 214 is used in a later stage in the process and reintroduced into the material. In various embodiments, as will be described in more detail below, the gas 400 extracted from the preheating zone 212 and the gas 404 extracted from the pyrolysis zone 214 are combined before being reintroduced into the material.

[0162] In the illustrated embodiment, the cooling zone 216 is associated with a gas introduction probe 408 and a gas extraction probe 406. In one embodiment, the gas introduction probe 408 introduces nitrogen into the cooling zone 216, and the gas extraction probe 406 extracts gas from the cooling zone 216. In various embodiments, it will be understood that the gas introduction probe 408 is configured to introduce a mixture of gases into the cooling zone 216. In various embodiments, it will be understood that the gas extraction probe 406 extracts gas from the cooling zone 216 so that it can be reused in a heat or energy recovery system, as detailed above.

[0163] It will be understood that the gas introduction probes and gas extraction probes of the various embodiments described above are configured to work with the aforementioned controller and multiple sensors to adjust the level and concentration of gas introduced into each zone and gas extracted from each zone.

[0164] In various embodiments, the gas introduction probe and gas extraction probe are made of suitable tubing configured to withstand high-temperature fluctuations. In one embodiment, the gas introduction probe and gas extraction probe include multiple openings through which gas is introduced or extracted. In various embodiments, the multiple openings are located beneath the inlet and gas extraction probes. In various embodiments, each of the multiple openings extends over a considerable length within its respective zone.

[0165] In one embodiment, the gas introduction probe extends from one side of the BPU 202 through each zone. In one such embodiment, each of the four gas introduction probes extends from one side of the BPU to each of the respective zones. In various embodiments, a gaseous catalyst is added to increase the fixed carbon level. In such embodiments, it will be understood that multiple openings for each of the four gas introduction probes are located only within the respective zones associated with that particular gas introduction probe.

[0166] For example, referring to Figure 4, if each gas introduction probe extends from the left side of the drying zone into one of each zone, all four gas introduction probes pass through the drying zone, and the drying zone gas introduction probe terminates within the drying zone. The remaining three gas introduction probes all pass through the preheating zone, and the preheating zone gas introduction probe terminates within the preheating zone. The remaining two gas introduction probes pass through the pyrolysis zone, and the pyrolysis zone gas introduction probe terminates within the pyrolysis zone. The cooling zone gas introduction probe is the only gas introduction probe that enters and terminates within the cooling zone. In various embodiments, it will be understood that gas extraction probes are configured similarly to the gas introduction probes described in this example. It will also be understood that gas introduction probes and gas extraction probes can each be started from either side of the BPU.

[0167] In various embodiments, the gas introduction probes are arranged concentrically with each other to save space used by the multi-port configuration described in the example above. In one such embodiment, each of the four intake probes / ports will have a smaller diameter than the intake probe / port before it. For example, in one embodiment, the dry zone gas introduction probe has the largest internal diameter, then the preheating zone gas introduction probe is located within the internal diameter of the dry zone intake probe / port, the pyrolysis zone gas introduction probe is located within the internal diameter of the preheating zone gas introduction probe, and the cooling zone gas introduction probe is located within the pyrolysis zone gas introduction probe. In one embodiment, appropriate connectors are attached to each of the four gas introduction probes on the outside of the BPU 202 to individually control the air injected into each of the four gas introduction probes.

[0168] In one such embodiment, as in the example above, the dry zone gas introduction probe terminates within the dry zone, while the other three gas introduction probes extend into the preheating zone. However, in a concentric or substantially concentric arrangement, only the outermost gas introduction probes are exposed within each zone before being terminated. Thus, in one such embodiment, the individual zone gas introductions are efficiently controlled independently of each other, requiring only one continuous gas introduction probe conduit. It will be understood that a similar concentric or substantially concentric configuration is appropriately used for gas extraction probes in one embodiment.

[0169] In one embodiment, each zone or reactor is adapted to extract and collect off-gases from one or more individual zones or reactors. In another embodiment, the off-gases from each zone / reactor are left separate for disposal, analysis, and / or later use. In various embodiments, each reactor / zone includes a gas detection system, such as FTIR, that can monitor gas generation within the zone / reactor. In another embodiment, off-gases from multiple zones / reactors are combined for disposal, analysis, and / or later use, and in various embodiments, off-gases from one or more zones / reactors are supplied to a process gas heater. In another embodiment, off-gases from one or more zones / reactors are supplied to a carbon recovery unit. In another embodiment, off-gases from one or more zones / reactors are supplied to a gas phase separator before being introduced into the carbon recovery unit. In one embodiment, the gas phase separator includes a fractionation column. Any fractionation column known to those skilled in the art may be used. In one embodiment, the off-gases are separated into non-polar and polar compounds using a standard fractionation column or packed column heated to a suitable temperature. In another embodiment, nonpolar compounds or concentrated gases from the gas phase separator are extracted for optional subsequent use, and in various embodiments, off-gases from one or more zones / reactors are supplied to a process gas heater. In one embodiment, gases extracted from a preheating zone / reactor, a pyrolysis zone / reactor, and an optional cooling zone / reactor are extracted into a combined stream and supplied to the gas phase separator. In various embodiments, one or more zones / reactors are configured to control whether and how much gas is introduced into the combined stream.

[0170] As previously mentioned and roughly shown in Figure 5, the off-gas 124 / 224 from BPU 102 / 202 is directed to the gas phase separator. In various embodiments, the off-gas 124 / 224 includes gas 120 extracted from the first / preheating zone / reactor 112 / 212 combined with gas 122 / 222 extracted from the second / pyrolysis zone / reactor 114 / 214, or just one of the gas streams. When the off-gas 124 / 224 enters the gas phase separator, it is separated into polar compounds 128 / 228 / 136 / 236 and nonpolar compounds 204, such as nonpolar gases. In various embodiments, the gas phase separator 200 is a known fractional distillation column.

[0171] In various embodiments, the concentrated gas 204 extracted from the coupled off-gas 124 / 224 is directed from the gas phase separator 200 through input 524 to the carbon recovery unit 500, where the material is concentrated. As previously mentioned and as shown in Figures 8 and 11, in various embodiments, the extracted gas is first introduced to the material concentration unit and then to the separated carbon recovery unit. In the embodiment shown in Figure 5, material concentration occurs within the carbon recovery unit 500. In one embodiment (Figure 5), the gas phase separator 200 includes multiple outputs. In various embodiments, one output from the gas phase separator 200 is connected to the carbon recovery unit 500 to introduce the concentrated gas stream into the carbon recovery unit 500. In one embodiment, a portion of the concentrated gas stream is directed to the carbon recovery unit 500, while another portion is directed to a scrubber or another suitable purification device for purification and disposal of unwanted gases. In various embodiments, off-gases not sent to the carbon recovery unit may be used for energy recovery (e.g., in a process gas heater) or as an inert gas (e.g., in a degassing unit, reactor, BPU, or cooling unit). Similarly, in various embodiments, off-gases from the carbon recovery unit may be used for energy recovery (e.g., in a process gas heater), as an inert gas (e.g., in a degassing unit, reactor, BPU, or cooling unit) or in a secondary recovery unit.

[0172] In one embodiment, another output from the gas phase separator extracts polar compounds and optionally condenses them into a liquid component comprising several different fluid portions. In various embodiments, the liquids include water, acetic acid, methanol, and furfural. In various embodiments, the resulting liquids are stored, discarded, further processed, or reused. For example, it will be understood that the water produced in one embodiment can be reused to heat or cool another part of the system. In another embodiment, the water is discharged. It will also be understood that the acetic acid, methanol, and furfural produced in one embodiment can be sent to a storage tank for reuse, resale, distillation, or purification.

[0173] As shown in Figure 5, a carbon recovery unit 500 in one embodiment comprises a housing having an upper and a lower section. In various embodiments in which a material concentration unit is separated from the carbon recovery unit, it will be understood that the material concentration unit has similar features to those described in relation to the carbon recovery unit 500 in Figure 5. In one embodiment, the carbon recovery unit comprises: a housing 502 having an upper section 502a and a lower section 502b; an inlet 524 on the bottom surface of the lower section of the housing configured to transport reactor off-gas; an outlet 534 on the top surface of the upper section of the housing configured to transport a concentrated gas stream; a defined path 504 between the upper and lower sections of the housing; and a transport system 528 following that path, the transport system configured to transport a reagent, and the housing is formed such that the reagent adsorbs at least a portion of the reactor off-gas. In various embodiments, the upper section includes a plurality of outlets, and the lower section includes a plurality of inlets.

[0174] In one embodiment, the housing 502 is free to have corners having angles of 110 degrees or less, 90 degrees or less, 80 degrees or less, or 70 degrees or less. In one embodiment, the housing 502 is free to have convex corners. In another embodiment, the housing 502 is free to have convex corners capable of generating vortices or trapping air. In another embodiment, the housing 502 is formed substantially like a cube, a right prism, an ellipsoid, a stereographic ellipsoid, a spheroid, two cones with their bases glued together, two regular tetrahedrons with their bases glued together, two rectangular pyramids with their bases glued together, or two isosceles triangular prisms with their bases glued together.

[0175] In one embodiment, the upper 502a and lower 502b of the housing 502 are substantially formed as a semi-ellipse, a semi-right prism, a semi-solid ellipsoid, a semi-spherical ellipsoid, a cone, a regular tetrahedron, a rectangular pyramid, an isosceles triangular prism, or a round-to-rectangular duct transition, respectively.

[0176] In another embodiment, the inlet 524 on the lower bottom surface of housing 502b and the outlet 534 on the upper top surface of housing 502a are configured to connect to a pipe. In another embodiment, the lower top surface of housing 502b and the upper bottom surface of housing 502a are substantially rectangular, circular, or elliptical. In another embodiment, the width between the lower top surface of housing 502b and the upper bottom surface of housing 502a is wider than the width of the transport system 528. In one embodiment, the width of the transport system 528 is its height.

[0177] In one embodiment, the carbon recovery unit 500 includes a path 504 defined between an upper and lower section, an intake opening 506, and an exhaust opening 508. In one embodiment, the intake and exhaust openings are configured to receive a transport system. In one embodiment, the transport system 528 is at least semi-permeable or permeable to concentrated gas.

[0178] In one embodiment, the intake opening 506 includes an intake opening sealing mechanism to reduce gas leakage, and the exhaust opening 508 includes an exhaust opening sealing mechanism to reduce gas leakage. In one embodiment, the intake and exhaust opening sealing mechanisms include an airlock.

[0179] In various embodiments, the lower part 502b of the carbon recovery unit housing has a narrow, rounded-bottom coupling opening, which is connected to the gas phase separator 200 for transporting the gas stream 204. In various embodiments, the upper surface of the lower part 502b of the carbon recovery unit housing is substantially rectangular and also substantially wider than the narrow, rounded-bottom coupling opening. In one embodiment, the lower part will be understood to transition from a rounded-bottom opening to a rectangular upper opening. In one embodiment, the rectangular upper opening of the lower part is about 6 feet wide (along the direction of the conveyor system). In various embodiments, the upper part of the carbon recovery unit 500 is formed substantially similarly to the lower part. In one embodiment, the lower opening of the upper part is wider than the upper opening of the lower part. In one embodiment, the rectangular lower opening of the upper part is about 6.5 feet wide (along the direction of the conveyor system). In one embodiment, the upper part is configured to capture all gas passing through the carbon recovery unit 500 that is not adsorbed by the activated material.

[0180] In various embodiments, it will be understood that the shape of the lower part of the carbon recovery unit helps to slow and disperse the gas 204 over a wider surface area of ​​the conveyor that transports the bioreagents 126 / 226. In various embodiments, the exact shape of the lower part 502b and upper part 502a of the carbon recovery unit 500 is determined by the angle of gas dispersion coming from the gas phase separator pipe. In various embodiments, it will be understood that the gas tends to expand naturally when drawn up within a flare range of 5 to 30 degrees from the vertical line. In one embodiment, the flare angle is approximately 15 degrees. It will be understood that the lower part of the carbon recovery unit is constructed with as few creases and corners as possible to prevent the formation of air traps or vortices.

[0181] In one embodiment, the carbon recovery unit 500 is configured to connect not only to the BPU 102 / 202 but also to the gas phase separator 200, as previously described. In various embodiments, the carbon recovery unit 500 is connected to the output of the cooling reactor / zone 216 / 116, or to the output of the BPU 102 / 202 or the last cooling zone outside the BPU. In one embodiment, the output of the cooling reactor / zone 116 / 216 contains a bioreagent being processed within the BPU 102 / 202. In one embodiment, the bioreagent 126 / 226 enters the carbon recovery unit 500 along a suitable transport system. In various embodiments, the top and bottom surfaces of the carbon recovery unit are connected to each other to define a path through which the transport system passes. In one embodiment, the transport system is constructed of a porous or mesh material configured to allow gas to pass through it. It will be understood that the transport system is configured to pass through the opening of the carbon recovery unit 500 and then through the carbon recovery outlet opening. In some embodiments, the inlet to and outlet from the carbon recovery unit are properly sealed with an airlock or another suitable sealing mechanism to prevent gas leakage through the conveyor opening. In various embodiments, off-gas not sent to the carbon recovery unit may be used for energy recovery (e.g., in a process gas heater) or as an inert gas (e.g., in a degassing unit, reactor, BPU, or cooling unit). Similarly, in various embodiments, off-gas from the carbon recovery unit may be used for energy recovery (e.g., in a process gas heater), as an inert gas (e.g., in a degassing unit, reactor, BPU, or cooling unit) or in a secondary recovery unit.

[0182] In various embodiments, the process first operates by outputting the bioreagent 126 / 226 from the cooling zone 116 / 216 onto the transport system using a suitable release mechanism from the cooling reactor / zone 116 / 216. In one embodiment, the bioreagent 126 / 216 spreads across the width of the transport system to minimize stacking or bunching of the material and maximize the surface area for gas absorption. Once the bioreagent 126 / 216 has precipitated and spread appropriately onto the transport system, in various embodiments, the transport system transports the bioreagent 126 / 226 through an opening in the carbon recovery unit 104 defined between the lower and upper portions as described above. Within the carbon recovery unit 104, the bioreagent 126 / 216 adsorbs gas that has been piped from the gas phase separator 200 to the lower part of the carbon recovery unit 104. After the bioreagent has been concentrated with a nonpolar gas, it will be understood that the bioreagent becomes a high-carbon bioreagent. In various embodiments, the high-carbon bioreagent is the final product of the process disclosed herein and is transported from the carbon recovery unit 104 to a suitable storage or post-treatment device.

[0183] In one embodiment, after the concentrated gas 204 passes through the conveyor and bioreagents 126 / 216, the resulting gas is extracted at the top of the carbon recovery unit 104. In various embodiments, the exhausted gas 134 is transported to a suitable scrubber, stack, or recovery system. In some embodiments, the exhausted gas is utilized within the system for any reusable quality, including use in a secondary carbon recovery unit or for energy. In various embodiments, off-gas not sent to the carbon recovery unit may be used for energy recovery (e.g., in a process gas heater) or as an inert gas (e.g., in a degassing unit, reactor, BPU, or cooling unit). Similarly, in various embodiments, off-gas from the carbon recovery unit may be used for energy recovery (e.g., in a process gas heater), as an inert gas (e.g., in a degassing unit, reactor, BPU, or cooling unit) or in a secondary recovery unit.

[0184] It will be understood that the bioreagents 126 / 216 contain a large amount of carbon, which has high priority for adsorbing nonpolar gases. It will also be understood that the concentrated gas stream 204 mainly contains nonpolar gases such as terpenes, carbon monoxide, carbon dioxide, and methane. In various embodiments, the gas flow rate and conveyor speed are monitored and controlled as the concentrated gas moves from the gas phase separator to the carbon recovery unit to ensure maximum adsorption of nonpolar gases in the bioreagents 126 / 216. In another embodiment, high-energy organic compounds are eluted during the carbonization of biomass and are included in at least a portion of the concentrated gas 204 output from the gas phase separator 200 to the carbon recovery unit. In various embodiments, the concentrated gas 204 is further concentrated with additional additives before being introduced into the carbon recovery unit or material concentration unit.

[0185] As will be further detailed below, in various embodiments, the residence time of the bioreagent 126 / 216 in the carbon recovery unit is controlled and varied based on the composition of the bioreagent 126 / 216 as well as the gas flow and composition. In one embodiment, the bioreagent passes through one or more carbon recovery units multiple times. In various embodiments, the output of the concentrated gas from the gas phase separator and the output of the exhaust gas from the carbon recovery unit 104 can be diverted or branched to additional carbon recovery units, further purified, or used for energy or inert gas for use in the process.

[0186] Here, referring broadly to Figures 6 to 13, various embodiments of the present disclosure are shown and explained. It will be understood that the various embodiments and alternatives described below in relation to Figures 6 to 13 are applicable to the embodiments described above in Figures 1 to 5, and vice versa.

[0187] Referring in particular to Figure 6, this embodiment utilizes a BPU comprising a single reactor having two or more distinct zones. Although two zones are shown in the exemplary embodiment, any different number of zones can be employed. In one embodiment, each zone is connected to at least one other zone through a material transport unit (not shown). In one embodiment, the material transport unit controls atmospheric and temperature conditions.

[0188] In particular, in one embodiment shown in Figure 6, the system 600 includes a material supply system 602, a BPU 606 including a pyrolysis zone 608 and a cooling zone 610, a cooling device 614, and a carbon recovery unit 616. It will be understood that the cooling device 614 in Figure 6 is external to the BPU 606 and is in addition to the cooling zone 610 which is located inside the BPU 606.

[0189] In various embodiments, the system 600 includes an optional drying device between the material supply system 602 and the BPU 606. In various embodiments, the BPU 606 includes multiple zones. In Figure 6, the BPU 606 includes a pyrolysis zone 608 and a cooling zone 610. The BPU 606 also includes at least multiple inlets and outlets for adding various substances to the multiple zones 608, 610, and for removing various substances from the multiple zones 608, 610, including at least condensable vapors and noncondensable gases 612. In the various embodiments described below, it will be understood that one or more of the multiple zones 608 or 610 are surrounded by the BPU 606.

[0190] Referring now to FIG. 7, a system 700 of one embodiment is shown and described. System 700 includes a single reactor system that includes a material supply system 702, a preheater 706, a pyrolysis reactor 708, a cooling device 714, and a carbon recovery unit 716. In various embodiments, system 700 includes an optional drying device 704 between material supply system 702 and preheater 706. As seen in FIG. 7, a pyrolysis reactor 708 of one embodiment includes at least one gas inlet 710 and at least one gas outlet 712 for outputting substances from pyrolysis reactor 708. In various embodiments, the substances output through outlet 712 include condensable vapors and / or non-condensable gases. It will be appreciated that pyrolysis reactor 708 may include one or more zones not described in detail herein. In various embodiments, system 700 includes one or more reactors in addition to pyrolysis reactor 708.

[0191] Referring now to FIG. 8, a single reactor, multi-zone BPU system 800 of one embodiment is shown and described. System 800 includes a material supply system 802, a BPU 808 having a pyrolysis zone 810 and a cooling zone 812, a material concentration unit 818, and a carbon recovery unit 820. Similar to the embodiments described above, FIG. 8 also includes an optional drying device 804 disposed between material supply system 802 and BPU 808. It will be appreciated that moisture 806 from drying device 806 is removed during the drying process. FIG. 8 also includes an optional cooling device 816 outside of BPU 808 and prior to material concentration unit 818. As will be described in more detail below, material concentration unit 818 is in communication with gas outlet 814 of BPU 808, which conveys condensable vapors and non-condensable gases away from the BPU. It will be appreciated that the various embodiments shown in FIG. 8 include a carbon recovery unit 820 separate from material concentration unit 818. As described above, in various embodiments, carbon recovery unit 820 of FIG. 8 is a suitable container in which the concentrated material is stored following material concentration unit 818, and carbon recovery unit 820 does not further concentrate the material.

[0192] In various embodiments, it will be appreciated that an optional process gas heater 824 is disposed within the system and attached to the BPU 808. In various embodiments, the steam and other off-gases from the BPU 808 are introduced into the optional process gas heater 824 along with one or more external sources of any of air, natural gas, and nitrogen. As will be described below, in various embodiments, the air discharge from the process gas heater 824 is introduced into the drying device 804 as a heat or energy recovery system.

[0193] Referring now to FIG. 9, the BPU 908 of a system 900 of one embodiment is shown and described. The BPU 908 includes a plurality of zones: a preheating zone 904, a pyrolysis zone 910, and a cooling zone 914. The BPU 908 of one embodiment also includes a material supply system 902 in communication with one of the zones and at least one gas inlet 906 in communication with one or more of the zones 904, 910, 914. In various embodiments, as will be described below, one of the zones also includes at least one outlet 912 for outputting a substance, in one embodiment, a condensable vapor and / or a non-condensable gas. In various embodiments, one of the zones also includes an outlet for outputting advanced carbon from the system 900.

[0194] FIG. 9 shows the gas inlet 906 connected to the preheating zone 904, but it will be appreciated that various embodiments include inlets to any combination of the three zones. Similarly, the gas outlet 912 comes from the pyrolysis zone 910, but it will be appreciated that various embodiments include outlets coming from one or more of any combination of the three zones. As will be described below, various embodiments contemplated include inputs and outputs within the BPU: for example, the outlet of the pyrolysis zone 910 is then an input to the preheating zone 904. In the illustrated embodiment, it will be appreciated that each of the reactors within the BPU is connected to each other by a material supply system as described above.

[0195] In various embodiments, the preheating zone 904 of the BPU 908 is configured to supply biomass 902 (or another carbon-containing feedstock) in a manner that does not "shock" the biomass, although a "shock" can rupture cell walls and initiate rapid decomposition of the solid phase into vapor and gas. In one embodiment, the preheating zone 904 may be considered to be a gentle pyrolysis.

[0196] In various embodiments, the pyrolysis zone 910 of the BPU 908 is configured as a primary reaction zone, where preheated material undergoes pyrolysis chemistry to release gases and condensable vapors, resulting in solids that are high-carbon reaction intermediates. The biomass components (primarily cellulose, hemicellulose, and lignin) decompose to produce vapors, which leak out either by penetrating pores or by creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

[0197] In various embodiments, the cooling zone 914 of the BPU 908 is configured to receive high-carbon reaction intermediates and cool the solids thereof, i.e., the cooling zone 914 will be at a lower temperature than the pyrolysis zone 910. Chemical and mass transport may be complex in the cooling zone 914. In various embodiments, secondary reactions occur within the cooling zone 914. It will be understood that carbon-containing components in the gas phase may decompose to form additional fixed carbon and / or be adsorbed onto that carbon. Thus, the high-carbon 916 is not merely a solid, devolved residue of the processing steps, but rather includes additional carbon precipitated from the gas phase, such as by the decomposition of organic vapors (e.g., tar) capable of forming carbon.

[0198] Referring here to Figures 10 to 13, various multiple reactor embodiments of the system are shown and described. As with each embodiment, the system includes an optional degasser and an optional dryer, as detailed below. Referring to Figure 10, system 1000 includes a material supply system 1002, a pyrolysis reactor 1012, a cooling reactor 1018, a cooling unit 1020, and a carbon recovery unit 1022, which are configured to be injected into one or both, as further described below. In various embodiments, the pyrolysis reactor includes an outlet for outputting at least condensable vapor and / or non-condensable gas. In various embodiments, the carbon recovery unit 1022 includes an outlet 1024 for discharging activated carbon from system 1000.

[0199] In at least the various embodiments shown in Figures 10 to 13, it will be understood that the illustrated system includes an optional degasser and an optional dryer. As seen in Figure 10, for example, the optional degasser 1004, represented by a dashed line, is connected to system 1000 between the material supply system 1002 and the pyrolysis reactor 1012. Similarly, the dryer 1006 is connected to system 1000 between the material supply system 1002 and the pyrolysis reactor 1012. In various embodiments, the dryer 1006 and the degasser 1004 are also connected to each other so that material from the material supply system can follow any number of different paths through the material supply system, the degasser, and the dryer to the pyrolysis reactor. In some embodiments, it will be understood that material passes through only one of the optional degasser 1004 and the dryer 1006.

[0200] In some embodiments, with reference to Figure 10, the process for producing high-carbon bioreagents is as follows: (a) To supply carbon-containing raw materials including biomass, (b) optionally drying the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degas the feedstock to remove at least some of the interstitial oxygen contained in the feedstock, if any. (d) Thermally decompose the feedstock at at least one temperature selected from about 250°C to about 700°C for at least 10 minutes in the presence of a substantially inert gas phase to produce hot thermal decomposition solids, condensable vapors, and non-condensable gases. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) Cooling hot pyrolysis solids in order to produce cooled pyrolysis solids, and, (g) The process includes recovering a high-carbon bioreagent containing at least a portion of the cooled pyrolysis solids.

[0201] Referring now to Figure 11, a multiple reactor system 1100 of one embodiment is shown. Similar to the embodiment described above and shown in Figure 10, this embodiment includes a material supply system 1102, a pyrolysis reactor 1112, a cooling reactor 1118, and a carbon recovery unit 1124. In the embodiment illustrated in Figure 11, the cooling reactor 1120 is optional, and a material concentration unit 1122 is located between the optional cooling reactor 1120 and the carbon recovery unit 1124. In various embodiments, the material concentration unit 1122 concentrates the material before proceeding to a separate carbon recovery unit 1124, which may or may not further concentrate the material. In various embodiments, an optional degasser 1104 and an optional dryer 1106 are located between the material supply system 1102 and the pyrolysis reactor 1112. In the illustrated embodiment, the pyrolysis reactor 1112 also includes an outlet 1114 configured to remove substances such as condensable vapors and non-condensable gases and to send the removed substances to a material concentration unit 1122.

[0202] Various embodiments extend the concept of additional carbon formation by including separate material enrichment units 818, 1122 in which cooled carbon is exposed to an environment containing carbon-containing species, thereby increasing the carbon content of the final product. If the temperature of this unit is below the thermal decomposition temperature, the additional carbon is expected to be in the form of adsorbed carbonaceous species rather than additional fixed carbon.

[0203] As detailed below, there are numerous options regarding intermediate input and output (purge or probe) streams of one or more phases present within any particular reactor, various mass and energy reuse methods, various additives that can be introduced somewhere in the process, and the adjustability of process conditions, including both reaction and separation conditions to adjust product dispersion. Zone or reactor-specific input and output streams enable good process monitoring and control, such as through FTIR sampling and dynamic process adjustment.

[0204] This disclosure differs from both fast pyrolysis and conventional slow pyrolysis. The high-quality carbon materials in this disclosure include compositions having a high proportion of fixed carbon, but can be obtained from the disclosed processes and systems.

[0205] "Biomass" is interpreted in this disclosure as any biological feedstock or a mixture of biological and non-biological feedstocks. Elementally, biomass contains at least carbon, hydrogen, and oxygen. The methods and apparatus of the present invention are suitable for a wide range of feedstocks of various types, sizes, and moisture contents.

[0206] Biomass includes, for example, plants and plant-derived materials, vegetation, agricultural waste, forestry waste, waste wood, paper waste, poultry waste, and municipal solid waste. In various embodiments of the present invention that utilize biomass, the biomass supply material may include one or more materials selected from: wood harvest residues, softwood chips, hardwood chips, tree branches, tree stumps, knots, leaves, bark, sawdust, off-grade papermaking pulp, cellulose, corn, corn stalks and leaves, wheat straw, rice straw, sugarcane bagasse, switchgrass, pampas grass, livestock manure, municipal kitchen waste, municipal sewage, commercial waste, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, carbohydrates, plastics, and cloth. Those skilled in the art will readily understand that the choice of supply material is substantially limited.

[0207] Various embodiments of this disclosure can also be used with non-biomasous carbon-containing feedstocks, such as fossil fuels (e.g., coal or petroleum coke) or any mixture of biomass and fossil fuels (e.g., biomass / coal mixtures). In some embodiments, the bio-feedstock is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (e.g., petroleum coke). The feedstock may include waste tires, recycled plastics, recycled paper, and other waste or recycled materials. Any method, apparatus, or system described herein can be used with any carbonaceous feedstock. The carbon-containing feedstock may be transported by any known means, such as by truck, train, ship, barge, tractor trailer, or any other vehicle or means of transport.

[0208] The selection of specific or multiple supply materials is not considered technically important, but is carried out in a way that is favorable to the economic process. Typically, regardless of the selected supply materials, Sieving may be performed (in some embodiments) to remove undesirable materials. The feed material may optionally be dried before processing.

[0209] The feed material used may be provided in or processed into a wide range of particle sizes or shapes. For example, the feed material may be a fine powder or a mixture of fine and coarse particles. The feed material may be a larger form of material, such as wood chips or other forms of wood (e.g., circular, cylindrical, rectangular, etc.). In some embodiments, the feed material may include pellets or other aggregated forms of particles that are compressed together or bound together in other ways, such as with a binder.

[0210] It should be noted that size reduction is a costly and energy-intensive process. Pyrolytic materials can be reduced to a certain size with significantly less energy input, i.e., it may be more energy-efficient to reduce the particle size of the product rather than the feedstock. This is optional in this disclosure, as the process does not require fine starting material and does not require any micronization during the process. This disclosure provides the ability to process very large feedstock. In particular, many market applications of high-carbon products actually require large sizes (e.g., centimeters), and therefore, in some embodiments, large pieces are supplied, produced, and sold. It will be understood that smaller sizes, although not required in all embodiments of this disclosure, result in a higher fixed carbon number under similar process conditions and may be preferred in some embodiments.

[0211] In the context of the present invention, there are at least two options when it is desired to produce a final carbonaceous bioreagent with structural integrity, such as a cylindrical shape. First, the material produced from the process is collected and then further mechanically processed into the desired shape. For example, the product is compressed or pelletized with a binder. The second option is to utilize a feed material that has the desired size and / or shape for the final product and employ processing steps that do not destroy the basic structure of the feed material. In some embodiments, the feed and product have similar geometric shapes, such as spheres, cylinders, and cubes.

[0212] The function of maintaining the general shape of the feedstock throughout the process is beneficial when the strength of the product is important. Also, this control avoids the difficulties and costs of pelletizing high fixed-carbon materials.

[0213] As will be appreciated, the starting feedstocks in various embodiments are supplied at various moisture levels. In some embodiments, the feedstock is already sufficiently dry and does not need to be further dried prior to pyrolysis. Generally, it is desirable to utilize biomass from commercial sources, which typically contain moisture, and supply that biomass through a drying step prior to introducing it into the pyrolysis reactor. However, in some embodiments, dried feedstocks are used. In various embodiments, any biomass will function, but it will be appreciated that the following factors can affect the process and its product: namely, how the material was cultivated, harvested, watered, the choice of material species, and the carbon content. Specifically, in various embodiments, the use of less fertilizer and less phosphite during cultivation results in better properties for metal production. In various embodiments, low-shear harvesting with less impact results in greater strength. In various embodiments, less irrigation and smaller tree rings can result in greater strength.

[0214] It will be appreciated that in various embodiments, additives and / or catalysts are included within the BPU and that the temperature profile within the BPU is selected to promote the formation of carbon dioxide over carbon monoxide to result in greater fixed carbon in the final product.

[0215] It is desirable to provide a relatively low oxygen environment within the pyrolysis reactor, such as about 10 wt%, 5 wt%, 3 wt%, or 1 wt% O2 in the gas phase. First, for safety reasons, uncontrolled combustion should be avoided within the pyrolysis reactor. Oxidation of some amount of the total carbon to CO2 can occur, and the heat released from the exothermic oxidation can assist the endothermic pyrolysis chemistry. Substantial oxidation of carbon, including partial oxidation to syngas, will reduce the carbon that becomes solids.

[0216] In practice, achieving a strictly oxygen-free environment within each of the reactors or BPUs can be difficult. While it is possible to approach this limit, in some embodiments, the reactor or BPU is substantially free of molecular oxygen in the gas phase. To ensure little to no oxygen is present within the reactor or BPU, it may be desirable to remove air from the feed material before introducing it into the reactor or BPU. Various methods exist for removing or reducing air in the feed material.

[0217] In some embodiments, a degassing unit is used, as shown in Figures 10, 11, 12, and 13, in which the feedstock is transported in the presence of another gas that can remove adsorbed oxygen before or after drying and penetrate the pores of the feedstock to remove oxygen from those pores. Most gases with O2 below 21 vol% can be employed with varying degrees of effectiveness. In some embodiments, CO and / or CO2 can be employed. Mixtures, such as a mixture of nitrogen and a small amount of oxygen, can be used. Water vapor may be present in the degassed gas, but adding a significant amount of moisture back into the feedstock should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or an exhaust treatment unit) or reused.

[0218] In principle, the effluent (or a portion thereof) from the degassing unit can be introduced into the pyrolysis reactor itself, as the oxygen removed from the solid material is immediately highly diluted. In this embodiment, introducing the degassed exhaust gas into the final zone of the reactor may be advantageous when operating in a counterflow configuration.

[0219] Various types of degassing units can be employed. In one embodiment, if drying is performed, degassing after drying stops the step of removing soluble oxygen from the present moisture. In another embodiment, the drying and degassing steps are combined into a single unit, or a certain amount of degassing is achieved during drying.

[0220] The feed material, optionally dried and optionally degassed, is introduced into a pyrolysis reactor or a plurality of reactors, either sequentially or in parallel. In various embodiments, the material feeding system introduces the feed material using any known means, including, for example, a screw material feeding system or a lock hopper. In some embodiments, the material feeding system incorporates an airlock.

[0221] When a single reactor is employed (e.g., Figure 6, Figure 3, or Figure 4), multiple zones may be present. Multiple zones, such as two, three, four, or more, allow for separate control of temperature, solid retention time, gas retention time, gas composition, flow pattern, and / or pressure to adjust the overall process performance.

[0222] As previously stated, the reference to “zone” would be broadly interpreted to include regions of space within a single physical unit (e.g., Figures 6, 8, or 9), physically separate units (e.g., Figures 7, and 10-13), or any combination thereof. With respect to BPUs, the division of zones within a BPU may relate to structure, such as the presence of separate heating elements for supplying heat to the flight or individual zones within the BPU. Alternatively, or additionally, in various embodiments, the division of zones within a BPU may relate to features such as: separate temperatures, fluid flow patterns, solid flow patterns, and the range of the reactor. In a single batch reactor, “zone” is an operational regime in time rather than in space. Various embodiments include the use of multiple batch BPUs.

[0223] It will be understood that abrupt transitions from one zone to another do not necessarily exist. For example, the boundary between the preheating zone and the pyrolysis zone can be somewhat arbitrary; that is, some pyrolysis may occur in part of the preheating zone, and some "preheating" may continue in the pyrolysis zone. The temperature profile within the BPU is usually continuous, including at the zone boundaries within zones.

[0224] Some embodiments employ a preheating zone 304 operated under preheating and / or mild pyrolysis conditions, as seen, for example, in Figure 9. In various embodiments, the temperature of the preheating zone 304 is about 80°C to about 500°C, for example, about 300°C to about 400°C. In various embodiments, the temperature of the preheating zone 304 is not high enough to shock the biomass material, causing the cell walls to rupture and initiating rapid decomposition into solid-phase vapor and gas. Pyrolysis, commonly known as rapid or catastrophic pyrolysis, is avoided in this disclosure.

[0225] All references to zone temperatures in this specification should be interpreted in an unspecified manner, including temperatures applicable to the bulk solid present, the gas phase, or the reactor or BPU wall (process side). It will be understood that within each zone there are temperature gradients both axially and radially, as well as temporally (e.g., following the start or temporarily). Thus, references to zone temperatures may refer to the mean temperature or other effective temperature that may affect the actual reaction kinetics. Temperatures may be measured directly by a thermoelectric thermometer or other temperature probe, or indirectly by other means.

[0226] A second zone, or primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the pyrolysis zone can be selected from approximately 250°C to approximately 700°C, for example, approximately 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, preheated biomass undergoes pyrolysis chemistry, releasing gases and condensable vapors, leaving a considerable amount of solid material as high-carbon reaction intermediates. The biomass components (mainly cellulose, hemicellulose, and lignin) decompose to produce vapors, which leak out by penetrating pores or creating new pores. The temperature will be determined at least by the residence time in the pyrolysis zone, as well as the properties of the feedstock and the characteristics of the products.

[0227] The cooling zone is operated to cool the high-carbon reaction intermediate to a range of degrees. In various embodiments, the temperature of the cooling zone is lower than the temperature of the pyrolysis zone. In various embodiments, the temperature of the cooling zone is selected from about 100°C to about 550°C, for example, about 150°C to about 350°C.

[0228] In various embodiments, chemical reactions continue to occur within the cooling zone. In various embodiments, it will be understood that a secondary pyrolysis reaction is initiated in the cooling zone. The carbon-containing component, which is in the gas phase, may condense (due to the reduced temperature of the cooling zone). However, the temperature is high enough to facilitate the reaction, which can form additional fixed carbon from the condensed liquid (secondary pyrolysis) or at least form bonds between the adsorbed species and the fixed carbon. One exemplary reaction that may occur is the conversion of carbon monoxide to carbon dioxide + fixed carbon (Boudoit reaction).

[0229] The residence time in a zone can vary. For a desired amount of thermal decomposition, a higher temperature may allow for a shorter reaction time, and vice versa. The residence time in a continuous BPU (batch reactor) is the volume divided by the volumetric flow rate. The residence time in a batch reactor is the batch reaction time following heating to the reaction temperature.

[0230] In a multiphase BPU, it should be recognized that there are multiple residence times. In the current context, within each zone, there are residence times (and residence time distributions) for both the solid and vapor phases. For a given apparatus employing multiple zones and having a given processing capacity, the residence time across the entire zone is generally tied to the solid side, but if multiple intake and exhaust ports are used in individual zones, the residence time can be separated from the vapor side. In various embodiments, the residence times for solid and vapor are separated.

[0231] The residence time of the solid in the preheating zone can be selected from approximately 5 minutes to approximately 60 minutes, for example, approximately 10 minutes depending on the temperature and time required to reach the preheating temperature. The heat transfer rate can be determined by the type and size of the particles, the physical and mechanical properties, and the heating parameters, but it determines the minimum residence time required for the solid to reach the given preheating temperature.

[0232] The residence time of the solid in the pyrolysis zone can be selected from approximately 10 minutes to approximately 120 minutes, for example, approximately 20 minutes, 30 minutes, or 45 minutes. Depending on the pyrolysis temperature in this zone, there should be sufficient time to allow carbonization chemistry to occur after the necessary heat transfer. For time periods of approximately 10 minutes or less, the temperature would need to be extremely high, for example, above 700°C, in order to remove a large amount of non-carbon elements. This temperature can promote rapid pyrolysis and the generation of vapors and gases derived from carbon itself, which is to be avoided when the intended product is solid carbon.

[0233] In static systems of various embodiments, an equilibrium conversion rate is reached at some point. If, as in some embodiments, vapor flows continuously over a solid while continuously removing volatile substances, the equilibrium constraint may be removed, allowing thermal decomposition and devolatilization to continue until the reaction rate approaches zero. The longer the time, the more likely it is that the remaining stubborn solid will remain substantially unchanged.

[0234] The residence time of the solid in the cooling zone in various embodiments can be selected from approximately 5 minutes to approximately 60 minutes, for example, approximately 30 minutes. Based on the cooling temperature in this zone, there should be sufficient time to cool the carbon solid to the desired temperature. The cooling rate and temperature determine the minimum residence time required for the carbon to cool. Additional time would be undesirable unless some secondary thermal decomposition is desired.

[0235] As mentioned above, the residence time of the vapor phase can be separately selected and controlled. The residence time of the vapor in the preheating zone can be selected from about 0.1 minutes to about 10 minutes, for example, about 1 minute. The residence time of the vapor in the pyrolysis zone can be selected from about 0.1 minutes to about 20 minutes, for example, about 2 minutes. The residence time of the vapor in the cooling zone can be selected from about 0.1 minutes to about 15 minutes, for example, about 1.5 minutes. Short vapor residence times promote the rapid sweep of volatile substances from the system, while long vapor residence times promote the reaction of components in the vapor phase with the solid phase.

[0236] The operating mode for the reactor and the entire system can be continuous, semi-continuous, batch, or any combination or variation thereof. In some embodiments, the BPU is a continuous counterflow reactor in which solids and vapors flow substantially in opposite directions. The BPU can also operate in batch mode, but using simulated counterflow of vapor, such as by periodically introducing and removing the vapor phase from the batch vessel.

[0237] Various flow patterns may be desired or observed. In chemical reactions and simultaneous separations involving multiple phases within multiple zones, the fluid dynamics can be extremely complex. Typically, solid flows can approach plug flows (well-mixed in the radial dimension), while vapor flows can approach fully mixed flows (high-speed transport in both radial and axial dimensions). Multiple intake and exhaust ports for vapor can contribute to the overall mixing.

[0238] The pressure within each zone can be selected and controlled independently. The pressure in each zone can be independently selected from approximately 1 kPa to approximately 3000 kPa, for example, approximately 101.3 kPa (atmospheric pressure). Independent zone pressure control is possible when multiple gas inlets and outlets are used, including vacuum ports for venting gas when zone pressures lower than atmospheric pressure are desired. Similarly, in a multi-reactor system, the pressure within each reactor can be independently selected and controlled.

[0239] In some embodiments, the process may be operated at atmospheric pressure for convenience. Operation at atmospheric pressure offers many advantages, ranging from machine simplicity to improved safety. In some embodiments, the pyrolysis zone may be operated at pressures of approximately 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute pressure).

[0240] Vacuum operations (e.g., 10–100 kPa) can facilitate the rapid sweep of volatile substances from a system. Higher pressures (e.g., 100–1000 kPa) may be useful when an off-gas is supplied to the high-pressure operation. Increased pressure may also be useful to facilitate heat transfer, chemical, or separation.

[0241] The step of separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids can be achieved within the reactor itself or using a separate separation unit. A substantially inert sweep gas can be introduced into one or more zones. The condensable vapor and non-condensable gas are then carried out from the zones into the sweep gas and out of the BPU.

[0242] The sweep gas may be, for example, N2, Ar, CO, CO2, H2, H2O, CH4, other light hydrocarbons, or combinations thereof. The sweep gas may first be heated before introduction, or, if obtained from a heated source, may be cooled.

[0243] Sweep gases remove volatile components more completely by removing them from the system before they condense or react further. Sweep gases allow volatile substances to be removed at a higher rate than could be obtained simply from volatilization at a given process temperature. Alternatively, the use of sweep gases allows milder temperatures to be used to remove a certain amount of volatile substances. The reason sweep gases enhance the removal of volatile substances is that the separation mechanism is not simply relative volatility, but rather the liberation of the liquid / vapor phase assisted by the sweep gas. By continuously depleting a given volatile species, sweep gases can reduce both the mass transfer limit and the thermodynamic limit of volatilization, so that much of it vaporizes and achieves thermodynamic equilibrium.

[0244] To produce highly fixed carbon products, it is crucial to remove gases containing large amounts of volatile organic carbon from subsequent processing steps. If not removed, volatile carbon may be adsorbed or absorbed by the pyrolysis solids, thereby requiring additional energy (cost) to obtain the purer form of carbon desired. Rapid removal of vapors may also increase the porosity of the pyrolysis solids. In various embodiments, higher porosity, such as that found in activated carbon products, is desirable.

[0245] In one embodiment, the sweep gas provides rapid vapor removal without requiring a large amount of inert gas, along with a relatively low process pressure such as atmospheric pressure.

[0246] In some embodiments, the sweep gas flows opposite to the flow direction of the feed material. In other embodiments, the sweep gas flows parallel to the flow direction of the feed material. In some embodiments, the flow pattern of the solids approaches a plugged flow, while the flow pattern of the sweep gas and the gas phase in general approaches a fully mixed flow within one or more zones.

[0247] The sweep may be performed within any one or more zones. In some embodiments, the sweep gas is introduced into the cooling zone and extracted from the cooling zone and / or the pyrolysis zone (along with the generated volatile substances). In some embodiments, the sweep gas is introduced into the pyrolysis zone and extracted from the pyrolysis zone and / or the preheating zone. In some embodiments, the sweep gas is introduced into the preheating zone and extracted from the pyrolysis zone. In these and other embodiments, the sweep gas may also be introduced into each of the preheating, pyrolysis, and cooling zones and extracted from each zone.

[0248] In some embodiments, the zone or group of zones in which isolation is performed are physically separate units from the BPU. Isolation units or zones may be located between zones, if desired. For example, there may be isolation units located between a pyrolysis zone and a cooling zone.

[0249] Sweep gas can be introduced continuously, especially when a solid flow is continuous. When the pyrolysis reaction is operated as a batch process, sweep gas can be introduced after a certain period or periodically to remove volatile substances. Even when the pyrolysis reaction is operated continuously, sweep gas can be introduced semi-continuously or periodically, if desired, using appropriate valves and controls.

[0250] The volatile substance-containing sweep gas can be obtained from one or more zones, and if obtained from multiple zones, it can be combined. The resulting gas stream, containing various vapors, can then be supplied to a process gas heater for controlling air exhaust, as described above and shown in Figure 8. Any known thermal oxidation unit can be employed. In some embodiments, the process gas heater is supplied with natural gas and air and reaches a temperature sufficient to substantially destroy the volatile substances contained therein.

[0251] The process gas heater effluent would be a hot gas stream containing water, carbon dioxide, and nitrogen. This effluent stream can be purged directly into an air exhaust if desired. In some embodiments, the energy content of the process gas heater effluent is recovered, for example, in a waste heat recovery unit. The energy content can also be recovered by heat exchange with another stream (such as sweep gas). The energy content can be utilized to directly or indirectly heat, or assist in heating, a unit somewhere in the process, such as a dryer or reactor. In some embodiments, essentially all of the process gas heater effluent is used for indirect heating (utility side) of a dryer. Process gas heaters may also employ fuels other than natural gas.

[0252] The yield of carbonaceous materials can vary depending on the aforementioned factors, including the feedstock and process conditions. In some embodiments, the net yield of solids as a percentage of the starting feedstock is at least 25%, 30%, 35%, 40%, 45%, 50%, or more on an anhydrous basis. The remainder is divided into condensable vapors such as terpenes, tars, alcohols, acids, aldehydes, or ketones; and non-condensable gases such as carbon monoxide, hydrogen, carbon dioxide, and methane. The relative amounts of condensable vapors compared to non-condensable gases, including any water present, are also determined by the process conditions.

[0253] With respect to carbon balance, in some embodiments, the net yield of carbon as the proportion of starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 70%, or more. For example, in some embodiments, the carbonaceous material contains about 40% to about 70% of the carbon contained in the starting carbon. The remaining carbon results in the formation of various substances, such as methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatic compounds, tars, terpenes, alcohols, acids, aldehydes, or ketones.

[0254] In alternative embodiments, some of these compounds are combined with carbon-rich solids to increase the carbon and energy content of the product. In these embodiments, some or all of the resulting gas stream from the reactor, which contains various vapors, may be condensed and then pass over cooled pyrolysis solids obtained from a cooling zone and / or separate cooling devices. These embodiments are described in further detail below.

[0255] Following the reaction and cooling within the cooling zone (if present), the carbonaceous solid may be introduced into a cooling apparatus. In some embodiments, the solid is collected and simply cooled at a slow rate. If the carbonaceous solid is reactive or unstable in air, it may be desirable to maintain an inert atmosphere and / or rapidly cool the solid to a temperature below 40°C, e.g., ambient temperature. In some embodiments, a water quench is employed for rapid cooling. In some embodiments, a fluidized bed is employed. The term "cooling apparatus" should be broadly interpreted to include containers, tanks, pipes, or parts thereof. In various embodiments, it will be understood that the cooling apparatus is different from a cooling unit or a cooling reactor.

[0256] In some embodiments, the process further includes operating a cooling device to cool the warm pyrolysis solids in a stream, thereby producing cold pyrolysis solids and superheated steam, with drying being performed, at least in part, with the superheated steam obtained from the cooling device. Optionally, the cooling device may be operated to first cool the warm pyrolysis solids with steam to a first cooling device temperature, and then cool them with air to a second cooling device temperature, the second cooling device temperature being lower than the first cooling device temperature, which relates to a reduced risk of combustion for the warm pyrolysis solids in the presence of air.

[0257] Following cooling to ambient conditions, the carbonaceous solid may be recovered and then stored, transported to another site operation, shipped to another site, or disposed of, exchanged, or sold. The solid may be fed into a unit for particle size reduction. Various size reduction units, including pulverizers, shredders, grinders, fine grinders, jet mills, and ball mills, are well known in the art.

[0258] This may include sieving or some other means for separation based on particle size. Sieving, if present, may be upstream or downstream of grinding. Some of the sieved material (e.g., large lumps) may be returned to the grinding unit. Smaller and larger particles may be recovered for separate downstream use. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as finely ground carbon or activated carbon products or strength enhancers.

[0259] Various additives may be introduced at any point in the process, before, during, or after any step disclosed herein. Additives can be broadly classified into process additives, selected to improve process performance such as carbon yield or thermal decomposition time / temperature in order to obtain a desired carbon purity; and product additives, selected to improve one or more properties of high-carbon bioreagents or downstream products that incorporate the reagent. Some additives may provide enhanced process and product properties, such as the overall yield of the bioreagent compared to its amount of biomass feedstock.

[0260] Additives may be added before, during, or after any one or more steps of the process, including adding them to the feedstock itself at any time before or after the feedstock is harvested. Additive treatment may be incorporated before, during, or after feedstock sizing, drying, or other preparation. Additives may be incorporated in or on feedstock supply facilities, transport trucks, loading / unloading equipment, storage bins, conveyors (including open or closed conveyors), drying equipment, process heaters, or any other unit. Additives may be added to the pyrolysis process itself anywhere using appropriate means for introducing the additives. Additives may be added after carbonization, or even after pulverization if desired.

[0261] In some embodiments, the additive is selected from metals, metal oxides, metal hydroxides, or combinations thereof. For example, the additive may be selected from, but is not limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0262] In some embodiments, the additive is selected from acids, bases, or salts thereof. For example, the additive may be selected from, but is not limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0263] In some embodiments, the additive is selected from metal halides. Metal halides are compounds between a metal and a halogen (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form a number of compounds with metals. Metal halides are generally obtained by direct bonding, or more generally, by neutralization of a basic metal salt with a hydrohalic acid. In some embodiments, the additive is selected from iron halides (FeX2 and / or FeX3), iron chloride (FeCl2 and / or FeCl3), iron bromide (FeBr2 and / or FeBr3), or their hydrates, and any combination thereof.

[0264] Additives can result in a final product with a higher energy content (energy density). The increase in energy content may be due to an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. Alternatively or additionally, the increase in energy content may be due to the removal of non-combustible materials or substances with a lower energy density than carbon. In some embodiments, additives reduce the amount of liquid formed for solid and gas formation, or for solid formation.

[0265] In various embodiments, additives chemically alter the starting biomass or treated biomass before pyrolysis to reduce cell wall rupture for greater strength / integrity. In some embodiments, additives may increase the fixed carbon content of the biomass feedstock before pyrolysis.

[0266] Additives can result in a final bioreagent with enhanced mechanical properties, such as yield strength, compressive strength, tensile strength, fatigue strength, impact strength, elastic modulus, bulk modulus, or shear modulus. Additives can enhance mechanical properties simply by their presence (e.g., the additive itself imparts strength to the mixture) or due to some transformation occurring within the additive phase or the resulting mixture. For example, reactions such as vitrification may occur within a portion of the bioreagent containing the additive, thereby increasing the final strength.

[0267] Chemical additives can be applied to moist or dry biomass feedstock. Additives can be applied as solid powders, sprays, mists, liquids, or vapors. In some embodiments, additives can be introduced by spraying a liquid solution (e.g., in an aqueous solution or solvent) or by immersion in a tank, bottle, bag, or other container.

[0268] In one embodiment, a pre-immersion treatment is employed, in which the solid feed material is immersed in a bath containing the additive for a sufficient period of time, either in batches or continuously, to allow the additive to penetrate the solid feed material.

[0269] In some embodiments, additives applied to the feedstock can reduce the energy required for pyrolysis and / or increase the yield of the carbonaceous product. In these and other embodiments, additives applied to the feedstock can provide desirable functionality for the intended use of the carbonaceous product, as further described below with respect to composition.

[0270] Processing capacity, or process capacity, can vary widely from small laboratory-scale units, including any pilot, demonstration, or semi-commercial scale, to fully commercial biorefineries. In various embodiments, process capacity is at least about 1 kg / day, 10 kg / day, 100 kg / day, 1 ton / day (all tonns are metric tons), 10 ton / day, 100 ton / day, 500 ton / day, 1000 ton / day, 2000 ton / day, or more.

[0271] In some embodiments, a portion of the generated solid is recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the BPU or reactor. By returning to the front end and passing through the process again, the fixed carbon of the treated solid increases. The generated or present solid, liquid, and gas streams in the process can be independently reused and passed to subsequent steps, or removed / purged from the process at any point.

[0272] In some embodiments, the pyrolyzed material is recovered and then fed into a separate reactor for further pyrolysis to produce a product with increased carbon purity. In some embodiments, the secondary process may be carried out in a simple container such as a steel drum through which a heated inert gas (such as heated N2) passes. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas, containing volatile substances, may be sent, for example, to a process gas heater or returned to the main BPU. To cool the final product, for example, another stream of inert gas, initially at ambient temperature, may pass through the solid to cool it and then return to an inert gas preheating system. In various embodiments, the secondary process takes place in a separate carbonization or pyrolysis reactor through which a preheated, substantially inert gas is injected to pyrolyze and carbonize the material.

[0273] Some variations of the present invention provide a high-carbon bioreagent generation system, the system is (a) A material supply system configured to introduce carbon-containing raw materials, (b) An optional drying device, which is operably connected to the material supply system and configured to remove moisture contained in the carbon-containing feed material. (c) A biomass processing unit comprising a plurality of zones, which is operably connected to a drying apparatus, wherein the biomass processing unit comprises at least one pyrolysis zone which is operably connected to a spatially separated cooling zone, and the biomass processing unit is configured with an outlet for removing condensable vapors and noncondensable gases from solids, (d) External cooling devices, which are arranged in operable communication with the biomass processing unit, (e) A carbon recovery device that is operably connected to the cooling device. It is equipped with.

[0274] Some modified forms provide a high-carbon bioreagent generation system, and this system, (a) A material supply system configured to introduce carbon-containing raw materials, (b) An optional drying device, which is operably connected to the material supply system and configured to remove moisture contained in the carbon-containing feed material. (c) An optional preheater, which is operably connected to the drying apparatus and configured to heat and / or moderately thermally decompose the feed material. (d) A pyrolysis reactor, configured to be operably connected to a preheater and to pyrolyze the feed material, (e) A cooling device configured to be operably connected to the pyrolysis reactor and to cool the pyrolysis solids, and (f) A carbon recovery device that is configured to be operationally connected to the cooling device. Equipped with, The system is configured with at least one gas outlet for removing condensable vapors and non-condensable gases from solids.

[0275] The material supply system can be physically integrated with the BPU, for example, through the use of a screw material supply system or auger mechanism for introducing the supply solids into one of the reactors or zones.

[0276] In some embodiments, the system further includes a preheating zone operably connected to the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) may be located within a single BPU or within separate BPUs.

[0277] Optionally, a drying device may be configured as a drying zone within the BPU. Optionally, a cooling device may be located within the BPU (i.e., configured as an additional cooling zone or integrated with the aforementioned cooling zone).

[0278] The system may include purging means for removing oxygen from the system. For example, the purging means may include one or more intake ports for introducing a substantially inert gas, and one or more outlet ports for removing the substantially inert gas and replaced oxygen from the system. In some embodiments, the purging means is a degasser operably arranged in communication between the dryer and the BPU.

[0279] The BPU can be configured with at least a first gas inlet and a first gas outlet. The first gas inlet and the first gas outlet may be located in communication with different zones or with the same zone.

[0280] In some embodiments, the BPU is configured with a second gas inlet and / or a second gas outlet. In some embodiments, the BPU is configured with a third gas inlet and / or a third gas outlet. In some embodiments, the BPU is configured with a fourth gas inlet and / or a fourth gas outlet. In some embodiments, each zone within the BPU is configured with a gas inlet and a gas outlet.

[0281] Gas inlets and outlets not only enable the introduction and recovery of steam, but gas outlets (probes) in particular also allow for precise process monitoring and control across various stages of the process, potentially encompassing all stages of the process. Precise process monitoring is expected to lead to improvements in yield and efficiency, both dynamically and over long periods, when operational history is available to adjust process conditions.

[0282] In some embodiments (see roughly Figure 4), a reaction gas probe is positioned to communicate operably with the pyrolysis zone. Such a reaction gas probe may be useful for extracting and analyzing gases to determine the degree of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as feed rate, inert gas sweep rate, temperature (of one or more zones), pressure (of one or more zones), additives, etc.

[0283] As intended herein, “monitoring and control” through a reaction gas probe should be interpreted as including the extraction of any one or more samples through the reaction gas probe, and, optionally, if deemed necessary or desirable, process preparation or instrument adjustment based on measurements using well-known process control principles (such as feedback, feedforward, proportional-integral-differential logic, etc.).

[0284] A reaction gas probe can be configured to extract a gas sample in several ways. For example, the sampling pipe may have a pressure lower than the pyrolysis reactor pressure, allowing a certain amount of gas to be easily extracted from the pyrolysis zone when the sampling pipe is opened. The sampling pipe may be under vacuum, for example, when the pyrolysis zone is close to atmospheric pressure. Typically, a reaction gas probe will be associated with one gas outlet, or a part of it (e.g., a pipe separated from the gas outlet pipe).

[0285] In some embodiments, both gas injection and gas output are utilized as reaction gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with the process sample ("sample sweep"). Such configurations can be used in zones that do not otherwise have gas inlets / outlets for substantially inert gas for processing, or where the reaction gas probes may be associated with separate gas inlets / outlets in addition to the process inlets and outlets. (In embodiments utilizing sample sweep) the sampling inert gas periodically introduced and extracted for sampling may even differ from the process inert gas, if desired, either for accuracy in the analysis or for introducing tracers in the analysis.

[0286] For example, the acetic acid concentration in the gas phase of the pyrolysis zone can be measured using a gas probe to extract the sample, which is then analyzed using an appropriate technique (gas chromatography (GC), mass spectrometry (MS), GC-MS, or Fourier transform infrared spectroscopy (FTIR)). The CO and / or CO2 concentrations in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity for gases / vapors. The terpene concentrations in the gas phase can be measured and used, for example, as an indicator of pyrolysis selectivity for liquids.

[0287] In some embodiments, the system further includes at least one additional gas probe operably connected to a cooling zone and / or a drying zone (if present) or a preheating zone (if present).

[0288] Gas probes for cooling zones may be useful, for example, to determine the degree of any additional chemistry occurring within the cooling zone. Gas probes within the cooling zone may also be useful as an independent measure of temperature (for example, in addition to thermoelectric thermometers placed within the cooling zone). This independent measure may correlate with some kind of measured quantity of the cooling temperature. The correlation may develop or be established separately after a period of process operation.

[0289] A gas probe for the drying zone may be useful, for example, for determining the degree of drying by measuring the moisture content. A gas probe in the preheating zone may be useful, for example, for determining the degree of any mild thermal decomposition that is occurring.

[0290] In one embodiment, a cooling zone is configured with a gas inlet, and a pyrolysis zone is configured with a gas outlet to generate a gas flow substantially opposite to the solid phase. Alternatively, or additionally, a preheating zone (if present) may be configured with a gas outlet to generate a gas flow substantially opposite to the solid phase. Alternatively, or additionally, a drying zone may be configured with a gas outlet to generate a substantially opposite flow.

[0291] The pyrolysis reactor or reactor can be selected from any suitable reactor configuration capable of carrying out the pyrolysis process. Exemplary reactor configurations include, but are not limited to, fixed-bed reactors, fluidized-bed reactors, co-flow reactors, augers, rotary cones, rotary drum kilns, calciners, roasters, moving-bed reactors, transport-bed reactors, ablative reactors, rotary cones, or microwave-assisted pyrolysis reactors.

[0292] In some embodiments where an auger is used, sand or another heat transfer medium can be optionally employed. For example, the feed material and sand can be supplied at one end of the screw. The screw mixes the sand and feed material and carries them through the reactor. The screw can provide good control over the residence time of the feed material and does not dilute the pyrolysis products with a medium or fluidizing gas. The sand can be reheated in a separate container.

[0293] In some embodiments where an ablative process is used, the feed material is moved at high speed against a hot metal surface. The melting of any char formed on the surface can maintain high-speed heat transfer. Such apparatus can prevent dilution of the product. Alternatively, the feed material particles may be suspended in a conveyor gas and introduced at high speed through a cyclone with heated walls.

[0294] In some embodiments where a fluidized bed reactor is used, the feedstock can be introduced into a bed of hot sand fluidized by a gas, which is typically a recycled product gas. The term “sand” as used herein also includes similar, substantially inert materials such as glass particles, recovered ash particles, and the like. The high heat transfer rate from the fluidized sand can result in rapid heating of the feedstock. Some melting may occur due to friction with the sand particles. Heat is typically supplied by heat transfer tubes through which a hot combustion gas flows.

[0295] A circulating fluidized bed reactor can be employed, in which gas, sand, and feedstock move together. Exemplary transport gases include recirculated product gas and combustion gas. The high heat transfer rate from the sand ensures rapid heating of the feedstock, and melting is expected to be stronger than in a conventional fluidized bed. Separators can be employed to separate the product gas from the sand and char particles. The sand particles can be reheated in a fluidizing burner vessel and then recirculated back into the reactor.

[0296] In some embodiments, the BPU is a continuous reactor comprising a feedstock inlet, a plurality of spatially separated zones configured for mixing with separately controlled temperatures within each zone, and a carbonaceous solids outlet, one of the zones configured with a first gas inlet for introducing a substantially inert gas into the BPU, and one of the zones configured with a first gas outlet.

[0297] In various embodiments, the reactor includes at least two, three, four, or more zones. Each zone is arranged in communication with separately adjustable heating means, independently selected from a group consisting of electric heat transfer, steam heat transfer, hot oil heat transfer, phase change heat transfer, waste heat transfer, and combinations thereof. In some embodiments, at least one zone is heated by an effluent stream from a process gas heater, if present.

[0298] The BPU may be configured to separately adjust the gas phase composition and gas phase residence time of at least two zones below it, including all zones present within the BPU.

[0299] The BPU may include a second gas inlet and / or a second gas outlet. In some embodiments, the BPU is configured with gas inlets in each zone. In these or other embodiments, the BPU is configured with gas outlets in each zone. The BPU is a parallel-flow or counter-flow reactor.

[0300] In some embodiments, the material supply system includes a screw or auger supply mechanism. In some embodiments, the carbonaceous solid discharge port includes a screw or auger output mechanism.

[0301] One embodiment involves a rotating furnace along with a screw material feeding system. A calciner is used. In these embodiments, part or all of the BPU rotates axially, i.e., around its central axis. The speed of rotation affects the flow pattern of the solids, as well as the heat and mass transport. Each zone may be configured with flights positioned on the inner wall to provide agitation of the solids. The flights may be independently adjustable within each zone.

[0302] Other means of stirring the solids, such as augers, screws, or paddle conveyors, may be employed. In some embodiments, the BPU includes a single continuous auger positioned across each zone. In other embodiments, the reactor includes a twin-screw configuration positioned across each zone.

[0303] Some systems are designed with the ability to maintain the approximate size of the feed material throughout the process—that is, to process the biomass feed material without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not include an auger, screw, or rake, which can easily reduce the size of the feed material being pyrolyzed.

[0304] In some embodiments of the present invention, the system further includes a process gas heater operably connected to an outlet from which condensable vapors and non-condensable gases are removed. The process gas heater is configured to receive a separate fuel (such as natural gas) and an oxidizer (such as air) into a combustion chamber suitable for the combustion of at least a portion of the fuel and condensable vapors. Certain non-condensable gases, such as CO or CH4, may also be oxidized to CO2.

[0305] When a process gas heater is employed, the system may include a heat exchanger positioned between the process gas heater and the drying apparatus, configured to utilize at least a portion of the combustion heat for the drying apparatus. This embodiment can significantly contribute to the overall energy efficiency of the process.

[0306] In some embodiments, the system further includes a material concentration unit, which is operably connected to a cooling device and configured to combine condensable vapor, in at least a partially condensed form, with solid material. The material concentration unit can increase the carbon content of the high-carbon bioreagent obtained from the carbon recovery unit.

[0307] The system further includes a separate pyrolysis zone adapted to further pyrolyze high-carbon bioreagents to further increase their carbon content. The separate pyrolysis zone may be a relatively simple container, unit, or apparatus, such as a tank, barrel, bottle, drum, tote, sack, or roll-off.

[0308] The entire system may be in a fixed location or can be made portable. The system may be constructed using modules that can simply be duplicated for practical scaling up. The system may also be constructed using the principles of economies of scale, as is well known in the equipment industry.

[0309] Several variations relating to the carbon concentration of solids are described further here. In some embodiments, the process for producing high-carbon bioreagents is (a) To supply carbon-containing raw materials including biomass, (b) optionally drying the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degas the feedstock to remove at least some of the interstitial oxygen contained in the feedstock, if any. (d) In the pyrolysis zone, the feed material is pyrolyzed at a pyrolysis temperature selected from about 250°C to about 700°C for at least 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) In the cooling zone, cool the hot pyrolysis solids at a cooling temperature lower than the pyrolysis temperature for at least 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (g) Optionally, cool the warm pyrolysis solids in a cooling device to produce cold pyrolysis solids. (h) Thereafter, in order to form concentrated pyrolysis solids with increased carbon content, at least a portion of the condensable vapor and / or at least a portion of the non-condensable gas from step (e) passes through the warm pyrolysis solids and / or the cold pyrolysis solids, (i) Recover high-carbon bioreagents containing at least a portion of concentrated pyrolysis solids within the carbon recovery unit. Includes.

[0310] In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through the warm pyrolysis solids in vapor and / or condensed form to produce concentrated pyrolysis solids with increased carbon content. In some embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through the warm pyrolysis solids to produce concentrated pyrolysis solids with increased carbon content.

[0311] In various embodiments, carbon enrichment will be understood to increase carbon content, energy content, and mass yield.

[0312] Alternatively, or additionally, vapors and gases may be brought into contact with the cold pyrolysis solids. In some embodiments, step (h) includes passing at least a portion of the condensable vapor from step (e) through the cold pyrolysis solids in vapor and / or condensed form to produce concentrated pyrolysis solids with increased carbon content. In some embodiments, step (h) includes passing at least a portion of the non-condensable gas from step (e) through the cold pyrolysis solids to produce concentrated pyrolysis solids with increased carbon content.

[0313] In one embodiment, step (h) includes substantially all of the condensable vapor from step (e) passing through the cold pyrolysis solids in vapor and / or condensed form to produce concentrated pyrolysis solids with increased carbon content. In another embodiment, step (h) includes substantially all of the non-condensable gas from step (e) passing through the cold pyrolysis solids to produce concentrated pyrolysis solids with increased carbon content.

[0314] The process may include various methods for treating or separating steam or gas before use for carbon enrichment. For example, an intermediate feed stream, consisting of at least a portion of condensable steam and at least a portion of non-condensable gas, obtained from step (e), may be supplied to a separation unit configured to produce at least first and second output streams. In one embodiment, the intermediate feed stream may include all of the condensable steam, all of the non-condensable gas, or both.

[0315] Separation techniques include, or can be used, distillation columns, flash chambers, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separation can be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and can also utilize differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity to the stationary phase, and any combination thereof.

[0316] In some embodiments, the first and second output streams are separated from the intermediate feed stream based on their relative volatility. For example, the separation unit may be a distillation column, a flash tank, or a condenser.

[0317] Accordingly, in some embodiments, the first output stream contains condensable vapor and the second output stream contains non-condensable gas. The condensable vapor may contain at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapor from pyrolysis may contain aromatic compounds such as benzene, toluene, ethylbenzene, and xylene, for example. Heavier aromatic compounds, such as persistent tars, may be present in the vapor. The non-condensable gas may contain at least one carbon-containing molecule selected from the group consisting of carbon monoxide, carbon dioxide, and methane.

[0318] In some embodiments, the first and second output streams may be separated from the intermediate feed stream based on relative polarity. For example, the separation unit may be a strip column, a packed bed, a chromatography column, or a membrane.

[0319] Accordingly, in some embodiments, the first output stream includes a polar compound, and the second output stream includes a nonpolar compound. The polar compound may include at least one carbon-containing molecule selected from the group consisting of methanol, furfural, and acetic acid. The nonpolar compound may include at least one carbon-containing molecule selected from the group consisting of carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives.

[0320] Step (h) can increase the total carbon content of the high-carbon bioreagent compared to a process that is otherwise identical without step (h). The degree of increase in carbon content can be, in various embodiments, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more.

[0321] In some embodiments, step (h) increases the fixed carbon content of the high-carbon bioreagent. In these or other embodiments, step (h) increases the volatile carbon content of the high-carbon bioreagent. The volatile carbon content is the carbon due to volatile substances in the reagent. Volatile substances may be, but are not limited to, hydrocarbons containing aliphatic or aromatic compounds (e.g., terpenes); oxygenates containing alcohols, aldehydes, or ketones; and various tars. Volatile carbon is usually bound to or adsorbed to solids under ambient conditions, but upon heating, the fixed carbon is released before it is oxidized, vaporized, or otherwise released as vapor.

[0322] Depending on the conditions associated with step (h), a certain amount of volatile carbon can become fixed carbon (e.g., via carbon formation from Boudois CO). Typically, the volatile substances are expected to enter the micropores of the fixed carbon and exist as condensed / adsorbed species, but are still relatively volatile. This residual volatility is more advantageous for fuel applications compared to product applications that require high surface area and porosity.

[0323] Step (h) may increase the energy content (e.g., energy density) of the high-carbon bioreagent. The increase in energy content may be due to an increase in total carbon, fixed carbon, volatile carbon, or even hydrogen. The degree of increase in energy content may be, in various embodiments, for example, about 1%, 2%, 5%, 10%, 15%, 25%, or even more.

[0324] Further separation is employed to recover one or more non-condensable gases or condensable vapors for use in the process or for further processing. For example, further processing may be involved to produce purified CO or synthesis gas.

[0325] As another example, the separation of acetic acid may be carried out, followed by its reduction to ethanol. The reduction of acetic acid can be achieved, at least in part, using hydrogen derived from the resulting non-condensable gas.

[0326] Condensable vapors can be used either in-process (e.g., by thermal oxidation) or for energy in carbon enrichment to increase the carbon content of high-carbon bioreagents. Certain non-condensable gases, such as CO or CH4, can be used either for energy in-process or as part of a substantially inert gas for a pyrolysis step. Any combination of those described above is also possible.

[0327] The potential benefit of including step (h) is that the gas stream is de-impregnated, resulting in a gas stream concentrated with CO and CO2. The resulting gas stream can be used for energy recovery, recycled for carbon enrichment of solids, and / or used as an inert gas within a reactor. Similarly, by separating the non-condensable gas from the condensable vapor, the CO / CO2 stream can be prepared for use as an inert gas, for example, within a reactor system or cooling system.

[0328] Another variation of the present invention is based on the recognition that the principle of the carbon enrichment step can be applied to any feedstock to which carbon is to be added.

[0329] In some variant forms, batch or continuous processes for producing high-carbon bioreagents are used. (a) To provide a solid stream containing carbon-containing material, (b) To provide a gas stream containing condensable carbon-containing vapor, non-condensable carbon-containing gas, or a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas, and (c) The gas stream passes through the solid stream under appropriate conditions in order to form a carbon-containing product with an increased carbon content compared to the carbon-containing material. Includes.

[0330] In some embodiments, the starting carbon-containing material is pyrolysis biomass or heat-dried biomass. The gas stream may be obtained during the integrated process supplying the carbon-containing material. Alternatively, the gas stream may be obtained from a separate processing of the carbon-containing material. The gas stream, or a portion thereof, may be obtained from an external source (e.g., a sawmill furnace). Mixtures of gas streams from various sources, as well as mixtures of carbon-containing materials, are possible.

[0331] In some embodiments, the process further includes recirculating or reusing the gas stream to repeat the process in order to further increase the carbon and / or energy content of the carbon-containing product. In some embodiments, the process further includes recirculating or reusing the gas stream to run the process in order to increase the carbon and / or energy content of a different feedstock than the carbon-containing material.

[0332] In some embodiments, the process further includes introducing a gas stream into a separation unit configured to produce at least first and second output streams, the gas stream comprising a mixture of condensable carbon-containing vapor and non-condensable carbon-containing gas. The first and second output streams may be separated based on relative volatility, relative polarity, or any other property. The gas streams may be obtained from separate processing of the carbon-containing material.

[0333] In some embodiments, the process further includes recirculating or reusing the gas stream to repeat the process in order to further increase the carbon content of the carbon-containing product. In some embodiments, the process further includes recirculating or reusing the gas stream to run the process in order to increase the carbon content of another feedstock.

[0334] Carbon-containing products may have an increased total carbon content, a high fixed carbon content, a high volatile carbon content, a high energy content, or any combination thereof, compared to the starting carbon-containing material.

[0335] In related variant forms, the high-carbon bioreagent generation system is (a) A material supply system configured to introduce carbon-containing raw materials, (b) An optional drying device, which is operably connected to the material supply system and configured to remove moisture contained in the carbon-containing feed material. (c) A BPU operably connected to a material supply system or drying apparatus, wherein the BPU includes at least one pyrolysis zone operably connected to a spatially separated cooling zone, and the BPU is configured with outlets for removing condensable vapors and noncondensable gases from solids, (d) Cooling device located in operational communication with the BPU, (e) A material concentration unit, which is operably connected to a cooling device and configured to allow condensable vapors and / or noncondensable gases to pass through the solids in order to form concentrated solids with increased carbon content, as well as (f) Carbon recovery unit, which is operably connected to the material concentration unit. It is equipped with.

[0336] The system may further include a preheating zone operably connected to the pyrolysis zone. In some embodiments, the drying apparatus is configured as a drying zone within the BPU. Each zone may be located within a single BPU or within separate BPUs. Cooling apparatus may also be located within the BPU.

[0337] In some embodiments, a cooling zone is configured with a gas inlet and a pyrolysis zone with a gas outlet to generate a substantially opposing flow of the gas phase to the solid phase. In these and other embodiments, a preheating zone and / or drying zone (or drying apparatus) is configured with a gas outlet to generate a substantially opposing flow of the gas phase to the solid phase.

[0338] In certain embodiments, the system incorporates a material concentration unit, which is, (i) Housing having an upper and lower part, (ii) an inlet located at the bottom of the housing, configured to transport condensable vapors and non-condensable gases, (iii) An outlet located on the upper surface of the housing, configured to transport a concentrated gas stream obtained from condensable vapor and noncondensable gas, (iv) A defined path between the upper and lower parts of the housing, and (v) A material transport system following a path, wherein the material transport system is configured to transport solids, and the housing is molded such that the solids adsorb at least a portion of condensable vapors and / or at least a portion of noncondensable gases. It is equipped with.

[0339] The present invention makes it possible to produce various compositions useful as high-carbon bioreagents, and products that incorporate these reagents. In some modified forms, the high-carbon bioreagents are produced by any process disclosed herein, such process is (a) To supply carbon-containing raw materials including biomass, (b) optionally drying the feed material in order to remove at least some of the moisture contained in the feed material. (c) Optionally, degas the feedstock to remove at least some of the interstitial oxygen contained in the feedstock, if any. (d) In the pyrolysis zone, the feed material is pyrolyzed at a pyrolysis temperature selected from about 250°C to about 700°C for at least 10 minutes in the presence of a substantially inert gas to produce hot pyrolysis solids, condensable vapor, and non-condensable gas. (e) Separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the hot pyrolysis solids, (f) In the cooling zone, cool the hot pyrolysis solids at a cooling temperature lower than the pyrolysis temperature for at least 5 minutes in the presence of a substantially inert gas in order to generate warm pyrolysis solids. (g) Cooling a warm pyrolysis solid to produce a cold pyrolysis solid, and, (h) Recover the high-carbon bioreagent containing at least a portion of the cold pyrolysis solids. This includes each of the steps.

[0340] In some embodiments, the reagent may contain, on an anhydrous basis, at least 55 wt%, for example, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, or at least 95 wt% total carbon. The total carbon includes at least fixed carbon and may further include carbon from volatile substances. In some embodiments, the carbon from volatile substances accounts for about at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the high-carbon bioreagent. Fixed carbon can be measured using ASTM D3172, while volatile carbon can be estimated using, for example, ASTM D3175.

[0341] High-carbon bioreagents may contain approximately 10 wt% or less of hydrogen on an anhydrous basis, for example, approximately 5 wt% or less. Bioreagents may contain approximately 1 wt% or less of nitrogen on an anhydrous basis, for example, approximately 0.5 wt% or less. Bioreagents may contain approximately 0.5 wt% or less of phosphorus on an anhydrous basis, for example, approximately 0.2 wt% or less. Bioreagents may contain approximately 0.2 wt% or less of sulfur on an anhydrous basis, for example, approximately 0.1 wt% or less.

[0342] Carbon, hydrogen, and nitrogen can be measured, for example, using ASTM D5373 for elemental analysis. Oxygen can be estimated, for example, using ASTM D3176. Sulfur can be measured, for example, using ASTM D3177.

[0343] Some embodiments provide reagents that contain or are essentially free of hydrogen (except from any moisture that may be present), nitrogen, phosphorus, or sulfur, and are substantially carbon + any ash and any moisture present. Thus, some embodiments provide materials that are anhydrous / ashless (DAF) based and contain less than 100% carbon.

[0344] Generally speaking, feedstocks such as biomass contain non-volatile species, including silica and various metals, which are not readily released during pyrolysis. It is certainly possible to use ashless feedstocks, in which case there should be no significant amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0345] Various amounts of non-combustible materials, such as ash, may be present. High-carbon bioreagents may contain about 10 wt% or less of non-combustible materials on an anhydrous basis, for example, about 5 wt%, about 2 wt%, about 1 wt%, or less. In some embodiments, the reagent contains little to no ash, or essentially no ash or other non-combustible materials at all. Thus, some embodiments provide essentially pure carbon, containing 100% carbon on an anhydrous basis.

[0346] Various amounts of moisture may be present. On a total mass basis, high-carbon bioreagents may contain at least 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 25 wt%, 35 wt%, 50 wt%, or more moisture. As intended herein, “moisture” is interpreted to include any form of water present in the bioreagent, including absorbed water, absorbed water molecules, chemical hydrates, and physical hydrates. Equilibrium moisture content may vary depending on at least the local environment, such as relative humidity. Moisture may also change during transport, preparation for use, and other logistics. Moisture can be measured, for example, using ASTM D3173.

[0347] High-carbon bioreagents can have a variety of "energy content," which for the purposes of this discussion means an energy density based on the higher heat generation associated with the complete combustion of the oven-dry reagent. For example, high-carbon bioreagents may have an energy content of at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In some embodiments, the energy content is between approximately 14,000 and 15,000 Btu / lb. The energy content can be measured, for example, using ASTM D5865.

[0348] High-carbon bioreagents can be formed into powders such as coarse or fine powders. For example, in embodiments, the reagents can be formed into powders with an average mesh size of approximately 200 mesh, 100 mesh, 100 mesh, 50 mesh, 10 mesh, 6 mesh, 4 mesh, or 2 mesh.

[0349] In some embodiments, high-carbon bioreagents are formed into structures containing compressed, bound, or aggregated particles. The starting materials for forming these objects may be in powder form of the reagent, such as intermediates obtained by micronization. The objects may be formed by mechanical compression or other forces, optionally using a binder or other means to bring the particles together into a mass.

[0350] In some embodiments, the high-carbon bioreagent is produced in the form of a structure whose structure is substantially derived from the feedstock. For example, a feedstock chip may produce a product chip of the high-carbon bioreagent. Alternatively, a feedstock cylinder may produce a high-carbon bioreagent cylinder, which is somewhat smaller but otherwise retains the basic structure and shape of the starting material.

[0351] High-carbon bioreagents according to the present invention can be produced or formed as objects having a minimum dimension of at least about 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, or more. In various embodiments, the minimum or maximum dimension may be length, width, or diameter.

[0352] Other variations of the present invention relate to the incorporation of additives into the process, into the product, or both. In some embodiments, the high-carbon bioreagent comprises at least one process additive incorporated during the process. In these or other embodiments, the reagent comprises at least one product additive introduced into the reagent following the process.

[0353] In some embodiments, the high-carbon bioreagent is an anhydrous base. Total carbon content of 55 wt% or more; Hydrogen at a concentration of 5 wt% or less; Less than 1 wt% nitrogen; Phosphorus at 0.5 wt% or less; 0.2 wt% or less of sulfur; and Additives selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof. Includes.

[0354] Additives may be selected from, but are not limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0355] In some embodiments, the high-carbon bioreagent is an anhydrous base. Total carbon content of 55 wt% or more; Hydrogen at a concentration of 5 wt% or less; Less than 1 wt% nitrogen; Phosphorus at 0.5 wt% or less; 0.2 wt% or less of sulfur; and Additives selected from acids, bases, or their salts Includes.

[0356] The additives may be selected from, but are not limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0357] In one embodiment, the high-carbon bioreagent is an anhydrous base. Total carbon content of 55 wt% or more; Hydrogen at a concentration of 5 wt% or less; Less than 1 wt% nitrogen; Phosphorus at 0.5 wt% or less; Sulfur content of 0.2 wt% or less; A first additive selected from metals, metal oxides, metal hydroxides, metal halides, or combinations thereof; and A second additive selected from acids, bases, or salts thereof. Includes, The first additive is different from the second additive.

[0358] The first additive may be selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof. The second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromide, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

[0359] A certain high-carbon bioreagent can basically consist of an anhydrous base of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible materials, and additives selected from the group consisting of magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomite lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0360] A certain high-carbon bioreagent can basically consist of an anhydrous base of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustible materials, and additives selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, and combinations thereof.

[0361] The amount of additives (total additives) can vary considerably, ranging from approximately 0.01 wt% to approximately 25 wt%, including approximately 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, or 20 wt%. It will be understood that when relatively large amounts of additives are incorporated, such as more than approximately 1 wt%, the energy content calculated based on the total reagent weight (including additives) will decrease. Nevertheless, in various embodiments, high-carbon bioreagents containing additives will still have an energy content of at least approximately 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0362] The above description relating to the product form also applies to embodiments that incorporate additives. In fact, some embodiments incorporate additives as binders or modifiers to enhance the final properties for a particular application.

[0363] In some embodiments, the majority of the carbon contained in high-carbon bioreagents is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. There may be certain market principles (e.g., Renewable Identification Number, tax credits, etc.) where value is attributable to the renewable carbon content in high-carbon bioreagents.

[0364] In one embodiment, fixed carbon may be classified as non-renewable carbon (e.g., from coal), while volatile carbon may be added separately, but it may be renewable carbon that increases not only the energy content but also the renewable carbon value.

[0365] The high-carbon bioreagents produced as described herein are useful for a wide variety of carbonaceous products. High-carbon bioreagents can themselves be desirable market products. High-carbon bioreagents such as those provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including a high renewable carbon content) compared to the state of the art in question.

[0366] In a modified form, the product may be obtained by the disclosed process or may include any high-carbon bioreagents described in the compositions described herein, or any part, combination, or derivative thereof.

[0367] Generally speaking, high-carbon bioreagents can be used for various purposes: they can be combusted to generate energy (including electricity and heat); they can be partially oxidized or steam reformed to produce synthesis gas; they can be utilized for their adsorbent or absorbent properties; they can be utilized for their reactivity during metal refining (such as reduction of metal oxides) or other production processes; or they can be utilized in carbon steel and various other metal alloys for their material properties. Essentially, high-carbon bioreagents can be used for any market application of carbon-based commodities or advanced materials, including specialty uses that may be developed.

[0368] Prior to suitability for any product application or actual use, the disclosed high-carbon bioreagents can be modified in various ways, including analysis, measurement, and optionally (e.g., through additives). Beyond chemical composition and energy content, some properties of potential interest include, to name a few, density, particle size, surface area, microporosity, absorption rate, adsorption capacity, binding capacity, reactivity, desulfurization activity, and basicity.

[0369] Products or materials that can incorporate these high-carbon bioreagents include, but are not limited to, carbon-based blast furnace addition products, carbon-based taconite pellet addition products, ladle addition carbon-based products, MET coke carbon-based products, coal substitutes, carbon-based coking products, carbon coke powder products, fluidized bed carbon-based feedstocks, carbon-based furnace addition products, injectable carbon-based products, pulverized carbon-based products, stoker carbon-based products, carbon electrodes, or activated carbon products.

[0370] The use of disclosed high-carbon bioreagents in metal production can reduce slag, increase overall efficiency, and mitigate life-cycle environmental impacts. Therefore, embodiments of the present invention are particularly suitable for metal processing and manufacturing.

[0371] Some variations of the present invention utilize high-carbon bioreagents as carbon-based blast furnace addition products. A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals such as (but not limited to) iron. Smelting is a form of smelting whose primary use is to produce metals from their ore. Smelting uses heat and chemical reducing agents to decompose the ore. Carbon and / or carbon-derived carbon monoxide remove oxygen from the ore, leaving the elemental metal.

[0372] The reducing agent may consist of or contain high-carbon bioreagents. In a blast furnace, high-carbon bioreagents, ore, and usually limestone may be continuously supplied from the top of the furnace, while air (optionally oxygen-concentrated) is blown into the bottom of the chamber, causing chemical reactions to occur throughout the furnace as the material moves downward. The final products are usually the molten metal and slag phase removed from the bottom, as well as the combustion exhaust gases exiting from the top of the furnace. The downward flow of ore in contact with the rising flow of hot, carbon monoxide-concentrated gas is a countercurrent process.

[0373] The quality of carbon in a blast furnace is measured by its resistance to decomposition. The role of carbon as a permeation medium is crucial for rational blast furnace operation. Carbon decomposition varies depending on its location within the furnace, involving a combination of reactions with CO2, H2O, or O2, as well as abrasion between carbon particles and other components of the charged fuel. Decomposed carbon particles can cause plugging and performance degradation.

[0374] Coke reactivity testing is a highly valued measurement of carbon performance in blast furnaces. This test has two components: the Coke Reactivity Index (CRI) and the Coke Strength after Reaction (CSR). Carbon-based materials with low CRI values ​​(high reactivity) and high CSR values ​​can provide improved blast furnace performance. CRI can be measured according to any suitable method well known in the art, such as by the arrival-based ASTM method DS341.

[0375] In some embodiments, when the high-carbon bioreagent is mixed with another carbon source, for example, up to about 10 wt% or more, it provides a final carbon product with properties suitable for combustion in a blast furnace.

[0376] The strength of high-carbon bioreagents can be measured by any suitable method known in the art, such as by a drop-shatter test or a CSR test. In some embodiments, when mixed with another carbon source, the high-carbon bioreagent provides a final carbon product having at least about 50%, 60%, or 70% CSR. Combination products also provide a final coke product with reactivity suitable for combustion in a blast furnace. In some embodiments, the product has a CRI such that the high-carbon bioreagent is suitable for use as an additive or as a substitute for met coal, met coke, carbon coke powder, foundry coke, or injectable coal.

[0377] Some embodiments employ one or more additives in sufficient quantities to provide a high-carbon bioreagent that, when added to another carbon source (e.g., coke) having a CRI or CSR unsuitable for use as a blast furnace product, provides a composite product having a CRI and / or CSR sufficient for use in a blast furnace. In some embodiments, one or more additives are present in sufficient quantities to provide a high-carbon bioreagent having a CRI of up to about 40%, 30%, or 20%.

[0378] In some embodiments, one or more additives selected from alkaline earth metals, or their oxides or carbonates, are introduced during or after the process of producing high-carbon bioreagents. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate may be introduced as additives. The addition of these compounds before, during, or after pyrolysis may increase or decrease the reactivity of the high-carbon bioreagent in the blast furnace. These compounds may result in stronger materials, i.e., higher CSR, thereby increasing blast furnace efficiency. Furthermore, additives such as those selected from alkaline earth metals, or their oxides or carbonates, may result in lower emissions (e.g., SO2).

[0379] In some embodiments, high-carbon bioreagents contain not only a high fixed carbon content, as described above, but also a considerably high proportion of volatile carbon. Volatile substances are expected to have better mass transport to metal oxides at lower temperatures and may therefore be desirable for metal oxide reduction. Compared to fossil fuel-based products such as coke, high-carbon bioreagents can have sufficient strength as well as more fixed and volatile carbon, which results in greater reactivity.

[0380] In some embodiments, the blast furnace substitute product is a high-carbon bioreagent according to the present invention, comprising at least about 55 wt% carbon, less than or equal to about 0.5 wt% sulfur, less than or equal to about 8 wt% non-combustible material, and a calorific value of at least about 11,000 Btu per pound. In some embodiments, the blast furnace substitute product further comprises about 0.035 wt% or less phosphorous acid, about 0.5 wt% to about 50 wt% volatile matter, and optionally one or more additives. In some embodiments, the blast furnace substitute product comprises about 2 wt% to about 15 wt% dolomite, about 2 wt% to about 15 wt% dolomite lime, about 2 wt% to about 15 wt% bentonite, and / or about 2 wt% to about 15 wt% calcium oxide. In some embodiments, the blast furnace substitute product has dimensions substantially in the range of about 1 cm to about 10 cm.

[0381] In some embodiments, the high-carbon bioreagents according to the present invention are useful as a substitute for foundry coke. Foundry coke is generally characterized by having a carbon content of at least about 85 wt%, a sulfur content of about 0.6 wt%, volatile substances of about 1.5 wt% or less, ash of about 13 wt% or less, moisture of about 8 wt% or less, phosphorus of about 0.035 wt%, a CRI value of about 30, and dimensions ranging from about 5 cm to about 25 cm.

[0382] Some variations of the present invention utilize high-carbon bioreagents as carbon-based taconite pellet addition products. The ores used in the production of iron and steel are iron oxides. The main iron oxide ores are hematite, limonite (also called brown iron ore), taconite, and magnetite / black ore. Taconite is a low-grade but important ore and contains both magnetite and hematite. The iron content of taconite is generally 25 wt% to 30 wt%. Blast furnaces typically require iron-containing ore of at least 50 wt% for efficient operation. Iron ore can undergo beneficiation, including crushing, sieving, tumbling, flotation, and magnetic separation. The refined ore is concentrated to over 60% iron and is often formed into pellets before shipment.

[0383] For example, taconite can be ground into a fine powder and bound with binders such as bentonite clay and limestone. For instance, pellets about 1 centimeter in diameter containing approximately 65 wt% iron can be formed. The pellets are burned to oxidize the magnetite to hematite. The pellets are durable, which ensures that the blast furnace charge remains sufficiently porous so that heated gases can pass through and react with the pelletized ore.

[0384] Taconite pellets can be supplied to a blast furnace to produce iron, as previously mentioned in relation to blast furnace addition products. In some embodiments, a high-carbon bioreagent is introduced into the blast furnace. In these and other embodiments, the high-carbon bioreagent is incorporated into the taconite pellet itself. For example, after beneficiation, taconite ore powder is mixed with a high-carbon bioreagent and a binder, rolled into small bodies, and then hardened. In such embodiments, taconite carbon pellets with a suitable composition can be conveniently introduced into the blast furnace without requiring a separate source of carbon.

[0385] Some variations of the present invention utilize high-carbon bioreagents as ladle-addition carbon products. A ladle is a container used to transport and pour molten metal. Casting ladles are used to pour molten metal into molds to produce castings. Transfer ladles are used to transport large quantities of molten metal from one process to another. Transfer ladles are used for processes occurring within the ladle to alter several aspects of the molten metal, such as the conversion of cast iron to ductile cast iron by adding various elements to the ladle.

[0386] High-carbon bioreagents can be introduced into any type of ladle, but typically the carbon will be added to the processing ladle in an appropriate amount based on the target carbon content. The carbon introduced into the processing ladle may be in the form of a fine powder for good mass transport to the final carbon composition. In some embodiments, when the high-carbon bioreagent according to the present invention is used as a ladle addition product, the minimum dimensions are about 0.5 cm, e.g., about 0.75 cm, about 1 cm, about 1.5 cm, or more.

[0387] In some embodiments, the high-carbon bioreagents according to the present invention are useful as ladle addition carbon additives in any basic oxygen converter or electric arc furnace facility where ladle addition of carbon is used (e.g., added to ladle carbon during steelmaking). In some embodiments, the ladle addition carbon additive is a high-carbon bioreagent containing at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous acid, and at least about 11,000 BTU per pound.

[0388] In some embodiments, the ladle carbon additive further contains up to about 5 wt% manganese, up to about 5 wt% calcium oxide, and / or up to about 5 wt% dolomite lime. In some embodiments, the ladle carbon additive has a minimum dimension of about 1 / 4 inch. In some embodiments, the ladle carbon product has a maximum dimension of about 1 / 2 inch. In some embodiments, the ladle carbon additive has a minimum dimension of about 1 / 4 inch and a maximum dimension of about 1 / 2 inch. In some embodiments, the ladle carbon product is substantially free of fossil fuels.

[0389] Directly reduced iron (DRI), also known as sponge iron, is produced from the direct reduction of iron ore (in the form of lumps, pellets, or powder) by a reducing gas generated from natural gas or coal. The reducing gas is typically synthesis gas, a mixture of hydrogen and carbon monoxide acting as reducing agents. High-carbon bioreagents, such as those provided herein, can be converted into a gas stream containing CO to act as reducing agents to produce directly reduced iron.

[0390] Iron nuggets are a high-quality steelmaking and iron casting supply material. Iron nuggets are essentially all iron and carbon, containing little to no gangue (slag) and having low levels of residual metal. They are a high-grade pig iron product with excellent shippable and handling properties. The carbon contained in the iron nuggets, or any portion thereof, may be high-carbon bioreagents provided herein. Iron nuggets can be produced through the reduction of iron ore in a rotary hearth furnace using high-carbon bioreagents as a reducing agent or energy source.

[0391] Some variations of the present invention utilize high-carbon bioreagents as metallurgical coke carbon products. Metallurgical coke, also known as "met" coke, is a carbon material commonly produced by the decomposition distillation of various mixtures of bituminous coal. The final solid is an insoluble carbon called metallurgical coke. As a result of the loss of volatile gases and partial dissolution, met coke has an open, porous morphology. met coke has very low volatile components. However, ash components, which were part of the original bituminous coal feedstock, remain encapsulated within the resulting carbon. met coke feedstock is available in a wide range of sizes, from fine powder to basketball-sized chunks.

[0392] Metallurgical coke is used when high-quality, robust, elastic, and wearable carbon is required. Applications include, but are not limited to, conductive floor finishes, friction materials (e.g., carbon linings), foundry coatings, casting carburizers, corrosive materials, drilling applications, reducing agents, heat treatment agents, ceramic fillers, electrolytic processes, and oxygen elimination.

[0393] MET coke is characterized by having a calorific value of at least about 11,000 to 14,000 Btu per pound and an ash content of at least about 10 wt%. Accordingly, in some embodiments, the MET coke substitute includes a high-carbon bioreagent according to the present invention, containing at least about 80 wt%, 85 wt%, or 90 wt% carbon, less than about 0.8 wt% sulfur, less than about 3 wt% volatile substances, less than about 15 wt% ash, less than about 13 wt% moisture, and less than about 0.035 wt% phosphorus. In some embodiments, the MET coke substitute contains at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous acid, and a calorific value of at least about 11,000 Btu per pound. In some embodiments, the MET coke substitute further contains about 2 wt% to about 15 wt% of dolomite, for example, about 1 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt% of dolomite. In some embodiments, the MET coke substitute further contains about 2 wt% to about 15 wt% bentonite, for example, about 1 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt% bentonite. In some embodiments, the MET coke substitute further contains about 2 wt% to about 15 wt% of calcium oxide, for example, about 1 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt% of calcium oxide. In some embodiments, the MET coke substitute further contains about 2 wt% to about 15 wt% of dolomite lime, for example, about 1 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt% of dolomite lime.In some embodiments, the MET coke substitute comprises about 2 wt% to about 15 wt% dolomite, about 2 wt% to about 15 wt% bentonite, about 2 wt% to about 15 wt% calcium oxide, and / or any combination of about 2 wt% to about 15 wt% dolomite lime. When used as a MET coke substitute, the high-carbon bioreagent according to the present invention may have a size ranging, for example, from about 2 cm to about 15 cm. In some embodiments, the MET coke substitute has a minimum dimension of about 3 / 4 inch. In some embodiments, the MET coke substitute has a maximum dimension of about 4 inches. In some embodiments, the MET coke substitute has a minimum dimension of about 3 / 4 inch and a maximum dimension of about 4 inches. In some embodiments, the MET coke substitute is substantially fossil fuel-free.

[0394] In some embodiments, the MET coke substitute further contains additives such as chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorspar, calcium oxide, lime, dolomite lime, bentonite, and combinations thereof.

[0395] Some variations of the present invention utilize high-carbon bioreagents as a coal substitute. Any process or system that uses coal can, in principle, be adapted to use high-carbon bioreagents.

[0396] In some embodiments, high-carbon bioreagents combine with one or more carbon-based products to form a composite product that has a higher rank than the carbon-based products and / or emits fewer emissions during combustion than pure carbon-based products.

[0397] For example, lower-grade coals, such as subvitaminous coal, can be used in applications requiring higher coal products, such as bituminous coal, by combining them with a selected amount of a high-carbon bioreagent according to the present invention. In other embodiments, the grade of a blended coal product (e.g., a combination of several coals of different grades) can be increased by combining the blended coal with a certain amount of a high-carbon bioreagent. The amount of high-carbon bioreagent mixed with the coal product may vary depending on the grade of the coal product, the properties of the high-carbon bioreagent (e.g., carbon content, calorific value, etc.), and the desired grade of the final composite product.

[0398] For example, anthracite is generally characterized by having at least about 80 wt% carbon, about 0.6 wt% sulfur, about 5 wt% volatile substances, up to about 15 wt% ash, up to about 10 wt% water, and a calorific value of about 29 MJ / kg (approximately 12,494 Btu / lb). In some embodiments, anthracite substitutes are high-carbon bioreagents according to the present invention, containing at least about 80 wt% carbon, about 0.6 wt% or less sulfur, about 15 wt% or less ash, and a calorific value of at least about 12,000 Btu / lb.

[0399] In some embodiments, high-carbon bioreagents according to the present invention may be useful as fuel coal substitutes. Fuel coal products are generally characterized by high sulfur levels, high phosphorus levels, high ash content, and a calorific value of up to about 15,000 Btu / lb. In some embodiments, the fuel coal substitute is a high-carbon bioreagent containing about 0.5 wt% or less of sulfur, about 4 wt% or less of ash, and a calorific value of at least about 12,000 Btu / lb.

[0400] Some variations of the present invention utilize high-carbon bioreagents as carbon-based coking products. Any coking process or system can be adapted to use high-carbon bioreagents to produce coke or to use them as coke feedstock.

[0401] In some embodiments, the high-carbon bioreagent according to the present invention is useful as a fuel coal or coke substitute. For example, the fuel coal or coke substitute may consist of a high-carbon bioreagent containing at least about 50 wt% carbon, about 8 wt% or less ash, about 0.5 wt% or less sulfur, and at least about 11,000 Btu / lb in calorific value. In other embodiments, the fuel coke substitute further contains about 0.5 wt% to about 50 wt% of volatile substances. The fuel coal or coke substitute may contain about 0.4 wt% to about 15 wt% of water.

[0402] In some embodiments, the high-carbon bioreagents according to the present invention are useful as substitutes for petroleum (PET) coke or calcined petroleum coke. Calcined petroleum coke is generally characterized by having at least about 66 wt% carbon, up to about 4.6 wt% sulfur, up to about 5.5 wt% volatile substances, up to about 19.5 wt% ash, and up to about 2 wt% water, and is also typically about 3 mesh or smaller. In some embodiments, the calcined petroleum coke substitute is a high-carbon bioreagent containing at least about 66 wt% carbon, up to about 4.6 wt% sulfur, up to about 19.5 wt% ash, and up to about 2 wt% water, and is about 3 mesh or smaller.

[0403] In some embodiments, the high-carbon bioreagents according to the present invention are useful as coking carbon substitutes (e.g., co-combusted with raw coal in a coking furnace). In one embodiment, the coking carbon substitute is a high-carbon bioreagent containing at least about 55 wt% carbon, about 0.5 wt% or less sulfur, about 8 wt% or less noncombustible material, and at least about 11,000 Btu per pound. In some embodiments, the coking carbon substitute is a high-carbon bioreagent containing at least about 55 wt% carbon, about 0.4 wt% or less sulfur, about 0.035 wt% or less phosphorous acid, and at least about 11,000 Btu per pound. In some embodiments, the coking carbon substitute has a minimum dimension of about 3 / 4 inch. In some embodiments, the coking carbon substitute is substantially fossil fuel-free. In some embodiments, the coking carbon substitute comprises about 0.5 wt% to about 50 wt% of volatile substances and one or more additives.

[0404] Some variations of the present invention utilize a high-carbon bioreagent as a carbon coke powder product, which typically has fine particle sizes such as 6 mm, 3 mm, 3 mm, 1 mm, or less. In some embodiments, the high-carbon bioreagent according to the present invention is useful as a carbon coke powder substitute. Carbon coke powder is generally characterized by having a maximum size of about 6 mm or less, a carbon content of at least about 80 wt%, 0.6 to 0.8 wt% sulfur, 1 to 20 wt% volatile substances, up to about 13 wt% ash, and up to about 13 wt% moisture. In some embodiments, the carbon coke powder substitute is a high-carbon bioreagent according to the present invention, comprising at least about 80 wt% carbon, about 0.8 wt% or less sulfur, about 20 wt% or less volatile substances, about 13 wt% or less ash, about 13 wt% or less moisture, and a maximum size of about 6 mm.

[0405] In some embodiments, high-carbon bioreagents according to the present invention are useful, for example, as a carbon coke substitute in taconite pellet production or iron production processes. In some embodiments, the carbon coke substitute is a high-carbon bioreagent containing at least about 55 wt% carbon, less than or equal to about 0.4 wt% sulfur, less than or equal to about 0.035 wt% phosphorous acid, and at least about 11,000 Btu per pound. In some embodiments, the carbon coke substitute has a minimum dimension of about 1 / 8 inch. In some embodiments, the carbon coke substitute is substantially fossil fuel-free.

[0406] Some variations of the present invention utilize high-carbon bioreagents as feedstocks for various fluidized bed furnaces, or as substitutes for carbon-based feedstocks in fluidized bed furnaces. Carbon can be employed in fluidized bed furnaces for complete combustion, partial oxidation, vaporization, steam reforming, or similar processes. Carbon can be converted primarily into synthesis gas for various downstream uses, including the production of energy (e.g., cogeneration) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel fuel).

[0407] In some embodiments, high-carbon bioreagents according to the present invention are useful as fluidized bed carbon substitutes in any fluidized bed furnace where coal may be used (e.g., for process heat or energy generation). In some embodiments, the fluidized bed substitute is a high-carbon bioreagent containing at least about 55 wt% carbon, less than or equal to about 0.4 wt% sulfur, less than or equal to about 0.035 wt% phosphorous acid, and at least about 11,000 Btu per pound. In some embodiments, the fluidized bed substitute has a minimum dimension of about 1 / 4 inch. In some embodiments, the fluidized bed substitute has a maximum dimension of about 2 inches. In some embodiments, the fluidized bed substitute has a minimum dimension of about 1 / 4 inch and a maximum dimension of about 2 inches. In some embodiments, the fluidized bed substitute is substantially fossil fuel-free.

[0408] Some variations of the present invention utilize high-carbon bioreagents as carbon-based furnace addition products. Carbon-based furnace addition products are generally characterized by high sulfur levels, high phosphorus levels, and high ash content, which contribute to the degradation of metal products and generate air pollution. In some embodiments, the furnace addition substitute containing high-carbon bioreagents contains about 0.5 wt% or less of sulfur, about 4 wt% or less of ash, about 0.03 wt% or less of phosphorous acid, and a maximum dimension of about 7.5 cm. In some embodiments, the furnace addition substitute contains about 0.5 wt% to about 50 wt% of volatile substances and about 0.4 wt% to about 15 wt% of water. In some embodiments, the furnace addition substitute is a high-carbon bioreagent containing at least about 80 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous acid, less than about 5 wt% manganese, less than 5 wt% fluorspar, and at least about 11,000 Btu / lb of heat. In some embodiments, the furnace addition substitute further contains about 5 wt% to about 10 wt% dolomite, for example, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% dolomite. In some embodiments, the furnace addition substitute further contains about 5 wt% to about 10 wt% dolomite lime, for example, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% dolomite lime. In some embodiments, the furnace addition substitute further contains about 5 wt% to about 10 wt% calcium oxide, for example, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% calcium oxide. In some embodiments, the furnace addition substitute further contains about 5 wt% to about 10 wt% dolomite lime and about 5 wt% to about 10 wt% calcium oxide. In some embodiments, the furnace addition substitute further contains about 5 wt% to about 10 wt% dolomite, about 5 wt% to about 10 wt% dolomite lime and about 5 wt% to about 10 wt% calcium oxide. In some embodiments, the furnace addition substitute has a minimum dimension of about 3 / 4 inch. In some embodiments, the furnace addition substitute has a maximum dimension of about 2 inches.In some embodiments, the reactor additive has a minimum dimension of about 3 / 4 inch and a maximum dimension of about 2 inches. In some embodiments, the reactor additive is substantially fossil fuel-free.

[0409] In some embodiments, high-carbon bioreagents according to the present invention are useful as furnace addition carbon additives in any basic oxygen converter or electric arc furnace facility where furnace addition carbon may be used. For example, furnace addition carbon may be added to scrap steel during steelmaking in an electric arc furnace facility. For electric arc furnace applications, high-purity carbon is desirable so that impurities are not reintroduced into the process after the initial removal of impurities.

[0410] In some embodiments, the furnace carbon additive is a high-carbon bioreagent according to the present invention, comprising at least about 80 wt% carbon, less than or equal to about 0.5 wt% sulfur, less than or equal to about 8 wt% non-combustible material, and at least about 11,000 Btu per pound. In some embodiments, the furnace carbon additive further comprises up to about 5 wt% manganese, up to about 5 wt% fluorite, about 5 wt% to about 10 wt% dolomite, about 5 wt% to about 10 wt% dolomite lime, and / or about 5 wt% to about 10% calcium oxide.

[0411] Some variations of the present invention utilize high-carbon bioreagents as stoker furnace carbon-based products. In some embodiments, high-carbon bioreagents according to the present invention are useful as stoker coal substitutes in any stoker furnace where coal may be used (e.g., for process heat or energy generation). In some embodiments, the stoker carbon substitute is a high-carbon bioreagent containing at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous acid, and at least about 11,000 BTU per pound. In some embodiments, the stoker carbon substitute has a minimum dimension of about 1 inch. In some embodiments, the stoker carbon substitute has a maximum dimension of about 3 inches. In some embodiments, the stoker carbon substitute has a minimum dimension of about 1 inch and a maximum dimension of about 3 inches. In some embodiments, the stoker carbon substitute is substantially fossil fuel-free.

[0412] Some variations of the present invention utilize high-carbon bioreagents as injectable (e.g., finely ground) carbon-based materials. In some embodiments, high-carbon bioreagents according to the present invention are useful as injection-grade calcined petroleum coke substitute products. Injection-grade calcined petroleum coke is generally characterized by having at least about 66 wt% carbon, about 0.55 to about 3 wt% sulfur, up to about 5.5 wt% volatile substances, up to about 10 wt% ash, up to about 2 wt% moisture, and a size of about 6 mesh or less. In some embodiments, the calcined petroleum coke substitute product is a high-carbon bioreagent containing at least about 66 wt% carbon, about 3 wt% or less sulfur, about 10 wt% or less ash, and about 2 wt% or less moisture, and a size of about 6 mesh or less. In various embodiments, injectable carbon is also known as finely ground carbon, finely ground carbon for extraction, or PCI. In various embodiments, injectable carbon is used as a direct energy source, a reagent, or both.

[0413] In some embodiments, high-carbon bioreagents according to the present invention are useful as injectable carbon substitute products in basic oxygen converter or electric arc furnace facilities in any application where injectable carbon may be available (e.g., injected into slag or ladles during steelmaking). In some embodiments, the injectable carbon substitute product is a high-carbon bioreagent containing at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous acid, and at least about 11,000 BTU per pound. In some embodiments, the injectable carbon substitute product further contains up to about 10 wt% dolomite lime. In some embodiments, the injectable carbon substitute product further contains up to about 10 wt% calcium oxide. In some embodiments, the injectable carbon substitute product further contains up to about 10 wt% dolomite lime and up to about 10 wt% calcium oxide. In some embodiments, the injectable carbon substitute product has a minimum dimension of about 1 / 8 inch. In some embodiments, the injectable carbon substitute product is substantially free of fossil fuels.

[0414] In some embodiments, high-carbon bioreagents according to the present invention are useful as pulverized carbon substitute products wherever pulverized coal may be used (e.g., for process heat or energy generation). In some embodiments, the pulverized coal substitute product further contains up to about 10 wt% calcium oxide. In some embodiments, the pulverized coal substitute product is a high-carbon bioreplacement containing at least about 55 wt% carbon, less than about 0.4 wt% sulfur, and at least about 11,000 BTU per pound. In some embodiments, the pulverized coal substitute product has a minimum dimension of about 1 / 8 inch. In some embodiments, the pulverized coal substitute product is substantially fossil fuel-free.

[0415] Some variations of the present invention utilize high-carbon bioreagents as carbon addition products for metal production. In some embodiments, high-carbon bioreagents according to the present invention are useful as carbon addition products for the production of carbon steel or other metal alloys containing carbon. Late-stage carbon addition products of carbon systems are generally characterized by high sulfur levels, high phosphorous acid levels, and high ash content, as well as high mercury levels that degrade metal quality and contribute to air pollution. In some embodiments of the present invention, the carbon addition product contains about 0.5 wt% or less of sulfur, about 4 wt% or less of ash, about 0.03 wt% or less of phosphorus, a minimum dimension of about 1 to 5 mm, and a maximum dimension of about 8 to 12 mm.

[0416] Some variations of the present invention utilize a high-carbon bioreagent as a carbon electrode. In some embodiments, the high-carbon bioreagent according to the present invention is useful as an electrode (e.g., anode) material suitable for use in, for example, aluminum production. In some embodiments, the electrode material comprises a high-carbon bioreagent according to the present invention in any embodiment. This high-carbon bioreagent contains at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous acid, and at least about 11,000 BTU per pound. In some embodiments, the carbon electrode comprises a high-carbon bioreagent containing at least about 55 wt% carbon and less than about 0.5 wt% sulfur. In some embodiments, the carbon electrode is substantially free of fossil fuels.

[0417] Other uses of high-carbon bioreagents in carbon electrodes include applications in batteries, fuel cells, capacitors, and other energy storage or energy supply devices. For example, in lithium-ion batteries, high-carbon bioreagents may be used to insert lithium on the anode side. In these applications, carbon purity and low ash content can be very important. In some embodiments, the method for producing the metal includes a step in which the carbon electrode is consumed. In some embodiments, the carbon electrode comprises a high-carbon bioreagent containing at least about 55 wt% carbon and less than about 0.5 wt% sulfur. In some embodiments, the carbon electrode is substantially free of fossil fuels.

[0418] Some variations of the present invention utilize high-carbon bioreagents as catalyst supports. Carbon is known as a catalyst support in a wide range of catalytic chemical reactions, such as the synthesis of mixed alcohols from synthesis gas, using cobalt-molybdenum sulfide metal catalysts supported on a carbon phase for the Fischer-Tropsch synthesis of higher hydrocarbons from synthesis gas, or iron-based catalysts supported on carbon.

[0419] Several variations of the present invention utilize high-carbon bioreagents as activated carbon products. Activated carbon products are used in a wide variety of liquid-phase and gas-phase applications, including water treatment, air purification, solvent vapor recovery, food and beverage processing, and pharmaceuticals. With regard to activated carbon, the porosity and surface area of ​​the material are generally important. The high-carbon bioreagents provided herein may, in various embodiments, provide superior activated carbon products due to (i) a larger surface area than fossil fuel-based activated carbon; (ii) the renewable nature of carbon; (iii) the vascular properties of the biomass feedstock used with additives, which allow for better penetration / dispersion of additives that enhance pollutant control; and (iv) a less inert substance (ash) that results in greater reactivity.

[0420] In some embodiments, the amounts of various components of the high-carbon bioreagent compositions disclosed herein are measured on an anhydrous basis. In some embodiments, the amounts of various components of the high-carbon bioreagent compositions disclosed herein are measured on an ashless basis. In some embodiments, the amounts of various components of the high-carbon bioreagent compositions disclosed herein are measured on an anhydrous, ashless basis.

[0421] In the above description of market applications for high-carbon bioreagents, it should be acknowledged that the described applications are neither exclusive nor comprehensive. Therefore, a high-carbon bioreagent described as suitable for one type of carbon product may, in various embodiments, be suitable for any other described applications. These applications are merely illustrative, and there are other applications for high-carbon bioreagents. In various embodiments, implantable carbon is used as a direct energy source, as a reagent, or both.

[0422] Furthermore, in some embodiments, the same physical material may be used in multiple market processes, either in an integrated manner or sequentially. Thus, for example, a high-carbon bioreagent used as a carbon electrode or activated carbon may, at the end of its effective life as a performance material, be introduced into a combustion process or metalworking for energy value, etc.

[0423] In some embodiments, activated carbon may be employed both for its reactivity / adsorption properties and as a fuel. For example, activated carbon injected into an exhaust stream may be suitable for removing pollutants, followed by combustion of the activated carbon particles and possibly the pollutants, generating energy to thermally destroy or chemically oxidize the pollutants.

[0424] Significant environmental and product use advantages may be associated with high-carbon bioreagents compared to conventional fossil fuel-based products. High-carbon bioreagents are not only environmentally superior, but also functionally superior from a processing standpoint, for example, due to their higher purity.

[0425] Regarding metal production, the generation of bioreagents in the disclosed process involves the coking of carbon-based products, which is necessary for preparation for use in metal production, compared to the coking of CO, CO2, and NO. x This results in significantly lower emissions of SO2 and hazardous air pollutants.

[0426] The use of high-carbon bioreagents as alternatives to coal or coke also significantly reduces environmental emissions of SO2, hazardous air pollutants, and mercury.

[0427] Furthermore, due to the purity of these high-carbon bioreagents (including low ash content), bioreagents have the potential to reduce slag and increase production capacity in batch metal manufacturing processes. [Examples]

[0428] 〔example〕 Example 1. Preparation of bioreagents - General method Large chips of Japanese red pine, Douglas fir columns (1.25-inch diameter pieces), and Douglas fir pieces (approximately 2 inches x 2 inches) of wood substrate were loaded into a loading hopper with an optional heated nitrogen gas stream. Optionally, a 1% aqueous solution of an additive (e.g., NaOH and / or KOH) was applied by spraying it onto the wood substrate while it was in the hopper, or by immersing the biomass in the additive solution. Regardless of the application method, the additive solution was allowed to permeate the biomass for 30 minutes before the biomass was dried. Once the reactor reached the desired temperature, the reactor was started to rotate, and the wood substrate was slowly fed by activating the material feeding system. The average residence time in the heated section of the reactor for each batch is shown in Table 1. After leaving the heated section of the reactor, the pyrolyzed material was collected in a discharge hopper. A conveyor moved the bioreagents from the discharge hopper for further analysis.

[0429] The bioreagents were prepared according to the general method described above, using various feedstock sizes, different reactor temperatures, heating, or ambient nitrogen, additives, and residence times. Table 1 summarizes the pyrolysis parameters for each batch. [Table 1]

[0430] Example 2. Analysis of biological reagents The parameters of the bioreagents prepared according to the general method of Example 1 were analyzed according to Table 2 below. [Table 2]

[0431] The results for samples A through F, prepared without the use of additives, are shown in Table 3 below. [Table 3]

[0432] The results for samples G to J2, prepared using additives, are shown in Table 4 below. [Table 4]

[0433] Example 3. Generation of high-calorie bioreagents This example demonstrates the generation of a bioreagent that generates a high amount of heat.

[0434] A feedstock containing cylindrical pieces of Douglas fir (1–1 / 8 inches in diameter, approximately 1.5 inches in length) was thermally decomposed according to the general method of Example 1. The reactor was heated to 600°C, and the feedstock was thermally decomposed with a residence time of 30 minutes. After cooling, the resulting bioreagent was analyzed according to the method described in Example 2. The results are shown in Table 5. [Table 5]

[0435] Example 4. Generation of high-calorie bioreagents This example demonstrates the generation of a bioreagent that generates a high amount of heat.

[0436] A feedstock containing Japanese red pine chips with an average particle size of approximately 1 inch × 1 / 2 inch × 1 / 8 inch was thermally decomposed according to the general method of Example 1. The reactor was heated to 550°C, and the feedstock was thermally decomposed with a residence time of 30 minutes. After cooling, the resulting bioreagent was analyzed according to the method described in Example 2. The results are shown in Table 6. [Table 6]

[0437] Example 5. Production of a biocoke substitute for mixing with Met coke. The bioreagents were prepared from pulverized, kiln-dried wood dowels, substantially following the general method of Example 1.

[0438] Mixtures of 2% and 5% bioreagents with met coke (sample ID No. SGS / 427-1104014-001) were prepared by mixing met coke with appropriate amounts of biocoke substitutes. Strength and reactivity values ​​were measured according to ASTM D5341, compared to the mixtures with met coke alone, and are shown in Table 7 (values ​​are the average of the minimum values ​​from two tests per sample). [Table 7]

[0439] This example demonstrates that when bioreagents prepared substantially according to the general method of Example 1 are mixed with MET coke at 2 wt% and 5 wt%, they can achieve CRI values ​​of 30% or less and CSR values ​​of 60% or more, which is consistent with standard specifications for the use of MET coke in large-scale blast furnaces.

[0440] Example 6. Production of enhanced hot-strength biocoke substitutes Japanese red pine wood chips, approximately 1" × 1 / 2" × 1 / 8" in size, were thermally decomposed at 600°C for a residence time of 30 minutes, following the general method of Example 1. The resulting bioreagent is referred to as "Sample A".

[0441] Grinding kiln-dried wooden dowels, having a diameter of 1 to 1 / 8 inches, were cut into pieces, each approximately 1.5 inches long. The pieces were thermally decomposed at 600°C for a residence time of 2 hours, according to the general method of Example 1. The resulting bioreagent is referred to as "Sample B".

[0442] Samples A and B were each placed separately in quartz tubes and heated at 1,100°C for 1 hour in the presence of CO2 gas. After 1 hour, Sample A had a CSR value of approximately 0%. After 1 hour, Sample B had a CSR value of approximately 64.6%. These results demonstrate the potential of biocoke substitutes to enhance hot strength and their suitability for use as a substitute for MET coke in various metal production applications.

[0443] Example 7. Preparation of biological reagents of specific dimensions As shown in Table 8 below, bioreagents having specific shapes and average dimensions were produced according to the general method of Example 1. [Table 8]

[0444] Example 8: Impact of residence time on fixed carbon levels The effect of residence time on fixed carbon levels in bioreagents was investigated by dividing a batch of feedstock into four groups of nearly equal mass, each consisting of feedstock pieces of nearly equal particle size. Each of the four groups was subjected to thermal decomposition at 350°C for residence times of 0, 30, 60, and 120 minutes, respectively, according to the general method of Example 1. The fixed carbon content of each sample was measured by ASTM D3172. The results are shown in Table 9 and the corresponding Figure 14. [Table 9]

[0445] Example 9. Effect of pyrolysis temperature on fixed carbon levels The effect of thermal decomposition temperature on fixed carbon levels in bioreagents was investigated by dividing a batch of feedstock into five groups of nearly equal mass, each consisting of feedstock pieces of nearly equal particle size. Each of the five groups was subjected to thermal decomposition for a residence time of 30 minutes, according to the general method of Example 1. The fixed carbon content of each sample was measured by ASTM D3172. The results are shown in Table 10 and the corresponding Figure 15. [Table 10]

[0446] Example 10. Influence of raw material particle size on fixed carbon levels The effect of feedstock particle size on fixed carbon levels in bioreagents was investigated by pyrolysis of three groups of Japanese red pine biomass: sawdust (average particle size approximately 0.0625 inches), chips (average particle size approximately 1 inch × 1 / 2 inch × 1 / 8 inch), and large chunks (cylinders with a diameter of 1–1 / 8" and a length of approximately 1.5 inches). Each of the three groups was subjected to pyrolysis at 400°C for 30 minutes, following the general method of Example 1. The fixed carbon content of each sample was measured by ASTM D3172. The results are shown in Table 11 and the corresponding Figure 16. [Table 11]

[0447] Example 11: Effect of oxygen level during thermal decomposition on the mass yield of bioreagents This example demonstrates the effect of oxygen levels on the mass yield of bioreagents.

[0448] Two samples of hardwood sawdust (4.0g each) were placed in quartz tubes. The quartz tubes were then placed in a tubular furnace (Lindberg Model 55035). The gas flow was set to 2,000 ccm. One sample was exposed to a 100% nitrogen atmosphere, while the other sample was exposed to a gas flow containing 96% nitrogen and 4% oxygen. The furnace temperature was set to 290°C. Once 290°C was reached (approximately 20 minutes), the temperature was maintained at 290°C for 10 minutes, at which point the heat source was switched off, and the tube and furnace were cooled for 10 minutes. The tube was removed from the furnace (the gas was still flowing at 2,000 ccm). Once the tube and samples had cooled sufficiently to be processed, the gas was stopped, the thermally decomposed material was removed, and it was weighed (Table 12). [Table 12]

[0449] Example 12. Effects of oxygen levels during thermal decomposition on fixed carbon levels and heat generation of bioreagents. The use of carbon capture units ("CRUs") demonstrates an increase in fixed carbon content and calorific value.

[0450] According to Example 10, the pyrolysis of hardwood sawdust was performed. A standard coconut shell charcoal ("CSC") tube (SKC Cat. No. 226-09) was placed in an off-gas stream, followed by a standard miniature impinger containing 10 mL of HPLC-grade water. Increases in fixed carbon levels and calorific value were compared with CSC tubes not exposed to any off-gas (Table 13, ashless and anhydrous data). [Table 13]

[0451] The results of Examples 11 and 12 demonstrate the benefit of maintaining a near-zero oxygen atmosphere to the mass yield and commercial value of the disclosed pyrolysis process. Using the off-gases from these two experiments, it was also possible to show that the gas exiting the process, which contains a large amount of BTU, can be captured for the purpose of increasing the BTU and / or carbon content of carbon substrates (coal, coke, activated carbon, carbon).

[0452] Example 13. Effect of heated nitrogen on the fixed carbon content of bioreagents This example demonstrates the effects of introducing heated nitrogen gas into a biomass processing unit.

[0453] Typically, the production of bioreagents using biomass consisting of Japanese red pine wood chips with dimensions of 1 inch × 1 / 2 inch × 1 / 8 inch was carried out at 350°C using a pilot-scale reactor with four-zone heating, following the general method of Example 1. In the first run, nitrogen was introduced at ambient temperature. In the second run, which was carried out immediately after the first to minimize variations in other parameters, the nitrogen was preheated to 300°C before injection into the pyrolysis zone. In both cases, the nitrogen flow rate was 1.2 cubic feet / minute, and the biomass was treated for 30 minutes.

[0454] Fixed carbon content was measured for each run according to ASTM D3172, on an anhydrous, ash-free basis (Table 14). [Table 14]

[0455] The results of these tests show that using preheated nitrogen increases the fixed carbon content of the bioreagent carbonization product by 7.0% [(100)(55.3%-51.7%) / 55.3%].

[0456] Example 14. Improvement of mass yield by biomass pretreatment. This example demonstrates the formation of a bio-activated carbon product containing an additive, namely iron(II) bromide.

[0457] An aqueous solution of iron(II) bromide hydrate was prepared by mixing 72.6 grams of iron(II) bromide hydrate with 1 gallon of water (e.g., a 1.0% bromine aqueous solution). This solution was added to 5.23 pounds (2.37 kg) of air-dried (12% moisture content) Scots pine wood chips. Each wood chip measured approximately 1" × 1 / 2" × 1 / 8".

[0458] The containers of wood chips and solution were sealed with watertight lids. The contents of the containers were mixed by periodically tilting and rolling them over a period of about four hours. The wood chips and solution were left sealed overnight to allow the wood chips to saturate with the solution.

[0459] The contents were then transferred to a waterproof tub and air-dried for several hours, with regular mixing until all free liquid was absorbed by the wood chips or evaporated. The contents were then transferred to an air dryer and air-dried overnight.

[0460] The preheated and air-dried wood chips were verified to have a moisture content of 12%. The mass of the preheated and air-dried wood chips was determined to be 5.25 lbs (2.38 kg). The contents were transferred to a pyrolysis reactor preheated with nitrogen gas at 300°C and a flow rate of 0.4 cubic feet / minute. Pyrolysis was carried out at 370°C for 30 minutes.

[0461] The final product was removed from the reactor at a temperature below 100°C. Upon reaching room temperature (approximately 23°C), the final product had a mass of 2.5 pounds (1.14 kg) and, with a moisture content of 12%, exhibited a mass yield of 47.6% based on the mass of the feedstock (e.g., after subtracting the mass contribution of pre-treated additives). On an anhydrous basis (adjusted for 12% moisture and the mass contribution of pre-treated additives), the mass yield was 54.1%. As shown in Table 15 below, this represents an 8–15% increase in mass yield compared to untreated wood chips processed under the same conditions.

[0462] [Table 15]

[0463] These data demonstrate a significant improvement in mass yield for wood chips pretreated with iron(II) bromide solution before pyrolysis.

[0464] This detailed description includes references to several embodiments of the present invention and to non-limiting examples relating to how the invention can be understood and implemented. Other embodiments that do not provide all of the features and advantages described herein may also be utilized without departing from the spirit and scope of the invention. The invention incorporates routine experimentation and optimization of the methods and systems described herein. Such modifications and variations are considered to be within the scope of the invention as defined by the claims.

[0465] All publications, patents, and patent applications cited herein are incorporated herein by reference as a whole, as if each publication, patent, and patent application were specifically and individually described herein.

[0466] If the methods and steps described above represent certain events occurring in a certain order, those skilled in the art will understand that the order of the steps can be changed, and that such changes constitute variations of the present invention. Furthermore, where possible, the steps can be performed not only sequentially but also simultaneously in parallel processes.

[0467] Therefore, to a certain extent, variations of the present invention are within the spirit of the present disclosure or equivalents of the present invention as found in the appended claims, but the intention is that the patent also includes those variations.

Claims

1. A process for producing high-carbon bioreagents, wherein the process is: A step of carrying out a first pyrolysis of a supply material, wherein the supply material includes biomass, and the first pyrolysis is carried out in a substantially inert gaseous atmosphere for at least 10 minutes at at least one temperature selected from 250°C to 700°C, thereby producing a first pyrolysis material, condensable vapor, and non-condensable gas. A step of separating at least a portion of the condensable vapor and at least a portion of the non-condensable gas from the first pyrolysis material, A step of applying an additive to the first pyrolysis material, thereby achieving penetration of the additive into the first pyrolysis material, and thereby producing a first pyrolysis material that has been treated. A step of drying the treated first pyrolysis material to reduce the moisture content of the treated first pyrolysis material, thereby producing a dried material. A step of carrying out a second thermal decomposition of the dried material to produce a second carbonized material, wherein the second thermal decomposition is achieved using a sweep gas, and Step of cooling the second pyrolysis material described above. A process that includes this.

2. The process according to claim 1, wherein the additive comprises an aqueous solution of about 1% potassium hydroxide.

3. The process according to claim 1, wherein the penetration of the additive into the raw material is achieved by allowing the additive to penetrate the raw material for about 30 minutes.

4. The process according to claim 1, wherein the first thermal decomposition is carried out using a temperature of about 650°C, a residence time of about 30 minutes, and a pressure of at least about -2 psi to a maximum of about +2 psi.

5. The process according to claim 1, wherein the second thermal decomposition is carried out using a temperature of about 680°C, a residence time of about 30 minutes, and a pressure of at least about -0.1 psi to a maximum of about -2 psi.

6. The process according to claim 1, further comprising the step of removing interlattice oxygen from the supply raw material or the dried material, thereby removing oxygen from the supply raw material or the dried material.

7. The aforementioned removal is up to approximately 21 vol% of O ２ The process according to claim 6, which is achieved by permeating the biomass supply material with a gas having the same properties.

8. The aforementioned gases are nitrogen, CO, CO ２ The process according to claim 7, or a combination thereof.

9. The process according to claim 1, further comprising the steps of introducing the biomass feed material, processed feed material, or processed dry feed material into an enclosed material transport unit before the second pyrolysis, and introducing an inert gas into the enclosed material transport unit, thereby forcing ambient air out of the enclosed material transport system.

10. The process according to claim 9, further comprising the step of heating the inert gas, which occurs before introducing the inert gas into the enclosed material transport unit.

11. The process according to claim 9, wherein forcibly expelling ambient air from the enclosed material transport system achieves an oxygen level in the enclosed material transport unit that does not necessarily have to be about 2% or less of oxygen, about 1% or less of oxygen, about 0.5% or less of oxygen, or about 0.2% or less of oxygen.

12. The process according to claim 1, wherein the oxygen level of the environment for the first thermal decomposition, the second thermal decomposition, or the cooling is about 0.5% to about 1.0%.

13. The process according to claim 1, wherein the sweeping gas comprises a substantially inert gas.

14. The process according to claim 1, wherein the sweep gas comprises about 32% carbon dioxide, 8% vapor, 10% carbon monoxide, and 50% nitrogen.

15. The process according to claim 1, wherein the residence time of the solid in the first thermal decomposition is at least about 5 minutes to a maximum of about 60 minutes.

16. The process according to claim 1, wherein the residence time of the solid in the second thermal decomposition is at least about 10 minutes to a maximum of about 120 minutes.

17. The process according to claim 1, wherein the second thermal decomposition is achieved using a temperature of at least about 250°C to a maximum of about 700°C.

18. The process according to claim 1, wherein the cooling is achieved using a temperature of at least about 100°C to a maximum of about 550°C.

19. The process according to claim 1, wherein a secondary thermal decomposition reaction occurs during the cooling, the secondary thermal decomposition reaction comprising the condensation of a carbon-containing gas that forms additional fixed carbon, the formation of bonds between adsorbed species and fixed carbon, or the conversion of carbon monoxide to carbon dioxide + fixed carbon (Boudoit reaction).

Images