System and device for generating high-carbon biogenic reagent

Abstract

To provide a process and a system for converting biomass into a high-carbon biogenic reagent suitable for various commercial applications.SOLUTION: In various embodiments,: thermal decomposition in the existence of an inert gas is adopted; hot thermal decomposition solid matter, condensable vapor and a non-condensed gas are generated; and thereafter the separation of vapor and the gas and the cooling of the hot thermal decomposition solid matter in the existence of the inert gas continue. An additive can be introduced during processing, coupled with a reagent or made both. A biogenic reagent can contain, on an anhydrous basis, at least 70 wt.%, 80 wt.%, 90 wt.% and 95 wt.% or more total carbon. The biogenic reagent can have, on an anhydrous basis, at least 12,000 Btu / lb, 13,000 Btu / lb, 14,000 Btu / lb or 14,500 Btu / lb energy content. The biogenic reagent can be shaped to a fine powder or a structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates generally to processes, systems and devices for the production of high-carbon biological reagents, and related compositions, products and uses. [Background technology]

[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 great chemical value for a variety of commercial products and advanced materials, including metals, metal alloys, composites, carbon fibers, electrodes, and catalyst supports. In metal manufacturing, carbon is useful as a reagent for reducing metal oxides to metals during processing; as a fuel to provide heat for processing; and as a component of final metal alloys. Carbon is a very important element in steel because it allows steel to be hardened by heat treatment.

[0003] Carbon-based reagents can in principle be produced from virtually any material containing carbon. Carbonaceous materials generally include fossil sources such as natural gas, oil, coal, and lignite; as well as renewable sources such as lignocellulosic biomass and various high-carbon waste materials.

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

[0005] By utilizing biogenic carbon for fuel, CO2 emissions associated with combustion do not contribute to net lifecycle carbon dioxide emissions because the carbon is recycled to grow more biomass. Also, the use of biogenic carbon as fuel will typically result in lower sulfur dioxide and mercury emissions compared to the use of coal or other solid fossil fuels for energy production.

[0006] By utilizing biogenic carbon for chemical and material applications where the carbon is not immediately combusted, the carbon can be effectively sequestered over long periods of time (e.g., when carbon is added to steel for permanent structures). In this way, the net carbon dioxide emissions are essentially negative, i.e., CO2 from the atmosphere is used to grow the biogenic feedstock, and the carbon is then sequestered within the biogenic product.

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

[0008] Pyrolysis is a process for the thermal conversion of solids in the complete absence of oxidizing agents (air or oxygen) or in such a limited supply that oxidation does not occur to a significant extent. Depending on the process conditions and additives, biomass pyrolysis can be tailored to produce widely varying amounts of gases, liquids, and solids. Low processing temperatures and long vapor residence times favor the production of solids. High temperatures and long residence times increase the conversion of biomass to syngas, while moderate temperatures and short vapor residence times are generally optimal for the production of liquids. Recently, there has been much interest in pyrolysis and related processes for converting biomass to liquids as precursors for high-quality syngas and / or liquid fuels.

[0009] On the other hand, little attention has been paid to improving the pyrolysis process, particularly to optimize the yield and quality of the solids as a high-carbon reagent. Historically, slow pyrolysis of wood has been carried out in large volumes, in simple batch processes, without emission controls. Conventional charcoal production technologies 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 the energy balance and controlling emissions. Summary of the Invention [Means for solving the problem]

[0010] In some variations, the present invention provides a process for producing a high-carbon biological reagent, the process comprising: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock or the dried feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) cooling the hot pyrolysis solids in a cooling zone at a cooling zone temperature below the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (g) further cooling the warm pyrolysis solids in an optional cooling device separate from the cooling zone to produce cold pyrolysis solids; and (h) recovering a high-carbon biological reagent containing at least a portion of the warm or cold pyrolysis solids; Includes.

[0011] As used herein, the term "reactor" refers to a discrete unit in which atmospheric and temperature conditions can be controlled and in which physical and / or chemical reactions can occur. In this context, the term "zone" refers to an area within the reactor in which the temperature and atmospheric conditions can be controlled relative to other zones within the reactor.

[0012] As used herein, the term "biomass processing unit" refers to a reactor that includes multiple zones, as described in more detail below. In various embodiments, the biomass processing unit ("BPU") includes multiple output passages configured to transfer feedstock, feedstock at different stages of processing, gases, condensate by-products, and heat from the various reactors and zones to other reactors or zones, material feed systems, carbon recovery units, and any other intended components of the systems described herein. In one embodiment, after the feedstock passes through each zone of the BPU, the feedstock is carbonized.

[0013] As used herein, the term "carbonization" means increasing the carbon content within a given amount of biomass. Illustratively, carbonization can be achieved by reducing non-carbon-containing material from biomass, adding carbon atoms to 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. It will be understood that other embodiments described below include multiple separate reactors, each reactor having at least one zone. For purposes of this disclosure, features, principles, alternatives, and embodiments described in connection with all single-reactor multi-zone BPU embodiments apply equally to all multiple separate reactor embodiments, and vice versa.

[0015] In some embodiments, the process includes drying the feedstock to remove at least a portion of the moisture contained within the feedstock, hi these or other embodiments, the process includes degassing the feedstock to remove at least a portion of the interstitial oxygen contained within the feedstock.

[0016] The process further includes, prior to step (d), preheating the feedstock in a preheat zone in the presence of a substantially inert gas for at least about 5 minutes at a preheat temperature selected from about 80°C to about 500°C, or selected 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 can be selected, for example, from about 150°C to about 350°C.

[0018] Pyrolysis conditions may be selected to maintain structural integrity or mechanical strength for the high carbon bioreagent feedstock, if desired for a given product application.

[0019] In some embodiments, each of the zones is located within a single reactor or BPU. In other embodiments, each of the zones is located within a separate BPU or reactor. It will be appreciated that some embodiments include one or more BPUs, each including at least one zone.

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

[0021] The process can be continuous, semi-continuous, or batch. In some continuous or semi-continuous embodiments, the inert gas flow is substantially countercurrent to the direction of solids flow. In other continuous or semi-continuous embodiments, the inert gas flow is substantially co-current to the direction of solids 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 attributes 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 may involve the combustion of natural gas. The heat generated from the thermal oxidation may be utilized at least in part to dry the feedstock. Additionally, the heat generated from the thermal oxidation may be utilized at least in part to heat the substantially inert gas prior to entering one of the zones or reactors, such as the pyrolysis zone.

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

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

[0026] In some embodiments, the process further comprises introducing at least one additive selected from an acid, a base, or a salt thereof, which may be selected from (but is 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 comprises 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, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

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

[0029] In some embodiments, the process further comprises 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 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 chiller to cool the warm pyrolysis solids, thereby producing cold pyrolysis solids and superheated steam, and drying is performed at least in part with superheated steam obtained from the external chiller. Optionally, the chiller can be operated to first cool the warm pyrolysis solids with steam to reach a first chiller temperature, and then with air to reach a second chiller temperature, the second chiller temperature being lower than the first chiller temperature and associated with a reduced risk of combustion for the warm pyrolysis solids in the presence of air.

[0031] In some variations, the present invention provides a process for producing a high-carbon biological reagent, the process comprising: (a) providing a carbon-containing feedstock comprising biomass (optionally with some or all of the moisture removed); (b) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (c) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (d) cooling the hot pyrolysis solids in a cooling zone at a cooling temperature below the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (e) further cooling the warm pyrolysis solids in an optional cooling device separate from the cooling zone to produce cold pyrolysis solids; and (f) recovering a high-carbon biological reagent containing at least a portion of the warm or cold pyrolysis solids; Includes:

[0032] In some variations, the present invention provides a process for producing a high-carbon biological reagent, the process comprising: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture, if any, contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) preheating the feedstock in a preheat zone in the presence of a substantially inert gas for at least about 5 minutes at a preheat temperature selected from about 80°C to about 500°C; (e) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (f) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (g) cooling the hot pyrolysis solids in a cooling zone at a cooling zone temperature below the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (h) further cooling the warm pyrolysis solids in an optional cooling device separate from the cooling zone to produce cold pyrolysis solids; and (i) recovering a high-carbon biological reagent comprising at least a portion of the warm or cold pyrolysis solids; The process further includes introducing at least one additive anywhere within the process (ie, at any one or more places or times).

[0033] In some variations, the present invention provides a process for producing a high-carbon biological reagent, the process comprising: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock or the dried feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) further cooling the hot pyrolysis solids in an optional cooling zone at a cooling zone temperature below the pyrolysis temperature for at least 5 minutes in the presence of the substantially inert gas to produce warm pyrolysis solids; (g) cooling the warm or cold pyrolysis solids in a cooling device separate from said cooling zone to produce cold pyrolysis solids; (h) recovering a high-carbon biological reagent comprising at least a portion of the cold pyrolysis solids; and (i) forming a fine powder from said high-carbon bio-reagent; The process optionally includes introducing at least one additive into the process before, during, or after step (i).

[0034] The high-carbon biological reagent 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, the high-carbon biological reagent contains between about 40% and 70% of the carbon contained in the feedstock.

[0035] In some embodiments, an additive is introduced into the dried feedstock before or during step (d), and the presence of the additive in the process increases the carbon content of the high-carbon biological reagent compared to an otherwise identical process in which the additive is not introduced.

[0036] The high-carbon biological reagent can contain at least 55 wt% carbon on a dry basis, for example, at least 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 90 wt%, 95 wt%, or more, etc., carbon on a dry basis. Total carbon includes fixed carbon and can also include carbon from volatile materials. In some embodiments, the high-carbon biological reagent contains at least 90 wt% or at least 95 wt% fixed carbon on a dry basis.

[0037] The high carbon bioreagent can have an energy content of at least 11,000 Btu / lb on a dry basis, such as 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 a dry basis.

[0038] The high-carbon bio-reagent may be formed into a fine powder by pulverization. Alternatively, or consecutively, the high-carbon bio-reagent may be formed into a structure by compacting, bonding, pelletizing, or agglomerating. In some embodiments, the high-carbon bio-reagent is in the form of a structure that derives its structure and / or strength substantially from the feedstock. In some embodiments, the high-carbon bio-reagent is in substantially the same structural form as the feedstock.

[0039] Another variation of the present invention provides a high carbon bio-reagent production system, the system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operable communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) a biomass processing unit disposed in operative communication with the material supply system or the drying device, if present, the biomass processing unit including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the biomass processing unit configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a cooling device disposed in operable communication with the biomass processing unit; and (e) a high-carbon biological reagent recovery device disposed in operable communication with the cooling device; Equipped with.

[0040] The dryer, 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 inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the solids. The purging system may be a deaerator located between the material feed system (or the dryer, if present) and the BPU.

[0041] Optionally, the system may include a preheating zone disposed in operable communication with the pyrolysis zone.

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

[0043] The system may further include one or more additive feeders for introducing additives into the system, such as any of the additives described above. In some embodiments, the additive feeder is configured to combine the additive with the carbon-containing feedstock. The additive feeder may be inserted between the material feed system (for biomass) and the BPU. The additive feeder may be disposed in operative communication with the BPU. The additive feeder may be disposed in operative communication with the cooling device. The additive feeder may be inserted between the cooling device and the carbon recovery unit. The additive feeder may be disposed in operative communication with 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 the first gas outlet may be located in communication with different zones or 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 within the BPU may be configured with a gas inlet and a gas outlet. The gas inlets and gas outlets not only allow for the introduction and recovery of steam or gas, but also allow for close process monitoring and control over various stages of the process, resulting in improved yields and efficiency.

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

[0046] The system may further include a first reactive gas probe disposed in operative communication with the pyrolysis zone and a gas monitor, such as (but not limited to) a GC, MS, GC-MS, or FTIR. In some embodiments, the system may further include a second reactive gas probe disposed in operative communication with a cooling zone and a second gas monitor, which may be a gas monitor or a different type of instrument. The system may further include an additional reactive gas probe disposed in operative communication with the drying zone (if present) and / or preheating zone (if present) and the gas monitor. If a reactive gas probe is included, the system may further include at least one computer-programmed controller executable to utilize output from the gas monitor to adjust system setpoints (such as the pyrolysis temperature or the inert gas flow rate).

[0047] In some embodiments, the system may further include a process gas heater disposed in operable communication with the outlet for removing condensable vapors and non-condensable gases, the process gas heater configured to introduce separate fuel and oxidant into a combustion chamber adapted for combustion of at least a portion of the fuel and condensable vapors.

[0048] The system may include a heat exchanger disposed between the process gas heater and the dryer and 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 disposed between the process gas heater and the gas inlet for the BPU and configured to utilize at least a portion of the heat of combustion to preheat the substantially inert gas prior to introduction into the BPU.

[0049] In some embodiments, the system may further include a carbon concentrating unit disposed in operative communication with the chiller or the BPU and configured to combine vapors with solids, including non-condensable vapors and / or condensable vapors in fully or at least partially condensed form, to increase the carbon content of the high-carbon biological reagent obtained from the carbon recovery unit.

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

[0051] In some embodiments, the system may further include a separate pyrolysis device adapted to further pyrolyze the high-carbon bio-reagent to further increase its carbon content.

[0052] Another variation provides a high carbon bio-reagent production system, the system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operable communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) a preheater disposed in operable communication with the material feed system or the drying apparatus (if present) and configured to heat and / or moderately pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operable communication with the preheater and configured to pyrolyze the feedstock; (e) a cooling device disposed in operable communication with the pyrolysis reactor and configured to cool the pyrolysis solids; and (f) a high-carbon biological reagent recovery device disposed in operable communication with the cooling device; Including, The system is configured with 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 located between the material feed system or the dryer (if present) and the preheater. The system may be configured with at least two gas inlets and at least two gas outlets, if desired.

[0054] In some embodiments, the pyrolysis reactor and / or cooler are configured with a gas inlet(s) and the dryer (if present) and / or preheater are configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase.

[0055] The system, in some embodiments, further includes a process gas heater disposed in operative communication with the at least one gas outlet for removing condensable vapors and non-condensable gases. The process gas heater may be configured to introduce separate fuel and oxidant into a combustion chamber adapted for combustion of at least a portion of the fuel and condensable vapors.

[0056] The system may include a heat exchanger disposed 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 include a heat exchanger disposed 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 the substantially inert gas prior to introduction into the pyrolysis reactor.

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

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

[0059] The BPU can be configured to separately adjust the gas phase composition and gas phase residence time of at least two zones. In some embodiments, the BPU can be configured to separately 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 certain embodiments, the BPU is configured with a gas inlet in each zone and / or a gas outlet in each zone. In some embodiments, the BPU is a countercurrent reactor.

[0061] Material feed systems include screw, auger, drop chamber, and drum material feed systems. The carbonaceous solids outlet may include an output mechanism selected from the group consisting of a screw, an auger, a drop chamber, and a drum material feed system. The BPU may include a single auger positioned across each zone.

[0062] In some embodiments, each reactor is configured with flights disposed on the interior walls to provide agitation of the solids. The flights may be separately adjustable within each zone. The BPU, in some embodiments, is an axially rotatable BPU.

[0063] Yet another variation of the present invention provides a process for producing a high carbon bio-reagent, the process comprising: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) cooling the hot pyrolysis solids in a cooling zone at a cooling temperature below the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (g) optionally cooling the warm pyrolysis solids in a separate cooling device to produce cold pyrolysis solids; (h) thereafter, passing at least a portion of the condensable vapors and / or at least a portion of the non-condensable gases from step (e) through the warm pyrolysis solids and / or the cold pyrolysis solids to form concentrated pyrolysis solids having an increased carbon content; and (i) recovering a high-carbon biological reagent comprising at least a portion of the concentrated pyrolysis solids.

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

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

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

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

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

[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 may be separated based on their relative polarities. 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 non-polar 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 biological reagent compared to an otherwise identical process without step (h). In some embodiments, step (h) increases the fixed carbon content of the high-carbon biological reagent 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 variations, the process for producing a high-carbon bio-reagent comprises: (a) providing a solid stream comprising a starting carbon-containing material; (b) providing a gas stream containing a condensable carbon-containing vapor, a non-condensable carbon-containing gas, or a mixture of a condensable carbon-containing vapor and a non-condensable carbon-containing gas; and (c) passing the gas stream through a solid stream under suitable conditions to form a carbon-containing product having an increased carbon and / or energy content relative to the carbon-containing material. Includes:

[0073] In some embodiments, the starting carbon-containing material is pyrolyzed biomass or torrefied biomass. The gas stream can be obtained during an integrated process that supplies the carbon-containing material. Alternatively, the gas stream can be obtained from a separate processing of the carbon-containing material. The gas stream, or a portion thereof, can be obtained from an external source. Mixtures of gas streams, as well as mixtures of carbon-containing materials from various sources, are possible.

[0074] In some embodiments, the process further comprises recycling or reusing the gas stream to repeat the process to further increase the carbon and / or energy content of the carbon-containing product. In some embodiments, the process further comprises recycling or reusing the gas stream to perform the process to increase the carbon and / or energy content of another feedstock different from the carbon-containing material.

[0075] The process can include introducing the 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 can 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 production system is also provided, the system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operable communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) A BPU disposed in operative communication with the material feed system or the drying device, if present, the BPU including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the BPU configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) an optional cooling device disposed in operable communication with the BPU; (e) a material enrichment unit disposed in operable communication with the BPU or cooling system, if present, and configured to pass condensable vapors and / or noncondensable gases through the solids to form enriched solids having an increased carbon content; and (f) a carbon capture unit disposed in operable communication with the material concentration unit; Equipped with.

[0078] In some embodiments, the system further includes a preheating zone disposed in operative communication with the pyrolysis zone. The pyrolysis zone, cooling zone, and preheating zone (if present) may each be disposed within a single unit or within separate units. The drying device, if present, may be configured as a drying zone within the BPU.

[0079] To generate a substantially countercurrent flow of the gas phase relative 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 countercurrent flow of the gas phase relative 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 an embodiment, the material enrichment unit comprises: (i) a housing having an upper and lower portion; (ii) an inlet at the bottom surface of the lower portion of the housing configured to convey condensable vapors and non-condensable gases; (iii) an outlet on the upper surface of the upper portion of the housing configured to convey a concentrated gas stream obtained from the condensable vapor and the non-condensable gas; (iv) a path defined between the upper and lower portions of the housing; and (v) a transport system following the pathway, the transport system configured to transport solids, the housing being shaped such that the solids adsorb at least a portion of the condensable vapors and / or at least a portion of the non-condensable gases. Equipped with.

[0081] The present invention also provides various products and compositions. In some variations, the high-carbon biological reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) cooling the hot pyrolysis solids in a cooling zone at a cooling zone temperature below the pyrolysis temperature for at least about 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (g) cooling the warm pyrolysis solids in an optional cooling device separate from said cooling zone to produce cold pyrolysis solids; and (h) recovering a high-carbon biological reagent containing at least a portion of the warm or cold pyrolysis solids; It is generated by a process that includes the steps:

[0082] The high-carbon biological reagent may further include at least one process additive incorporated during the process. Alternatively, or in addition, the high-carbon biological reagent may further include at least one product additive incorporated into the reagent following the process.

[0083] In some embodiments, the 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, the 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. The additives may be useful to help maintain structural morphology prior to use of the bioreagent.

[0084] In some embodiments, the high-carbon biological reagent may comprise 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. Total carbon includes fixed carbon and carbon from volatile matter. In some embodiments, carbon from volatile matter is at least 5%, at least 20%, or at least 40% of the total carbon.

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

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

[0087] The high-carbon bioreagent may have an energy content, on a dry basis, 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. The high-carbon bioreagent has an energy content, on a dry basis, of at least 14,700 Btu / lb and a fixed carbon content of at least 95 wt%.

[0088] In some embodiments, the high-carbon biological reagent is, on an anhydrous basis, ≥ 55 wt% total carbon; less than 5 wt% hydrogen; less than 1 wt% nitrogen; not more than 0.5 wt% phosphorus; Not more than 0.2 wt% sulfur; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; Includes:

[0089] The 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, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0090] In some embodiments, the high-carbon biological reagent is, on an anhydrous basis, ≥ 55 wt% total carbon; less than 5 wt% hydrogen; less than 1 wt% nitrogen; not more than 0.5 wt% phosphorus; Not more than 0.2 wt% sulfur; and an additive selected from an acid, a base, or a salt thereof Includes.

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

[0092] In certain embodiments, the high-carbon biological reagent is, on an anhydrous basis, ≥ 55 wt% total carbon; less than 5 wt% hydrogen; less than 1 wt% nitrogen; not more than 0.5 wt% phosphorus; not more than 0.2 wt% sulfur; a first additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; and a second additive selected from an acid, a base, or a salt thereof; Including, 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, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof, and 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] The high-carbon biological reagent may contain, on an anhydrous basis, about 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or more total carbon (total carbon includes fixed carbon and carbon associated with volatile matter).

[0095] In some embodiments, the reagent comprises about 8 wt. % or less non-combustible materials on a dry basis, such as about 4 wt. % or less non-combustible materials on a dry basis.

[0096] The high-carbon biological reagent may consist essentially of, on an anhydrous basis, carbon, hydrogen, oxygen, nitrogen, phosphorus, sulfur, non-combustibles, 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, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof. Water may or may not be present.

[0097] The high-carbon biological reagent may consist essentially of, on an anhydrous basis, carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustibles, 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] The high carbon bioreagent may have an energy content, on an anhydrous basis, 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.

[0099] The high-carbon biological reagent can be in the form of a fine powder or a structure. The structure can result from compacting, bonding, pelletizing, or agglomerating particles. In some embodiments, the structure has a structure and / or strength substantially derived from the carbon feedstock source. In certain embodiments, the structure is in substantially the same structural form as the carbon feedstock source.

[0100] In some embodiments of the high-carbon bio-reagent, the majority of the carbon is classified as renewable carbon. Substantially all of the carbon contained in the high-carbon bio-reagent can be classified as renewable carbon. In one embodiment, for example, the following items are provided: (Item 1) 1. A high carbon bioreagent production system, said system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operative communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone reactor disposed in operative communication with the material feed system or the drying device (if present), the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a cooling device disposed in operable communication with the multi-zone reactor; (e) a carbon recovery unit disposed in operable communication with said cooling device; A high-carbon biological reagent production system comprising: (Item 2) Item 10. The system of claim 1, further comprising a preheating zone disposed in operable communication with the pyrolysis zone. (Item 3) 3. The system of claim 1, wherein each of the at least one pyrolysis zone, the cooling zone, and the preheating zone (if present) is disposed within a single biomass processing unit. (Item 4) 3. The system of claim 1, wherein each of the at least one pyrolysis zone, the cooling zone, and the preheating zone (if present) is disposed within a separate biomass processing unit. (Item 5) Item 1. The system of item 1, wherein the drying device is present and configured as a drying zone within the multi-zone reactor. (Item 6) Item 10. The system of claim 1, further comprising a purging means for removing oxygen from the system. (Item 7) 7. The system of claim 6, wherein the purging means includes one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the system. (Item 8) 7. The system according to item 6, wherein the purging means is a degasser disposed between the material supply system or the drying device (if present) and the multi-zone reactor. (Item 9) 2. The system of claim 1, wherein the material supply system is physically integrated with the multi-zone reactor. (Item 10) Item 1. The system of item 1, wherein the cooling device is disposed within the multi-zone reactor. (Item 11) 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) Item 12. The system of item 11, wherein the additive supply device is configured to combine the additive with the carbon-containing feedstock. (Item 13) Item 12. The system of item 11, wherein the additive supply device is interposed between the material supply system and the multi-zone reactor. (Item 14) Item 12. The system of item 11, wherein the additive supply device is disposed in operable communication with the multi-zone reactor. (Item 15) Item 12. The system of item 11, wherein the additive supply device is disposed in operable communication with the cooling device. (Item 16) Item 12. The system of item 11, wherein the additive supply device is interposed between the cooling device and the carbon recovery unit. (Item 17) Item 12. The system of item 11, wherein the additive supply device is disposed in operable communication with the carbon recovery unit. (Item 18) Item 18. The system according to any one of items 1 to 17, wherein the multi-zone reactor is configured with a first gas inlet and a first gas outlet. (Item 19) Item 19. The system of item 18, wherein the first gas inlet and the first gas outlet are disposed in communication with different zones. (Item 20) Item 19. The system of item 18, wherein the first gas inlet and the first gas outlet are arranged in communication with the same zone. (Item 21) Item 19. The system of item 18, wherein the multi-zone reactor is configured with a second gas inlet. (Item 22) Item 19. The system of item 18, wherein the multi-zone reactor is configured with a second gas outlet. (Item 23) 22. The system of claim 21, wherein the multi-zone reactor is configured with a third gas inlet. (Item 24) 23. The system of claim 22, wherein the multi-zone reactor is configured with a third gas outlet. (Item 25) Item 24. The system of item 23, wherein the multi-zone reactor is configured with a fourth gas inlet. (Item 26) Item 25. The system of item 24, wherein the multi-zone reactor is configured with a fourth gas outlet. (Item 27) Item 1. The system of item 1, wherein the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. (Item 28) Item 3. The system of item 2, wherein the cooling zone is configured with a gas inlet and the preheating zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. (Item 29) Item 6. The system of 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 countercurrent flow of the gas phase relative to the solid phase. (Item 30) 30. The system according to any one of items 1 to 29, wherein each zone present in the multi-zone reactor is configured with a gas inlet and a gas outlet. (Item 31) 31. The system of any one of items 1 to 30, wherein the system further includes a first reaction gas probe disposed in operable communication with the pyrolysis zone and with a gas monitor. (Item 32) Item 32. The system of item 31, wherein the system further includes a second reactive gas probe disposed in operable communication with the cooling zone and with the gas monitor or a second gas monitor. (Item 33) Item 32. The system of item 31, wherein the system further includes an additional reactive gas probe disposed in operative communication with the drying zone (if present) and / or the preheating zone (if present) and with the gas monitor or additional gas monitor. (Item 34) 32. The system of claim 31, wherein the gas monitor is selected from the group consisting of GC, MS, GC-MS, FTIR, and combinations thereof. (Item 35) 35. The system of any one of items 31 to 34, further comprising at least one computer-programmed controller executable to utilize output from the gas monitor to adjust system settings. (Item 36) Item 37. The system of any one of items 1 to 35, further comprising a process gas heater disposed in operable communication with the outlet, the process gas heater configured to receive separate fuel and oxidant into a combustion chamber suitable for combustion of the fuel and at least a portion of the condensable vapors and / or non-condensable gases. Item 37. The system of item 36, wherein the system further comprises a separation unit interposed between the outlet and the process gas heater. (Item 38) Item 37. The system of item 36, further comprising a heat exchanger interposed between the process gas heater and the drying device and configured to utilize at least a portion of the combustion heat for the drying device. (Item 39) Item 37. The system of item 36, further comprising a heat exchanger disposed between the process gas heater and a gas inlet for the multi-zone reactor, the heat exchanger configured to utilize at least a portion of the heat of combustion to preheat a substantially inert gas prior to introduction into the multi-zone reactor. (Item 40) 39. The system of claim 1, further comprising a material enrichment unit disposed in operable communication with the cooling device and configured to combine condensable vapors in at least partially condensed form with the solids to increase the carbon content of the high-carbon biological reagent obtained from the carbon recovery unit. (Item 41) 41. The system of any one of items 1 to 40, further comprising a separate pyrolysis unit adapted to further pyrolyze the high-carbon biological reagent to further increase its carbon content. (Item 42) 42. The system of any one of items 1 to 41, further comprising a sizing unit disposed in operable communication with the carbon recovery unit, the sizing unit enabling particle size reduction of the high-carbon biological reagent and / or formation of structures from the high-carbon biological reagent. (Item 43) 1. A high carbon bioreagent production system, said system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operative communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) a preheater disposed in operable communication with the material feed system or the drying apparatus (if present) and configured to heat and / or moderately pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operable communication with the preheater and configured to pyrolyze the feedstock; (e) a cooling device disposed in operable communication with the pyrolysis reactor and configured to cool the pyrolysis solids; (f) a high-carbon biological reagent recovery unit disposed in operable communication with the cooling device; Equipped with A high-carbon bioreagent production system, the system being configured with 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) Item 44. The system according to item 43, further comprising a degasser disposed between the feeder or the dryer (if present) and the preheater. (Item 45) Item 44. The system of item 43, wherein the system is configured with at least two gas inlets and at least two gas outlets. (Item 46) Item 44. The system of item 43, wherein the pyrolysis reactor and / or the cooler are configured with a gas inlet(s) and the dryer (if present) and / or the preheater are configured with a gas outlet(s) to generate a substantially countercurrent flow of the gas phase relative to the solid phase. (Item 47) Item 47. The system according to any one of items 43 to 46, further comprising an additive supply device for introducing an additive into the system. (Item 48) 48. The system of any one of items 43 to 47, further comprising a first reaction gas probe disposed in operable communication with the pyrolysis reactor and with a gas monitor. (Item 49) Item 49. The system of item 48, further comprising an additional reaction gas probe disposed in operable communication with the preheater and / or the cooling device and with the gas monitor or an additional gas monitor. (Item 50) Item 49. The system of item 48, wherein the gas monitor is selected from the group consisting of GC, MS, GC-MS, FTIR, and combinations thereof. (Item 51) 51. The system of any one of items 48 to 50, wherein the system further comprises at least one computer-programmed controller executable to utilize output from the gas monitor to adjust system settings. (Item 52) 52. The system of any one of items 43 to 51, wherein the system further includes a process gas heater disposed in operable communication with the at least one gas outlet for removing condensable vapors and non-condensable gases, the process gas heater configured to receive separate fuel and oxidant into a combustion chamber suitable for combustion of the fuel and at least a portion of the condensable vapors. (Item 53) Item 53. The system of item 52, further comprising a heat exchanger disposed between the process gas heater and the dryer and configured to utilize at least a portion of the heat of combustion for the dryer. (Item 54) Item 53. The system of item 52, further comprising a heat exchanger disposed between the process gas heater and a gas inlet for the multi-zone reactor, the heat exchanger configured to utilize at least a portion of the heat of combustion to preheat a substantially inert gas prior to introduction into the pyrolysis reactor. (Item 55) 55. The system of any one of items 43 to 54, wherein the system further includes a material enrichment unit disposed in operable communication with the cooling device and configured to combine condensable vapors in at least partially condensed form with the solids to increase the carbon content of the high-carbon biological reagent obtained from the carbon recovery unit. (Item 56) 56. The system of any one of items 43 to 55, further comprising at least one additional pyrolysis reactor adapted to further pyrolyze the high-carbon bio-reagent to further increase its carbon content. (Item 57) 53. The system of claim 52, wherein the system comprises at least one additional pyrolysis reactor adapted to further pyrolyze the high-carbon biological reagent in the presence of a second substantially inert gas to further increase its carbon content, and wherein the process gas heater is configured to preheat the second substantially inert gas. (Item 58) 5. The system of claim 3, wherein the system is configured to extract and recycle gas from the biomass pyrolysis unit. (Item 59) 59. The system of any one of items 1 to 58, wherein the system is configured to extract and reuse gas from the carbon recovery unit. (Item 60) 1. A biomass pyrolysis continuous reactor comprising a material feed 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, one of the zones configured with a first gas inlet for introducing a substantially inert gas into the reactor, and one of the zones configured with a first gas outlet. (Item 61) Item 61. The reactor according to item 60, wherein the reactor comprises at least two zones. (Item 62) Item 58. The reactor of item 57, wherein the reactor comprises at least three zones. (Item 63) Item 63. The reactor of item 62, wherein the reactor comprises at least four zones. (Item 64) Item 61. The reactor of item 60, wherein each of the zones is placed in communication with separately adjustable indirect heating means, each independently selected from the group consisting of electrical heat transfer, steam heat transfer, hot oil heat transfer, waste heat transfer, and combinations thereof. (Item 65) Item 61. The reactor of 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) Item 66. The reactor of 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) Item 61. The reactor of item 60, wherein the reactor is configured with a second gas inlet and / or a second gas outlet. (Item 68) Item 5608. The reactor of item 5608, wherein the reactor is configured with a gas inlet in each zone. (Item 69) Item 61. The reactor of item 60, wherein the reactor is configured with a gas outlet in each zone. (Item 70) Item 61. The reactor according to item 60, wherein the reactor is a countercurrent reactor. (Item 71) Item 61. The reactor of item 60, wherein the material feeding system comprises a feeding mechanism selected from the group consisting of a screw, an auger, a drop chamber, and a drum feeder. (Item 72) Item 61. The reactor of item 60, wherein the carbonaceous solids outlet comprises an output mechanism selected from the group consisting of a screw, an auger, a drop chamber, and a drum feeder. (Item 73) Item 61. The reactor of item 60, wherein each of the zones is configured with flights disposed on the interior walls to provide agitation of the solids. (Item 74) Item 74. The reactor of item 73, wherein the flights are separately adjustable within each of the zones. (Item 75) Item 61. The reactor according to item 60, wherein the reactor is an axially rotatable reactor. (Item 76) Item 61. The reactor of item 60, wherein the reactor comprises a single auger positioned across each of the zones. (Item 77) Item 61. The reactor of item 60, wherein the reactor is configured for extracting and recycling gas from the first gas outlet. (Item 78) 70. The reactor of claim 69, wherein the reactor is configured for extracting and recycling gas from the gas outlet in each zone. [Effects of the Invention]

[0101] The present invention also provides a wide variety 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, coked 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 described in further detail below. [Brief explanation of the drawings]

[0102] [Figure 1] 1 illustrates a multiple reactor embodiment of the system of the present invention. [Figure 2]1 illustrates a single reactor, multi-zone embodiment of the system of the present invention. [Figure 3] 1 illustrates one embodiment of an oxygen-free continuous feed mechanism suitable for use in connection with the present invention. [Figure 4] 1 illustrates another embodiment of a single reactor, multi-zone biomass processing unit suitable for use in connection with the present invention. [Figure 5] 1 illustrates one embodiment of a carbon recovery unit suitable for use in connection with the present invention. [Figure 6] 1 shows an embodiment of a single reactor biomass processing unit of the present invention with an optional drying device. [Figure 7] 1 shows an embodiment of a pyrolysis reactor system of the present invention with an optional dryer and gas inlet. [Figure 8] 1 shows an embodiment of a single reactor biomass processing unit of the present invention equipped with a gas inlet and optional cooling device. [Figure 9] 1 shows an embodiment of a single reactor biomass processing unit system of the present invention, equipped with optional dryers and degassers, and an inert gas inlet. [Figure 10] 1 shows an embodiment of a multiple reactor system of the present invention, equipped with optional dryers and degassers, and an inert gas inlet. [Figure 11] 1 illustrates an embodiment of a multiple reactor system of the present invention with optional drying and cooling devices, and a material concentration unit. [Figure 12] 1 shows an embodiment of a multiple reactor system of the present invention, equipped with optional dryers, degassers, coolers, and inert gas inlets. [Figure 13] 1 shows an embodiment of a multiple reactor system of the present invention, equipped with optional dryers and degassers, an inert gas inlet, and a cooling system. [Figure 14] 1 shows a graph illustrating the effect of residence time on fixed carbon content of a bioreagent produced in accordance with one embodiment of the present disclosure. [Figure 15]1 shows a graph illustrating the effect of pyrolysis temperature on fixed carbon content of a bio-reagent produced in accordance with one embodiment of the present disclosure. [Figure 16] 1 shows a graph illustrating the effect of biomass particle size on fixed carbon content of a bio-reagent produced in accordance with one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0103] The present description enables one skilled in the art to make and use the invention and describes several embodiments, adaptations, variations, alternatives, and uses of the invention. These and other embodiments, features, and advantages of the invention will become more apparent to those skilled in the art upon review of the following detailed description of the invention in conjunction with the accompanying figures.

[0104] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless the content clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0105] Unless otherwise indicated, all numbers expressing reaction conditions, stoichiometries, concentrations of ingredients, and so forth used in the specification and claims are understood to be modified in all instances by the word "about." Consequently, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending, at least on particular analytical techniques.

[0106] The term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. "Comprising" is a term used in claim language to mean that the named claim element is essential, but that other claim elements may be added and still form subject matter within the scope of the claim.

[0107] As used herein, the phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase "consisting of" (or variations thereof) appears in a clause in the body of a claim rather than immediately following the prior art section, it limits only the elements recited in that clause and does not exclude other elements from the claim as a whole. As used herein, "consisting essentially of" limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basic and novel characteristics of the claimed subject matter.

[0108] With respect to the terms "comprising," "consisting of," and "consisting essentially of," when one of these three terms is used herein, the presently disclosed and claimed subject matter may include use of either of the other two terms. Thus, in some embodiments, unless otherwise specified, any instance of "comprising" may be replaced by "consisting of" or "consisting essentially of."

[0109] For present purposes, "biogenic" is intended to mean a material (whether a feedstock, product, or intermediate) that contains elements such as carbon that are renewable on time scales of months, years, or decades. Non-biological materials may be non-renewable or may be renewable on time scales of centuries, millennia, million years, or even longer geological time scales. Note that biomaterials may include a mixture of living and non-biological sources.

[0110] For present purposes, "reagent" is intended to mean a material in its broadest sense, and a reagent may be a fuel, chemical, material, compound, additive, mixture component, 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 adjusting the mechanical, physical, or hydraulic properties of a material to which it is added. For example, a reagent may be introduced into a metal to impart certain strength properties to the metal. A reagent may be a substance of sufficient purity (which, in the present context, is usually carbon purity) for use in chemical analysis or physical testing.

[0111] As used herein, by "high-carbon" to describe a bioreagent, we simply mean that the bioreagent has a relatively high carbon content compared to the original feedstock utilized to generate the high-carbon bioreagent. Typically, a high-carbon bioreagent will contain at least about half of its weight as carbon. More typically, a high-carbon bioreagent will contain at least 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 90 wt%, or more carbon.

[0112] Notwithstanding the above, the term "high-carbon bio-reagent" is used herein for purposes of consistency in describing materials that may be produced by the processes and systems of the present invention in various embodiments. Any limitations regarding carbon content, or any other concentration, are attributed only by reference to specific embodiments and equivalents thereof, and not by the term itself. For example, it will be understood that starting materials having very low carbon content, according to the disclosed processes, may produce high-carbon bio-reagents that are highly enriched in carbon compared to the starting material (high yield of carbon), but are nevertheless relatively low in carbon (low purity carbon), including less than 50 wt% carbon.

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

[0114] Exemplary changes that can occur during pyrolysis include any of the following: (i) heat transfer from a heat source increases the temperature within the feedstock; (ii) primary pyrolysis reactions begin at this high temperature, liberating volatiles and forming char; (iii) the flow of hot volatiles to the cold solids results in heat transfer between the hot volatiles and the cold, unpyrolyzed feedstock; (iv) condensation of some of the volatiles in the cooler portions of the feedstock, followed by a secondary reaction, can produce char; (v) an autocatalytic secondary pyrolysis reaction proceeds while competing with the first pyrolysis reaction; (vi) further pyrolysis, reforming, water-gas shift reactions, free-radical recombination, and / or dehydration can also occur, which is a function of residence time, temperature, and pressure profiles.

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

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

[0117] Generally speaking, temperatures and residence times are selected to achieve relatively slow pyrolysis chemistry. A potential benefit is substantial preservation of the cell walls contained within the biomass structure, meaning that the final product may retain some, most, or all of the shape and strength of the starting biomass. To maximize this potential benefit, equipment that does not mechanically disrupt cell walls or converts biomass particles into small fines may be utilized. Various reactor configurations are described following the process description below.

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

[0119] In various embodiments, measures are taken to maintain the vascular structure of the woody feedstock to create additional strength in the bioreagent. For example, and without limitation, in various embodiments, the feedstock is prepared by drying the feedstock for an extended period of time, such as 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, 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., to allow moisture and gases to escape from the biomass without destroying the vascular structure of the feedstock. In various embodiments, a slow progressive heat rate is used during pyrolysis over minutes or hours (e.g., as opposed to fast pyrolysis) to allow moisture and gases to escape from the biomass without destroying the vascular structure of the feedstock. For example, and without limitation, the temperature increase rate during the pyrolysis step can range from about 1°C per minute to about 40°C per minute, e.g., about 1°C per minute, about 2°C per minute, about 4°C per minute, about 5°C per minute, about 10°C per minute, about 15°C per minute, about 20°C per minute, about 25°C per minute, about 30°C per minute, about 35°C per minute, 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 primarily 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 increase occurs at least in part in the carbonization zone or pyrolysis zone. In some embodiments, the temperature increase occurs primarily or entirely in the carbonization zone or pyrolysis zone. In some embodiments, the preheat zone, pre-pyrolysis zone, carbonization zone, or pyrolysis zone is configured to increase in temperature during pyrolysis gradually from an initial low temperature to a final high temperature. In some embodiments, the temperature increase is linear or substantially linear with time.In some embodiments, the rate of temperature increase is gradually increased or decreased so that the temperature during preheating, pre-pyrolysis, and / or carbonization or pyrolysis is at least partially nonlinear, e.g., logarithmic or substantially logarithmic for at least a portion of the preheating, pre-pyrolysis, and / or carbonization or pyrolysis steps. In various embodiments, additives are used prior to drying or pyrolysis to reduce gas generation during pyrolysis, which can damage the vascular structure of the feedstock. In various embodiments, prior to pyrolysis, the dried feedstock is sized using a saw or other cutting device designed to less disrupt the vascular structure of the wood than other sizing methods, such as wet wood chipping or shearing, which break down the wood and reduce its strength. In such embodiments, the bioreagent has a greater strength index (e.g., CSR value) than an equivalent bioreagent not prepared by such a method.

[0120] In some embodiments, the feedstock is prepared by grinding the biomass to form a plurality of biomass pieces that are substantially uniform in size and shape. For example, and without limitation, the biomass can be processed to produce sawdust of approximately uniform particle size (e.g., mesh size). Alternatively, the biomass can be processed to produce chips having substantially uniform dimensions (e.g., about 1 inch by about ½ inch by about ⅛ inch pieces). In other embodiments, the feedstock can be prepared by grinding the biomass to form lengths of material (e.g., wooden sticks, boards, or dowels) of substantially uniform width and depth dimensions or diameter. In related embodiments, the lengths 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 a substantially uniform size and shape. For example, a wooden dowel having a uniform diameter (e.g., 1-⅛ inches) can be cut into pieces of substantially uniform length (e.g., about 1.5 inches). The resulting feedstock pieces have a substantially uniform shape (cylindrical) and a substantially uniform size (about 1-1 / 8 inch diameter x about 1.5 inches long). In some embodiments, bioreagents prepared from feedstock consisting of pieces of substantially uniform shape and size are produced in greater mass yield than equivalent bioreagents prepared from feedstock pieces of substantially non-uniform shape and / or size.

[0121] Referring now generally to FIGS. 1-13, block flow diagrams of several exemplary multiple reactor embodiments of the present disclosure are shown. Each figure is described in turn below. It will be understood that FIGS. 1-13 represent several example embodiments, but not all anticipated embodiments, of the present disclosure. As will be explained below, various additional non-illustrated embodiments and combinations of several components and features described herein are also anticipated. As will be understood in the following discussion, any of the multiple reactors described herein may be stand-alone reactors, or alternatively, the BPU may include multiple zones within a single reactor, or a combination thereof. While each figure illustrates a different alternative embodiment, it will be understood that all other discussion within this disclosure is applicable to each of the illustrated and non-illustrated embodiments.

[0122] Referring now generally to FIG. 1, a block flow diagram of a multiple reactor embodiment of the present disclosure is shown. This embodiment can utilize two or more different reactors. While three reactors are shown in the exemplary embodiment, any different number of reactors can be employed. In one embodiment, each reactor is coupled to at least one other reactor via a material transport unit 304 (shown in FIG. 3). In one embodiment, the material transport unit 304 controls atmospheric and temperature conditions.

[0123] In the illustrated embodiment, a feedstock 109, such as biomass, is optionally dried and sized outside the system and optionally introduced into a first reactor 112 in a low-oxygen atmosphere through the use of a material feed system 108. As described in further detail below and shown in FIG. 3, the material feed system 108 reduces the oxygen level of the ambient air in the system to about 3% or less. The feedstock 109 enters the first reactor 112 after the oxygen level has been reduced in the first reactor through an enclosed material transport unit 304. In one embodiment, the feedstock transport unit may include an encapsulated jacket or sleeve through which the stream and off-gas from the reactor are routed and used to either directly preheat the biomass or to route it to a process gas heater, which is then used to preheat or pyrolyze the biomass.

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

[0125] As described in more detail below, in one embodiment, the first reactor 112 is configured to be coupled to any other reactor in the system to recover waste heat 132 and store 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 feedstock 109, either internal or external to the system. In various embodiments, other by-products of the waste heat, such as substantially heated inert gas or the like, can be used elsewhere in the system to further concentrate the material at any point during the process.

[0126] In the illustrated embodiment, biomass 109 enters first reactor 112, where the temperature is increased from about ambient temperature to about 150°C to a temperature of about 100°C to about 200°C. In one embodiment, the temperature does not exceed 200°C in the first reactor. As described in more detail below, first reactor 112 can include an output mechanism that captures and discharges off-gas 120 from biomass 123 while the biomass 123 is being heated. In one embodiment, off-gas 120 is extracted for optional later use. In various embodiments, the heat source used for the various zones within BPU 102 is electric or gas. In one embodiment, the heat source used for the various reactors of BPU 102 is waste gas from other reactors in unit 102 or from an external source. In various embodiments, the heating is indirect.

[0127] Following preheating in the first reactor 112, the material transport unit 304 passes the preheated material 123 to the optional second reactor 114. In one embodiment, the reactor 114 is identical to the reactor 112. In one embodiment, where the reactor 114 is different from the reactor 112, the material transport unit 304 penetrates the second reactor 114 through a high-temperature steam seal system (e.g., an airlock), which allows the material transport unit 304 to penetrate the second reactor 114 while preventing gas from escaping. 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 the first reactor 112 for capturing and venting the gases 122 released from the preheated material 123 while the preheated material 123 is being carbonized. In one embodiment, gas 122 is extracted for optional later use. In one exemplary embodiment, off-gas 120 from first reactor 112 and off-gas 122 from second reactor 114 are combined into one gas stream 124. Once carbonized, carbonized biomass 125 exits second reactor 114 and enters third reactor 116 for cooling. Again, the third reactor can be the same reactor as 112 or 114, or it can be different.

[0128] In one embodiment, once the bio-reagents 125 enter the third reactor 115, the carbonized biomass 125 is cooled (actively or passively) to a specific temperature range, as described above, to form the carbonized biomass 126. In one embodiment, the temperature of the carbonized biomass 125 is reduced in the third reactor under substantially inert atmospheric conditions. In another embodiment, the third reactor uses an additional water cooling mechanism to cool the carbonized biomass 125. It will be appreciated that the carbonized biomass 126 can be cooled in 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 reduces the temperature of the carbonized biomass to 200°C or below. In one embodiment, the third reactor includes a mixer (not shown) to agitate and uniformly cool the carbonized biomass. It will be appreciated that cooling can occur directly or indirectly with water or other liquid; cooling can also occur directly or indirectly with air or other cooled gas, or any combination of the foregoing.

[0129] It will be appreciated that in some embodiments (not shown), one or more additional cooling devices or mechanisms are employed to further reduce the temperature of the carbonized biomass. In various such embodiments, the cooling device is separate from the other reactors 112, 114, 116 along the material transport system. In some embodiments, the cooling device follows the reactor. In some embodiments, the cooling device may be the same as the reactors 112, 114, 116. In other embodiments, the cooling device may be, for example, a screw, auger, conveyor (specifically a belt conveyor in one embodiment), drum, screen, pan, counterflow bed, or other cooling device, either directly or indirectly with water or other liquid, or directly or indirectly with other gas. The cooling device may be a bed, a vertical tower, a jacketed paddle, a cooled screw, or a combination thereof or a combination of the foregoing. In various embodiments, the cooling device may include a water spray, a cooled inert gas stream, liquid nitrogen, or ambient air if below its ignition temperature. It will be appreciated 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 FIGS. 1 and 5 , the gas-phase separator unit 200 includes at least one input and multiple outputs. At least one input is coupled to exhaust ports on the first reactor 112 and the second reactor 114 of the BPU 102. One of the outputs is coupled to the carbon recovery unit 104, and another of the outputs is coupled to collection or further processing equipment, such as the acid hydrogenation unit 106 or a distillation column. In various embodiments, the gas-phase separator processes the off-gases 120, 122 from the first reactor 112 and the second reactor 114 to produce a condensate 128 and a concentrated gas 204. In various embodiments, the condensables can be used for energy recovery (134) (e.g., in a dryer, reactor, or process gas heater) or for other carbon enrichment purposes. In various embodiments, the non-condensables (e.g., CO) can be used for energy recovery (134) (e.g., in a dryer, reactor, or process gas heater), as an inert gas in the process (e.g., in a degassing unit, reactor, BPU, or chiller, as described in more detail below), or for carbon enrichment.

[0131] In various embodiments, the condensate 128 includes polar compounds, such as acetic acid, methanol, and furfural. In another embodiment, the enriched gas 204 produced by the gas phase separation apparatus 200 includes at least non-polar compounds, such as, for example, carbon monoxide, terpenes, methane, and carbon dioxide. In one embodiment, the gas phase separation apparatus includes a fractionation column. In one embodiment, the acetic acid is sent to an optional acid hydrogenation unit via line 128. In another embodiment, the methanol and / or furfural are sent to a distillation / treatment unit 138 via optional additional line(s) 136.

[0132] In various embodiments, the carbon recovery unit itself has provisions for concentrating the material, as described in further detail below. In various other embodiments, the material is concentrated in a material concentration unit that is separate from the carbon recovery unit. It will be understood that in some such embodiments, 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 FIG. 5 and described above, the carbon recovery unit 500 also includes an input 524 coupled to the gas-phase separation device 200. In one embodiment, the concentrated gas 204 is directed to the carbon recovery unit and combined with the bio-reagent 126 to produce the high-carbon bio-reagent 136. In another embodiment, carbon-enriched gas from an external source can also be directed to the carbon recovery unit and combined with the carbonized biomass 126 to add additional carbon to the resulting ultimate high-carbon bio-reagent. In various embodiments, the carbonized biomass 126 is carbonized biomass that has been reduced in temperature. Illustratively, the system 100 can be co-located near a wood processing facility, and carbon-enriched gas from the wood processing facility can be used as the gas from the external source.

[0134] Referring now generally to FIG. 2 , a block flow diagram of a single reactor, multi-zone embodiment of the present disclosure is shown. In the illustrated embodiment, a feedstock 109, such as biomass, is introduced into a reactor 200 in a low-oxygen atmosphere, optionally through the use of the previously described material feed system 108. As described in further detail below, the material feed system 108 reduces the oxygen level of the ambient air in the system to approximately 3% or less. After the oxygen level has been reduced, the feedstock 209 enters a BPU 202 within an enclosed material transport unit 304. In one embodiment, the feedstock transport unit may include an encapsulated jacket or sleeve through which the stream and off-gas from the reactor 200 are routed and used to heat the biomass.

[0135] In the illustrated embodiment, the feedstock first travels from the material feed system 108 on the material transport unit 304 through an optional drying zone 210 within the BPU 202. In one embodiment, the optional drying zone 210 heats the feedstock to remove water and other moisture before passing it to the preheating zone 212. In one embodiment, the interior of the optional drying zone 210 is heated to between about ambient temperature and about 150°C. Water 238 or other moisture removed from the feedstock 209 can be exhausted from the optional drying zone 210, for example. In another embodiment, the optional drying zone is adapted to allow 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 steam and steam extracted from the optional drying zone can be used in a suitable waste heat recovery system with the material feed system. In one embodiment, steam and water vapor used in the material feed system preheats the material while oxygen levels are purged in the material feed system. In another embodiment, the biomass is dried outside the reactor and the reactor does not include a drying zone.

[0136] As described in more detail below, in one embodiment, optional drying zone 210 is configured to be coupled to cooling zone 216 to recover waste heat 232 and store energy through a suitable waste heat recovery system. In one embodiment, the waste heat released in cooling zone 216 is used to operate a heating mechanism configured to dry feedstock 209 in optional drying zone 210. After being dried for a desired period of time, dried biomass 221 exits optional drying zone 210 and enters preheating zone 212.

[0137] In the illustrated embodiment, the dried biomass 221 enters the first (preheating) zone, where the temperature is increased from a range of about ambient temperature to about 150°C to a temperature range of about 100°C to about 200°C. In one embodiment, the temperature does not exceed 200°C in the first / preheating zone 212. It will be appreciated that if the preheating zone 212 is too hot or not hot enough, the dried biomass 221 may be inadvertently processed before entering the second zone 214. As described in more detail below, the preheating zone 212 may include an output mechanism that captures and exhausts off-gases 220 from the dried biomass 221 while the dried biomass 221 is being preheated. In another embodiment, the off-gases 220 are extracted for optional later use. In various embodiments, the heating source used for the various zones in the BPU 202 is electric or gas. In one embodiment, the heat source used for the various zones of BPU 202 is waste gas from other zones of unit 202 or from an external source. In various embodiments, the heating is indirect.

[0138] Following the preheating zone 212, the material transport unit 304 delivers the preheated material 223 to the second (pyrolysis) zone 214. In one embodiment, the material transport unit 304 penetrates the second (pyrolysis) zone 214 through a high-temperature steam seal system (e.g., airlock, not shown), which allows the material transport unit 304 to penetrate 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 the preheating zone 212 for capturing and discharging gases 222 released from the preheated biomass 223 while it is being carbonized. In one embodiment, the gases 222 are extracted for optional later use. In one exemplary embodiment, off-gas 220 from preheating zone 212 and off-gas 222 from pyrolysis zone 214 are combined into one gas stream 224. Once carbonized, carbonized biomass 225 exits second / pyrolysis zone 214 and enters third / temperature reduction or cooling zone 216.

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

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

[0141] In the illustrated embodiment, the carbonized biomass exits the cooling reactor / zone along material transport unit 304 and enters carbon recovery unit 500. In various embodiments, as shown in more detail in FIG. 5 and described above, carbon recovery unit 500 also includes an input 524 coupled to gas phase separation device 200. In one embodiment, enriched gas 204 is directed to carbon recovery unit 500 and combined with bio-reagent 226 to produce high-carbon bio-reagent 136. In another embodiment, carbon-enriched gas from an external source can also be directed to carbon recovery unit 500 and combined with bio-reagent 226 to add additional carbon to the bio-reagent. In various embodiments, gas removed from carbon recovery unit 500 at 234 is optionally used in an energy recovery system and / or a system for further carbon enrichment. Similarly, in various embodiments, gas removed from one or more zones of BPU 202 is optionally used in an energy recovery system and / or a system for further carbon enrichment. By way of example, the system 200 can be co-located near a wood processing facility, with carbon-enriched gas from the wood processing facility being available as gas from an external source.

[0142] Referring now generally to FIG. 3 , one material feed system embodiment of the present disclosure is illustrated. As previously discussed, high oxygen levels in the ambient air surrounding the feedstock during processing can result in undesirable combustion or oxidation of the feedstock, which reduces the quantity and quality of the final product. In one embodiment, the material feed system is a closed system and includes one or more manifolds configured to purge oxygen from the air surrounding the feedstock. 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 appreciated that a primary objective of a closed material feed 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 is reduced, the biomass is moved along the material feed system to the BPU. It will be appreciated that, in various embodiments, preheating an inert gas through recovered process energy and subsequently introducing the preheated inert gas into a BPU, reactor, or trimming reactor can further enhance the efficiency of the system.

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

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

[0145] In one embodiment, the feedstock hopper 300 is any suitable open-air or closed-air container configured to receive raw or sized / dried biomass 109 / 209. The feedstock 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 feedstock 109 / 209 is poured into the material transport unit 304 via a gravity-fed system. It will be appreciated that the material transport unit 304 of FIG. 3 is adapted such that the screw or auger 305 is surrounded by a suitable enclosure 307. In one embodiment, the enclosure 307 is substantially cylindrical in shape. In various embodiments, the material feed system includes a screw, auger, conveyor, drum, screen, ramp, drop chamber, or pneumatic conveyor, including a rotary airlock or a double or triple flap airlock.

[0146] As the raw material 109 / 209 is fed from the raw material feed 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. It will be appreciated that when the raw material 109 / 209 reaches the oxygen purge manifold 302, 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 positioned adjacent to or near the material transport unit 304. Within the oxygen purge manifold of one embodiment, an enclosure 307 of the material transport unit 304 includes multiple gas inlet ports 310a, 310b, 310c and multiple gas exhaust ports 308a, 308b, 308c.

[0147] The oxygen purge manifold 302 includes at least one gas inlet line 312 and at least one gas outlet line 314. In various embodiments, the at least one gas inlet line 312 of the oxygen purge manifold 302 is in operative communication with each of the plurality of gas inlet ports 310a, 310b, 310c. Similarly, in various embodiments, the at least one gas outlet line 314 of the oxygen purge manifold 302 is in operative communication with each of the plurality of gas outlet ports 308a, 308b, 308c. It will be appreciated that in one embodiment, the gas inlet line 312 is configured to admit an inert gas to the gas inlet ports 310a, 310b, 310c. In one such embodiment, the inert gas is substantially oxygen-free nitrogen. In one embodiment, the inert gas will flow countercurrently to the biomass.

[0148] Naturally, the introduction of inert gas 312 into the enclosed material transport unit 304 forces ambient air out of the enclosed system. During operation, when inert gas 312 is introduced into the first gas inlet port 310a of one embodiment, a large amount of ambient air rich in oxygen is forced out the exhaust port 308a. It will be appreciated that at this point, the desired levels of about 2% oxygen or less, about 1% oxygen or less, about 0.5% oxygen or less, or about 0.2% oxygen or less may not be reached. Therefore, in various embodiments, additional injection of inert gas 312 is required to purge the necessary amount of oxygen from the air surrounding the raw material 109 in the enclosed system. In one embodiment, following injection at the first gas inlet port 310a, the second gas inlet port 310b admits inert gas 312 into the enclosed system, thereby purging much of the remaining oxygen from the enclosed system. It will be appreciated that the desired level of less oxygen may be reached after one or two injections of inert gas 312 to purge the oxygen 314. In one embodiment, if the desired oxygen level is still not achieved after two inert gas injections, a third injection of inert gas 312 at gas inlet port 310c will purge any remaining undesired amounts of oxygen 314 from the enclosed system at gas outlet port 308c. Additional inlets / outlets may also be incorporated if desired. In various embodiments, oxygen levels are monitored throughout the material delivery system to allow for calibration of the amount and location of inert gas injection.

[0149] In an alternative embodiment, the heat, steam, and gases recovered from the reactor are directed to a feed system where they are enclosed within a jacket and isolated from direct contact with the feed, but indirectly heat the feed material prior to introduction into the reactor.

[0150] In an alternative embodiment, the heat, steam, and gases recovered from the drying zone of the reactor are directed to a feed system where they are enclosed within a jacket and isolated from direct contact with the feedstock, but indirectly heat the feed material prior to introduction into the reactor.

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

[0152] It will be appreciated that in one embodiment, the feedstock 109 / 209, and subsequently the dried biomass 221, preheated biomass 123 / 223, carbonized biomass 125 / 225, and carbonized biomass 126 / 226, travel along successive material transport units 304 to the reactor 102 (or multiple reactors). In another embodiment, the material transport units conveying the material are different at different stages in the process. In one embodiment, the process of moving 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 an associated controller and processor so that operation of the material transport unit 304 does not require interruption as material moves through the reactor or multiple reactors.

[0153] In another embodiment, a controller associated with the reactor 102 or reactor (112 / 114 / 116) is configured to adjust the speed of the material transport unit 304 based on one or more feedback sensors, sensed gases (e.g., from an optional FTIR), measured parameters, thermometers, or other suitable variables in the reactor process. It will be understood that in various embodiments, any suitable humidity, temperature, or gas sensors in operative communication with the controller and processor can be incorporated within or between each of the zones / reactors or at suitable locations along the material transport unit 304. In one embodiment, the controller and processor uses sensor or meter information to optimize the speed and efficiency of the BPU 100 / 200. In one embodiment, a controller associated with the reactor 102 or reactor (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 concentration of gas, temperature, and humidity within the material transport unit 304 or within any reactor. In one embodiment, the controller is configured to adjust the speed of the material transport unit 304, the injection of gas into the material transport unit, and the heat applied to the material in the material transport unit based on one or more measurements obtained by the various sensors.

[0154] 2 and 4, one embodiment of BPU 102 is shown. It will be understood that the graphical representation of BPU 202 in FIG. 4 substantially corresponds to BPU 202 in FIG. 2. It will also be understood that in various embodiments, BPU 202 is surrounded by a kiln shell to control and manipulate the bulk of the heat required for the reactor process. As seen in FIG. 4, in one embodiment, the kiln shell of BPU 202 includes several insulated chambers (416, 418) that surround 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 BPU 202 includes at least one inlet flight and at least one outlet flight. As described in more detail below, within each zone in one such embodiment, the inlet and outlet flights are adjustable to control the flow of feedstock, gas, and heat to and from the zone. An inert gas supply can be introduced into an inlet flight, and purged air can be extracted from a corresponding outlet flight. In various embodiments, one or more of the outlet flights of a zone within BPU 202 are connected to one or more of the other inlet or outlet flights within BPU 202.

[0155] In one embodiment, the feedstock 209 is deoxygenated in the material supply system 108 before being transferred to the BPU 202, specifically the first of four zones, optional drying zone 210. As seen in FIG. 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 feedstock 209. The biomass is then moved to the second or preheating zone 212, where the biomass is preheated as previously described.

[0156] In another embodiment, the optionally dried and preheated material is transferred to a third, or carbonization, zone. In one embodiment, carbonization is performed at a temperature of about 200°C to about 700°C, e.g., 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 430°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, about 500°C, about 510°C, about 520°C, about 530°C, about 540°C, about 550°C, about 560°C, about 570°C, about 580°C, about 590°C, about 600°C, about 610°C, about 620°C, about 630°C, about 640°C, about 650°C, about 660°C, about 670°C, about 680°C, about 690°C, about 700°C, about 710°C, about 720°C, about 730°C, about 740°C, about 750°C, about 760° The carbonization may occur at temperatures of about 30°C, about 440°C, about 450°C, about 460°C, about 470°C, about 480°C, about 490°C, about 500°C, about 510°C, about 520°C, about 530°C, about 540°C, about 550°C, about 560°C, about 570°C, about 580°C, about 590°C, about 600°C, about 610°C, about 620°C, about 630°C, about 640°C, about 650°C, about 660°C, about 670°C, about 680°C, about 690°C, or about 700°C. In another embodiment, the carbonization zone of reactor 421 is adapted to allow gases produced during carbonization to be extracted. In another embodiment, gases produced during carbonization are extracted for optional later use. In one embodiment, the carbonization temperature is selected to minimize or eliminate the production of methane (CH4) and maximize the carbon content of the carbonized biomass.

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

[0158] In various embodiments, the BPU includes multiple gas introduction probes and gas extraction probes. In the embodiment of the BPU shown in FIG. 4, the BPU further includes multiple gas introduction probes 408, 410, 412, and 414, and multiple gas extraction probes 400, 402, 404, and 406. It will be appreciated that in various embodiments, one of each gas introduction probe and one of each gas extraction probe corresponds to a different one of the multiple zones 210, 212, 214, and 216. It will also be appreciated that in various alternative embodiments, the BPU 202 includes any suitable 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. It will be appreciated that in various embodiments, the gas introduction probe 412 is configured to introduce a mixture of gases into the drying zone 210. In one embodiment, the extracted gas is oxygen. It will be appreciated that in various embodiments, the gas extraction probe 402 extracts gas from the drying zone 210 for reuse 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. It will be appreciated that in various embodiments, 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 comprises carbon-enriched off-gas. It will be appreciated that in one embodiment, as previously discussed, 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 gases extracted from either zone of the reactor are used for energy recovery in a dryer 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 gases from the pyrolysis zone 214. It will be appreciated that in various embodiments, 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 comprises carbon-enriched off-gas. It will be appreciated that in one embodiment, as previously discussed, the carbon-enriched gas extracted from the pyrolysis zone 214 is used at a later stage in the process and reintroduced to the material. In various embodiments, the gas 400 extracted from the preheat zone 212 and the gas 404 extracted from the pyrolysis zone 214 are combined before being reintroduced to the material, as described in further detail below.

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

[0163] It will be appreciated that the gas introduction and extraction probes of the various embodiments described above are configured to operate in conjunction with the controller and sensors described above to regulate the level and concentration of gas being introduced into and extracted from each zone.

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

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

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

[0167] In various embodiments, the gas introduction probes are arranged concentrically with one another to conserve space used by the multi-port configuration described in the example above. In one such embodiment, each of the four inlet probes / ports will have a smaller diameter than the previous inlet probe / port. For example, in one embodiment, the drying zone gas introduction probe has the largest internal diameter, then the preheating zone gas introduction probe is positioned within the internal diameter of the drying zone inlet probe / port, the pyrolysis zone gas introduction probe is then positioned within the internal diameter of the preheating zone gas introduction probe, and the cooling zone gas introduction probe is positioned within the pyrolysis zone gas introduction probe. In one embodiment, appropriate connectors are attached to each of the four gas introduction probes outside of 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 drying zone gas introduction probe terminates in the drying zone, and the other three gas introduction probes continue to the preheat zone. However, in a concentric or substantially concentric arrangement, only the outermost gas introduction probe is exposed within each zone before being terminated. Thus, in one such embodiment, the individual zone gas introductions are efficiently controlled independently of one another, requiring only one continuous gas introduction probe line. It will be appreciated that a similar concentric or substantially concentric configuration is suitably used for the gas extraction probes in one embodiment.

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

[0170] As previously described and generally shown in FIG. 5 , the off-gas 124 / 224 from the BPU 102 / 202 is directed to a vapor-phase separator. In various embodiments, the off-gas 124 / 224 includes the gas 120 extracted from the first / preheating zone / reactor 112 / 212 combined with the gas 122 / 222 extracted from the second / pyrolysis zone / reactor 114 / 214, or only one gas stream. As the off-gas 124 / 224 enters the vapor-phase separator, the off-gas 124 / 224 is separated into polar compounds 128 / 228 / 136 / 236 and non-polar compounds 204, such as non-polar gases. In various embodiments, the vapor-phase separator 200 is a known fractionation column.

[0171] In various embodiments, the enriched gas 204 extracted from the combined off-gas 124 / 224 is directed from the gas-phase separation device 200 via input 524 to a carbon recovery unit 500 where the materials are enriched. As discussed above and shown in FIGS. 8 and 11 , it will be understood that in various embodiments, the extracted gas is first introduced to a material enrichment unit and then to a separate carbon recovery unit. In the embodiment shown in FIG. 5 , the material enrichment occurs within the carbon recovery unit 500. In one embodiment ( FIG. 5 ), the gas-phase separation device 200 includes multiple outputs. In various embodiments, one output from the gas-phase separation device 200 is coupled to the carbon recovery unit 500 for introducing the enriched gas stream into the carbon recovery unit 500. In one embodiment, a portion of the enriched gas stream is directed to the carbon recovery unit 500, and another portion is directed to a scrubber or other suitable purification device for purification and disposal of unwanted gases. In various embodiments, off-gas that is 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 chiller). 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 chiller), or in a secondary recovery unit.

[0172] In one embodiment, another output from the gas phase separation device extracts polar compounds and optionally condenses them into liquid components, including multiple distinct flowing portions. In various embodiments, the liquids include water, acetic acid, methanol, and furfural. In various embodiments, the liquids produced are stored, disposed of, further processed, or reused. For example, it will be appreciated that the water produced in one embodiment can be reused to heat or cool another portion of the system. In another embodiment, the water is discharged. It will also be appreciated that the acetic acid, methanol, and furfural produced in one embodiment can be sent to storage tanks for reuse, resale, distillation, or purification.

[0173] As seen in FIG. 5 , one embodiment of the carbon recovery unit 500 comprises a housing having an upper portion and a lower portion. In various embodiments in which the material enrichment unit is separate from the carbon recovery unit, it will be understood that the material enrichment unit includes similar features as those described in connection with the carbon recovery unit 500 of FIG. 5 . In one embodiment, the carbon recovery unit includes: a housing 502 having an upper portion 502 a and a lower portion 502 b; an inlet 524 at a bottom surface of the lower portion of the housing configured to convey the reactor off-gas; an outlet 534 at a top surface of the upper portion of the housing configured to convey the enriched gas stream; a pathway 504 defined between the upper and lower portions of the housing; and a transport system 528 following the pathway, the transport system configured to transport a reagent, the housing configured to adsorb at least a portion of the reactor off-gas. In various embodiments, the upper portion includes multiple outlets, and the lower portion includes multiple inlets.

[0174] In one embodiment, the housing 502 is substantially free of 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 substantially free of convex corners. In another embodiment, the housing 502 is substantially free of convex corners that can create vortices or trap air. In another embodiment, the housing 502 is substantially shaped like a cube, a rectangular prism, an ellipsoid, a stereographic ellipsoid, a spheroid, two cones glued together, two tetrahedrons glued together, two rectangular pyramids glued together, or two isosceles triangular prisms glued together.

[0175] In one embodiment, the upper portion 502a and the lower portion 502b of the housing 502 are each shaped substantially like a half ellipse, a half rectangular prism, a half solid ellipsoid, a half spheroid, a cone, a regular tetrahedron, a rectangular pyramid, an isosceles triangular prism, or a round-to-rectangular duct transition.

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

[0177] In one embodiment, carbon recovery unit 500 includes a pathway 504 defined between an upper portion and a lower portion, an inlet opening 506, and an outlet opening 508. In one embodiment, the inlet opening and the outlet opening are configured to receive a transport system. In one embodiment, transport system 528 is at least semi-permeable or permeable to the enriched gas.

[0178] In one embodiment, the inlet opening 506 includes an inlet 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 inlet and exhaust opening sealing mechanisms comprise airlocks.

[0179] In various embodiments, the lower portion 502b of the carbon recovery unit housing has a narrow, rounded-bottom connecting opening that connects to the gas-phase separation device 200 for transport of the gas stream 204. In various embodiments, the top of the lower portion 502b of the carbon recovery unit housing is substantially rectangular in shape and is substantially wider than the narrow, rounded-bottom connecting opening. It will be appreciated that in one embodiment, the lower portion transitions from the rounded-bottom opening to a rectangular top opening. In one embodiment, the rectangular top opening of the lower portion is approximately 6 feet wide (along the direction of the conveyor system). In various embodiments, the upper portion of the carbon recovery unit 500 is shaped substantially similarly to the lower portion. In one embodiment, the bottom opening of the upper portion is wider than the top opening of the lower portion. In one embodiment, the rectangular bottom opening of the upper portion is approximately 6.5 feet wide (along the direction of the conveyor system). In one embodiment, the upper portion is configured to capture all gas passing through the carbon recovery unit 500 that is not adsorbed by the activated material.

[0180] It will be appreciated that in various embodiments, the shape of the lower portion of the carbon recovery unit helps to slow and disperse the gas 204 over a larger surface area of the conveyor carrying the bioreagents 126 / 226. In various embodiments, the exact shape of the lower portion 502b and upper portion 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 appreciated that gases naturally tend to expand when pumped at a flare ranging from 5 to 30 degrees from vertical. In one embodiment, the flare angle is approximately 15 degrees. It will be appreciated that the lower portion of the carbon recovery unit is constructed with as few creases and corners as possible to prevent air trapping or the creation of vortices.

[0181] In one embodiment, the carbon recovery unit 500 is configured to couple to the BPU 102 / 202 as well as the gas phase separation device 200, as previously described. In various embodiments, the carbon recovery unit 500 is coupled to the output of the cooling reactor / zone 216 / 116, or the BPU 102 / 202 or the last cooling zone external to the BPU. In one embodiment, the output of the cooling reactor / zone 116 / 216 contains the bio-reagents being processed within the BPU 102 / 202. In one embodiment, the bio-reagents 126 / 226 enter the carbon recovery unit 500 along a suitable transport system. In various embodiments, the top and bottom sections of the carbon recovery unit are connected to each other and 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 therethrough. It will be appreciated that the transport system is configured to pass through an opening in the carbon recovery unit 500 and then through an outlet opening of the carbon recovery unit. In some embodiments, the inlets to and outlets from the carbon recovery unit are suitably sealed with airlocks or another suitable sealing mechanism to prevent gas from leaking through the conveyor openings. In various embodiments, off-gas that is 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 chiller). 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 chiller), or in a secondary recovery unit.

[0182] In various embodiments, the process operates by first outputting the bio-reagent 126 / 226 from the cooling reactor / zone 116 / 216 onto a transport system using an appropriate release mechanism from the cooling reactor / zone 116 / 216. In one embodiment, the bio-reagent 126 / 216 is spread across the width of the transport system to minimize stacking or bunching of material and maximize surface area for gas absorption. Once the bio-reagent 126 / 216 has been deposited and is appropriately spread across the transport system, in various embodiments, the transport system transports the bio-reagent 126 / 226 through the opening in the carbon recovery unit 104 defined between the lower and upper portions, as previously described. Within the carbon recovery unit 104, the bio-reagent 126 / 216 adsorbs gases piped from the vapor phase separator 200 to the lower portion of the carbon recovery unit 104. It will be appreciated that after the bio-reagent is enriched with non-polar gases, the bio-reagent becomes a high-carbon bio-reagent. In various embodiments, the high-carbon biological reagent is the end product of the processes disclosed herein and is transported from the carbon recovery unit 104 to suitable storage or post-treatment equipment.

[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 conveyed to a suitable scrubber, stack, or recovery system. In some embodiments, the exhausted gas is utilized for any reusable quality within the system, including use in a secondary carbon recovery unit or for energy. In various embodiments, off-gas not sent to the carbon recovery unit can 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 chiller). Similarly, in various embodiments, off-gas from the carbon recovery unit can 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 chiller), or in a secondary recovery unit.

[0184] It will be appreciated that the bio-reagent 126 / 216 contains a large amount of carbon, and carbon has a high priority for adsorbing non-polar gases. It will also be appreciated that the enriched gas stream 204 primarily contains non-polar 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 enriched gas passes from the gas-phase separator to the carbon recovery unit to ensure maximum adsorption of non-polar gases within the bio-reagent 126 / 216. In another embodiment, high-energy organic compounds are eluted during carbonization of the biomass and comprise at least a portion of the enriched gas 204 output from the gas-phase separator 200 to the carbon recovery unit. In various embodiments, the enriched gas 204 is further enriched with additional additives before being introduced into the carbon recovery unit or material enrichment unit.

[0185] As described in further detail below, in various embodiments, the residence time of the bio-reagent 126 / 216 in the carbon recovery unit is controlled and varied based on the components of the bio-reagent 126 / 216 and the gas flow and composition. In one embodiment, the bio-reagent is passed multiple times through one or more carbon recovery units. In various embodiments, the concentrated gas output from the gas phase separator and the exhaust gas output from the carbon recovery unit 104 can be diverted or diverted to additional carbon recovery units, or further purified or used for energy or inert gases for use in the process.

[0186]

[0023] Referring now generally to Figures 6-13, various embodiments of the present disclosure are shown and described. It will be understood that the various embodiments and alternatives described below in connection with Figures 6-13 also apply to the previously described embodiments of Figures 1-5, and vice versa.

[0187] Referring now particularly to Figure 6, this embodiment can utilize a BPU that includes a single reactor with two or more distinct zones. While 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, system 600 includes a material feed system 602, a BPU 606 including a pyrolysis zone 608 and a cooling zone 610, a chiller 614, and a carbon recovery unit 616. It will be understood that the chiller 614 in Figure 6 is external to BPU 606 and is in addition to the cooling zone 610 that is present within BPU 606.

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

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

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

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

[0193] 9, a BPU 908 of one embodiment of a system 900 is shown and described. The BPU 908 includes multiple zones: a preheating zone 904, a pyrolysis zone 910, and a cooling zone 914. The BPU 908 of one embodiment also includes a material feed 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, one of the zones also includes at least one outlet 912 for outputting a substance, in one embodiment, condensable vapors and / or non-condensable gases, as described below. In various embodiments, one of the zones also includes an outlet for outputting advanced carbon from the system 900.

[0194] 9 shows gas inlet 906 coupled to preheat zone 904, it will be understood that various embodiments include inlets to any combination of the three zones. Similarly, while gas outlet 912 comes from pyrolysis zone 910, it will be understood that various embodiments include outlets from one or more of any combination of the three zones. As described below, various contemplated embodiments include inputs and outputs within the BPU: for example, the outlet of pyrolysis zone 910 is then an input to preheat zone 904. It will be understood that in the illustrated embodiment, each of the reactors within the BPU are coupled to one another by a material supply system, as previously described.

[0195] In various embodiments, the preheat zone 904 of the BPU 908 is configured to feed the biomass 902 (or another carbon-containing feedstock) in a manner that does not "shock" the biomass, which may rupture cell walls and initiate rapid decomposition of the solid phase into vapors and gases. In one embodiment, the preheat zone 904 may be considered a mild 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, releasing gases and condensable vapors, resulting in solids that are high-carbon reaction intermediates. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to produce vapors that escape by penetrating pores or creating new nanopores. The latter effect contributes to the creation of porosity and surface area.

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

[0198] 10-13, various multi-reactor embodiments of the system are shown and described. As with each embodiment, the system includes an optional degasser and an optional dryer, as described in more detail below. Referring to FIG. 10, system 1000 includes a material feed system 1002, a pyrolysis reactor 1012, a cooling reactor 1018, a chiller 1020, and a carbon recovery unit 1022. As further described below, one or both are configured for injection. In various embodiments, the pyrolysis reactor includes an outlet for outputting at least condensable vapors and / or non-condensable gases. In various embodiments, the carbon recovery unit 1022 includes an outlet 1024 for discharging activated carbon from the system 1000.

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

[0200] In some embodiments, with reference to FIG. 10, a process for producing a high-carbon bio-reagent comprises the following steps: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock 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 pyrolysis solids, condensable vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) cooling the hot pyrolysis solids to produce cooled pyrolysis solids; and (g) recovering the high-carbon biological reagent comprising at least a portion of the cooled pyrolysis solids.

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

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

[0203] As detailed below, there are numerous options with regard to intermediate input and output (purge or probe) streams of one or more phases present in any particular reactor, various mass and energy recycling schemes, various additives that may be introduced anywhere in the process, adjustability of process conditions, including both reaction and separation conditions to adjust product distribution, etc. Zone or reactor specific input and output streams allow for better process monitoring and control, such as through FTIR sampling and dynamic process adjustments.

[0204] The present disclosure differs from fast pyrolysis and also differs from conventional slow pyrolysis. High quality carbon materials in the present disclosure, including compositions with a high percentage of fixed carbon, can be obtained from the disclosed processes and systems.

[0205] "Biomass" is understood in this disclosure to mean any living feedstock or a mixture of living and non-living feedstocks. Elementally, biomass contains at least carbon, hydrogen, and oxygen. The methods and apparatus of the present invention are compatible with 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 utilizing biomass, the biomass feedstock may include one or more materials selected from: wood harvest residues, softwood chips, hardwood chips, tree branches, tree stumps, knots, leaves, bark, sawdust, off-spec paper pulp, cellulose, corn, corn stover, wheat straw, rice straw, sugarcane pomace, switchgrass, miscanthus, 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 textiles. Those skilled in the art will readily appreciate that the choice of feedstock is virtually limitless.

[0207] Various embodiments of the present disclosure are also used with carbon-containing feedstocks other than biomass, such as fossil fuels (e.g., coal or petroleum coke) or any mixture of biomass and fossil fuels (such as a biomass / coal mixture). In some embodiments, the biological feedstock is or includes coal, oil shale, crude oil, asphalt, or solids from crude oil processing (such as petroleum coke). Feedstocks may include scrap tires, recycled plastics, recycled paper, and other waste or recycled materials. Any method, apparatus, or system described herein may be used with any carbonaceous feedstock. The carbon-containing feedstock may be transportable in any known manner, such as by truck, train, ship, barge, tractor-trailer, or any other vehicle or transportation means.

[0208] The selection of a particular feedstock or feedstocks is not considered technically critical, but is carried out in a manner that favors process economics. Generally, regardless of the feedstock selected, There may be screening (in some embodiments) to remove undesired materials. The feedstock may optionally be dried prior to processing.

[0209] The feedstock employed can be provided in or processed into a wide variety of particle sizes or shapes. For example, the feedstock can be a fine powder or a mixture of fine and coarse particles. The feedstock can be in larger forms, such as wood chips or other forms of wood (e.g., round, cylindrical, rectangular, etc.). In some embodiments, the feedstock comprises pellets or other agglomerated forms of particles that are compressed together or otherwise bound, such as with a binder.

[0210] It should be noted that size reduction is an expensive and energy-intensive process. Pyrolyzed materials can be sized with significantly less energy input, i.e., it can be more energy efficient to reduce the particle size of the product rather than the feedstock. This is an option in the present disclosure, as the process does not require fine starting materials, nor does it require any pulverization during the process. The present disclosure provides the ability to process very large feedstocks. 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, while not required in all embodiments of the present disclosure, smaller sizes result in higher fixed carbon numbers under similar process conditions and may be preferred in some embodiments.

[0211] If it is desired to produce a final carbonaceous bio-reagent with structural integrity, such as a cylindrical shape, there are at least two options in the context of the present invention. First, the material produced from the process is collected and then further processed mechanically into the desired shape. For example, the product is compressed or pelletized using a binder. The second option is to utilize a feed material that generally 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, cubes, etc.

[0212] The ability to maintain the approximate shape of the feed material throughout the process is beneficial when product strength is important, and this control avoids the difficulty and expense of pelletizing high fixed carbon materials.

[0213] The starting feedstock in various embodiments is provided with various moisture levels, as will be appreciated. In some embodiments, the feedstock is already sufficiently dry and does not require further drying prior to pyrolysis. Generally, it is desirable to utilize biomass from commercial sources, which typically contain moisture, and to feed the biomass through a drying step before introducing it into the pyrolysis reactor. However, in some embodiments, dried feedstock is used. While various embodiments will work with any biomass, it will be appreciated that the following factors can affect the process and its products: how the material was grown, harvested, and watered; material species selection; and carbon content. Specifically, in various embodiments, the use of less fertilizer and less phosphorous acid during cultivation results in better properties for metal production. In various embodiments, lower shear impact during harvesting 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 the temperature profile within the BPU is selected to promote the production of carbon dioxide over carbon monoxide, resulting 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 total carbon to CO2 may occur, and the heat released from the exothermic oxidation may support the endothermic pyrolysis chemistry. Bulk oxidation of carbon, including partial oxidation to syngas, will reduce the carbon that becomes solids.

[0216] In practice, it can be difficult to achieve a strictly oxygen-free environment within each reactor or BPU. This limit can be approached, and in some embodiments, the reactor or BPU is substantially free of molecular oxygen in the gas phase. To ensure there is little or no oxygen within the reactor or BPU, it may be desirable to remove air from the feed material before introducing it into the reactor or BPU. There are various methods for removing or reducing air within the feedstock.

[0217] In some embodiments, as seen in Figures 10, 11, 12, and 13, a degassing unit is utilized in which the feedstock, before or after drying, is conveyed in the presence of another gas that can remove adsorbed oxygen and penetrate the pores of the feedstock to remove oxygen therefrom. Almost any gas with an O content below 21 vol% can be employed with varying effectiveness. In some embodiments, CO and / or CO can be employed. Mixtures can be used, such as a mixture of nitrogen and a small amount of oxygen. Water vapor can be present in the degassed gas, but adding significant moisture back to the feed should be avoided. The effluent from the degassing unit can be purged (to the atmosphere or an exhaust treatment unit) or recycled.

[0218] In principle, the effluent from the degassing unit (or a portion thereof) could be introduced into the pyrolysis reactor itself, since the oxygen removed from the solids would immediately be highly diluted. In this embodiment, introducing the degassed tail gas into the last zone of the reactor could be advantageous when operating in a countercurrent 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 moisture present. In some embodiments, the drying and degassing steps are combined in a single unit, or some amount of degassing is achieved during drying.

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

[0221] When a single reactor is employed (such as in Figure 6, Figure 3, or Figure 4), there can be multiple zones. Multiple zones, such as two, three, four, or more zones, can allow for separate control of temperature, solids residence time, gas residence time, gas composition, flow pattern, and / or pressure to tailor overall process performance.

[0222] As previously mentioned, references to "zones" will 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 the BPU may relate to structure, such as flights within the BPU or the presence of separate heating elements to provide heat to individual zones. Alternatively, or additionally, in various embodiments, the division of zones within the BPU relates to function, such as at least: separate temperatures, fluid flow patterns, solids flow patterns, and reactor ranges. In a single batch reactor, a "zone" is an operating regime in time rather than in space. Various embodiments include the use of multiple batch BPUs.

[0223] It will be understood that there is not necessarily an abrupt transition from one zone to another. For example, the boundary between the preheat zone and the pyrolysis zone may be somewhat arbitrary; i.e., some pyrolysis may occur in part of the preheat zone, and some "preheating" may continue in the pyrolysis zone. The temperature profile within the BPU is typically continuous, including at zone boundaries within the 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 between about 80°C and about 500°C, such as between about 300°C and about 400°C. In various embodiments, the temperature of the preheating zone 304 is not so high as to shock the biomass material, which would rupture cell walls and initiate rapid decomposition of the solid phase into vapors and gases. Pyrolysis, commonly known as fast or flash pyrolysis, is avoided in the present disclosure.

[0225] All references to zone temperatures herein should be interpreted in a non-limiting manner to include temperatures that may be applied to the bulk solids or gas phase present, or to the reactor or BPU walls (process side). It will be understood that within each zone there are temperature gradients both axially and radially, and over time (e.g., following startup or temporarily). Thus, references to zone temperatures may refer to average temperatures or other effective temperatures that may affect actual reaction kinetics. Temperatures may be measured directly by thermocouples or other temperature probes, or may be measured or estimated indirectly by other means.

[0226] The second zone, or primary pyrolysis zone, is operated under pyrolysis or carbonization conditions. The temperature of the pyrolysis zone can be selected from about 250°C to about 700°C, such as about 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, or 650°C. Within this zone, the preheated biomass undergoes pyrolysis chemistry, releasing gases and condensable vapors and leaving a significant amount of solids as high-carbon reaction intermediates. Biomass components (primarily cellulose, hemicellulose, and lignin) decompose to produce vapors that escape by penetrating pores or creating new pores. The temperature will depend, at least, on the residence time in the pyrolysis zone, as well as the nature of the feedstock and product properties.

[0227] The cooling zone is operated to cool the high-carbon reaction intermediates to various 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, from about 150°C to about 350°C.

[0228] In various embodiments, chemical reactions continue to occur within the cooling zone. It will be appreciated that in various embodiments, secondary pyrolysis reactions are initiated in the cooling zone. Carbon-containing components that are in the gas phase may condense (due to the reduced temperature of the cooling zone). However, the temperature is sufficiently high to promote reactions that may 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 plus fixed carbon (Boudouid reaction).

[0229] Zone residence times can vary. For a desired amount of pyrolysis, higher temperatures may allow for less reaction time, and vice versa. Residence time in a continuous BPU (reactor) is the volume divided by the volumetric flow rate. Residence time in a batch reactor is the batch reaction time following heating to the reaction temperature.

[0230] It should be recognized that in a multiphase BPU, there are multiple residence times. In the present context, within each zone, there are residence times (and residence time distributions) for both the solid and vapor phases. For a given unit employing multiple zones and having a given throughput, the residence time across the zones is generally tied to the solids side, although if multiple inlet and exhaust ports are utilized in individual zones, the residence time can be separated from the vapor side. In various embodiments, the solid and vapor residence times are separated.

[0231] The residence time of the solids in the preheat zone can be selected from about 5 minutes to about 60 minutes, such as about 10 minutes, depending on the temperature and time required to reach the preheat temperature. The heat transfer rate, which can depend on the type and size of the particulate, the physical machinery, and the heating parameters, determines the minimum residence time required to allow the solids to reach the desired preheat temperature.

[0232] The residence time of the solids in the pyrolysis zone can be selected from about 10 minutes to about 120 minutes, such as about 20 minutes, 30 minutes, or 45 minutes. Depending on the pyrolysis temperature in this zone, there should be sufficient time after the necessary heat transfer to allow the carbonization chemistry to occur. For times of about 10 minutes or less, the temperature would need to be extremely high, e.g., 700°C or higher, to remove large amounts of non-carbon elements. This temperature can promote rapid pyrolysis and the production of vapors and gases derived from the carbon itself, which is avoided when the intended product is solid carbon.

[0233] In static systems of various embodiments, equilibrium conversion is reached at some point. When, as in some embodiments, steam is continuously flowing over the solids while continuously removing volatiles, the equilibrium constraint may be removed, allowing pyrolysis and devolatilization to continue until the reaction rate approaches zero. Longer times may tend to leave the remaining recalcitrant solids substantially unchanged.

[0234] The residence time of the solids in the cooling zone in various embodiments can be selected from about 5 minutes to about 60 minutes, such as about 30 minutes. Based on the cooling temperature in this zone, there should be enough time to allow the carbon solids to cool to the desired temperature. The cooling rate and temperature determine the minimum residence time required to allow the carbon to cool. Additional time may not be desirable unless some secondary pyrolysis is desired.

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

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

[0237] A variety of flow patterns may be desired or observed. For chemical reactions and simultaneous separations involving multiple phases in multiple zones, the fluid dynamics may be quite complex. Typically, solids flow may approach plug flow (well mixed in the radial dimension), while vapor flow may approach fully mixed flow (high velocity transport in both the radial and axial dimensions). Multiple inlet and exhaust ports for vapor may contribute to overall mixing.

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

[0239] The process may, in some embodiments, be conveniently operated at atmospheric pressure. There are many advantages associated with operating at atmospheric pressure, from mechanical simplicity to improved safety. In certain embodiments, the pyrolysis zone may be operated at a pressure of about 90 kPa, 95 kPa, 100 kPa, 101 kPa, 102 kPa, 105 kPa, or 110 kPa (absolute).

[0240] Vacuum operation (e.g., 10-100 kPa) can facilitate rapid sweeping of volatiles from the system. Higher pressures (e.g., 100-1000 kPa) can be useful when off-gas is fed to high-pressure operation. Elevated pressures can also be useful to facilitate heat transfer, chemical, or separation processes.

[0241] Separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids can be accomplished 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 vapors and non-condensable gases are then carried from the zones into the sweep gas and out of the BPU.

[0242] The sweep gas may be, for example, N, Ar, CO, CO, H, H0, CH, other light hydrocarbons, or combinations thereof. The sweep gas may first be heated before introduction, or possibly cooled if obtained from a heated source.

[0243] The sweep gas more completely removes volatile components by moving them out of the system before they condense or further react. The sweep gas allows a higher rate of volatile material to be removed than would be obtainable from volatilization alone at a given process temperature. Alternatively, the use of a sweep gas allows milder temperatures to be used to remove a certain amount of volatile material. The reason the sweep gas enhances volatile material removal is that the mechanism of separation is not simply relative volatility, but rather liquid / vapor phase liberation assisted by the sweep gas. The sweep gas can both reduce the mass transfer limitation of volatilization as well as the thermodynamic limit by continually depleting a given volatile species, much of which is vaporized to achieve thermodynamic equilibrium.

[0244] To produce a high fixed carbon product, it is important to remove gases containing large amounts of volatile organic carbon from subsequent processing stages. Otherwise, the volatile carbon may adsorb or be absorbed into the pyrolysis solids, thereby requiring additional energy (expense) to obtain the purer forms of carbon that may be desired. It is also believed that rapid removal of vapors may increase porosity in the pyrolyzing solids. In various embodiments, higher porosity, such as in activated carbon products, is desirable.

[0245] In some embodiments, the sweep gas provides rapid vapor removal at relatively low process pressures, such as atmospheric pressure, without requiring large amounts of inert gas.

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

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

[0248] In some embodiments, the zone or zones in which separation is performed are physically separate units from the BPU. Separation units or zones can be located between zones, if desired. For example, there can be a separation unit located between the pyrolysis zone and the cooling zone.

[0249] The sweep gas may be introduced continuously, especially if the solids flow is continuous. If the pyrolysis reaction is operated as a batch process, the sweep gas may be introduced after a period of time or periodically to remove volatiles. Even if the pyrolysis reaction is operated continuously, the sweep gas may be introduced semi-continuously or periodically, if desired, using appropriate valves and controls.

[0250] The volatile-containing sweep gas may exit one or more zones and may be combined if obtained from multiple zones. The resulting gas stream, containing various vapors, may then be fed to a process gas heater for controlled air emissions, as previously described and shown in FIG. 8. Any known thermal oxidation unit may be employed. In some embodiments, the process gas heater is fed with natural gas and air to reach a temperature sufficient for substantial destruction of the volatiles contained therein.

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

[0252] The yield of carbonaceous materials can vary depending on the factors mentioned above, 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 a dry 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 amount of condensable vapors compared to non-condensable gases, including any water present, also depends on the process conditions.

[0253] With respect to carbon balance, in some embodiments, the net yield of carbon as a percentage of the starting carbon in the feedstock is at least 25%, 30%, 40%, 50%, 60%, 70%, or more. For example, in some embodiments, the carbonaceous material contains from about 40% to about 70% of the carbon contained in the starting carbon. The remaining carbon results in the formation, to varying degrees, of methane, carbon monoxide, carbon dioxide, light hydrocarbons, aromatics, 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, including various vapors, may be at least partially condensed and then passed over cooled pyrolysis solids obtained from the cooling zone and / or from a separate cooling device. These embodiments are described in more detail below.

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

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

[0257] Following cooling to ambient conditions, the carbonaceous solids can be recovered and stored, transported to another site operation, shipped to another site, or disposed of, exchanged, or sold. The solids can be fed to a unit to reduce particle size. A variety of size reduction units are known in the art, including crushers, shredders, grinders, pulverizers, jet mills, and ball mills.

[0258] Sieving or some other means for separating based on particle size may be included. Sieving, if present, may be upstream or downstream of grinding. A portion of the sieved material (e.g., large chunks) may be returned to the grinding unit. Small and large particles may be recovered for separate downstream uses. In some embodiments, the cooled pyrolysis solids are ground into a fine powder, such as a pulverized carbon or activated carbon product or strength enhancement.

[0259] Various additives can be introduced anywhere in the process, before, during, or after any of the steps disclosed herein. Additives can be broadly categorized into process additives, which are selected to improve process performance, such as carbon yield or pyrolysis time / temperature to achieve a desired carbon purity; and product additives, which are selected to improve one or more properties of the high-carbon bioreagent or downstream products incorporating that reagent. Certain additives can provide enhanced process and product properties, such as the overall yield of the bioreagent compared to that amount of biomass feedstock.

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

[0261] In some embodiments, the additive is selected from a metal, a metal oxide, a metal hydroxide, or a combination thereof. For example, the additive may be selected from, but is in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0262] In some embodiments, the additive is selected from an acid, a base, or a salt thereof. For example, the additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, or a combination thereof.

[0263] In some embodiments, the additive is selected from metal halides. Metal halides are compounds between metals and halogens (fluorine, chlorine, bromine, iodine, and astatine). Halogens can form numerous compounds with metals. Metal halides are generally obtained by direct bonding or, more commonly, by neutralization of a basic metal salt with 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 hydrates thereof, and any combination thereof.

[0264] The additives may result in a final product with increased 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 materials with lower energy density than carbon. In some embodiments, the additives reduce the amount of liquid formed due to solids and gas formation, or due to solids formation.

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

[0266] Additives may 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 may enhance mechanical properties by mere 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, a reaction such as vitrification may occur within a portion of the bioreagent containing the additive, thereby enhancing the final strength.

[0267] Chemical additives can be applied to wet or dry biomass feedstock. The additives can be applied as a solid powder, spray, mist, liquid, or vapor. In some embodiments, the additives can be introduced through spraying of a liquid solution (e.g., in an aqueous solution or solvent) or by immersion in a tank, bin, bag, or other container.

[0268] In some embodiments, a soaking pretreatment is employed, in which the solid feedstock is soaked, either batchwise or continuously, in a bath containing the additive for a period of time sufficient to allow the additive to penetrate the solid feedstock.

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

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

[0271] In some embodiments, a portion of the solids produced are recycled to the front end of the process, i.e., to a drying or degassing unit, or directly to the BPU or reactor. Returning to the front end and passing through the process again enhances the fixed carbon of the treated solids. Solids, liquids, and gas streams produced or present in the process can be independently recycled 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 to a separate reactor for further pyrolysis to create a product with increased carbon purity. In some embodiments, the secondary process can be carried out in a simple container, such as a steel drum, through which a heated inert gas (such as heated N2) is passed. Other containers useful for this purpose include process tanks, barrels, bins, totes, sacks, and roll-offs. This secondary sweep gas, containing volatiles, can be sent, for example, to a 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, can be passed through the solids to cool them and then returned to the inert gas preheat system. In various embodiments, the secondary process occurs in a separate carbonization or pyrolysis reactor into which preheated substantially inert gas is injected to pyrolyze and carbonize the material.

[0273] Some variations of the present invention provide a high-carbon bio-reagent production system, the system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operable communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) a multi-zone biomass processing unit disposed in operative communication with a drying apparatus, the biomass processing unit including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the biomass processing unit configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) an external cooling device disposed in operable communication with the biomass processing unit; and (e) a carbon capture device disposed in operable communication with the cooling device; Equipped with.

[0274] Some variations provide a high carbon bio-reagent production system, the system comprising: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operable communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) an optional preheater disposed in operable communication with the drying apparatus and configured to heat and / or moderately pyrolyze the feedstock; (d) a pyrolysis reactor disposed in operable communication with the preheater and configured to pyrolyze the feedstock; (e) a cooling device disposed in operable communication with the pyrolysis reactor and configured to cool the pyrolysis solids; and (f) a carbon capture device disposed in operable communication with the cooling device; Equipped with The system is configured with at least one gas outlet for removing condensable vapors and non-condensable gases from the solids.

[0275] The material feed system may be physically integrated with the BPU, for example, through the use of a screw material feed system or an auger mechanism to introduce the feed solids into one of the reactors or zones.

[0276] In some embodiments, the system further includes a preheating zone disposed in operative communication with the pyrolysis zone. Each of the pyrolysis zone, cooling zone, and preheating zone (if present) may be disposed within a single BPU or may be disposed within separate BPUs.

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

[0278] The system may include a purging means for removing oxygen from the system. For example, the purging means may include one or more inlets for introducing a substantially inert gas and one or more outlets for removing the substantially inert gas and displaced oxygen from the system. In some embodiments, the purging means is a degasser disposed in operative communication between the drying apparatus and the BPU.

[0279] The BPU can be configured with at least a first gas inlet and a first gas outlet, which can be positioned in communication with different zones or 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 present within the BPU is configured with a gas inlet and a gas outlet.

[0281] Gas inlets and outlets not only allow for the introduction and recovery of vapors, but gas outlets (probes) in particular also allow for close process monitoring and control over various stages of the process, potentially including all stages of the process. Close process monitoring would be expected to result in improved yields and efficiencies both dynamically and over the long term, when operating history is available to adjust process conditions.

[0282] In some embodiments (see generally FIG. 4), a reactive gas probe is placed in operative communication with the pyrolysis zone. Such a reactive gas probe can be useful for extracting and analyzing gases to determine the extent of reaction, pyrolysis selectivity, or other process monitoring. Based on the measurements, the process can then be controlled or adjusted in any number of ways, such as feed rates, inert gas sweep rates, temperature (in one or more zones), pressure (in one or more zones), additives, etc.

[0283] As intended herein, "monitoring and controlling" via a reactive gas probe should be interpreted to include any one or more samplings via a reactive gas probe and, optionally, making process or equipment adjustments based on the measurements, if deemed necessary or desirable, using well-known process control principles (e.g., feedback, feedforward, proportional-integral-derivative logic, etc.).

[0284] The reaction gas probe may be configured to extract a gas sample in several ways. For example, the sampling line may have a pressure lower than the pyrolysis reactor pressure, allowing a quantity of gas to be easily extracted from the pyrolysis zone when the sampling line is opened. The sampling line may be under vacuum, such as when the pyrolysis zone is at near atmospheric pressure. Typically, the reaction gas probe will be associated with one gas outlet, or a portion thereof (e.g., a line split off from the gas outlet line).

[0285] In some embodiments, both the gas inlet and gas output are utilized as reactive gas probes by periodically introducing an inert gas into the zone and withdrawing the inert gas from the gas output along with a process sample (a "sample sweep"). Such an arrangement can be used in zones that otherwise do not have gas inlets / outlets for a substantially inert gas for processing, or where the reactive gas probe can be associated with a separate gas inlet / outlet that is in addition to the process inlets and outlets. The sampling inert gas that is periodically introduced and extracted for sampling (in embodiments utilizing a sample sweep) can even be different from the process inert gas, if desired, either for accuracy in the analysis or to introduce a tracer for 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 a 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 concentration in the gas phase can be measured and used, for example, as an indication of pyrolysis selectivity for the gas / vapor. The terpene concentration in the gas phase can be measured and used, for example, as an indication of pyrolysis selectivity for the liquid.

[0287] In some embodiments, the system further includes at least one additional gas probe disposed in operative communication with the cooling zone, or with the drying zone (if present) or the preheating zone (if present).

[0288] A gas probe for the cooling zone can be useful, for example, to determine the extent of any additional chemistry occurring within the cooling zone. A gas probe within the cooling zone can also be useful as an independent measurement of temperature (e.g., in addition to a thermocouple placed within the cooling zone). This independent measurement can be a correlation of cooling temperature with some species of measured quantity. The correlation can be developed separately or established after a period of process operation.

[0289] A gas probe for the drying zone may be useful to determine the degree of drying, for example, by measuring moisture content. A gas probe in the preheat zone may be useful, for example, to determine the degree of any mild pyrolysis that is occurring.

[0290] In some embodiments, the cooling zone is configured with a gas inlet and the pyrolysis zone is configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively, or in addition, the preheating zone (if present) may be configured with a gas outlet to generate a substantially countercurrent flow of the gas phase relative to the solid phase. Alternatively, or in addition, the drying zone may be configured with a gas outlet to generate a substantially countercurrent flow.

[0291] The pyrolysis reactor or reactors may be selected from any suitable reactor configuration capable of carrying out a pyrolysis process. Exemplary reactor configurations include, but are not limited to, a fixed bed reactor, a fluidized bed reactor, an entrained flow reactor, an auger, a rotating cone, a rotating drum kiln, a calciner, a roaster, a moving bed reactor, a transport bed reactor, an ablative reactor, a rotating cone, or a microwave-assisted pyrolysis reactor.

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

[0293] In some embodiments where an ablative process is used, the feedstock is moved at high velocity against a hot metal surface. Ablation of any char that has formed on the surface can maintain high heat transfer rates. Such an arrangement can prevent dilution of the product. Alternatively, the feedstock particles can be suspended in a carrier gas and introduced at high velocity through a cyclone with heated walls.

[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 recycled product gas. References herein to "sand" also include similar, substantially inert materials such as glass particles, recovered ash particles, and the like. The high heat transfer rate from the fluidized sand can result in rapid heating of the feedstock. There may be some ablation due to friction with the sand particles. Heat is typically supplied by heat transfer tubes through which hot combustion gases flow.

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

[0296] In some embodiments, the BPU is a continuous reactor including a feedstock inlet, a plurality of spatially separated zones configured for separate temperature control and mixing 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 of which is disposed in communication with a separately adjustable heating means independently selected from the group consisting of electrical 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 with 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 up to and 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 a gas inlet in each zone. In these or other embodiments, the BPU is configured with a gas outlet in each zone. The BPU is a co-current or counter-current reactor.

[0300] In some embodiments, the material feed system includes a screw or auger feed mechanism. In some embodiments, the carbonaceous solids outlet includes a screw or auger output mechanism.

[0301] Some embodiments involve a rotating calciner with a screw material feed system. In these embodiments, part or all of the BPU rotates axially, i.e., rotates about its centerline axis. The speed of rotation affects the solids flow pattern and heat and mass transport. Each of the zones can be configured with flights located on the interior walls to provide agitation of the solids. The flights can be separately adjustable within each zone.

[0302] Other means of agitating the solids may be employed, such as an auger, screw, or paddle conveyor. In some embodiments, the BPU includes a single continuous auger positioned over each zone. In other embodiments, the reactor includes twin screws positioned over each zone.

[0303] Some systems are specifically designed with the ability to maintain the approximate size of the feed material throughout the process—i.e., to process the biomass feedstock without destroying or significantly damaging its structure. In some embodiments, the pyrolysis zone does not contain augers, screws, or rakes that tend to significantly 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 disposed in operable communication with the outlet through which the condensable vapors and non-condensable gases are removed. The process gas heater is configured to receive separate fuel (such as natural gas) and oxidant (such as air) into a combustion chamber suitable for combustion of at least a portion of the fuel and condensable vapors. Certain non-condensable gases, such as CO or CH, may also be oxidized to CO.

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

[0306] In some embodiments, the system further includes a material enrichment unit disposed in operative communication with the cooling device and configured to combine the condensable vapor in at least partially condensed form with the solid matter, the material enrichment unit being capable of increasing the carbon content of the high-carbon biological reagent obtained from the carbon recovery unit.

[0307] The system further includes a separate pyrolysis zone adapted to further pyrolyze the high-carbon bio-reagent to further increase its carbon content. The separate pyrolysis zone may be a relatively simple container, unit, or apparatus, such as, for example, a tank, barrel, bin, drum, tote, sack, or roll-off.

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

[0309] Several variations relating to carbon enrichment of solids are further described herein. In some embodiments, the process for producing a high-carbon bio-reagent comprises: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) cooling the hot pyrolysis solids in a cooling zone at a cooling temperature below the pyrolysis temperature for at least 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (g) optionally, cooling the warm pyrolysis solids in a cooling device to produce cold pyrolysis solids; (h) thereafter, passing at least a portion of the condensable vapors and / or at least a portion of the non-condensable gases from step (e) through the warm pyrolysis solids and / or the cold pyrolysis solids to form concentrated pyrolysis solids having an increased carbon content; and (i) recovering, in a carbon recovery unit, a high-carbon biological reagent comprising at least a portion of the concentrated pyrolysis solids; Includes:

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

[0311] It will be appreciated that in various embodiments, carbon enrichment increases carbon content, energy content, and mass yield.

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

[0313] In some embodiments, step (h) comprises passing substantially all of the condensable vapors from step (e) in vapor and / or condensed form through cold pyrolysis solids to produce concentrated pyrolysis solids having an increased carbon content. In some embodiments, step (h) comprises passing substantially all of the non-condensable gases from step (e) through cold pyrolysis solids to produce concentrated pyrolysis solids having an increased carbon content.

[0314] The process can include various methods of treating or separating the vapor or gas before using it for carbon enrichment. For example, the intermediate feed stream obtained from step (e), consisting of at least a portion of the condensable vapor and at least a portion of the non-condensable gas, can be fed to a separation unit configured to produce at least first and second output streams. In some embodiments, the intermediate feed stream includes all of the condensable vapor, all of the non-condensable gas, or both.

[0315] Separation techniques may include or use distillation columns, flash chambers, centrifuges, cyclones, membranes, filters, packed beds, capillary columns, etc. Separations may be based primarily on, for example, distillation, absorption, adsorption, or diffusion, and may take advantage of differences in vapor pressure, activity, molecular weight, density, viscosity, polarity, chemical functionality, affinity for stationary phases, 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 can be a distillation column, a flash tank, or a condenser.

[0317] Thus, in some embodiments, the first output stream includes condensable vapors and the second output stream includes non-condensable gases. The condensable vapors may include at least one carbon-containing compound selected from terpenes, alcohols, acids, aldehydes, or ketones. The vapors from pyrolysis may include aromatic compounds such as benzene, toluene, ethylbenzene, and xylene. Heavier aromatic compounds, such as refractory tars, may be present in the vapors. The non-condensable gases may include at least one carbon-containing molecule selected from the group consisting of carbon monoxide, carbon dioxide, and methane.

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

[0319] Thus, in some embodiments, the first output stream comprises polar compounds and the second output stream comprises non-polar compounds. The polar compounds may comprise at least one carbon-containing molecule selected from the group consisting of methanol, furfural, and acetic acid. The non-polar compounds may comprise at least one carbon-containing molecule selected from the group consisting of carbon monoxide, carbon dioxide, methane, terpenes, and terpene derivatives.

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

[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 carbon attributable to volatile materials within the reagent. Volatile materials can be, but are not limited to, hydrocarbons, including aliphatic or aromatic compounds (e.g., terpenes); oxygenates, including alcohols, aldehydes, or ketones; and various tars. Volatile carbon typically remains bound to or adsorbed on solids at ambient conditions, but upon heating, is released before the fixed carbon is oxidized, vaporized, or otherwise released as vapor.

[0322] Depending on the conditions associated with step (h), it is possible for some volatile carbon to become fixed carbon (e.g., via carbon formation from CO in Boudoir). Typically, volatile materials are expected to enter the micropores of the fixed carbon, existing as condensed / adsorbed species but still relatively volatile. This residual volatility is more favorable for fuel applications compared to product applications requiring high surface area and porosity.

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

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

[0325] As another example, separation of acetic acid can be performed, followed by reduction of the acetic acid to ethanol, which can be accomplished, at least in part, using hydrogen derived from the non-condensable gases produced.

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

[0327] A potential benefit of including step (h) is that the gas stream is purified of impurities, resulting in a gas stream enriched in CO and CO. The resulting gas stream can be utilized for energy recovery, recycled for carbon enrichment of solids, and / or used as an inert gas in the reactor. Similarly, by separating the non-condensable gases from the condensable vapors, a CO / CO stream is prepared for use as an inert gas, for example, in the reactor system or in a cooling system.

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

[0329] In some variations, a batch or continuous process for producing a high-carbon bio-reagent comprises: (a) providing a solid stream comprising a carbon-containing material; (b) providing 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 the gas stream through the solid stream under suitable conditions to form a carbon-containing product having an increased carbon content relative to the carbon-containing material; Includes:

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

[0331] In some embodiments, the process further comprises recycling or reusing the gas stream to repeat the process to further increase the carbon and / or energy content of the carbon-containing product. In some embodiments, the process further comprises recycling or reusing the gas stream to perform the process to increase the carbon and / or energy content of another feedstock different from the carbon-containing material.

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

[0333] In some embodiments, the process further comprises recycling or reusing the gas stream to repeat the process to further increase the carbon content of the carbon-containing product, hi some embodiments, the process further comprises recycling or reusing the gas stream to carry out the process to increase the carbon content of another feedstock.

[0334] The carbon-containing product can have an increased total carbon content, a higher fixed carbon content, a higher volatile carbon content, a higher energy content, or any combination thereof, compared to the starting carbon-containing material.

[0335] In a related variation, the high carbon bio-reagent production system comprises: (a) a material feed system configured to introduce a carbon-containing feedstock; (b) an optional drying device disposed in operable communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; (c) a BPU disposed in operative communication with a material feed system or a drying apparatus, the BPU including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the BPU configured with an outlet for removing condensable vapors and non-condensable gases from the solids; (d) a cooling device disposed in operable communication with the BPU; (e) a material enrichment unit disposed in operable communication with the cooling device and configured to pass condensable vapors and / or noncondensable gases through the solids to form enriched solids having an increased carbon content; and (f) a carbon capture unit disposed in operable communication with the material concentration unit; Equipped with.

[0336] The system may further include a preheating zone disposed in operable communication with the pyrolysis zone. In some embodiments, the drying device is configured as a drying zone within the BPU. Each zone may be located within a single BPU or within separate BPUs. A cooling device may also be located within the BPU.

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

[0338] In certain embodiments, the system incorporates a material enrichment unit, which comprises: (i) a housing having an upper and lower portion; (ii) an inlet at the bottom surface of the lower portion of the housing configured to convey condensable vapors and non-condensable gases; (iii) an outlet on the upper surface of the upper portion of the housing configured to convey a concentrated gas stream obtained from the condensable vapor and the non-condensable gas; (iv) a path defined between the upper and lower portions of the housing; and (v) a material transport system following the pathway, the material transport system being configured to transport solids, the housing being shaped such that the solids adsorb at least a portion of the condensable vapors and / or at least a portion of the non-condensable gases. Equipped with.

[0339] The present invention is capable of producing a variety of compositions useful as high-carbon biological reagents, and products incorporating these reagents. In some variations, the high-carbon biological reagents are produced by any of the processes disclosed herein, including, but not limited to, the following: (a) providing a carbon-containing feedstock comprising biomass; (b) optionally drying the feedstock to remove at least a portion of the moisture contained within the feedstock; (c) optionally degassing the feedstock to remove at least a portion of the interstitial oxygen, if any, contained within the feedstock; (d) pyrolyzing the feedstock in a pyrolysis zone 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 vapors, and non-condensable gases; (e) separating at least a portion of the condensable vapors and at least a portion of the non-condensable gases from the hot pyrolysis solids; (f) cooling the hot pyrolysis solids in a cooling zone at a cooling temperature below the pyrolysis temperature for at least 5 minutes in the presence of a substantially inert gas to produce warm pyrolysis solids; (g) cooling the warm pyrolysis solids to produce cold pyrolysis solids; and (h) recovering the high-carbon biological reagents, including at least a portion of the cooled pyrolysis solids; This includes each step of the above.

[0340] In some embodiments, the reagent may comprise at least 55 wt%, e.g., 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 on an anhydrous basis. Total carbon includes at least fixed carbon and may also include carbon from volatile materials. In some embodiments, carbon from volatile materials is about at least 5%, at least 10%, at least 25%, or at least 50% of the total carbon present in the high-carbon biological reagent. Fixed carbon may be measured using ASTM D3172, while volatile carbon may be estimated using, for example, ASTM D3175.

[0341] The high-carbon biological reagent may contain about 10 wt% or less, e.g., about 5 wt% or less, hydrogen on an anhydrous basis. The biological reagent may contain about 1 wt% or less, e.g., about 0.5 wt% or less, nitrogen on an anhydrous basis. The biological reagent may contain about 0.5 wt% or less, e.g., about 0.2 wt% or less, phosphorus on an anhydrous basis. The biological reagent may contain about 0.2 wt% or less, e.g., about 0.1 wt% or less, sulfur on an anhydrous basis.

[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 little or essentially no hydrogen (except from any moisture that may be present), nitrogen, phosphorus, or sulfur, and are essentially carbon plus any ash and moisture that is present. Thus, some embodiments provide materials that have less than, including 100%, carbon on a dry / ash-free (DAF) basis.

[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, of course, possible to utilize ashless feedstocks, but in that case, there should not be a significant amount of ash in the pyrolysis solids. Ash can be measured, for example, using ASTM D3174.

[0345] Varying amounts of non-combustible materials, such as ash, may be present. The high-carbon bioreagent may contain about 10 wt. % or less, e.g., about 5 wt. %, about 2 wt. %, about 1 wt. % or less, of non-combustible materials on a water-free basis. In certain embodiments, the reagent contains little or essentially no ash or other non-combustible materials. Thus, some embodiments provide essentially pure carbon, containing 100% carbon on a water-free basis.

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

[0347] High-carbon bioreagents can have a variety of "energy contents," which, for present purposes, refers to the energy density based on the higher calorific value associated with the complete combustion of bone-dry reagents. For example, high-carbon bioreagents can have an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb. In some embodiments, the energy content is between about 14,000 and 15,000 Btu / lb. Energy content can be measured, for example, using ASTM D5865.

[0348] The high-carbon biological reagent may be formed into a powder, such as a coarse or fine powder. For example, the reagent may, in embodiments, be formed into a powder having an average mesh size of about 200 mesh, 100 mesh, 100 mesh, 50 mesh, 10 mesh, 6 mesh, 4 mesh, or 2 mesh.

[0349] In some embodiments, the high-carbon biological reagent is formed into structures comprising compressed, bonded, or agglomerated particles. The starting material for forming these bodies may be a powder form of the reagent, such as an intermediate obtained by micronization. The bodies may be formed by mechanical compression or other forces, optionally using a binder or other means to agglomerate the particles together.

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

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

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

[0353] In some embodiments, the high-carbon biological reagent is, on an anhydrous basis, ≥ 55 wt% total carbon; less than 5 wt% hydrogen; less than 1 wt% nitrogen; not more than 0.5 wt% phosphorus; Not more than 0.2 wt% sulfur; and an additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; Includes:

[0354] The additive may be selected from, but is in no way limited to, magnesium, manganese, aluminum, nickel, chromium, silicon, boron, cerium, molybdenum, phosphorus, tungsten, vanadium, iron halides, iron chloride, iron bromide, magnesium oxide, dolomite, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0355] In some embodiments, the high-carbon biological reagent is, on an anhydrous basis, ≥ 55 wt% total carbon; less than 5 wt% hydrogen; less than 1 wt% nitrogen; not more than 0.5 wt% phosphorus; Not more than 0.2 wt% sulfur; and an additive selected from an acid, a base, or a salt thereof Includes:

[0356] The additive may be selected from, but is in no way limited to, sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, or combinations thereof.

[0357] In certain embodiments, the high-carbon biological reagent is, on an anhydrous basis, ≥ 55 wt% total carbon; less than 5 wt% hydrogen; less than 1 wt% nitrogen; not more than 0.5 wt% phosphorus; not more than 0.2 wt% sulfur; a first additive selected from a metal, a metal oxide, a metal hydroxide, a metal halide, or a combination thereof; and a second additive selected from an acid, a base, or a salt thereof; Including, 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, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof, and the second additive may be independently selected from sodium hydroxide, potassium hydroxide, magnesium oxide, hydrobromic acid, hydrogen chloride, sodium silicate, potassium permanganate, and combinations thereof.

[0359] A high carbon bio-reagent may consist essentially, on an anhydrous basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustibles, 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, dolomitic lime, fluorite, fluorspar, bentonite, calcium oxide, lime, and combinations thereof.

[0360] A high-carbon biological reagent may consist essentially, on an anhydrous basis, of carbon, hydrogen, nitrogen, phosphorus, sulfur, non-combustibles, and an additive 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 additive (total additives) can vary widely, such as from about 0.01 wt% to about 25 wt%, including about 0.1 wt%, about 1 wt%, about 5 wt%, about 10 wt%, or about 20 wt%. It will be understood that when relatively large amounts of additive are incorporated, such as about 1 wt% or more, the energy content calculated based on the total reagent weight (including additives) will be reduced. Still, in various embodiments, the high-carbon biological reagent with additives possesses an energy content of about at least 11,000 Btu / lb, at least 12,000 Btu / lb, at least 13,000 Btu / lb, at least 14,000 Btu / lb, or at least 15,000 Btu / lb.

[0362] The above discussion relating to product morphology also applies to embodiments incorporating additives. Indeed, some embodiments incorporate additives as binders or modifiers to enhance final properties for specific applications.

[0363] In some embodiments, the majority of the carbon contained in the high-carbon bio-reagent is classified as renewable carbon. In some embodiments, substantially all of the carbon is classified as renewable carbon. There may be a market mechanism (e.g., Renewable Identification Number, tax credit, etc.) where value is attributed to the renewable carbon content in the high-carbon bio-reagent.

[0364] In some embodiments, fixed carbon may be classified as non-renewable carbon (e.g., from coal), while volatile carbon may be renewable carbon that may be added separately but 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. The high-carbon bioreagents may themselves be desirable market products. The high-carbon bioreagents as provided herein are associated with lower levels of impurities, reduced process emissions, and improved sustainability (including high renewable carbon content) compared to the state of the art.

[0366] In variations, the product comprises any of the high-carbon biological reagents obtainable by the disclosed processes or described in the compositions described herein, or any portion, combination, or derivative thereof.

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

[0368] Prior to suitability or actual use in any product application, the disclosed high-carbon bioreagents can be analyzed, measured, and optionally modified (such as through additives) in a variety of ways. Besides chemical composition and energy content, some properties of potential interest include density, particle size, surface area, microporosity, absorptivity, adsorption, binding capacity, reactivity, desulfurization activity, and basicity, to name a few.

[0369] Products or materials that may incorporate these high carbon bioreagents include, but are in no way 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 breeze 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] Use of the disclosed high carbon bio-reagents in metal production can reduce slag, increase overall efficiency, and reduce life cycle environmental impacts. Thus, 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, and its primary use is to produce metals from their ores. Smelting uses heat and chemical reducing agents to break down the ore. Carbon and / or carbon monoxide derived from the carbon removes oxygen from the ore, leaving behind the elemental metal.

[0372] The reducing agent may consist of or include a high-carbon bioreagent. In a blast furnace, the high-carbon bioreagent, ore, and usually limestone may be fed continuously from the top of the furnace while air (optionally oxygen-enriched) is blown into the bottom of the chamber to allow chemical reactions to occur throughout the furnace as the material moves downward. The end products are usually molten metal and a slag phase removed from the bottom, and flue gases exiting the top of the furnace. The downward flow of ore in contact with the upward flow of hot, carbon monoxide-enriched gas is a countercurrent process.

[0373] Carbon quality in a blast furnace is measured by its resistance to decomposition. The role of carbon as an infiltration medium is crucial for efficient blast furnace operation. Carbon decomposition varies with location in the blast furnace and results from a combination of reactions with CO2, H2O, or O2, as well as attrition of carbon particles to each other and to other components of the charge. Decomposed carbon particles can cause plugging and poor performance.

[0374] The coke reactivity test is a highly regarded measure of carbon performance in a blast furnace. This test has two components: the Coke Reactivity Index (CRI) and the Coke Strength after Reaction (CSR). Carbonaceous 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 known in the art, such as, for example, by the arrival-based ASTM method DS341.

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

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

[0377] Some embodiments employ one or more additives in an amount sufficient to provide a high-carbon bio-reagent that, when added to another carbon source (e.g., coke) having an inadequate CRI or CSR for use as a blast furnace product, provides a composite product having a sufficient CRI and / or CSR for use in a blast furnace. In some embodiments, the one or more additives are present in an amount sufficient to provide a high-carbon bio-reagent 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 the high-carbon bioreagent. For example, calcium, calcium oxide, calcium carbonate, magnesium oxide, or magnesium carbonate can be introduced as an additive. The addition of these compounds before, during, or after pyrolysis can increase or decrease the reactivity of the high-carbon bioreagent in a blast furnace. These compounds can 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, can result in lower emissions (e.g., SO2).

[0379] In some embodiments, the high-carbon bioreagent not only has a high fixed carbon content, as previously described, but also contains a fairly high proportion of volatile carbon. Volatile materials may be desirable for metal oxide reduction because they are expected to have better mass transport to the metal oxide at low temperatures. Compared to fossil fuel-based products such as coke, the high-carbon bioreagent may have sufficient strength and more fixed and volatile carbon, which leads to greater reactivity.

[0380] In some embodiments, the blast furnace replacement product is a high-carbon bioreagent according to the present invention, comprising at least about 55 wt% carbon, not more than about 0.5 wt% sulfur, not more than about 8 wt% non-combustible materials, and a calorific value of at least about 11,000 Btu per pound. In some embodiments, the blast furnace replacement product further comprises not more than about 0.035 wt% phosphorous acid, about 0.5 wt% to about 50 wt% volatiles, and optionally one or more additives. In some embodiments, the blast furnace replacement product comprises about 2 wt% to about 15 wt% dolomite, about 2 wt% to about 15 wt% dolomitic 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 replacement product has dimensions substantially in the range of about 1 cm to about 10 cm.

[0381] In some embodiments, the high carbon bioreagent according to the present invention is useful as a foundry coke substitute. Foundry coke is generally characterized as having a carbon content of at least about 85 wt.%, a sulfur content of about 0.6 wt.%, volatile matter not exceeding about 1.5 wt.%, ash not exceeding about 13 wt.%, moisture not exceeding about 8 wt.%, phosphorus not exceeding 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. Iron oxides are the ores used in iron and steel production. The primary iron oxide ores are hematite, limonite (also called limonite), taconite, and magnetite, a black ore. Taconite is a low-grade but important ore that contains both magnetite and hematite. The iron content of taconite is generally 25% to 30% by weight. Blast furnaces typically require at least 50% iron-containing ore for efficient operation. Iron ore may undergo beneficiation processes, including crushing, sieving, tumbling, flotation, and magnetic separation. Refined ore is concentrated to over 60% iron and is often formed into pellets before shipping.

[0383] For example, taconite can be crushed into a fine powder and combined with a binder such as bentonite clay and limestone. For example, pellets about 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, ensuring that the blast furnace charge remains sufficiently porous to allow heated gases to pass through and react with the pelletized ore.

[0384] Taconite pellets may be fed into a blast furnace to produce iron, as described above in connection with blast furnace additives. In some embodiments, a high-carbon bioreagent is introduced into the blast furnace. In these or other embodiments, the high-carbon bioreagent is incorporated into the taconite pellets themselves. For example, taconite ore flour, after beneficiation, is mixed with a high-carbon bioreagent and a binder, rolled into small bodies, and then hard-fired. In such embodiments, taconite carbon pellets having the appropriate composition may be conveniently introduced into a blast furnace without the need for a separate source of carbon.

[0385] Some variations of the present invention utilize high-carbon bioreagents as ladle-added carbon-based products. A ladle is a vessel used to transport and pour molten metal. A casting ladle is used to pour molten metal into molds to produce castings. A transfer ladle is used to transport large quantities of molten metal from one process to another. Transfer ladles are used for processes that occur in the ladle to change some aspect of the molten metal, such as converting cast iron to ductile iron by adding various elements to the ladle.

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

[0387] In some embodiments, the high carbon bioreagent according to the present invention is useful, for example, as a ladle addition carbon additive in any basic oxygen furnace or electric arc furnace facility where ladle addition of carbon is used (e.g., added to ladle carbon during steel production). In some embodiments, the ladle addition carbon additive is a high carbon bioreagent comprising at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous, and a heating value of at least about 11,000 BTU per pound.

[0388] In some embodiments, the ladle added carbon additive further comprises up to about 5 wt% manganese, up to about 5 wt% calcium oxide, and / or up to about 5 wt% dolomitic lime. In some embodiments, the ladle added carbon additive has a minimum dimension of about ¼ inch. In some embodiments, the ladle added carbon product has a maximum dimension of about ½ inch. In some embodiments, the ladle added carbon additive has a minimum dimension of about ¼ inch and a maximum dimension of about ½ inch. In some embodiments, the ladle added carbon product is substantially fossil fuel free.

[0389] Direct reduced iron (DRI), also known as sponge iron, is produced from the direct reduction of iron ore (in lump, pellet, or fine powder form) with reducing gas generated from natural gas or coal. The reducing gas is typically syngas, a mixture of hydrogen and carbon monoxide, which acts as a reducing agent. High-carbon bioreagents, such as those provided herein, can be converted into a gas stream containing CO to act as a reducing agent to produce direct reduced iron.

[0390] Iron nuggets are a high-quality steelmaking and iron casting feed material. Iron nuggets are essentially all iron and carbon, with little gangue (slag) and low levels of residual metals. They are a premium pig iron product with excellent shipping and handling characteristics. The carbon contained in the iron nuggets, or any portion thereof, can be the high-carbon bioreagent provided herein. Iron nuggets can be produced through the reduction of iron ore in a rotary hearth furnace using the high-carbon bioreagent as a reducing agent or energy source.

[0391] Some variations of the present invention utilize high-carbon bioreagents as metallurgical coke carbonaceous products. Metallurgical coke, also known as "met" coke, is a carbonaceous material commonly produced by destructive distillation of various blends of bituminous coal. The final solid is an undissolved 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 content. However, ash components that 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 where high quality, tough, resilient, wearing carbon is required. Applications include, but are not limited to, conductive floor coverings, friction materials (e.g., carbon liner), foundry coatings, foundry recarburizers, corrosion materials, drilling applications, reducing agents, heat treatment agents, ceramic fillers, electrolytic processes, and oxygen scavenging.

[0393] Met coke is characterized as having a heating value of at least about 11,000-14,000 Btu per pound and an ash content of about 10 wt% or greater. Thus, in some embodiments, a met coke substitute comprises a high-carbon bioreagent according to the present invention, comprising at least about 80 wt%, 85 wt%, or 90 wt% carbon, about 0.8 wt% or less sulfur, about 3 wt% or less volatiles, about 15 wt% or less ash, about 13 wt% or less moisture, and about 0.035 wt% or less phosphorus. In some embodiments, a met coke substitute comprises at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous, and a heating 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% dolomite, e.g., 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% 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% calcium oxide, e.g., 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% calcium oxide. In some embodiments, the met coke substitute further contains about 2 wt% to about 15 wt% dolomitic 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% dolomitic lime.In some embodiments, the met coke substitute comprises any combination of 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 about 2 wt% to about 15 wt% dolomitic lime. High-carbon bioreagents according to the present invention, when used as met coke substitutes, can have sizes ranging from about 2 cm to about 15 cm, for example. In some embodiments, the met coke substitute has a minimum dimension of about ¾ 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 ¾ 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, for example, chromium, nickel, manganese, magnesium oxide, silicon, aluminum, dolomite, fluorspar, calcium oxide, lime, dolomitic lime, bentonite, and combinations thereof.

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

[0396] In some embodiments, the high-carbon biological reagent combines with one or more carbon-based products to form composite products that have a higher rank than the carbon-based products and / or emit less carbon upon combustion than the pure carbon-based products.

[0397] For example, a low-rank coal, such as a subbituminous coal, can be used in applications that typically require a higher-rank coal product, such as a bituminous coal, by combining a selected amount of a high-carbon bioreagent according to the present invention with the low-rank coal product. In other embodiments, the rank of a blended coal product (e.g., a combination of multiple coals of different ranks) can be increased by combining the blended coal with an amount of high-carbon bioreagent. The amount of high-carbon bioreagent mixed with the coal product can vary depending on the rank of the coal product, the properties of the high-carbon bioreagent (e.g., carbon content, heating value, etc.), and the desired rank of the final composite product.

[0398] For example, anthracite coal is generally characterized as having at least about 80 wt% carbon, about 0.6 wt% sulfur, about 5 wt% volatiles, up to about 15 wt% ash, up to about 10 wt% moisture, and a heating value of about 29 MJ / kg (approximately 12,494 Btu / lb). In some embodiments, anthracite coal substitutes are high-carbon bioreagents according to the present invention that include at least about 80 wt% carbon, no more than about 0.6 wt% sulfur, no more than about 15 wt% ash, and a heating value of at least about 12,000 Btu / lb.

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

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

[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 can be comprised of a high-carbon bioreagent containing at least about 50 wt% carbon, not more than about 8 wt% ash, not more than about 0.5 wt% sulfur, and a heating value of at least about 11,000 Btu / lb. In other embodiments, the fuel coke substitute further contains between about 0.5 wt% and about 50 wt% volatile matter. The fuel coal or coke substitute can contain between about 0.4 wt% and about 15 wt% moisture.

[0402] In some embodiments, the high-carbon bioreagent according to the present invention is useful as a petroleum (PET) coke or calcined petroleum coke substitute. Calcined petroleum coke is generally characterized as having at least about 66 wt% carbon, up to about 4.6 wt% sulfur, up to about 5.5 wt% volatiles, up to about 19.5 wt% ash, and up to about 2 wt% moisture, and is typically about 3 mesh or smaller in size. In some embodiments, the calcined petroleum coke substitute is a high-carbon bioreagent comprising 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 in size.

[0403] In some embodiments, the high-carbon bioreagent according to the present invention is useful as a coking carbon substitute (e.g., co-fired with raw coal in a coking oven). In one embodiment, the coking carbon substitute is a high-carbon bioreagent comprising at least about 55 wt% carbon, not more than about 0.5 wt% sulfur, not more than about 8 wt% non-combustibles, and a heating value of at least about 11,000 Btu per pound. In some embodiments, the coking carbon substitute is a high-carbon bioreagent comprising at least about 55 wt% carbon, not more than about 0.4 wt% sulfur, not more than about 0.035 wt% phosphorous, and a heating value of at least about 11,000 Btu per pound. In some embodiments, the coking carbon substitute has a minimum dimension of about ¾ inch. In some embodiments, the coking carbon substitute is substantially free of fossil fuels. In some embodiments, the coked carbon substitute comprises about 0.5 wt% to about 50 wt% volatile materials and one or more additives.

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

[0405] In some embodiments, the high-carbon bioreagent according to the present invention is useful as a carbon coke breeze substitute, for example, during taconite pellet production or iron manufacturing processes. In some embodiments, the carbon coke breeze substitute is a high-carbon bioreagent comprising at least about 55 wt% carbon, not more than about 0.4 wt% sulfur, not more than about 0.035 wt% phosphorous, and a heating value of at least about 11,000 Btu per pound. In some embodiments, the carbon coke breeze substitute has a minimum dimension of about 1 / 8 inch. In some embodiments, the carbon coke breeze substitute is substantially fossil fuel-free.

[0406] Some variations of the present invention utilize high-carbon bioreagents as feedstocks for various fluidized-bed reactors or as carbonaceous feedstock replacements for fluidized-bed reactors. The carbon can be employed in fluidized-bed reactors for complete combustion, partial oxidation, gasification, steam reforming, or the like. The carbon can be converted primarily to synthesis gas for various downstream uses, including the production of energy (e.g., cogeneration) or liquid fuels (e.g., methanol or Fischer-Tropsch diesel).

[0407] In some embodiments, the high-carbon bioreagent according to the present invention is useful, for example, as a fluidized bed carbon substitute 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 comprising at least about 55 wt% carbon, no more than about 0.4 wt% sulfur, no more than about 0.035 wt% phosphorous, and a heating value of 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 free of fossil fuels.

[0408] Some variations of the present invention utilize a high-carbon bioreagent as a carbon-based furnace addition product. Carbon-based carbon furnace addition products are generally characterized as having high sulfur levels, high phosphorus levels, and high ash content, which contribute to the degradation of metal products and create air pollution. In some embodiments, the carbon furnace addition substitute containing the high-carbon bioreagent contains about 0.5 wt% or less sulfur, about 4 wt% or less ash, about 0.03 wt% or less phosphorous, and a maximum dimension of about 7.5 cm. In some embodiments, the carbon furnace addition substitute contains about 0.5 wt% to about 50 wt% volatiles and about 0.4 wt% to about 15 wt% moisture. In some embodiments, the furnace additive 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, less than about 5 wt% manganese, less than about 5 wt% fluorspar, and a calorific value of at least about 11,000 Btu / lb. In some embodiments, the furnace additive substitute further contains about 5 wt% to about 10 wt% dolomite, e.g., 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 additive substitute further contains about 5 wt% to about 10 wt% dolomitic lime, e.g., about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% dolomitic lime. In some embodiments, the furnace addition replacement further contains about 5 wt% to about 10 wt% calcium oxide, e.g., 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 replacement further contains about 5 wt% to about 10 wt% dolomitic lime, and about 5 wt% to about 10 wt% calcium oxide. In some embodiments, the furnace addition replacement further contains about 5 wt% to about 10 wt% dolomite, about 5 wt% to about 10 wt% dolomitic lime, and about 5 wt% to about 10 wt% calcium oxide. In some embodiments, the furnace addition replacement has a minimum dimension of about ¾ inch. In some embodiments, the furnace addition replacement has a maximum dimension of about 2 inches.In some embodiments, the furnace addition replacement has a minimum dimension of about 3 / 4 inch and a maximum dimension of about 2 inches. In some embodiments, the furnace addition replacement is substantially fossil fuel free.

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

[0410] In some embodiments, the furnace-added carbon additive is a high-carbon bioreagent according to the present invention comprising at least about 80 wt% carbon, not more than about 0.5 wt% sulfur, not more than about 8 wt% non-combustibles, and a heating value of at least about 11,000 Btu per pound. In some embodiments, the furnace-added carbon additive further contains up to about 5 wt% manganese, up to about 5 wt% fluorspar, about 5 wt% to about 10 wt% dolomite, about 5 wt% to about 10 wt% dolomitic lime, and / or about 5 wt% to about 10% calcium oxide.

[0411] Some variations of the present invention utilize a high-carbon bioreagent as a stoker furnace carbon-based product. In some embodiments, the high-carbon bioreagent according to the present invention is useful, for example, as a stoker coal substitute 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 comprising at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous, and a heating value of 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 a high-carbon bio-reagent as an injectable (e.g., pulverized) carbon-based material. In some embodiments, the high-carbon bio-reagent according to the present invention is useful as an injection-grade calcined petroleum coke replacement product. Injection-grade calcined petroleum coke is generally characterized as having at least about 66 wt% carbon, about 0.55 to about 3 wt% sulfur, up to about 5.5 wt% volatiles, up to about 10 wt% ash, and up to about 2 wt% moisture, and is about 6 mesh or smaller in size. In some embodiments, the calcined petroleum coke replacement product is a high-carbon bio-reagent containing at least about 66 wt% carbon, up to about 3 wt% sulfur, up to about 10 wt% ash, and up to about 2 wt% moisture, and is about 6 mesh or smaller in size. In various embodiments, the injectable carbon is also known as pulverized carbon, pulverized extractive carbon, or PCI. In various embodiments, the injectable carbon is used as a direct energy source, a reagent, or both.

[0413] In some embodiments, the high-carbon bioreagent according to the present invention is useful as an injectable carbon replacement product, for example, in basic oxygen furnace or electric arc furnace facilities, in any application where injectable carbon may be utilized (e.g., injected into slag or ladles during steel production). In some embodiments, the injectable carbon replacement product is a high-carbon bioreagent comprising at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous, and a heating value of at least about 11,000 BTU per pound. In some embodiments, the injectable carbon replacement product further contains up to about 10 wt% dolomitic lime. In some embodiments, the injectable carbon replacement product further contains up to about 10 wt% calcium oxide. In some embodiments, the injectable carbon replacement product further contains up to about 10 wt% dolomitic lime and up to about 10 wt% calcium oxide. In some embodiments, the injectable carbon replacement product has a minimum dimension of about 1 / 8 inch. In some embodiments, the injectable carbon replacement product is substantially free of fossil fuels.

[0414] In some embodiments, the high-carbon bioreagent according to the present invention is useful, for example, as a pulverized carbon replacement product wherever pulverized coal may be utilized (e.g., for process heat or energy generation). In some embodiments, the pulverized coal replacement product further contains up to about 10 wt% calcium oxide. In some embodiments, the pulverized coal replacement product is a high-carbon bioreplacement comprising at least about 55 wt% carbon, less than about 0.4 wt% sulfur, and a heating value of at least about 11,000 BTU per pound. In some embodiments, the pulverized coal replacement product has a minimum dimension of about 1 / 8 inch. In some embodiments, the pulverized coal replacement 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 carbon-containing metal alloys. Carbon-based late-stage carbon addition products are generally characterized as having high sulfur levels, high phosphorous 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 products contain less than about 0.5 wt.% sulfur, less than about 4 wt.% ash, less than about 0.03 wt.% phosphorus, a minimum dimension of about 1-5 mm, and a maximum dimension of about 8-12 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, in any embodiment, a high-carbon bioreagent according to the present invention. The high-carbon bioreagent comprises at least about 55 wt% carbon, less than about 0.4 wt% sulfur, less than about 0.035 wt% phosphorous, and a calorific value of at least about 11,000 BTU per pound. In some embodiments, the carbon electrode comprises a high-carbon bioreagent comprising at least about 55 wt% carbon and less than about 0.5 wt% sulfur. In some embodiments, the carbon electrode is substantially fossil-fuel-free.

[0417] Other uses of the high-carbon bio-reagent in carbon electrodes include applications in batteries, fuel cells, capacitors, and other energy storage or energy delivery devices. For example, in lithium-ion batteries, the high-carbon bio-reagent can be used to intercalate 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 metals includes a step in which a carbon electrode is consumed. In some embodiments, the carbon electrode comprises a high-carbon bio-reagent comprising 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 Fischer-Tropsch synthesis of higher hydrocarbons from syngas using sulfided cobalt-molybdenum metal catalysts supported on a carbon phase, or the synthesis of mixed alcohols from syngas using iron-based catalysts supported on carbon.

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

[0420] In some embodiments, the amounts of the various components of the high-carbon biological reagent compositions disclosed herein are measured on a dry basis. In some embodiments, the amounts of the various components of the high-carbon biological reagent compositions disclosed herein are measured on an ash-free basis. In some embodiments, the amounts of the various components of the high-carbon biological reagent compositions disclosed herein are measured on a dry, ash-free basis.

[0421] In the above description of market applications for high-carbon bioreagents, it will be recognized that the applications described are neither exclusive nor comprehensive. Thus, a high-carbon bioreagent described as suitable for one type of carbon product may, in various embodiments, be suitable for any other application described. These applications are exemplary only, and there are other applications for high-carbon bioreagents. In various embodiments, injectable 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 be introduced at the end of its useful life as a performance material, and then into a combustion process or metal processing for energy value, etc.

[0423] Some embodiments may employ activated carbon both for its reactive / adsorptive properties and as a fuel. For example, activated carbon injected into an exhaust stream may be suitable to remove pollutants, followed by combustion of the activated carbon particles and possibly the pollutants to generate energy and either thermally destroy or chemically oxidize the pollutants.

[0424] Significant environmental and product use advantages can 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] With respect to metal production, the generation of bioreagents in the disclosed process reduces CO, CO2, and NO emissions compared to the coking required to prepare carbonaceous products for use in metal production. x , resulting in significantly lower emissions of SO2 and hazardous air pollutants.

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

[0427] Additionally, 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. [Example]

[0428] 〔example〕 Example 1. Preparation of biological reagents - general method The wood substrate, consisting of large red pine chips, Douglas-fir cylinders (1.25-inch diameter pieces), and Douglas-fir chips (approximately 2 inches by 2 inches), was loaded into a loading hopper with an optional heated nitrogen gas flow. Optionally, a 1% aqueous solution of additive (e.g., NaOH and / or KOH) was applied by spraying 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 soak into the biomass for 30 minutes before it was dried. Once the reactor reached the desired temperature, reactor rotation was initiated, 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 exiting the heated section of the reactor, the pyrolyzed material was collected in a discharge hopper. A conveyor removed the bioreagents from the discharge hopper for further analysis.

[0429] Bioreagents were prepared according to the general method above, using various feedstock sizes, different reactor temperatures, heated 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-F, which were prepared without any additives, are shown in Table 3 below. [Table 3]

[0432] The results for Samples G-J2, which were prepared using additives, are shown in Table 4 below. [Table 4]

[0433] Example 3. Production of high-heat-generating biological reagents This example demonstrates the production of a bioreagent with a high calorific value.

[0434] Feedstock containing Douglas-fir cylindrical pieces (1-1 / 8" diameter, approximately 1.5 inches long) was pyrolyzed according to the general method of Example 1. The reactor was heated to 600°C and the feedstock was pyrolyzed 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. Production of high-heat-generating biological reagents This example demonstrates the production of a bioreagent with a high calorific value.

[0436] A feedstock comprising red pine chips having an average particle size of approximately 1 inch by 1 / 2 inch by 1 / 8 inch was pyrolyzed according to the general method of Example 1. The reactor was heated to 550°C and the feedstock was pyrolyzed 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 biocoke substitute for blending with Met-coke A bioreagent was prepared from crushed kiln-dried wood doweling substantially according to the general method of Example 1.

[0438] Blends of met-coke (sample ID No. SGS / 427-1104014-001) with 2% and 5% bio-reagent were prepared by blending met-coke with appropriate amounts of bio-coke substitute. Strength and reactivity values were measured for the blends compared to met-coke alone according to ASTM D5341 and are shown in Table 7 (values are the average of a minimum of two tests per sample). [Table 7]

[0439] This example shows that bioreagent prepared substantially according to the general method of Example 1, when mixed with met coke at 2 wt % and 5 wt %, can achieve CRI values of up to 30% and CSR values of over 60%, which meet the standard specifications for the use of met coke in large-scale blast furnaces.

[0440] Example 6. Production of enhanced hot strength biocoke substitute Red pine wood chips approximately 1" x 1 / 2" x 1 / 8" in size were pyrolyzed at 600°C with a residence time of 30 minutes according to the general method of Example 1. The resulting bioreagent is referred to as "Sample A."

[0441] Ground kiln-dried wooden dowels having a diameter of 1 1 / 8" were cut into pieces each having a length of approximately 1.5 inches. The pieces were pyrolyzed at 600°C with a dwell time of 2 hours according to the general method of Example 1. The resulting bioreagent is referred to as "Sample B."

[0442] Sample A and Sample B were each placed separately in a quartz tube 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 for enhancing the hot strength of biocoke substitutes and their suitability for use as a replacement for met-coke in various metal production applications.

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

[0444] Example 8. Effect 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 approximately equal mass, consisting of feedstock pieces of approximately equal particle size. Each of the four groups was subjected to pyrolysis 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 according to 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 pyrolysis temperature on fixed carbon levels in bioreagents was investigated by dividing a batch of feedstock into five groups of approximately equal mass, consisting of feedstock pieces of approximately equal particle size. Each of the five groups was subjected to pyrolysis according to the general method of Example 1, with a residence time of 30 minutes. The fixed carbon content of each sample was measured according to ASTM D3172. The results are shown in Table 10 and corresponding Figure 15. [Table 10]

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

[0447] Example 11. Effect of oxygen level during pyrolysis on mass yield of biological reagents This example shows the effect of oxygen levels on the mass yield of a bioreagent.

[0448] Two samples of hardwood sawdust (4.0 g) were each placed in a quartz tube. The quartz tube was then placed in a tube 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 turned off and the tube and furnace were allowed to cool for 10 minutes. The tube was removed from the furnace (with gas still flowing at 2,000 ccm). Once the tube and sample had cooled sufficiently for processing, the gas was turned off and the pyrolyzed material was removed and weighed (Table 12). [Table 12]

[0449] Example 12. Effect of oxygen level on fixed carbon level and calorific value of biological reagents during pyrolysis Use of a carbon recovery unit ("CRU") shows an increase in fixed carbon content and heating value.

[0450] Pyrolysis of hardwood sawdust was carried out according to Example 10. A standard coconut shell charcoal ("CSC") tube (SKC Cat. No. 226-09) was placed in the off-gas stream following a standard small impinger containing 10 mL of HPLC-grade water. The increase in fixed carbon level and heating value was compared to a CSC tube that had not been exposed to any off-gassing (Table 13, ashless and anhydrous data). [Table 13]

[0451] The results of Examples 11 and 12 demonstrate the benefits of maintaining a near-zero oxygen atmosphere to the mass yield and commercial value of the disclosed pyrolysis process. Using the off-gas from these two experiments, it was also possible to show that the BTU-laden gases exiting the process could be captured to enhance 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 biological reagents This example demonstrates the effect of introducing heated nitrogen gas into a biomass processing unit.

[0453] Production of bioreagents using biomass consisting of red pine wood chips, typically measuring 1 inch x 1 / 2 inch x 1 / 8 inch, was carried out at 350°C using a four-zone heated pilot-scale reactor according to 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 per minute, and the biomass was treated for 30 minutes.

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

[0455] The results of these tests indicate a 7.0% increase in the fixed carbon content of the bioreagent carbonized product [(100)(55.3%-51.7%) / 55.3%] by utilizing preheated nitrogen.

[0456] Example 14. Improving mass yield by pretreatment of biomass This example demonstrates the production of a bioactivated carbon product with an additive, namely, iron (II) bromide.

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

[0458] The wood chip and solution containers were sealed with watertight lids. The containers and contents were mixed by periodically tilting and rolling them for approximately four hours. The wood chips and solution were left sealed overnight to allow saturation of the wood chips with the solution.

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

[0460] The preheated, air-dried wood chips were verified to have a moisture content of 12%. The mass of the preheated, 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 per minute. Pyrolysis occurred 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), representing a mass yield of 47.6% based on the mass of the feedstock (e.g., minus the mass contribution of the pretreatment additives) at a moisture content of 12%. On a dry basis (correcting for the 12% moisture and the mass contribution of the pretreatment additives), the mass yield was 54.1%. As shown in Table 15 below, this represents an 8-15% increase in mass yield over untreated wood chips processed under the same conditions.

[0462] [Table 15]

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

[0464] In this detailed description, reference is made to multiple embodiments of the invention and to non-limiting examples relating to how the invention can be realized and practiced. Other embodiments that do not provide all of the features and advantages described herein may be utilized without departing from the spirit and scope of the invention. The invention incorporates routine experimentation and optimization of the methods and systems described herein. Such modifications and variations are considered to be within the scope of the invention, as defined by the claims.

[0465] All publications, patents, and patent applications cited in this application are herein incorporated by reference in their entirety, to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference herein.

[0466] While the methods and steps described above show certain events occurring in a certain order, those skilled in the art will understand that the ordering of certain steps may be changed and that such changes are consistent with variations of the present invention. Furthermore, certain steps may be performed not only sequentially but also simultaneously in a parallel process, where possible.

[0467] Therefore, to the extent there are variations of the present invention that are within the spirit of the disclosure or equivalents of the present invention found in the appended claims, it is intended that this patent cover those variations as well.

Claims

1. A high-carbon biological reagent production system, the system comprising: purge means for removing oxygen from the system, said purge means including one or more inlets for introducing an inert gas and one or more outlets for removing the inert gas and displaced oxygen from the system; a material supply system configured to introduce a carbon-containing feedstock; an optional drying device disposed in operative communication with the material supply system and configured to remove moisture contained within the carbon-containing feedstock; a multi-zone reactor disposed in operative communication with the material feed system or the drying device (if present), the multi-zone reactor including at least one pyrolysis zone disposed in operative communication with a spatially separated cooling zone, the multi-zone reactor configured with an outlet for removing condensable vapors and non-condensable gases from the solids; a cooling device disposed in operative communication with the multi-zone reactor; a carbon recovery unit disposed in operative communication with the cooling device; and A high-carbon biological reagent production system comprising:

2. The system described in claim 1, further comprising a preheating zone arranged in operative communication with the at least one pyrolysis zone.

3. The system described in claim 2, wherein the multi-zone reactor comprises the at least one pyrolysis zone, the cooling zone, and the preheating zone.

4. The system described in claim 2, further comprising a second multi-zone reactor comprising the preheating zone.

5. The system of claim 1, wherein the multi-zone reactor is equipped with a drying device.

6. The system described in claim 1, wherein the multi-zone reactor is equipped with the cooling device.

7. The system described in claim 1, further comprising an additive supply device for introducing an additive into the system.

8. The system described in claim 7, wherein the additive supply device is configured to combine the additive with the carbon-containing feedstock.

9. The system described in claim 7, wherein the additive supply device is inserted between the material supply system and the multi-zone reactor.

10. The system of claim 7, wherein the additive supply device is arranged in operable communication with the multi-zone reactor and the cooling device.

11. The system described in claim 7, wherein the additive supply device is inserted between the cooling device and the carbon recovery unit and is arranged in operative communication with the carbon recovery unit.

12. The system of claim 1, wherein the multi-zone reactor is configured with a first gas inlet and a first gas outlet.

13. The system described in claim 12, wherein the first gas inlet and the first gas outlet are arranged in operative communication with the same or different zones.

14. The system of claim 12, wherein the multi-zone reactor is configured with a second gas inlet and a second gas outlet.

15. The system described in claim 2, wherein the cooling zone is configured with a gas inlet to generate a counterflow of gas phase relative to the solid phase, the pyrolysis zone is configured with a gas outlet, and the preheating zone is configured with a gas outlet to generate a counterflow of gas phase relative to the solid phase.

16. The system described in claim 2, wherein the cooling zone is configured with a gas inlet and the preheating zone is configured with a gas outlet to generate a counterflow of gas phase against a solid phase.

17. The system described in claim 1, further comprising a first reactive gas probe positioned in operable communication with the pyrolysis zone and with a gas monitoring device.

18. The system described in claim 17, further comprising a second reactive gas probe positioned in operative communication with the cooling zone and with the gas monitoring device or a second gas monitoring device.

19. The system described in claim 17, further comprising an additional reactive gas probe positioned in operative communication with the optional drying zone and with the gas monitoring device.

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